Novel thermoresponsive ether-based electrolyte for wide-temperature operating lithium metal batteries

Novel thermoresponsive ether-based electrolyte for wide-temperature operating lithium metal batteries | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Novel thermoresponsive ether-based electrolyte for wide-temperature operating lithium metal batteries Yulin Min, rong gu, Da Zhang, Shengtao Xu, Xiaoyu Guo, Hua Jiang, and 7 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5101221/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 01 Jul, 2025 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract Developing wide-temperature range and safety electrolytes for lithium metal batteries (LMBs) is expected to possess high redox interfacial stability, rapid kinetics and intrinsic safety. However, traditional electrolytes are rarely able to satisfy all of these characteristics simultaneously, often exhibiting preference for one over the other. Herein, we present a novel ether-based thermoresponsive electrolyte, that are designed by temperature-dependent Li + solvation structure and forming polycrystalline electrode/electrolyte interface, can achieve the above characteristics at conventional salt concentration. The solvation sheath in the novel electrolyte is reconstructed by 1,3,5-trioxane (TO), accelerating the dissociation and charge transfer kinetics of anions. TO also induces cationic-ring-opening polymerization of tetrahydrofuran solvent molecules at 60 o C to produce oxidation-resistant ether-based polymers, which enhances the high-temperature performance and safety of LMBs. Consequently, the Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) cells using this thermoresponsive electrolyte operate well over a wide temperature range (from −60 to 60 o C). Besides, the Li||NCM811 pouch cell (1.5 Ah) achieve a high capacity-retention of 74.7% after 60 cycles at −40 °C, accompanied by an impressive energy density of 317.1 Wh kg −1 . Physical sciences/Chemistry/Energy Physical sciences/Energy science and technology/Energy storage/Batteries Wide temperature Thermoresponsive electrolyte Interfacial chemistry Li-metal batteries Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Introduction With the global community pursuit of carbon neutrality, there is an immediate requirement for high-specific-energy batteries to promote energy storage and conversion efficiency 1 – 3 . The energy density of advanced Lithium metal batteries (LMBs) has exceeded 400 Wh kg − 1 , becoming a strong contender for next-generation secondary batteries 4 , 5 . However, the practical application of LMBs is limited by persistent parasitic reactions, disordered dendrite growth and low ionic conductivity, further resulting in rapid capacity decay and battery failure 6 – 9 . In theory, the homogeneous and stable solid electrolyte interface (SEI) and cathode electrolyte interface (CEI) enhance the electrochemical performance of LMBs 10 , 11 . For commercial electrolyte, the unstable organic components, including lithium dicarbonate ((ROCO 2 Li) 2 ), semicarbonate (ROCO 2 Li) and alcohol salts (ROLi), leading to slow transfer rate of Li + and harmful side reactions 3 , 12 . Notably, the viscosity of electrolyte will form local anion agggregation at ultra-low temperature (below − 40 o C) 13 , 14 . Therefore, developing robust interfaces and adaptable solvation structure through electrolyte engineering is benefical for the rapid desolvation process and stable operation of LMBs across a wide temperature range 15 . Recently, researchers have proposed a series of electrolyte strategies to improve the cycling stability, temperature adaptability, and safety of LMBs. The novel liquefied gas electrolytes 16 , 17 , (locally) highly concentrated electrolytes 18 , 19 , mixed salt systems 20 , 21 have achieved significant results at ultra-low temperatures, but due to the thermodynamically unstable SEI and the presence of low flash point free-solvent molecules, the battery still experiences thermal runaway. The cyclophosphazene-based flame-retardant electrolyte system 22 is capable of ensuring the safe and stable operation of batteries at high temperatures. However, the increased viscosity of the electrolyte at low temperatures poses a challenge to Li + desolvation, leading to battery failure. Moreover, realizing stable ultra-low-temperature ( ≤ − 40°C) performance with lean electrolyte (≤ 2.5 g Ah − 1 ) and conventional salt concentration still faces challenges 6 , 23 . Compared with other solvents (Supplementary Table 1), tetrahydrofuran (THF) is an optimal solvent for low-temperature LMBs due to its exceptionally low freezing point (− 108.4 o C), excellent Li + transport kinetics, and extremely low viscosity 24 , 25 . In this work, we developed a novel thermoresponsive electrolyte comprising THF, 1,3,5-trioxane (TO), and lithium bis(fluorosulfonyl)imide (LiFSI) to ensure the safe and stable operation of LMBs over wide temperature (from − 60 to 60 o C). The addition of TO can not only weaken the binding energy of Li + -THF and improve the charge transport kinetics at low temperatures, but also form Li-polyoxymethylene (LiPOM) in the CEI and SEI, promoting uniform Li + flux and impeding the electrochemical corrosion by the electrolyte, and realize the suitability for high-voltage cathode and conventional salt concentration. More importantly, TO can also trigger cationic-ring-opening polymerization of THF molecules at high temperatures, resulting in the formation of ion-aggregates-dominated solvated structure and polyether, which increases the high-temperature performance and safety of LMBs. As a result, the 1.5 Ah pouch cell demonstrates an impressive energy density of 386.8 Wh kg − 1 at 25 o C. Even at − 40 o C, the energy density of LMBs reaches 317.1 Wh kg − 1 , accompanied by a high capacity-retention of 74.7% after 60 cycles. This work presents a novel approach to design thermoresponsive electrolyte for up-and-coming LMBs over a wide temperature range. Results Design of the thermoresponsive electrolyte and temperature-dependent solvated structures The primary requirements for stable operation of LMBs at ultra-low temperatures are high ionic conductivity, low viscosity, and low freezing point 26 . In contrast, THF has excellent physical properties in all aspects and is the optimal solvent for ultra-low temperature LMBs (Supplementary Table 1). The results of quantum chemical calculations indicate that THF exhibits the highest lowest unoccupied molecular orbital (LUMO) energy level with a high propensity to supply power, enabling excellent reduction stability to the anode. In comparison, LiFSI exhibits the lowest LUMO and the highest highest Occupied Molecular Orbital (HOMO), which suggests that it will be preferentially reduced and oxidized to form an inorganic-rich inner SEI and CEI. The additive TO exhibits a lower LUMO and higher HOMO than THF, and is capable of preferential redox to form LiPOM, which serves to protect against the decomposition of the solvent THF (Fig. 1 a and Supplementary Fig. 1a). The reduction potentials of the three compounds were quantified, leading to the same conclusion. The reduction potential of TO (0.57 V) was higher than that of THF (0.38 V), while both were significantly lower than that of FSI- (1.64 V) (Fig. 1 d) 3 , 27 . Furthermore, electrostatic potential (ESP) simulation revealed that the ESP of the entire solvated structure was transferred from FSI − to the solvent upon TO addition. The ESP of the solvent was markedly reduced, indicating that TO can balance the energy in the solvated sheath and inhibit the continuous decomposition of the lithium salt. This is anticipated to result in excellent low-temperature performance at conventional Li-salt concentration (Supplementary Fig. 2). Based on the above design ideas, we selected 1M LiFSI THF as the reference electrolyte (denoted as THF-based electrolyte). The additive TO with 20% molar ratios was introduced into the THF-based electrolyte denoted as TO-based electrolyte. Molecular dynamics (MD) simulations and the corresponding radial distribution functions (RDFs) were employed to evaluate the coordination structures of solvents, cations, and anions in THF-based and TO-based electrolytes 8 , 28 . The calculations indicate that the average coordination in THF- and TO-based electrolytes is Li + (THF-O) 2.8 (FSI-O) 0.9 and Li + (THF-O) 1.9 (TO-O) 0.7 (FSI-O) 1.3 , respectively. These findings show that TO can engage in the solvation of the Li + solvation sheath within the electrolyte (Li-OTO peaks at ~ 2.1 Å) and diminish the coordination of Li + -THF, while enhancing the coordination of Li + - FSI − (Fig. 1 b, c). The blue shift of the S-N-S peaks observed in the Raman spectra, along with the shift of the 7 Li NMR spectra to the lower field, provide further support for the aforementioned conclusion (Fig. 1 e-g). The fitted curves of the 700–780 cm − 1 Raman spectral bands indicate that the TO-based electrolyte forms a solvated structure dominated by contact ion pairs (CIPs) at − 40 o C. This enhanced anionic interfacial chemistry ensures high charge-transfer kinetics at low temperatures and enhances the electrochemical performance (Fig. 1 f). Variable-temperature Raman and NMR spectroscopy tests can directly reveal changes in the solvated structure as a function of temperature. In the TO-based electrolyte, the contents of AGG I (one FSI − coordinating to two Li + ) and AGG II (one FSI − coordinating to more than two Li + ) 29 increased with temperature, indicating a significant reduction in free solvent molecules and more anions involved in the composition of the solvated sheath at high temperature (Fig. 1 f). Furthermore, the shift of variable-temperature 7 Li NMR to higher field provides additional evidence for the enhancement of Li + coordination with anions (Fig. 1 g). Additionally, the MD snapshots illustrate the strong aggregation of anions and the formation of ionic clusters at 60 o C, and the corresponding RDFs demonstrate that the coordination of Li-O THF becomes weaker and the coordination of Li-O FSI − stronger with increasing temperature (Supplementary Fig. 3). The above results indicate that the thermal motion of the polar THF solvent molecules increases during the temperature increase, thereby modifying the original ion-dipole mode of action and prompting the formation of temperature-dependent solvated structures. In general, the optimal electrolyte for high-temperature LMBs operation should possess a stable solvated structure, a robust redox-stable interface, and a high safety solvent 30 . By means of MD simulations conducted at 60 o C, three typical solvated structures (with a ratio higher than 75%) were extracted from each electrolyte, and their binding energies were calculated by density functional theory (DFT). The results show that the solvated structures of the TO-based electrolyte have higher binding energies than those of the THF-based electrolyte, which indicates that it has high thermal and oxidative stability (Supplementary Fig. 4). As shown in Fig. 1 h and Supplementary Fig. 5, the characteristic peaks of THF in the TO-based electrolyte were markedly diminished, and novel NMR peaks of hydrogen and carbon were discerned, culminating in the formation of a polyether (PTHF) with enhanced thermal stability. According to gel permeation chromatography, PTHF has high number average molecular weight ( M n ) and high weight average molecular weight ( M w ) of 1.82×10 5 and 3.47×10 5 g mol − 1 , respectively. The polymer dispersity index is approximately 2, which corresponds to a homogeneous molecular weight distribution, and effectively enhances the high temperature performance and safety of the batteries (Fig. 1 i). The thermal polymerization mechanism and the evolution of solvated structure of TO-based electrolyte are described in detail in Fig. 1 j, Supplementary Figs. 6–9 and Supplementary Note 1. The thermal motion of the molecules is insignificant at − 40 o C, and THF, TO maintains relatively high ionic dipole interactions with Li + to form a CIP-dominated solvated structure, which accelerates the Li + desolvation process and achieves fast charge transfer kinetics at low temperatures. The thermal motion and kinetic energy of THF molecules increase at high temperature and undergo cationic ring-opening polymerization reaction in the presence of primary TO-oxonium-ions to form PTHF (Supplementary Fig. 9). This will drastically reduce the free solvent molecules in the electrolyte and decouple the solvents in the solvated structure, resulting in the formation of a more thermally stable anion-rich solvated sheath (i.e., the solvated structure is transformed from CIP to AGG I and AGG II). Notably, in contrast to the polymerization mechanism of THF at high temperatures, TO is in contact with Li-metal and undergoes a ring-opening polymerization reaction initiated by a minute quantity of H + (FSIOH) − to form a robust and compact LiPOM layer 31 , which effectively enhances the redox stability of SEI and CEI (Supplementary Fig. 7, 8). Consequently, the TO-based electrolyte demonstrates excellent safety and wide-temperature performance, overcoming the limitations of conventional electrolytes to achieve the compatibility of thermodynamically stable interface, high safety and fast charge transfer kinetics at low temperatures. Electrolyte properties and interfacial dynamics Although the increase in TO content enhances the degree of electrolyte polymerization at high temperatures, it also forms an excessively thick LiPOM layer at the interface, which impedes the interfacial charge transfer kinetics. To obtain the LiPOM layer with an optimal thickness, we configured TO-based electrolytes with varying molar ratios. Figure 2 a shows the variation of ionic conductivity with temperature for the five electrolytes. The TO-base (20%) electrolyte exhibits the highest ionic conductivity of 3.928 mS cm − 1 at − 40°C. It is noteworthy that the ionic conductivity of the TO-based electrolytes exhibited a decreasing trend as the temperature was increased to 60°C. This is primarily due to the ring-opening polymerization of electrolyte solvent molecules and the formation of strong interactions between cations and anions in the solvated structure. The Arrhenius equation was employed to calculate the activation energy (Ea) of the electrolyte at low temperatures (Fig. 2 b) 32 , resulting in a lower Ea value for the TO-based electrolyte in comparison to the THF-based electrolyte. Furthermore, the TO-based (20%) electrolyte exhibited an Ea of only 12.1 kJ mol − 1 . The lower Ea indicates accelerated ion diffusion kinetics, resulting in the highest Li + transference number of 0.629 (Supplementary Fig. 10). This enhances the prolonged sand time and is advantageous for inhibiting dendrite growth 33 . The results of linear scanning voltammetry (LSV) also indicated a positive shift in the oxidation onset potential to 4.73 V with increasing TO content (Fig. 2 c). Although it has the potential to considerably enhance the oxidation window of the electrolyte, it also causes a deterioration in the wettability of the electrolyte with the separator (Supplementary Fig. 11). Overall, the TO-base (20%) electrolyte was observed to effectively enhance the ionic conductivity, ion transference number, and oxidative decomposition potential, while also exhibiting moderate viscosity at low temperatures. An in situ IR cell device was constructed for the purpose of monitoring the dynamic alterations in the interfacial electrolyte conformation of copper electrodes throughout the processes of plating/stripping (Supplementary Fig. 12 and Supplementary Note 2) 34 , 35 . This device was designed to facilitate insight into the modifications in solvation structure that occur in THF-based and TO-based electrolytes during the processes of charging/discharging, and to elucidate the impact of these modifications on the SEI derivatization. Figures 2 d-f show the raw IR transmission spectra of in situ FTIR using TO-based electrolytes. The data demonstrate a decline in the peak of ROLi (835 ~ 845 cm − 1 ) and an increase in the peak of C = O (1725 ~ 1825 cm − 1 ) 36 , indicating that the organic SEI formed is a robust and dense LiPOM layer derived from TO, as opposed to an unstable ROLi layer derived from THF. For comparison, the THF-based electrolyte exhibited strong ROLi and C-S (~ 800 cm − 1 ) signals 37 (lithium salt decomposition), and no C = O signal was observed (Supplementary Fig. 13). These findings indicate that the TO-derived LiPOM layer can act as a barrier to impede the inward diffusion of LiFSI to the Li anode, thereby slowing the successive decomposition of LiFSI and reducing the occurrence of side reactions. The impact of TO on the electrode interface kinetics was further elucidated through the examination of the distribution of relaxation times (DRT) (Fig. 2 g, h and Supplementary Fig. 14) 38 , 39 . This analysis classifies distinct electrochemical processes based on local maxima in a continuous distribution function 40 . Li + diffusion and interfacial charge transfer demonstrate a pronounced temperature dependence, with these processes dominating at low temperatures. It is noteworthy that the resistance values of these two processes for the TO-based electrolyte are only one-tenth of those for the THF-based electrolyte. This highlights the crucial role of TO in enhancing Li + desolvation and electrode interface charge transfer at ultra-low temperatures. Effect of the designed electrolyte on Li plating/stripping at ultra-low temperatures To evaluate the impact of the designed LiPOM layer on Li plating/stripping, the Coulombic efficiency (CE) of THF-based and TO-based electrolytes in Li||Cu cells was initially assessed using the Aurbach method 41 . As shown in Fig. 3 a, the TO-based electrolyte exhibits an exceptional CE of 99.06% at − 40°C and 0.5 mA cm − 2 , which is considerably higher than THF-based electrolyte (76.03%), and its initial lithium nucleation overpotential is also only 278 mV. This indicates that the addition of TO effectively improves the Li plating/stripping efficiency and kinetics. Furthermore, long cycling tests were conducted at a current density of 0.5 mA cm − 2 and a capacity of 1 mAh cm − 2 . The 250-cycle average CE of the Li||Cu cell utilizing TO-based electrolytes reached 98.56% (Fig. 3 b), exhibiting a comparatively lower and more stable polarization voltage in its corresponding voltage profile (Fig. 3 c). Moreover, the Li||Li symmetric cell demonstrated stable operation for 450 h under these conditions (Fig. 3 d). In contrast, the CE of the THF-based electrolyte exhibited pronounced fluctuations during the initial stage, and a notable short-circuit phenomenon was observed after 20 cycles. This proves that the TO-derived LiPOM layer can effectively safeguard the Li anode from solvent molecule erosion, impede the growth of lithium dendrites and the formation of dead lithium, and demonstrate excellent Li plating/stripping reversibility and long-term stability at ultra-low temperature. As shown in Fig. 3 e, the Li||Cu cell assembled by TO-based electrolyte exhibits remarkable rate performance at − 40°C, with a CE reaching 95.97% at a high current density of 1 mA cm − 2 . The cell is able to maintain stability when the current density is returned to 0.1 mA cm − 2 , and the corresponding voltage profile is consistent with the initial state (Fig. 3 f). In contrast, the THF-based electrolyte demonstrated a notable decline in CE at 0.5 mA cm − 2 , resulting in direct short-circuiting and failure at 1 mA cm − 2 . This fully demonstrates that the addition of TO improves the interfacial charge transfer kinetics of the cell at ultra-low temperature. To elucidate the substantial discrepancies in CE and cycling stability among different electrolytes, scanning electron microscopy (SEM) and Kelvin probe force microscopy (KPFM) were employed to examine the morphology and surface potential of Li deposits, thereby facilitating an initial assessment of the underlying causes of these discrepancies from a morphological perspective. As shown in Fig. 3 g, the quantity of Li plating on the Cu collector was markedly diminished in the THF-based electrolyte, and a considerable amount of whisker-like Li generation was also observed under SEM, which resulted in a notable increase in Li plating porosity, surface roughness, and surface potential. This is attributed to the slow Li + desolventization and interfacial charge transfer process of the THF-based electrolyte at ultra-low temperatures. This ultimately results in tip-driven Li-deposition, which leads to severe short-circuiting and failure of the cell 8 . In contrast, following the introduction of TO, the Li deposits exhibited a dense and uniform bulk deposition morphology, with a surface roughness and surface potential of only 823.1 nm and 115 mV (Fig. 3 h), respectively. This contributes to the achievement of higher CE and longer cycle life, indicating a significant enhancement of the solvation process and SEI kinetics in the TO-based electrolyte. Notably, the Li||Cu and Li||Li cells assembled by TO-based electrolyte also exhibit outstanding CE and long-cycle stability at room temperature. Specifically, the Li||Cu cell cycled 400 turns with an average CE of 99.38%, the Li||Li cell cycled stably for 1400 h at a current density of 1 mA cm − 2 and a capacity of 2 mAh cm − 2 . Furthermore, the Li||Cu cell still has a CE of 96.36% at a high current density of 5 mA cm − 2 (Supplementary Fig. 15). The Li-deposits formed in the TO-based electrolyte were also more homogeneous and flat, forming larger bulk deposits with a surface roughness and surface potential of only 504.7 nm and 11.9 mV, respectively. This was observed from SEM and KPFM (Supplementary Fig. 16). This was corroborated by in-situ observations made with polarized light microscopy (Fig. 3 i). The TO-based electrolyte, formed a denser and more homogeneous Li layer, which enhanced the efficiency of Li deposition and effectively suppressed the growth of lithium dendrites. In contrast, the Li deposition of the THF-based electrolyte was sparse, exhibiting the formation of lithium dendrites and dead lithium. Interfacial Chemistry Study To obtain the nanostructures of SEI formed at ultra-low temperatures, we first observe the Li deposits on Cu grid via high-resolution transmission electron microscopy (HRTEM). As shown in Supplementary Fig. 17, the thickness of the TO-based electrolyte-derived SEI is mere 9.74 nm. It comprises an inner inorganic phase comprising LiF, Li 2 O, and Li 2 CO 3 , and an outer organic layer of a "mosaic" type amorphous organic SEI. This structure of SEI exhibits high strength and elasticity, which effectively inhibit the electron tunneling effect and homogenize the Li + flux 42 . Consequently, the electrolyte is capable of achieving high CE and dense and uniform lithium deposition at ultra-low temperatures. In contrast, the SEI in the THF-based electrolyte is 22.3 nm thick, which impedes Li + diffusion. Furthermore, the outer organic layer of SEI is distributed intermittently, indicating severe erosion by the electrolyte and a lack of stability and robustness. To gain further insight into the composition and relative content of the structure of dual-layered SEI, depth profiling XPS tests were conducted (Fig. 4 a-d and Supplementary Fig. 18). According to the fine fitting results of XPS C 1s spectra, the presence of additional O-C-O and C = O signals was observed in TO-based electrolyte, which provided insight into the pathways and products of TO decomposition 3 . The O-C-O signal was attributed to the TO-derived LiPOM layer, while the C-O signal was attributed to the THF derivative, which formed a short-chain organic SEI. As Ar + sputtering deepens, the relative content of organic species declines precipitously, while the relative content of inorganic components, including LiF, Li 2 O, and Li 3 N, rises markedly. This increase in inorganic components will facilitate the enhancement of ionic conductivity in the SEI and reduce kinetic barriers for Li + passage through the SEI. Figure 4 d depicts the percent composition of each species in the SEI derived from both electrolytes at ultra-low temperatures. The SEI derived from the THF-based electrolyte exhibit elevated C-O (27%) in the surface layer and augmented Li 2 CO 3 (23%) in the interior. This suggests that the formed SEI are of low strength and poorly stabilized, with the solvent molecules persistently eroding and undergoing side reactions with the Li metal. In contrast, the TO-based electrolyte derived SEI exhibits higher O-C-O (19%) in surface layer and a greater abundance of LiF (64%) and LiO 2 (8%) in internal layer. This suggests that the dense LiPOM layer effectively inhibits the erosion of Li metal by the solvent. The time-of-flight secondary ion mass spectrometry (TOF-SIMS) also provided dependable supporting information for the SEI derived from TO-based electrolytes 43 . The initial detection of ion fragments pertaining to SEI components is presented in Supplementary Fig. 19. The LiF 2 − and C 2 HO − ionic fragments are characteristic of LiF and organic components, respectively. The presence of abundant organic components in SEI indicates that TO can decompose to form LiPOM and participate in the formation of SEI. The three-dimensional structure of SEI and the spatial distribution of each component were further resolved by depth profile analysis of TOF-SIMS (Fig. 4 e-g). The organic component of SEI is dense in the surface layer, which is capable of forming a solid layer. With the increase of the sputtering time, the content of the organic component starts to decrease, and the SEI gradually transitions to a LiF-dominated structure. By combining evidence from TOF-SIMS, HR-TEM, and XPS, we conclude that TO in the electrolyte is able to form a dense LiPOM outer layer on conventional anion-derived SEI, which protects the Li anode and enables the cell to have high CE and long-cycle stability. In-situ X-ray diffraction (XRD) was employed to investigate the impact of two electrolyte-derived CEIs on the structural transformation of the NCM811 cathode during the charging/discharging processes (Fig. 5 a, b). In 3.0 ~ 4.5 V, the NCM811 cathode underwent a series of phase transitions: H1→M→H2→H3a, which corresponded to the expansion and contraction of the lattice volume (Supplementary Fig. 20a, b) 44 , 45 . Notably, the intensity and Brag angle of the (003) and (101) peaks of the NCM811 cathode were significantly changed throughout the phase transition using the THF-based electrolyte (the H1→M phase transition was particularly pronounced). In comparison, the volume expansion of the NCM811 cathode and the trailing of the peaks were significantly suppressed in the TO-based electrolyte, indicating a reversible phase transition and excellent structural stability. The fully charged Li||NCM811 cell was subjected to accelerated degradation tests at 4.5 V (Supplementary Fig. 20c). The results demonstrated that the leakage current density of the cell with TO-based electrolyte was only 5.44 µA cm − 2 , indicating that the TO-derived CEI effectively reduced the interfacial side reaction rate and passivated the cathode. Furthermore, to examine the safeguarding of the CEI formed by the two electrolytes against the structural transformation of the cathode at − 40 o C, the NCM811 cathode after 100 cycles was dismantled for XRD pattern analysis (Supplementary Fig. 21a-f). The separation of the (006)/(102) peaks was observed to be more pronounced in the TO-based electrolyte, which suggests that the structural transition from the layered to the rock salt phase was effectively suppressed 46 . Furthermore, the SEM of the cathode, which was circulated in the TO-based electrolyte, did not develop intergranular cracks and exhibited a stable structure (Supplementary Fig. 22). Collectively, these findings illustrate that the TO-based electrolyte is effective in forming a dense and robust CEI, which serves to safeguard the NCM811 electrode from structural deterioration during the phase transition. To gain further insight into the chemical state and compositional information of the CEI, the NCM811 cathode was subjected to a depth profiling XPS test following 100 cycles. From the C 1s spectrum, it can be observed that the THF-based electrolyte-derived CEI has a strong C-O signal, indicating that its surface consists of short-chained and unstable organics, which is the main reason why it exhibits poor cathodic reversibility and structural disruption (Fig. 5 c). As a comparison, the TO-based electrolyte-derived CEI surface displays a greater abundance of O-C-O and C = O signals, indicative of the successful formation of the surface LiPOM layer (Fig. 5 d) 3 . As the Ar + sputtering progresses, there is a notable decline in the relative content of organic species, accompanied by a pronounced increase in the relative content of LiF. This shift is expected to significantly enhance the kinetics of Li + transport in CEI. The organic-inorganic bilayer CEI was also demonstrated with high reliability using TOF-SIMS. The initial detection of LiF 2 − , CO 3 − and C 2 HO − indicated the presence of characteristic ion fragments of LiF, Li 2 CO 3 and organic components, respectively (Supplementary Fig. 23a-c). The 3D structure of CEI and the spatial distribution of each component were further resolved by TOF-SIMS depth profiling (Supplementary Fig. 23d-f and 24). CEI consists of a dense organic layer on the surface and a LiF-dominated inorganic layer in the interior, and the content of Li 2 CO 3 in the surface layer is extremely low, which suggests that CEI effectively inhibits the occurrence of the side reactions 10 . In light of the evidence derived from in situ XRD, XPS and TOF-SIMS, it can be proved that the CEI formed by TO-based electrolyte is constituted by a dense and homogeneous LiPOM outer layer and a LiF-rich inner layer. This structure inhibits interfacial side reactions and the dissolution of TMs, preserves the initial structure of NCM811, and enhances interfacial stability. From the experimental and theoretical results, the function of TO is shown in Fig. 5 e. TO is capable of participating in the Li + solvation structure, weakening the binding energy of Li + -THF, promoting Li + desolvation, and enhancing the charge transfer kinetics at the interface. More importantly, TO is able to prioritize THF reduction and oxidation to build a uniform, thin and robust LiPOM layer on the surface of Li-Metal and NCM electrodes. The double-layer SEI inhibits interfacial side reactions and lithium dendrite growth, while the double-layer CEI inhibits the dissolution of transition metal (TM) ions. This electrolyte design effectively enhances the cycling performance of the battery under high voltage and wide-temperature. In contrast, in the THF-based electrolyte, the inability to form a dense polymer layer to block the solvent attack on the both electrodes resulted in the growth of lithium dendrites, the dissolution of TMs, and the rupture of NCM particles (Fig. 5 f). Performance of practical Li-metal cells at wide temperature In order to demonstrate the effectiveness of the designed electrolyte operating over a wide temperature range, Li||NMC811 full cells were assembled to fully evaluate the TO-based electrolyte system. As shown in Fig. 6 a, b, the TO-based electrolyte full cell exhibits excellent long-cycle performance, with a capacity retention of 87.3% after 500 cycles at 25°C and 1C. Furthermore, the dQ/dV curves exhibit a high degree of overlap, with only a slight voltage change of 16 mV, indicating phase change reversibility and structural stability of the cathode (Fig. 6 c). More importantly, the Li||NMC811 full cell employing a TO-based electrolyte still exhibits a capacity residual of 176.8 mAh g − 1 after 200 cycles, with a capacity retention of 90% and an average CE of 99.4% at an ultra-low temperature of − 40°C (0.2C charge/discharge) (Fig. 6 d, e). It is worthy of note that the polarization of the cell increases significantly at ultra-low temperatures. Thanks to the improved solvation structure of TO and the formation of dual-layered CEI and SEI, which effectively enhances the Li + diffusion and interfacial charge transfer kinetics at low temperatures. Thus, a reversible phase transition of the anode was achieved (especially for the H1→M phase change process, where the potential increased by only 48 mV after 200 cycles), reducing the polarization and the loss of cell capacity (Fig. 6 f). In contrast, the initial capacity of the cell with THF-based electrolyte was only 120 mAh g − 1 , which decayed to 41% of the initial capacity after 200 cycles. Furthermore, the TO-based electrolyte is capable of achieving 400 cycles at 60 o C with a capacity retention rate of up to 88.9% (Fig. 6 g, h), due to the solvation structure transformation and solvent molecule reconfiguration at elevated temperatures. As shown in Fig. 6 i, the "six-star diagram" visualization demonstrates that the TO-based electrolyte system exhibits significant advantages in terms of Li anode stability, wide temperature discharge, multiplicity performance, thermal stability, desolvation, and cycling stability. Excellent wide-temperature performance and long cycle stability make advanced TO-based electrolytes promising for use in practical LMBs. Li||NCM811 pouch cells (1.5 Ah) with lean electrolytes (2 g Ah − 1 ) and a N/P ratio of 2.2 were assembled, allowing an initial specific energy density of 386.8 Wh kg − 1 (Supplementary Fig. 25). The energy density of a cell is calculated by taking the masses of all components in pouch cells into consideration (Supplementary Table 2). Surprisingly, the LMB pouch cell was able to achieve an unprecedented initial energy density of 317.1 Wh kg − 1 at − 40 o C, and exhibited remarkable cycling stability, retaining 74.7% of its capacity after 60 cycles (Fig. 6 j). In contrast, the discharge capacity of THF-based electrolytes decays to 0 after 10 cycles. The disassembly of the cycled Li||NCM811 pouch cells was employed to investigate the underlying cause of the notable discrepancy in cycling performance at low temperatures between two electrolytes. The Li anodes that were cycled in the THF-based electrolyte exhibited a notable depletion and displayed considerable quantities of dead lithium and whisker-like formations (Supplementary Fig. 26a, b). Conversely, in the TO-based electrolyte, the lithium remained in the form of lumpy deposits, although the distribution of lithium on the Cu collector exhibited slight inhomogeneity after repeated cycling (Supplementary Fig. 26c, d). Further, the temperature adaptability of Li||NCM811 pouch cells was evaluated. The cells were observed to operate stably at − 60 ~ 60 o C, exhibiting excellent room temperature capacity retention of 81.5% and 61.7% at − 60 and − 40 o C, respectively (Fig. 6 k). Furthermore, our designed TO-based electrolyte exhibits the most optimal overall performance in terms of wide-temperature performance, capacity retention, and energy density when compared with advanced electrolytes designed in the literature (Fig. 6 i and Supplementary Table 3). To further demonstrate the practical application potential of the TO-based electrolyte, it was assembled into a pouch cell and assembled on a robot, which was able to drive the robot to work stably under the harsh temperature conditions of − 40 o C (Supplementary Fig. 27 and Supplementary Movie 1). The safety of LMB is typically determined by the combination of the intrinsic safety of the electrolyte and the thermal runaway temperature of the cathode material in a fully charged state 47 , 48 . As shown in Supplementary Fig. 28a, b and Supplementary Movie 2, the polymerization products of the TO-based electrolyte did not exhibit combustion in ignition test, and the thermal decomposition temperature of the electrolyte reached 211°C with minimal heat release. In-situ variothermal XRD demonstrated that the formation of dual-layered CEI effectively suppressed the release of oxygen from the cathode during charging and enhanced the thermodynamic stability (Supplementary Fig. 28c, d). Consequently, the thermal safety of LMBs utilising a TO-based electrolyte was markedly enhanced. Discussion In summary, we present a novel thermoresponsive electrolyte design strategy that enables the safe and stable operation of LMBs at − 60 ~ 60°C. The theoretical and experimental evidence demonstrates that the additive TO is able to participate in the Li + solvation structure, thereby promoting Li + transport and charge transfer kinetics. Combined with the evidence from HRTEM, XPS, TOF-SIMS and in-situ XRD, the SEI, CEI derived from TO-based electrolyte is composed of a uniform, thin and robust outer layer of LiPOM and an inner layer enriched with LiF, Li 2 O, which is able to effectively prevent the degradation of both electrodes. More importantly, when the temperature rises, the solventized structure of the electrolyte undergoes a transformation, with solvent molecules reorganizing to form a polyether with enhanced oxidation resistance. This significantly enhances the safety of the battery. Consequently, the practical 1.5 Ah Li||NCM811 pouch cell with optimized electrolyte is able to operate at − 60 ~ 60°C. Specifically, the pouch cell is capable of achieving 100 cycles at 25°C with an initial energy density of 386.8 Wh kg − 1 . Surprisingly, it still has a room temperature discharge capacity of 61.7% at − 60°C, and achieves an unprecedented initial energy density of 317.1 Wh kg − 1 at − 40°C with a capacity retention of 74.7% for 60 cycles. Methods Materials Active materials (LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) powders), polyvinylidene difluoride (PVDF), Super P, carbon-coated aluminum foil (Al, 15 µm-thick), separator (Celgard 2325, thickness: 25 µm, PP/PE/PP three-layer membrane), Coin cell components (CR2032, spacer: 15.8 × 1 mm, spring: 15.4 × 1.1 mm) were purchased from Nanjing Mojiesi Energy Technology. Lithium Bis(fluorosulfonyl)imide (LiFSI, > 98%), tetrahydrofuran (THF, ≥ 99.9%), N-methyl-2-pyrrolidone (NMP, ≥ 99.5%) were purchased from Shanghai Aladdin Bio-Chem Technology Co., Ltd. 1,3,5trioxane (TO, > 99.0% (GC)) were purchased from Tokyo Chemical Industry Co., Ltd. The 450 µm Li-metal sheets were procured from Beijing InnoChem Science & Technology Co., Ltd. The NCM811 cathodes (22 mg cm − 2 ) were procured from Guangdong Canrd New Energy Technology Co., Ltd. The preparation of electrolyte The THF-based electrolyte was prepared by dissolving 1M LiFSI (0.187 g) into the 1 mL THF. Next, 0.018g TO was dissolved in THF-based electrolyte to prepare the TO-based electrolyte (LiFSI:TO molar ratios of 1:0.2). All the preparation steps mentioned above were conducted at room temperature (~ 25°C) in an Ar-filled glove box (H 2 O < 0.1 ppm and O 2 < 0.1 ppm). Coin cells and pouch cells assembling All coin cells were assembled in the Argon-filled glove box with H 2 O < 0.1 ppm and O 2 < 0.1 ppm. Li||Li CR-2032 type coin cells were assembled in the following order: cathode case, Li-metal sheet, Celgard 2325 separator (18 mm), Li-metal sheet, spacer, spring, and anode case. Li||Cu CR-2032 type coin cells were assembled in the following order: cathode case, Cu foil (14mm), Celgard 2325 separator, Li sheet, spacer, spring, and anode case. Li||NCM811 full cell were assembled in the following order: cathode case, aluminum disk (19 mm), NCM811 cathode disk, Celgard 2325 separator, Li anode sheet, spacer, spring, and anode shell. All coin cells were added with 75 µL electrolyte. Additionally, to prevent corrosion of the stainless-steel case under high voltages, an additional piece of Al foil must be placed between the cathode case and NCM cathode disk. For Li||NCM811 pouch cell (10.0 × 7.0 cm 2 ), Li anode (composed of Cu current collector and double-layer Li foil) and cathode of double-layer active material were stacked one by one and separated by Celgard 2325, the electrolyte volume is 3.0 mL. The thickness and mass loading of anode, cathode and other components are provided in Supplementary Table 3. The Li||NCM811 pouch cell was assembled in a dry room whose dew point is − 50°C. Electrochemical Testing All electrochemical data presented in this work were generated from CR-2032 coin cells. Low temperature galvanostatic tests were performed on a Neware BTS 4000 system, while room temperature galvanostatic tests were performed on a LANHE-CT 2001A system. The Low temperature tests were measured in a JHY-H-50L temperature chamber to maintain the cell at a set temperature. All potentiostatic tests were performed on a CHI-760E. The electrochemical impedance spectroscopy (EIS), from 1 MHz to 100 mHz with an amplitude of 5 mV was tested using a Chenhua electrochemical workstation. In the LSV tests, a carbon-coated aluminium foil (c-Al foil) was used as a working electrode with a sweep rate of 1 mV s − 1 . Round cycles from 3 to 6 V (vs. Li/Li + ) were performed, and then the stable recorded cathodic scan for each Li||c-Al foil cell with different electrolytes was recorded as the LSV curve. The electrochemical floating test was performed in Li||NCM811 cells with different electrolyte. The cells were first charged to 4.5 V at 0.1C and then maintained for 12 h with the current monitored by LANHE-CT 2001A system. The ionic conductivity of the electrolyte was measured by a customized two-electrode coin cell. The two stainless steel electrodes were placed symmetrically between a polytetrafluoroethylene disc with a thickness of 0.027 inches. A glass-fiber separator soaked with electrolyte was placed inside the washer, which constrained its surface area to a known value. The electrolyte conductivity values were then obtained with electrochemical impedance spectroscopy (EIS) using the following equation: 𝜎 = \(\:\frac{\varvec{L}}{\varvec{A}\ast\:\varvec{R}}\) where R is the measured ionic resistance and A and L are the area of the electrodes and the space between the electrodes, respectively. The data points from 40°C to − 60°C were measured in a JHY-H-50L temperature chamber to maintain the cell at a set temperature for 2h intervals before each measurement. The transfer numbers of the electrolytes were determined by a commonly used potentiostatic polarisation technique on a CHI-760E, and the transfer coefficient was then calculated using the following equation: $$\:{\varvec{t}}_{+}=\frac{{\varvec{I}}_{\varvec{S}\varvec{S}}(\varDelta\:\varvec{V}-{\varvec{I}}_{0}{\varvec{R}}_{0})}{{\varvec{I}}_{0}(\varDelta\:\varvec{V}-{\varvec{I}}_{\varvec{S}\varvec{S}}{\varvec{R}}_{\varvec{S}\varvec{S}})}$$ where 𝛥𝑉 is the applied bias, R 0 is the initial cell impedance and R SS is the steady-state cell impedance. To evaluate the CE of Li||Cu cells, Aurbach’s method was applied. The overall CE was calculated by the following Eq. 3 8 $$\:{\varvec{C}\varvec{E}}_{\varvec{a}\varvec{v}\varvec{g}-\varvec{n}}=\frac{\varvec{n}{\varvec{Q}}_{\varvec{c}}+{\varvec{Q}}_{\varvec{s}}}{\varvec{n}{\varvec{Q}}_{\varvec{c}}+{\varvec{Q}}_{\varvec{t}}}$$ Q c represents the deposition or dissolution capacity in n cycles. Its fixed value is 1 mAh cm − 2 . Q t is the initial Li reservoir capacity deposited on the Cu foil and Q s indicates the capacity finally stripped from the Cu foil. Pouch cells were cycled in the voltage range of 3.0–4.3V at 0.1C at 25°C. Pouch cells were cycled in the voltage range of 2.8–4.3 V at 0.05C at − 40°C. The cycling performance of the pouch cells was tested under a fixing device to provide 1.0 MPa external pressure. Material characterizations The Nuclear Magnetic Resonance (NMR) spectrometer was used to characterize the organic solvents or electrolytes in this work, and each test dissolved a 20 µL sample in deuterated chloroform. The 1 H and 7 Li Nuclear Magnetic Resonance (NMR) spectra were acquired using the Bruker 400 MHz and Bruker AVANCE NEO 600 MHz, respectively. The gel permeation chromatography measurements (1260 Infinity II, Agilent Technologies) were performed by dissolving the polymerization product in THF. The Contact Angle (CA) measuring instrument (JC2000DS2) was used to characterise the wettability of the four electrolytes studied. The amount of electrolyte is controlled at 10 uL at a time. The Raman spectroscopy data of the electrolytes were obtained using a LabRAM HR Evolution Raman micro-spectrometer equipped with 633 nm laser. The morphologies of Li deposition in different electrolytes were collected by FESEM (JSM-7800F, JEOL), HR-TEM (JEM-2100F, JEOL) was used to observe the thickness and morphology of CEI and SEI films. The roughness and potential of the lithium-embedded negative electrode surface were obtained by KPFM (SPM-9700HT). XPS data was collected using Thermo Scientific K-Alpha + . The analysis chamber has a vacuum degree of approximately 2×10 − 7 mbar, X-ray source: monochromatic Al Kα source, energy: 1486.6 eV, voltage: 12 kV, beam current: 6 mA, analyzer scanning mode: CAE, work function: 4.2 eV. The depth-profiling XPS was carried out at an etching rate of 0.2 nm s − 1 . ToF-SIMS (PHI nano ToF II, ULVAC-PHI) also investigated SEI and CEI components. The area of analysis is 100 µm × 100 µm, while the sputtering area is 400 µm × 400 µm. Data for X-ray diffraction was acquired using a Bruker D8 Advance X-ray diffractometer outfitted with a LynxEye 1-dimensional detector with Cu-Ka radiation at 40 kV and 40 mA (λ = 1.5418 Å) with a step increment of 0.02 and a duration per step of 0.1 s. The operando XRD test during charging and discharging rate of 0.5 mA cm − 2 were performed at 25°C and diffraction patterns were collected every 8 min. The LIB-MS-R is provided by the Beijing Scistar Technology Co. Ltd. The device simulates a lithium-ion coin cell to observe the growth of lithium dendrite and its corresponding changes. Density functional theory calculations The DFT calculations were performed using Gauss 16 quantum chemistry software. All the molecules were pre-optimised at the B3LYP/6-31G* level. Next, the Molclus program was used to search for configurations of the complex. The optimized geometry was obtained using the DFT-D3 van der Waals (vdW) correction proposed by Grimme. During the correction process, all atoms were allowed to relax until the atomic force on each atom was below 0.005 eV Å −1 and the energy was less than 1.0 × 10 − 6 eV. A total of 200 initial configurations were generated and each configuration was optimised at the B3LYP/3-21G* level. The configuration with the lowest energy was then further optimised to the B3LYP/6-311G(d) level. The intermolecular interactions were described using the Grimme d3bj dispersion. The binding energy was calculated according to the following equation. Binding energy = Ecomplex–(Efragment 1 + Efragment 2 ) 49 Molecular dynamics simulations All molecular dynamics (MD) simulations were performed by the GROMACS 2023 simulation package 50 , 51 . The systems were described by the OPLS-AA force field 52 . The parameters of THF and TO molecules were generated by the LigParGen web server and that of Li + and FSI − were obtained from Jensen et al 53 and Lopes et al 54 , respectively. The Lorentz-Berthelot mixing rules were chosen to calculate the LJ parameters of the cross interactions. The molar ratios of the electrolytes were obtained from the experimental part of this work. The periodic boundary condition was applied to all three dimensions. The Particle Mesh Ewald (PME) method was used to calculate the long-range electrostatic interaction with a cut-off for a real space of 1.2 nm. The short-range van der Waals cut-off was set to be 1.2 nm. The initial simulation boxes were constructed by Packmol 55 . All the cases, after energy minimization, were first equilibrated in 20 ns NPT ensemble and 35 ns NVT ensemble, respectively, and every production run was performed for 5 ns in the NVT ensemble with 2 fs time step and saved every 0.2 ps. The temperature of the system was controlled by the Nosé-Hoover thermostat, and the simulated temperature was maintained at 233.15 K. The Berendsen pressure coupling regulated the system at 1 bar 56 . The visualization was generated via the VMD package. The binding energy of Li + containing internal term (ΔE int ), van der Waals (ΔE vdW ) and electrostatic (ΔE ele ) energies was calculated with Generalized Born model by gmx_MMPBSA 57 . Declarations Acknowledgements This work was supported by National Natural Science Foundation of China (22479094, 22075174), the Science and Technology Commission of Shanghai Municipality (20520740900 and 19DZ2271100), and International Joint Laboratory on Resource Chemistry. References Zhou, G., Chen, H. & Cui, Y. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-5101221","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":359211905,"identity":"a35f4369-58e5-4187-8f85-2fa85797667f","order_by":0,"name":"Yulin 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07:08:38","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5101221/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5101221/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41467-025-60524-8","type":"published","date":"2025-07-01T04:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":65427322,"identity":"12e498b9-9b63-4878-8c1c-a647b3e4bc89","added_by":"auto","created_at":"2024-09-27 09:25:27","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":572165,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eDesign of electrolytes for wide-temperature LMBs. a \u003c/strong\u003eComparison of the\u003cstrong\u003e \u003c/strong\u003eHOMO and LUMO energy levels for various commonly used Li salts and ether-based solvents.\u003cstrong\u003e b,c,\u003c/strong\u003e RDF plots of Li–O\u003csub\u003eTHF\u003c/sub\u003e, Li–O\u003csub\u003eFSI\u003c/sub\u003e\u003csup\u003e−\u003c/sup\u003e, Li–N\u003csub\u003eFSI\u003c/sub\u003e\u003csup\u003e−\u003c/sup\u003e and Li‒O\u003csub\u003eTO\u003c/sub\u003e pairs in THF- (\u003cstrong\u003eb\u003c/strong\u003e) and TO-based (\u003cstrong\u003ec\u003c/strong\u003e) electrolytes. \u003cstrong\u003ed \u003c/strong\u003eThe calculated reduction potential of THF, TO and FSI\u003csup\u003e−\u003c/sup\u003e based on DFT. \u003cstrong\u003ee,f,\u003c/strong\u003e Fitted Raman spectra in THF- (\u003cstrong\u003ee\u003c/strong\u003e) and TO-based (\u003cstrong\u003ef\u003c/strong\u003e) electrolytes at different temperatures.\u003cstrong\u003e g,h, \u003c/strong\u003e\u003csup\u003e7\u003c/sup\u003eLi-NMR (\u003cstrong\u003eg\u003c/strong\u003e) and \u003csup\u003e1\u003c/sup\u003eH-NMR (\u003cstrong\u003eh\u003c/strong\u003e) spectra of THF- and TO-based electrolytes.\u003cstrong\u003e i\u003c/strong\u003e Gel permeation chromatography (GPC) test results of TO-based electrolyte at 60 °C.\u003cstrong\u003e j\u003c/strong\u003e Schematic diagram of temperature dependent solvation structure of TO-based electrolyte.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-5101221/v1/251f2284eec433204ba9fe2d.png"},{"id":65426399,"identity":"7944440c-1029-46cd-b487-146bddc54e9b","added_by":"auto","created_at":"2024-09-27 09:17:27","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":468167,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eProperties of the designed electrolyte. a \u003c/strong\u003eIonic conductivity, \u003cstrong\u003eb\u003c/strong\u003e Arrhenius curves and corresponding calculated Ea, \u003cstrong\u003ec\u003c/strong\u003e LSV measurements of the five designed electrolytes. \u003cstrong\u003ed-f, \u003c/strong\u003eIn situ raw FTIR spectra of TO-based electrolyte during potentiostatic plating/stripping. \u003cstrong\u003eg,h, \u003c/strong\u003eTemperature dependent distribution of relaxation times (DRT) plot derived from EIS data for the THF- (\u003cstrong\u003eg\u003c/strong\u003e) and TO-based (\u003cstrong\u003eh\u003c/strong\u003e) electrolytes in Li||NCM811 coin cells.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-5101221/v1/cf1f069baed233370f07d7ba.png"},{"id":65426396,"identity":"23ed6185-8e7f-4262-9431-c0ea6471ae28","added_by":"auto","created_at":"2024-09-27 09:17:27","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":725400,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eElectrochemical performance and deposit morphology of Li metal plating/stripping in designed electrolyte at ultra-low temperature. a \u003c/strong\u003eCE of Li||Cu cells with designed electrolytes under 0.5 mA cm\u003csup\u003e−2\u003c/sup\u003e. \u003cstrong\u003eb\u003c/strong\u003e Long-term CE of Li||Cu cells with designed electrolytes at 0.5 mA cm\u003csup\u003e−2\u003c/sup\u003e and 1 mAh cm\u003csup\u003e−2\u003c/sup\u003e. \u003cstrong\u003ec\u003c/strong\u003e Voltage profiles of Li||Cu cells with TO-based electrolyte for different cycles. \u003cstrong\u003ed\u003c/strong\u003e Long-term cycling performance of Li||Li cells with designed electrolytes at 0.5 mA cm\u003csup\u003e−2\u003c/sup\u003e and 1 mAh cm\u003csup\u003e−2\u003c/sup\u003e. \u003cstrong\u003ee\u003c/strong\u003e Rate performance of Li||Cu cells with designed electrolytes at different current densities. \u003cstrong\u003ef\u003c/strong\u003e Voltage profiles of Li||Cu cells with TO-based electrolyte for different current densities.Morphology of lithium deposits with THF- (\u003cstrong\u003eg\u003c/strong\u003e) and TO-based (\u003cstrong\u003eh\u003c/strong\u003e) electrolytes at −40 \u003csup\u003eo\u003c/sup\u003eC. \u003cstrong\u003ei\u003c/strong\u003e Optical images of the \u003cem\u003ein situ\u003c/em\u003e Li deposition on Bare-Cu in THF and TO-based electrolytes at 1 mA cm\u003csup\u003e−2\u003c/sup\u003e.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-5101221/v1/d92f62e20e1c5b503bcb8461.png"},{"id":65427325,"identity":"f0bde982-8206-4e5c-a602-03b9db8e27bf","added_by":"auto","created_at":"2024-09-27 09:25:27","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":555115,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eThe composition and 3D nanostructure of SEI obtained by depth-profiling XPS and TOF-SIMS. \u003c/strong\u003eC 1s, F 1s and Li 1s spectra of SEI in THF- (\u003cstrong\u003ea\u003c/strong\u003e) and TO-based (\u003cstrong\u003eb\u003c/strong\u003e) electrolytes at the sputtering times of 0, 25, and 50s. \u003cstrong\u003ec\u003c/strong\u003e The atomic ratio of N, O, S, F, C, Li in the SEI formed in designed electrolytes. \u003cstrong\u003ed\u003c/strong\u003e Relative compositions of Li-containing and C-containing species in SEI formed in designed electrolytes. \u003cstrong\u003ee\u003c/strong\u003e Depth sputtering profiles of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003eO\u003csup\u003e−\u003c/sup\u003e and LiF\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e−\u003c/sup\u003e segments by ToF-SIMS. \u003cstrong\u003ef,g,\u003c/strong\u003e 3D renders of the SEI formed in the TO-based electrolyte.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-5101221/v1/cf3c1881adfab92f4f63bddf.png"},{"id":65427321,"identity":"acbb50ff-dbd1-4513-8e8c-f5a46cabdcb9","added_by":"auto","created_at":"2024-09-27 09:25:27","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":639003,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eStructure characterizations of NCM811 cathode and the 3D nanostructure of CEI. \u003c/strong\u003e\u003cem\u003eIn situ\u003c/em\u003e XRD characterization of the NCM811 cathode during the initial charge/discharge in THF- (\u003cstrong\u003ea\u003c/strong\u003e) and TO-based (\u003cstrong\u003eb\u003c/strong\u003e) electrolytes. C 1s and F 1s spectra of CEI in THF (\u003cstrong\u003ec\u003c/strong\u003e) and TO-based (\u003cstrong\u003ed\u003c/strong\u003e) electrolytes at the sputtering times of 0, 25s. \u003cstrong\u003ee,f\u003c/strong\u003e Schematic representation of SEI and CEI formed by THF- (\u003cstrong\u003ee\u003c/strong\u003e) and TO-based (\u003cstrong\u003ef\u003c/strong\u003e) electrolytes.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-5101221/v1/3062082075249c93a8f6cacb.png"},{"id":65427651,"identity":"60fdbda2-c982-4041-87ef-3e1020ddb025","added_by":"auto","created_at":"2024-09-27 09:33:27","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":347460,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eElectrochemical performances of Li||NCM811 cells with THF and TO-based electrolytes at wide-temperature. a \u003c/strong\u003eLong-term cycling performance of Li||NCM811 cells with different electrolytes at 1 C at 25 \u003csup\u003eo\u003c/sup\u003eC. \u003cstrong\u003eb\u003c/strong\u003e Corresponding charge/discharge curves with TO-based electrolyte, and (\u003cstrong\u003ec\u003c/strong\u003e) the dQ/dV curves for different cycles. \u003cstrong\u003ed \u003c/strong\u003eLong-term cycling performance of Li||NCM811 cells with different electrolytes at 0.2 C and −40 \u003csup\u003eo\u003c/sup\u003eC. \u003cstrong\u003ee\u003c/strong\u003e Corresponding charge/discharge curves with TO-based electrolyte, and (\u003cstrong\u003ef\u003c/strong\u003e) the dQ/dV curves for different cycles. \u003cstrong\u003eg \u003c/strong\u003eLong-term cycling performance of Li||NCM811 cells with different electrolytes at 0.5 C and 60 \u003csup\u003eo\u003c/sup\u003eC. \u003cstrong\u003eh\u003c/strong\u003e Corresponding charge/discharge curves with TO-based electrolyte. \u003cstrong\u003ei\u003c/strong\u003e Comparision of performance of THF- and TO-based electrolytes in terms of cyclic stability, stability against LMA, wide-temperature discharge, rate capability, thermal stability, de-solvation.\u003cstrong\u003e j\u003c/strong\u003e Cycling performance of Li||NCM811 pouch cell at 0.05 C and −40 \u003csup\u003eo\u003c/sup\u003eC. \u003cstrong\u003ek\u003c/strong\u003e Discharge profiles (0.1 C) of Li||NMC811pouch cell using TO-based electrolyte at different temperatures. \u003cstrong\u003el\u003c/strong\u003e Comparison of the state-of-the-art performance of energy-density and capacity rentention Li metal pouch cells in reported literature.\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-5101221/v1/a4a683e3df9faa470fb91cfb.png"},{"id":85826042,"identity":"3a687180-854b-41aa-ad67-b4a063336916","added_by":"auto","created_at":"2025-07-02 07:11:46","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4800033,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5101221/v1/40c8e269-7d7a-47ff-a879-7e4c39cfa00d.pdf"},{"id":65426402,"identity":"ffc40d98-5b21-449b-bdce-ee08c2aadc0b","added_by":"auto","created_at":"2024-09-27 09:17:27","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":30973562,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"SI0913.docx","url":"https://assets-eu.researchsquare.com/files/rs-5101221/v1/4088d43651c0df78342c54d1.docx"},{"id":65426395,"identity":"f6aa3c2f-a48a-403c-b838-0b25fcfae349","added_by":"auto","created_at":"2024-09-27 09:17:27","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":98942,"visible":true,"origin":"","legend":"","description":"","filename":"TOC.png","url":"https://assets-eu.researchsquare.com/files/rs-5101221/v1/f6c8d514fec31b16020f7ed8.png"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Novel thermoresponsive ether-based electrolyte for wide-temperature operating lithium metal batteries","fulltext":[{"header":"Introduction","content":"\u003cp\u003eWith the global community pursuit of carbon neutrality, there is an immediate requirement for high-specific-energy batteries to promote energy storage and conversion efficiency\u003csup\u003e\u003cspan additionalcitationids=\"CR2\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e. The energy density of advanced Lithium metal batteries (LMBs) has exceeded 400 Wh kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, becoming a strong contender for next-generation secondary batteries\u003csup\u003e\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e,\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u003c/sup\u003e. However, the practical application of LMBs is limited by persistent parasitic reactions, disordered dendrite growth and low ionic conductivity, further resulting in rapid capacity decay and battery failure\u003csup\u003e\u003cspan additionalcitationids=\"CR7 CR8\" citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u003c/sup\u003e. In theory, the homogeneous and stable solid electrolyte interface (SEI) and cathode electrolyte interface (CEI) enhance the electrochemical performance of LMBs\u003csup\u003e\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e,\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u003c/sup\u003e. For commercial electrolyte, the unstable organic components, including lithium dicarbonate ((ROCO\u003csub\u003e2\u003c/sub\u003eLi)\u003csub\u003e2\u003c/sub\u003e), semicarbonate (ROCO\u003csub\u003e2\u003c/sub\u003eLi) and alcohol salts (ROLi), leading to slow transfer rate of Li\u003csup\u003e+\u003c/sup\u003e and harmful side reactions\u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e,\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e. Notably, the viscosity of electrolyte will form local anion agggregation at ultra-low temperature (below \u0026minus;\u0026thinsp;40 \u003csup\u003eo\u003c/sup\u003eC)\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e,\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e. Therefore, developing robust interfaces and adaptable solvation structure through electrolyte engineering is benefical for the rapid desolvation process and stable operation of LMBs across a wide temperature range\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eRecently, researchers have proposed a series of electrolyte strategies to improve the cycling stability, temperature adaptability, and safety of LMBs. The novel liquefied gas electrolytes\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e,\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e, (locally) highly concentrated electrolytes\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e,\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e, mixed salt systems\u003csup\u003e\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e,\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e have achieved significant results at ultra-low temperatures, but due to the thermodynamically unstable SEI and the presence of low flash point free-solvent molecules, the battery still experiences thermal runaway. The cyclophosphazene-based flame-retardant electrolyte system\u003csup\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e is capable of ensuring the safe and stable operation of batteries at high temperatures. However, the increased viscosity of the electrolyte at low temperatures poses a challenge to Li\u003csup\u003e+\u003c/sup\u003e desolvation, leading to battery failure. Moreover, realizing stable ultra-low-temperature (\u0026thinsp;\u0026le;\u0026thinsp;\u0026minus;\u0026thinsp;40\u0026deg;C) performance with lean electrolyte (\u0026le;\u0026thinsp;2.5 g Ah\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and conventional salt concentration still faces challenges\u003csup\u003e\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e,\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e. Compared with other solvents (Supplementary Table\u0026nbsp;1), tetrahydrofuran (THF) is an optimal solvent for low-temperature LMBs due to its exceptionally low freezing point (\u0026minus;\u0026thinsp;108.4 \u003csup\u003eo\u003c/sup\u003eC), excellent Li\u003csup\u003e+\u003c/sup\u003e transport kinetics, and extremely low viscosity\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e,\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eIn this work, we developed a novel thermoresponsive electrolyte comprising THF, 1,3,5-trioxane (TO), and lithium bis(fluorosulfonyl)imide (LiFSI) to ensure the safe and stable operation of LMBs over wide temperature (from \u0026minus;\u0026thinsp;60 to 60 \u003csup\u003eo\u003c/sup\u003eC). The addition of TO can not only weaken the binding energy of Li\u003csup\u003e+\u003c/sup\u003e-THF and improve the charge transport kinetics at low temperatures, but also form Li-polyoxymethylene (LiPOM) in the CEI and SEI, promoting uniform Li\u003csup\u003e+\u003c/sup\u003e flux and impeding the electrochemical corrosion by the electrolyte, and realize the suitability for high-voltage cathode and conventional salt concentration. More importantly, TO can also trigger cationic-ring-opening polymerization of THF molecules at high temperatures, resulting in the formation of ion-aggregates-dominated solvated structure and polyether, which increases the high-temperature performance and safety of LMBs. As a result, the 1.5 Ah pouch cell demonstrates an impressive energy density of 386.8 Wh kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at 25 \u003csup\u003eo\u003c/sup\u003eC. Even at \u0026minus;\u0026thinsp;40 \u003csup\u003eo\u003c/sup\u003eC, the energy density of LMBs reaches 317.1 Wh kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, accompanied by a high capacity-retention of 74.7% after 60 cycles. This work presents a novel approach to design thermoresponsive electrolyte for up-and-coming LMBs over a wide temperature range.\u003c/p\u003e"},{"header":"Results","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eDesign of the thermoresponsive electrolyte and temperature-dependent solvated structures\u003c/h2\u003e \u003cp\u003eThe primary requirements for stable operation of LMBs at ultra-low temperatures are high ionic conductivity, low viscosity, and low freezing point\u003csup\u003e\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u003c/sup\u003e. In contrast, THF has excellent physical properties in all aspects and is the optimal solvent for ultra-low temperature LMBs (Supplementary Table\u0026nbsp;1). The results of quantum chemical calculations indicate that THF exhibits the highest lowest unoccupied molecular orbital (LUMO) energy level with a high propensity to supply power, enabling excellent reduction stability to the anode. In comparison, LiFSI exhibits the lowest LUMO and the highest highest Occupied Molecular Orbital (HOMO), which suggests that it will be preferentially reduced and oxidized to form an inorganic-rich inner SEI and CEI. The additive TO exhibits a lower LUMO and higher HOMO than THF, and is capable of preferential redox to form LiPOM, which serves to protect against the decomposition of the solvent THF (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea and Supplementary Fig.\u0026nbsp;1a). The reduction potentials of the three compounds were quantified, leading to the same conclusion. The reduction potential of TO (0.57 V) was higher than that of THF (0.38 V), while both were significantly lower than that of FSI- (1.64 V) (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed) \u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e,\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u003c/sup\u003e. Furthermore, electrostatic potential (ESP) simulation revealed that the ESP of the entire solvated structure was transferred from FSI\u003csup\u003e\u0026minus;\u003c/sup\u003e to the solvent upon TO addition. The ESP of the solvent was markedly reduced, indicating that TO can balance the energy in the solvated sheath and inhibit the continuous decomposition of the lithium salt. This is anticipated to result in excellent low-temperature performance at conventional Li-salt concentration (Supplementary Fig.\u0026nbsp;2). Based on the above design ideas, we selected 1M LiFSI THF as the reference electrolyte (denoted as THF-based electrolyte). The additive TO with 20% molar ratios was introduced into the THF-based electrolyte denoted as TO-based electrolyte.\u003c/p\u003e \u003cp\u003eMolecular dynamics (MD) simulations and the corresponding radial distribution functions (RDFs) were employed to evaluate the coordination structures of solvents, cations, and anions in THF-based and TO-based electrolytes\u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e,\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e. The calculations indicate that the average coordination in THF- and TO-based electrolytes is Li\u003csup\u003e+\u003c/sup\u003e(THF-O)\u003csub\u003e2.8\u003c/sub\u003e(FSI-O)\u003csub\u003e0.9\u003c/sub\u003e and Li\u003csup\u003e+\u003c/sup\u003e(THF-O)\u003csub\u003e1.9\u003c/sub\u003e(TO-O)\u003csub\u003e0.7\u003c/sub\u003e(FSI-O)\u003csub\u003e1.3\u003c/sub\u003e, respectively. These findings show that TO can engage in the solvation of the Li\u003csup\u003e+\u003c/sup\u003e solvation sheath within the electrolyte (Li-OTO peaks at ~\u0026thinsp;2.1 \u0026Aring;) and diminish the coordination of Li\u003csup\u003e+\u003c/sup\u003e-THF, while enhancing the coordination of Li\u003csup\u003e+\u003c/sup\u003e- FSI\u003csup\u003e\u0026minus;\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb, c). The blue shift of the S-N-S peaks observed in the Raman spectra, along with the shift of the \u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u003c/sup\u003eLi NMR spectra to the lower field, provide further support for the aforementioned conclusion (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ee-g). The fitted curves of the 700\u0026ndash;780 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e Raman spectral bands indicate that the TO-based electrolyte forms a solvated structure dominated by contact ion pairs (CIPs) at \u0026minus;\u0026thinsp;40 \u003csup\u003eo\u003c/sup\u003eC. This enhanced anionic interfacial chemistry ensures high charge-transfer kinetics at low temperatures and enhances the electrochemical performance (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ef).\u003c/p\u003e \u003cp\u003eVariable-temperature Raman and NMR spectroscopy tests can directly reveal changes in the solvated structure as a function of temperature. In the TO-based electrolyte, the contents of AGG I (one FSI\u003csup\u003e\u0026minus;\u003c/sup\u003e coordinating to two Li\u003csup\u003e+\u003c/sup\u003e) and AGG II (one FSI\u003csup\u003e\u0026minus;\u003c/sup\u003e coordinating to more than two Li\u003csup\u003e+\u003c/sup\u003e)\u003csup\u003e29\u003c/sup\u003e increased with temperature, indicating a significant reduction in free solvent molecules and more anions involved in the composition of the solvated sheath at high temperature (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ef). Furthermore, the shift of variable-temperature \u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u003c/sup\u003eLi NMR to higher field provides additional evidence for the enhancement of Li\u003csup\u003e+\u003c/sup\u003e coordination with anions (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eg). Additionally, the MD snapshots illustrate the strong aggregation of anions and the formation of ionic clusters at 60 \u003csup\u003eo\u003c/sup\u003eC, and the corresponding RDFs demonstrate that the coordination of Li-O\u003csub\u003eTHF\u003c/sub\u003e becomes weaker and the coordination of Li-O\u003csub\u003eFSI\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e stronger with increasing temperature (Supplementary Fig.\u0026nbsp;3). The above results indicate that the thermal motion of the polar THF solvent molecules increases during the temperature increase, thereby modifying the original ion-dipole mode of action and prompting the formation of temperature-dependent solvated structures.\u003c/p\u003e \u003cp\u003eIn general, the optimal electrolyte for high-temperature LMBs operation should possess a stable solvated structure, a robust redox-stable interface, and a high safety solvent\u003csup\u003e\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u003c/sup\u003e. By means of MD simulations conducted at 60 \u003csup\u003eo\u003c/sup\u003eC, three typical solvated structures (with a ratio higher than 75%) were extracted from each electrolyte, and their binding energies were calculated by density functional theory (DFT). The results show that the solvated structures of the TO-based electrolyte have higher binding energies than those of the THF-based electrolyte, which indicates that it has high thermal and oxidative stability (Supplementary Fig.\u0026nbsp;4). As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eh and Supplementary Fig.\u0026nbsp;5, the characteristic peaks of THF in the TO-based electrolyte were markedly diminished, and novel NMR peaks of hydrogen and carbon were discerned, culminating in the formation of a polyether (PTHF) with enhanced thermal stability. According to gel permeation chromatography, PTHF has high number average molecular weight (\u003cem\u003eM\u003c/em\u003e\u003csub\u003en\u003c/sub\u003e) and high weight average molecular weight (\u003cem\u003eM\u003c/em\u003e\u003csub\u003ew\u003c/sub\u003e) of 1.82\u0026times;10\u003csup\u003e5\u003c/sup\u003e and 3.47\u0026times;10\u003csup\u003e5\u003c/sup\u003e g mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively. The polymer dispersity index is approximately 2, which corresponds to a homogeneous molecular weight distribution, and effectively enhances the high temperature performance and safety of the batteries (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ei).\u003c/p\u003e \u003cp\u003eThe thermal polymerization mechanism and the evolution of solvated structure of TO-based electrolyte are described in detail in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ej, Supplementary Figs.\u0026nbsp;6\u0026ndash;9 and Supplementary Note 1. The thermal motion of the molecules is insignificant at \u0026minus;\u0026thinsp;40 \u003csup\u003eo\u003c/sup\u003eC, and THF, TO maintains relatively high ionic dipole interactions with Li\u003csup\u003e+\u003c/sup\u003e to form a CIP-dominated solvated structure, which accelerates the Li\u003csup\u003e+\u003c/sup\u003e desolvation process and achieves fast charge transfer kinetics at low temperatures. The thermal motion and kinetic energy of THF molecules increase at high temperature and undergo cationic ring-opening polymerization reaction in the presence of primary TO-oxonium-ions to form PTHF (Supplementary Fig.\u0026nbsp;9). This will drastically reduce the free solvent molecules in the electrolyte and decouple the solvents in the solvated structure, resulting in the formation of a more thermally stable anion-rich solvated sheath (i.e., the solvated structure is transformed from CIP to AGG I and AGG II). Notably, in contrast to the polymerization mechanism of THF at high temperatures, TO is in contact with Li-metal and undergoes a ring-opening polymerization reaction initiated by a minute quantity of H\u003csup\u003e+\u003c/sup\u003e(FSIOH)\u003csup\u003e\u0026minus;\u003c/sup\u003e to form a robust and compact LiPOM layer\u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/sup\u003e, which effectively enhances the redox stability of SEI and CEI (Supplementary Fig.\u0026nbsp;7, 8). Consequently, the TO-based electrolyte demonstrates excellent safety and wide-temperature performance, overcoming the limitations of conventional electrolytes to achieve the compatibility of thermodynamically stable interface, high safety and fast charge transfer kinetics at low temperatures.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003eElectrolyte properties and interfacial dynamics\u003c/h2\u003e \u003cp\u003eAlthough the increase in TO content enhances the degree of electrolyte polymerization at high temperatures, it also forms an excessively thick LiPOM layer at the interface, which impedes the interfacial charge transfer kinetics. To obtain the LiPOM layer with an optimal thickness, we configured TO-based electrolytes with varying molar ratios. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea shows the variation of ionic conductivity with temperature for the five electrolytes. The TO-base (20%) electrolyte exhibits the highest ionic conductivity of 3.928 mS cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at \u0026minus;\u0026thinsp;40\u0026deg;C. It is noteworthy that the ionic conductivity of the TO-based electrolytes exhibited a decreasing trend as the temperature was increased to 60\u0026deg;C. This is primarily due to the ring-opening polymerization of electrolyte solvent molecules and the formation of strong interactions between cations and anions in the solvated structure. The Arrhenius equation was employed to calculate the activation energy (Ea) of the electrolyte at low temperatures (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb)\u003csup\u003e\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e, resulting in a lower Ea value for the TO-based electrolyte in comparison to the THF-based electrolyte. Furthermore, the TO-based (20%) electrolyte exhibited an Ea of only 12.1 kJ mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The lower Ea indicates accelerated ion diffusion kinetics, resulting in the highest Li\u003csup\u003e+\u003c/sup\u003e transference number of 0.629 (Supplementary Fig.\u0026nbsp;10). This enhances the prolonged sand time and is advantageous for inhibiting dendrite growth\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e. The results of linear scanning voltammetry (LSV) also indicated a positive shift in the oxidation onset potential to 4.73 V with increasing TO content (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec). Although it has the potential to considerably enhance the oxidation window of the electrolyte, it also causes a deterioration in the wettability of the electrolyte with the separator (Supplementary Fig.\u0026nbsp;11). Overall, the TO-base (20%) electrolyte was observed to effectively enhance the ionic conductivity, ion transference number, and oxidative decomposition potential, while also exhibiting moderate viscosity at low temperatures.\u003c/p\u003e \u003cp\u003eAn \u003cem\u003ein situ\u003c/em\u003e IR cell device was constructed for the purpose of monitoring the dynamic alterations in the interfacial electrolyte conformation of copper electrodes throughout the processes of plating/stripping (Supplementary Fig.\u0026nbsp;12 and Supplementary Note 2) \u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e,\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/sup\u003e. This device was designed to facilitate insight into the modifications in solvation structure that occur in THF-based and TO-based electrolytes during the processes of charging/discharging, and to elucidate the impact of these modifications on the SEI derivatization. Figures\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed-f show the raw IR transmission spectra of \u003cem\u003ein situ\u003c/em\u003e FTIR using TO-based electrolytes. The data demonstrate a decline in the peak of ROLi (835\u0026thinsp;~\u0026thinsp;845 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and an increase in the peak of C\u0026thinsp;=\u0026thinsp;O (1725\u0026thinsp;~\u0026thinsp;1825 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003csup\u003e36\u003c/sup\u003e, indicating that the organic SEI formed is a robust and dense LiPOM layer derived from TO, as opposed to an unstable ROLi layer derived from THF. For comparison, the THF-based electrolyte exhibited strong ROLi and C-S (~\u0026thinsp;800 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) signals\u003csup\u003e\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/sup\u003e (lithium salt decomposition), and no C\u0026thinsp;=\u0026thinsp;O signal was observed (Supplementary Fig.\u0026nbsp;13). These findings indicate that the TO-derived LiPOM layer can act as a barrier to impede the inward diffusion of LiFSI to the Li anode, thereby slowing the successive decomposition of LiFSI and reducing the occurrence of side reactions.\u003c/p\u003e \u003cp\u003eThe impact of TO on the electrode interface kinetics was further elucidated through the examination of the distribution of relaxation times (DRT) (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eg, h and Supplementary Fig.\u0026nbsp;14)\u003csup\u003e\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e,\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e. This analysis classifies distinct electrochemical processes based on local maxima in a continuous distribution function\u003csup\u003e\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u003c/sup\u003e. Li\u003csup\u003e+\u003c/sup\u003e diffusion and interfacial charge transfer demonstrate a pronounced temperature dependence, with these processes dominating at low temperatures. It is noteworthy that the resistance values of these two processes for the TO-based electrolyte are only one-tenth of those for the THF-based electrolyte. This highlights the crucial role of TO in enhancing Li\u003csup\u003e+\u003c/sup\u003e desolvation and electrode interface charge transfer at ultra-low temperatures.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003eEffect of the designed electrolyte on Li plating/stripping at ultra-low temperatures\u003c/h2\u003e \u003cp\u003eTo evaluate the impact of the designed LiPOM layer on Li plating/stripping, the Coulombic efficiency (CE) of THF-based and TO-based electrolytes in Li||Cu cells was initially assessed using the Aurbach method\u003csup\u003e\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u003c/sup\u003e. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea, the TO-based electrolyte exhibits an exceptional CE of 99.06% at \u0026minus;\u0026thinsp;40\u0026deg;C and 0.5 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e, which is considerably higher than THF-based electrolyte (76.03%), and its initial lithium nucleation overpotential is also only 278 mV. This indicates that the addition of TO effectively improves the Li plating/stripping efficiency and kinetics. Furthermore, long cycling tests were conducted at a current density of 0.5 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e and a capacity of 1 mAh cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e. The 250-cycle average CE of the Li||Cu cell utilizing TO-based electrolytes reached 98.56% (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb), exhibiting a comparatively lower and more stable polarization voltage in its corresponding voltage profile (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec). Moreover, the Li||Li symmetric cell demonstrated stable operation for 450 h under these conditions (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed). In contrast, the CE of the THF-based electrolyte exhibited pronounced fluctuations during the initial stage, and a notable short-circuit phenomenon was observed after 20 cycles. This proves that the TO-derived LiPOM layer can effectively safeguard the Li anode from solvent molecule erosion, impede the growth of lithium dendrites and the formation of dead lithium, and demonstrate excellent Li plating/stripping reversibility and long-term stability at ultra-low temperature. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ee, the Li||Cu cell assembled by TO-based electrolyte exhibits remarkable rate performance at \u0026minus;\u0026thinsp;40\u0026deg;C, with a CE reaching 95.97% at a high current density of 1 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e. The cell is able to maintain stability when the current density is returned to 0.1 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e, and the corresponding voltage profile is consistent with the initial state (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ef). In contrast, the THF-based electrolyte demonstrated a notable decline in CE at 0.5 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e, resulting in direct short-circuiting and failure at 1 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e. This fully demonstrates that the addition of TO improves the interfacial charge transfer kinetics of the cell at ultra-low temperature.\u003c/p\u003e \u003cp\u003eTo elucidate the substantial discrepancies in CE and cycling stability among different electrolytes, scanning electron microscopy (SEM) and Kelvin probe force microscopy (KPFM) were employed to examine the morphology and surface potential of Li deposits, thereby facilitating an initial assessment of the underlying causes of these discrepancies from a morphological perspective. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eg, the quantity of Li plating on the Cu collector was markedly diminished in the THF-based electrolyte, and a considerable amount of whisker-like Li generation was also observed under SEM, which resulted in a notable increase in Li plating porosity, surface roughness, and surface potential. This is attributed to the slow Li\u003csup\u003e+\u003c/sup\u003e desolventization and interfacial charge transfer process of the THF-based electrolyte at ultra-low temperatures. This ultimately results in tip-driven Li-deposition, which leads to severe short-circuiting and failure of the cell\u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e. In contrast, following the introduction of TO, the Li deposits exhibited a dense and uniform bulk deposition morphology, with a surface roughness and surface potential of only 823.1 nm and 115 mV (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eh), respectively. This contributes to the achievement of higher CE and longer cycle life, indicating a significant enhancement of the solvation process and SEI kinetics in the TO-based electrolyte.\u003c/p\u003e \u003cp\u003eNotably, the Li||Cu and Li||Li cells assembled by TO-based electrolyte also exhibit outstanding CE and long-cycle stability at room temperature. Specifically, the Li||Cu cell cycled 400 turns with an average CE of 99.38%, the Li||Li cell cycled stably for 1400 h at a current density of 1 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e and a capacity of 2 mAh cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e. Furthermore, the Li||Cu cell still has a CE of 96.36% at a high current density of 5 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e (Supplementary Fig.\u0026nbsp;15). The Li-deposits formed in the TO-based electrolyte were also more homogeneous and flat, forming larger bulk deposits with a surface roughness and surface potential of only 504.7 nm and 11.9 mV, respectively. This was observed from SEM and KPFM (Supplementary Fig.\u0026nbsp;16). This was corroborated by in-situ observations made with polarized light microscopy (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ei). The TO-based electrolyte, formed a denser and more homogeneous Li layer, which enhanced the efficiency of Li deposition and effectively suppressed the growth of lithium dendrites. In contrast, the Li deposition of the THF-based electrolyte was sparse, exhibiting the formation of lithium dendrites and dead lithium.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003eInterfacial Chemistry Study\u003c/h2\u003e \u003cp\u003eTo obtain the nanostructures of SEI formed at ultra-low temperatures, we first observe the Li deposits on Cu grid via high-resolution transmission electron microscopy (HRTEM). As shown in Supplementary Fig.\u0026nbsp;17, the thickness of the TO-based electrolyte-derived SEI is mere 9.74 nm. It comprises an inner inorganic phase comprising LiF, Li\u003csub\u003e2\u003c/sub\u003eO, and Li\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e, and an outer organic layer of a \"mosaic\" type amorphous organic SEI. This structure of SEI exhibits high strength and elasticity, which effectively inhibit the electron tunneling effect and homogenize the Li\u003csup\u003e+\u003c/sup\u003e flux\u003csup\u003e42\u003c/sup\u003e. Consequently, the electrolyte is capable of achieving high CE and dense and uniform lithium deposition at ultra-low temperatures. In contrast, the SEI in the THF-based electrolyte is 22.3 nm thick, which impedes Li\u003csup\u003e+\u003c/sup\u003e diffusion. Furthermore, the outer organic layer of SEI is distributed intermittently, indicating severe erosion by the electrolyte and a lack of stability and robustness.\u003c/p\u003e \u003cp\u003eTo gain further insight into the composition and relative content of the structure of dual-layered SEI, depth profiling XPS tests were conducted (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea-d and Supplementary Fig.\u0026nbsp;18). According to the fine fitting results of XPS C 1s spectra, the presence of additional O-C-O and C\u0026thinsp;=\u0026thinsp;O signals was observed in TO-based electrolyte, which provided insight into the pathways and products of TO decomposition\u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e. The O-C-O signal was attributed to the TO-derived LiPOM layer, while the C-O signal was attributed to the THF derivative, which formed a short-chain organic SEI. As Ar\u003csup\u003e+\u003c/sup\u003e sputtering deepens, the relative content of organic species declines precipitously, while the relative content of inorganic components, including LiF, Li\u003csub\u003e2\u003c/sub\u003eO, and Li\u003csub\u003e3\u003c/sub\u003eN, rises markedly. This increase in inorganic components will facilitate the enhancement of ionic conductivity in the SEI and reduce kinetic barriers for Li\u003csup\u003e+\u003c/sup\u003e passage through the SEI. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed depicts the percent composition of each species in the SEI derived from both electrolytes at ultra-low temperatures. The SEI derived from the THF-based electrolyte exhibit elevated C-O (27%) in the surface layer and augmented Li\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e (23%) in the interior. This suggests that the formed SEI are of low strength and poorly stabilized, with the solvent molecules persistently eroding and undergoing side reactions with the Li metal. In contrast, the TO-based electrolyte derived SEI exhibits higher O-C-O (19%) in surface layer and a greater abundance of LiF (64%) and LiO\u003csub\u003e2\u003c/sub\u003e (8%) in internal layer. This suggests that the dense LiPOM layer effectively inhibits the erosion of Li metal by the solvent.\u003c/p\u003e \u003cp\u003eThe time-of-flight secondary ion mass spectrometry (TOF-SIMS) also provided dependable supporting information for the SEI derived from TO-based electrolytes\u003csup\u003e\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e. The initial detection of ion fragments pertaining to SEI components is presented in Supplementary Fig.\u0026nbsp;19. The LiF\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e and C\u003csub\u003e2\u003c/sub\u003eHO\u003csup\u003e\u0026minus;\u003c/sup\u003e ionic fragments are characteristic of LiF and organic components, respectively. The presence of abundant organic components in SEI indicates that TO can decompose to form LiPOM and participate in the formation of SEI. The three-dimensional structure of SEI and the spatial distribution of each component were further resolved by depth profile analysis of TOF-SIMS (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ee-g). The organic component of SEI is dense in the surface layer, which is capable of forming a solid layer. With the increase of the sputtering time, the content of the organic component starts to decrease, and the SEI gradually transitions to a LiF-dominated structure. By combining evidence from TOF-SIMS, HR-TEM, and XPS, we conclude that TO in the electrolyte is able to form a dense LiPOM outer layer on conventional anion-derived SEI, which protects the Li anode and enables the cell to have high CE and long-cycle stability.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn-situ X-ray diffraction (XRD) was employed to investigate the impact of two electrolyte-derived CEIs on the structural transformation of the NCM811 cathode during the charging/discharging processes (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea, b). In 3.0\u0026thinsp;~\u0026thinsp;4.5 V, the NCM811 cathode underwent a series of phase transitions: H1\u0026rarr;M\u0026rarr;H2\u0026rarr;H3a, which corresponded to the expansion and contraction of the lattice volume (Supplementary Fig.\u0026nbsp;20a, b)\u003csup\u003e\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e,\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e\u003c/sup\u003e. Notably, the intensity and Brag angle of the (003) and (101) peaks of the NCM811 cathode were significantly changed throughout the phase transition using the THF-based electrolyte (the H1\u0026rarr;M phase transition was particularly pronounced). In comparison, the volume expansion of the NCM811 cathode and the trailing of the peaks were significantly suppressed in the TO-based electrolyte, indicating a reversible phase transition and excellent structural stability. The fully charged Li||NCM811 cell was subjected to accelerated degradation tests at 4.5 V (Supplementary Fig.\u0026nbsp;20c). The results demonstrated that the leakage current density of the cell with TO-based electrolyte was only 5.44 \u0026micro;A cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e, indicating that the TO-derived CEI effectively reduced the interfacial side reaction rate and passivated the cathode. Furthermore, to examine the safeguarding of the CEI formed by the two electrolytes against the structural transformation of the cathode at \u0026minus;\u0026thinsp;40 \u003csup\u003eo\u003c/sup\u003eC, the NCM811 cathode after 100 cycles was dismantled for XRD pattern analysis (Supplementary Fig.\u0026nbsp;21a-f). The separation of the (006)/(102) peaks was observed to be more pronounced in the TO-based electrolyte, which suggests that the structural transition from the layered to the rock salt phase was effectively suppressed\u003csup\u003e\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e\u003c/sup\u003e. Furthermore, the SEM of the cathode, which was circulated in the TO-based electrolyte, did not develop intergranular cracks and exhibited a stable structure (Supplementary Fig.\u0026nbsp;22). Collectively, these findings illustrate that the TO-based electrolyte is effective in forming a dense and robust CEI, which serves to safeguard the NCM811 electrode from structural deterioration during the phase transition.\u003c/p\u003e \u003cp\u003eTo gain further insight into the chemical state and compositional information of the CEI, the NCM811 cathode was subjected to a depth profiling XPS test following 100 cycles. From the C 1s spectrum, it can be observed that the THF-based electrolyte-derived CEI has a strong C-O signal, indicating that its surface consists of short-chained and unstable organics, which is the main reason why it exhibits poor cathodic reversibility and structural disruption (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec). As a comparison, the TO-based electrolyte-derived CEI surface displays a greater abundance of O-C-O and C\u0026thinsp;=\u0026thinsp;O signals, indicative of the successful formation of the surface LiPOM layer (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed)\u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e. As the Ar\u003csup\u003e+\u003c/sup\u003e sputtering progresses, there is a notable decline in the relative content of organic species, accompanied by a pronounced increase in the relative content of LiF. This shift is expected to significantly enhance the kinetics of Li\u003csup\u003e+\u003c/sup\u003e transport in CEI. The organic-inorganic bilayer CEI was also demonstrated with high reliability using TOF-SIMS. The initial detection of LiF\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e, CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e and C\u003csub\u003e2\u003c/sub\u003eHO\u003csup\u003e\u0026minus;\u003c/sup\u003e indicated the presence of characteristic ion fragments of LiF, Li\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e and organic components, respectively (Supplementary Fig.\u0026nbsp;23a-c). The 3D structure of CEI and the spatial distribution of each component were further resolved by TOF-SIMS depth profiling (Supplementary Fig.\u0026nbsp;23d-f and 24). CEI consists of a dense organic layer on the surface and a LiF-dominated inorganic layer in the interior, and the content of Li\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e in the surface layer is extremely low, which suggests that CEI effectively inhibits the occurrence of the side reactions\u003csup\u003e\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u003c/sup\u003e. In light of the evidence derived from \u003cem\u003ein situ\u003c/em\u003e XRD, XPS and TOF-SIMS, it can be proved that the CEI formed by TO-based electrolyte is constituted by a dense and homogeneous LiPOM outer layer and a LiF-rich inner layer. This structure inhibits interfacial side reactions and the dissolution of TMs, preserves the initial structure of NCM811, and enhances interfacial stability.\u003c/p\u003e \u003cp\u003eFrom the experimental and theoretical results, the function of TO is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ee. TO is capable of participating in the Li\u003csup\u003e+\u003c/sup\u003e solvation structure, weakening the binding energy of Li\u003csup\u003e+\u003c/sup\u003e-THF, promoting Li\u003csup\u003e+\u003c/sup\u003e desolvation, and enhancing the charge transfer kinetics at the interface. More importantly, TO is able to prioritize THF reduction and oxidation to build a uniform, thin and robust LiPOM layer on the surface of Li-Metal and NCM electrodes. The double-layer SEI inhibits interfacial side reactions and lithium dendrite growth, while the double-layer CEI inhibits the dissolution of transition metal (TM) ions. This electrolyte design effectively enhances the cycling performance of the battery under high voltage and wide-temperature. In contrast, in the THF-based electrolyte, the inability to form a dense polymer layer to block the solvent attack on the both electrodes resulted in the growth of lithium dendrites, the dissolution of TMs, and the rupture of NCM particles (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ef).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003ePerformance of practical Li-metal cells at wide temperature\u003c/h2\u003e \u003cp\u003eIn order to demonstrate the effectiveness of the designed electrolyte operating over a wide temperature range, Li||NMC811 full cells were assembled to fully evaluate the TO-based electrolyte system. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea, b, the TO-based electrolyte full cell exhibits excellent long-cycle performance, with a capacity retention of 87.3% after 500 cycles at 25\u0026deg;C and 1C. Furthermore, the dQ/dV curves exhibit a high degree of overlap, with only a slight voltage change of 16 mV, indicating phase change reversibility and structural stability of the cathode (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ec). More importantly, the Li||NMC811 full cell employing a TO-based electrolyte still exhibits a capacity residual of 176.8 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e after 200 cycles, with a capacity retention of 90% and an average CE of 99.4% at an ultra-low temperature of \u0026minus;\u0026thinsp;40\u0026deg;C (0.2C charge/discharge) (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ed, e). It is worthy of note that the polarization of the cell increases significantly at ultra-low temperatures. Thanks to the improved solvation structure of TO and the formation of dual-layered CEI and SEI, which effectively enhances the Li\u003csup\u003e+\u003c/sup\u003e diffusion and interfacial charge transfer kinetics at low temperatures. Thus, a reversible phase transition of the anode was achieved (especially for the H1\u0026rarr;M phase change process, where the potential increased by only 48 mV after 200 cycles), reducing the polarization and the loss of cell capacity (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ef). In contrast, the initial capacity of the cell with THF-based electrolyte was only 120 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, which decayed to 41% of the initial capacity after 200 cycles. Furthermore, the TO-based electrolyte is capable of achieving 400 cycles at 60 \u003csup\u003eo\u003c/sup\u003eC with a capacity retention rate of up to 88.9% (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eg, h), due to the solvation structure transformation and solvent molecule reconfiguration at elevated temperatures. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ei, the \"six-star diagram\" visualization demonstrates that the TO-based electrolyte system exhibits significant advantages in terms of Li anode stability, wide temperature discharge, multiplicity performance, thermal stability, desolvation, and cycling stability.\u003c/p\u003e \u003cp\u003eExcellent wide-temperature performance and long cycle stability make advanced TO-based electrolytes promising for use in practical LMBs. Li||NCM811 pouch cells (1.5 Ah) with lean electrolytes (2 g Ah\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and a N/P ratio of 2.2 were assembled, allowing an initial specific energy density of 386.8 Wh kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e(Supplementary Fig.\u0026nbsp;25). The energy density of a cell is calculated by taking the masses of all components in pouch cells into consideration (Supplementary Table\u0026nbsp;2). Surprisingly, the LMB pouch cell was able to achieve an unprecedented initial energy density of 317.1 Wh kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at \u0026minus;\u0026thinsp;40 \u003csup\u003eo\u003c/sup\u003eC, and exhibited remarkable cycling stability, retaining 74.7% of its capacity after 60 cycles (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ej). In contrast, the discharge capacity of THF-based electrolytes decays to 0 after 10 cycles. The disassembly of the cycled Li||NCM811 pouch cells was employed to investigate the underlying cause of the notable discrepancy in cycling performance at low temperatures between two electrolytes. The Li anodes that were cycled in the THF-based electrolyte exhibited a notable depletion and displayed considerable quantities of dead lithium and whisker-like formations (Supplementary Fig.\u0026nbsp;26a, b). Conversely, in the TO-based electrolyte, the lithium remained in the form of lumpy deposits, although the distribution of lithium on the Cu collector exhibited slight inhomogeneity after repeated cycling (Supplementary Fig.\u0026nbsp;26c, d). Further, the temperature adaptability of Li||NCM811 pouch cells was evaluated. The cells were observed to operate stably at \u0026minus;\u0026thinsp;60\u0026thinsp;~\u0026thinsp;60 \u003csup\u003eo\u003c/sup\u003eC, exhibiting excellent room temperature capacity retention of 81.5% and 61.7% at \u0026minus;\u0026thinsp;60 and \u0026minus;\u0026thinsp;40 \u003csup\u003eo\u003c/sup\u003eC, respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ek). Furthermore, our designed TO-based electrolyte exhibits the most optimal overall performance in terms of wide-temperature performance, capacity retention, and energy density when compared with advanced electrolytes designed in the literature (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ei and Supplementary Table\u0026nbsp;3).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo further demonstrate the practical application potential of the TO-based electrolyte, it was assembled into a pouch cell and assembled on a robot, which was able to drive the robot to work stably under the harsh temperature conditions of \u0026minus;\u0026thinsp;40 \u003csup\u003eo\u003c/sup\u003eC (Supplementary Fig.\u0026nbsp;27 and Supplementary Movie 1). The safety of LMB is typically determined by the combination of the intrinsic safety of the electrolyte and the thermal runaway temperature of the cathode material in a fully charged state\u003csup\u003e\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e,\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/sup\u003e. As shown in Supplementary Fig.\u0026nbsp;28a, b and Supplementary Movie 2, the polymerization products of the TO-based electrolyte did not exhibit combustion in ignition test, and the thermal decomposition temperature of the electrolyte reached 211\u0026deg;C with minimal heat release. In-situ variothermal XRD demonstrated that the formation of dual-layered CEI effectively suppressed the release of oxygen from the cathode during charging and enhanced the thermodynamic stability (Supplementary Fig.\u0026nbsp;28c, d). Consequently, the thermal safety of LMBs utilising a TO-based electrolyte was markedly enhanced.\u003c/p\u003e \u003c/div\u003e"},{"header":"Discussion","content":"\u003cp\u003eIn summary, we present a novel thermoresponsive electrolyte design strategy that enables the safe and stable operation of LMBs at \u0026minus;\u0026thinsp;60\u0026thinsp;~\u0026thinsp;60\u0026deg;C. The theoretical and experimental evidence demonstrates that the additive TO is able to participate in the Li\u003csup\u003e+\u003c/sup\u003e solvation structure, thereby promoting Li\u003csup\u003e+\u003c/sup\u003e transport and charge transfer kinetics. Combined with the evidence from HRTEM, XPS, TOF-SIMS and in-situ XRD, the SEI, CEI derived from TO-based electrolyte is composed of a uniform, thin and robust outer layer of LiPOM and an inner layer enriched with LiF, Li\u003csub\u003e2\u003c/sub\u003eO, which is able to effectively prevent the degradation of both electrodes. More importantly, when the temperature rises, the solventized structure of the electrolyte undergoes a transformation, with solvent molecules reorganizing to form a polyether with enhanced oxidation resistance. This significantly enhances the safety of the battery. Consequently, the practical 1.5 Ah Li||NCM811 pouch cell with optimized electrolyte is able to operate at \u0026minus;\u0026thinsp;60\u0026thinsp;~\u0026thinsp;60\u0026deg;C. Specifically, the pouch cell is capable of achieving 100 cycles at 25\u0026deg;C with an initial energy density of 386.8 Wh kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Surprisingly, it still has a room temperature discharge capacity of 61.7% at \u0026minus;\u0026thinsp;60\u0026deg;C, and achieves an unprecedented initial energy density of 317.1 Wh kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at \u0026minus;\u0026thinsp;40\u0026deg;C with a capacity retention of 74.7% for 60 cycles.\u003c/p\u003e"},{"header":"Methods","content":"\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003eMaterials\u003c/h2\u003e \u003cp\u003eActive materials (LiNi\u003csub\u003e0.8\u003c/sub\u003eCo\u003csub\u003e0.1\u003c/sub\u003eMn\u003csub\u003e0.1\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e (NCM811) powders), polyvinylidene difluoride (PVDF), Super P, carbon-coated aluminum foil (Al, 15 \u0026micro;m-thick), separator (Celgard 2325, thickness: 25 \u0026micro;m, PP/PE/PP three-layer membrane), Coin cell components (CR2032, spacer: 15.8 \u0026times; 1 mm, spring: 15.4 \u0026times; 1.1 mm) were purchased from Nanjing Mojiesi Energy Technology. Lithium Bis(fluorosulfonyl)imide (LiFSI, \u0026gt; 98%), tetrahydrofuran (THF, \u0026ge; 99.9%), N-methyl-2-pyrrolidone (NMP, \u0026ge; 99.5%) were purchased from Shanghai Aladdin Bio-Chem Technology Co., Ltd. 1,3,5trioxane (TO, \u0026gt;\u0026thinsp;99.0% (GC)) were purchased from Tokyo Chemical Industry Co., Ltd. The 450 \u0026micro;m Li-metal sheets were procured from Beijing InnoChem Science \u0026amp; Technology Co., Ltd. The NCM811 cathodes (22 mg cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e) were procured from Guangdong Canrd New Energy Technology Co., Ltd.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003eThe preparation of electrolyte\u003c/h2\u003e \u003cp\u003eThe THF-based electrolyte was prepared by dissolving 1M LiFSI (0.187 g) into the 1 mL THF. Next, 0.018g TO was dissolved in THF-based electrolyte to prepare the TO-based electrolyte (LiFSI:TO molar ratios of 1:0.2). All the preparation steps mentioned above were conducted at room temperature (~\u0026thinsp;25\u0026deg;C) in an Ar-filled glove box (H\u003csub\u003e2\u003c/sub\u003eO\u0026thinsp;\u0026lt;\u0026thinsp;0.1 ppm and O\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;\u0026lt;\u0026thinsp;0.1 ppm).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003eCoin cells and pouch cells assembling\u003c/h2\u003e \u003cp\u003eAll coin cells were assembled in the Argon-filled glove box with H\u003csub\u003e2\u003c/sub\u003eO\u0026thinsp;\u0026lt;\u0026thinsp;0.1 ppm and O\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;\u0026lt;\u0026thinsp;0.1 ppm. Li||Li CR-2032 type coin cells were assembled in the following order: cathode case, Li-metal sheet, Celgard 2325 separator (18 mm), Li-metal sheet, spacer, spring, and anode case. Li||Cu CR-2032 type coin cells were assembled in the following order: cathode case, Cu foil (14mm), Celgard 2325 separator, Li sheet, spacer, spring, and anode case. Li||NCM811 full cell were assembled in the following order: cathode case, aluminum disk (19 mm), NCM811 cathode disk, Celgard 2325 separator, Li anode sheet, spacer, spring, and anode shell. All coin cells were added with 75 \u0026micro;L electrolyte. Additionally, to prevent corrosion of the stainless-steel case under high voltages, an additional piece of Al foil must be placed between the cathode case and NCM cathode disk.\u003c/p\u003e \u003cp\u003eFor Li||NCM811 pouch cell (10.0 \u0026times; 7.0 cm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e), Li anode (composed of Cu current collector and double-layer Li foil) and cathode of double-layer active material were stacked one by one and separated by Celgard 2325, the electrolyte volume is 3.0 mL. The thickness and mass loading of anode, cathode and other components are provided in Supplementary Table\u0026nbsp;3. The Li||NCM811 pouch cell was assembled in a dry room whose dew point is \u0026minus;\u0026thinsp;50\u0026deg;C.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003eElectrochemical Testing\u003c/h2\u003e \u003cp\u003eAll electrochemical data presented in this work were generated from CR-2032 coin cells. Low temperature galvanostatic tests were performed on a Neware BTS 4000 system, while room temperature galvanostatic tests were performed on a LANHE-CT 2001A system. The Low temperature tests were measured in a JHY-H-50L temperature chamber to maintain the cell at a set temperature. All potentiostatic tests were performed on a CHI-760E. The electrochemical impedance spectroscopy (EIS), from 1 MHz to 100 mHz with an amplitude of 5 mV was tested using a Chenhua electrochemical workstation. In the LSV tests, a carbon-coated aluminium foil (c-Al foil) was used as a working electrode with a sweep rate of 1 mV s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Round cycles from 3 to 6 V (vs. Li/Li\u003csup\u003e+\u003c/sup\u003e) were performed, and then the stable recorded cathodic scan for each Li||c-Al foil cell with different electrolytes was recorded as the LSV curve. The electrochemical floating test was performed in Li||NCM811 cells with different electrolyte. The cells were first charged to 4.5 V at 0.1C and then maintained for 12 h with the current monitored by LANHE-CT 2001A system.\u003c/p\u003e \u003cp\u003eThe ionic conductivity of the electrolyte was measured by a customized two-electrode coin cell. The two stainless steel electrodes were placed symmetrically between a polytetrafluoroethylene disc with a thickness of 0.027 inches. A glass-fiber separator soaked with electrolyte was placed inside the washer, which constrained its surface area to a known value. The electrolyte conductivity values were then obtained with electrochemical impedance spectroscopy (EIS) using the following equation:\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec14\" class=\"Section2\"\u003e \u003ch2\u003e\u0026#120590; =\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\frac{\\varvec{L}}{\\varvec{A}\\ast\\:\\varvec{R}}\\)\u003c/span\u003e\u003c/span\u003e\u003c/h2\u003e \u003cp\u003ewhere R is the measured ionic resistance and A and L are the area of the electrodes and the space between the electrodes, respectively. The data points from 40\u0026deg;C to \u0026minus;\u0026thinsp;60\u0026deg;C were measured in a JHY-H-50L temperature chamber to maintain the cell at a set temperature for 2h intervals before each measurement.\u003c/p\u003e \u003cp\u003eThe transfer numbers of the electrolytes were determined by a commonly used potentiostatic polarisation technique on a CHI-760E, and the transfer coefficient was then calculated using the following equation:\u003cdiv id=\"Equa\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\n$$\\:{\\varvec{t}}_{+}=\\frac{{\\varvec{I}}_{\\varvec{S}\\varvec{S}}(\\varDelta\\:\\varvec{V}-{\\varvec{I}}_{0}{\\varvec{R}}_{0})}{{\\varvec{I}}_{0}(\\varDelta\\:\\varvec{V}-{\\varvec{I}}_{\\varvec{S}\\varvec{S}}{\\varvec{R}}_{\\varvec{S}\\varvec{S}})}$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003ewhere \u0026#120549;\u0026#119881; is the applied bias, R\u003csub\u003e0\u003c/sub\u003e is the initial cell impedance and R\u003csub\u003eSS\u003c/sub\u003e is the steady-state cell impedance.\u003c/p\u003e \u003cp\u003eTo evaluate the CE of Li||Cu cells, Aurbach\u0026rsquo;s method was applied. The overall CE was calculated by the following Eq.\u0026nbsp;3\u003csup\u003e8\u003c/sup\u003e\u003cdiv id=\"Equb\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equb\" name=\"EquationSource\"\u003e\n$$\\:{\\varvec{C}\\varvec{E}}_{\\varvec{a}\\varvec{v}\\varvec{g}-\\varvec{n}}=\\frac{\\varvec{n}{\\varvec{Q}}_{\\varvec{c}}+{\\varvec{Q}}_{\\varvec{s}}}{\\varvec{n}{\\varvec{Q}}_{\\varvec{c}}+{\\varvec{Q}}_{\\varvec{t}}}$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eQ\u003csub\u003ec\u003c/sub\u003e represents the deposition or dissolution capacity in n cycles. Its fixed value is 1 mAh cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e. Q\u003csub\u003et\u003c/sub\u003e is the initial Li reservoir capacity deposited on the Cu foil and Q\u003csub\u003es\u003c/sub\u003e indicates the capacity finally stripped from the Cu foil.\u003c/p\u003e \u003cp\u003ePouch cells were cycled in the voltage range of 3.0\u0026ndash;4.3V at 0.1C at 25\u0026deg;C. Pouch cells were cycled in the voltage range of 2.8\u0026ndash;4.3 V at 0.05C at \u0026minus;\u0026thinsp;40\u0026deg;C. The cycling performance of the pouch cells was tested under a fixing device to provide 1.0 MPa external pressure.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec15\" class=\"Section2\"\u003e \u003ch2\u003eMaterial characterizations\u003c/h2\u003e \u003cp\u003eThe Nuclear Magnetic Resonance (NMR) spectrometer was used to characterize the organic solvents or electrolytes in this work, and each test dissolved a 20 \u0026micro;L sample in deuterated chloroform. The \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH and \u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u003c/sup\u003eLi Nuclear Magnetic Resonance (NMR) spectra were acquired using the Bruker 400 MHz and Bruker AVANCE NEO 600 MHz, respectively. The gel permeation chromatography measurements (1260 Infinity II, Agilent Technologies) were performed by dissolving the polymerization product in THF. The Contact Angle (CA) measuring instrument (JC2000DS2) was used to characterise the wettability of the four electrolytes studied. The amount of electrolyte is controlled at 10 uL at a time. The Raman spectroscopy data of the electrolytes were obtained using a LabRAM HR Evolution Raman micro-spectrometer equipped with 633 nm laser. The morphologies of Li deposition in different electrolytes were collected by FESEM (JSM-7800F, JEOL), HR-TEM (JEM-2100F, JEOL) was used to observe the thickness and morphology of CEI and SEI films. The roughness and potential of the lithium-embedded negative electrode surface were obtained by KPFM (SPM-9700HT). XPS data was collected using Thermo Scientific K-Alpha\u003csup\u003e+\u003c/sup\u003e. The analysis chamber has a vacuum degree of approximately 2\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;7\u003c/sup\u003e mbar, X-ray source: monochromatic Al Kα source, energy: 1486.6 eV, voltage: 12 kV, beam current: 6 mA, analyzer scanning mode: CAE, work function: 4.2 eV. The depth-profiling XPS was carried out at an etching rate of 0.2 nm s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. ToF-SIMS (PHI nano ToF II, ULVAC-PHI) also investigated SEI and CEI components. The area of analysis is 100 \u0026micro;m \u0026times; 100 \u0026micro;m, while the sputtering area is 400 \u0026micro;m \u0026times; 400 \u0026micro;m.\u003c/p\u003e \u003cp\u003eData for X-ray diffraction was acquired using a Bruker D8 Advance X-ray diffractometer outfitted with a LynxEye 1-dimensional detector with Cu-Ka radiation at 40 kV and 40 mA (λ\u0026thinsp;=\u0026thinsp;1.5418 \u0026Aring;) with a step increment of 0.02 and a duration per step of 0.1 s. The operando XRD test during charging and discharging rate of 0.5 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e were performed at 25\u0026deg;C and diffraction patterns were collected every 8 min. The LIB-MS-R is provided by the Beijing Scistar Technology Co. Ltd. The device simulates a lithium-ion coin cell to observe the growth of lithium dendrite and its corresponding changes.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec16\" class=\"Section2\"\u003e \u003ch2\u003eDensity functional theory calculations\u003c/h2\u003e \u003cp\u003eThe DFT calculations were performed using Gauss 16 quantum chemistry software. All the molecules were pre-optimised at the B3LYP/6-31G* level. Next, the Molclus program was used to search for configurations of the complex. The optimized geometry was obtained using the DFT-D3 van der Waals (vdW) correction proposed by Grimme. During the correction process, all atoms were allowed to relax until the atomic force on each atom was below 0.005 eV \u0026Aring;\u003csup\u003e\u0026minus;1\u003c/sup\u003e and the energy was less than 1.0 \u0026times; 10\u003csup\u003e\u0026minus;\u0026thinsp;6\u003c/sup\u003e eV. A total of 200 initial configurations were generated and each configuration was optimised at the B3LYP/3-21G* level. The configuration with the lowest energy was then further optimised to the B3LYP/6-311G(d) level. The intermolecular interactions were described using the Grimme d3bj dispersion. The binding energy was calculated according to the following equation.\u003c/p\u003e \u003cp\u003eBinding energy\u0026thinsp;=\u0026thinsp;Ecomplex\u0026ndash;(Efragment\u003csub\u003e1\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;Efragment\u003csub\u003e2\u003c/sub\u003e)\u003csup\u003e49\u003c/sup\u003e\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec17\" class=\"Section2\"\u003e \u003ch2\u003eMolecular dynamics simulations\u003c/h2\u003e \u003cp\u003eAll molecular dynamics (MD) simulations were performed by the GROMACS 2023 simulation package\u003csup\u003e\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e,\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e\u003c/sup\u003e. The systems were described by the OPLS-AA force field\u003csup\u003e\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e\u003c/sup\u003e. The parameters of THF and TO molecules were generated by the LigParGen web server and that of Li\u003csup\u003e+\u003c/sup\u003e and FSI\u003csup\u003e\u0026minus;\u003c/sup\u003e were obtained from Jensen et al\u003csup\u003e\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e\u003c/sup\u003eand Lopes et al\u003csup\u003e\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e\u003c/sup\u003e, respectively. The Lorentz-Berthelot mixing rules were chosen to calculate the LJ parameters of the cross interactions. The molar ratios of the electrolytes were obtained from the experimental part of this work. The periodic boundary condition was applied to all three dimensions. The Particle Mesh Ewald (PME) method was used to calculate the long-range electrostatic interaction with a cut-off for a real space of 1.2 nm. The short-range van der Waals cut-off was set to be 1.2 nm.\u003c/p\u003e \u003cp\u003eThe initial simulation boxes were constructed by Packmol\u003csup\u003e\u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e\u003c/sup\u003e. All the cases, after energy minimization, were first equilibrated in 20 ns NPT ensemble and 35 ns NVT ensemble, respectively, and every production run was performed for 5 ns in the NVT ensemble with 2 fs time step and saved every 0.2 ps. The temperature of the system was controlled by the Nos\u0026eacute;-Hoover thermostat, and the simulated temperature was maintained at 233.15 K. The Berendsen pressure coupling regulated the system at 1 bar\u003csup\u003e\u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e56\u003c/span\u003e\u003c/sup\u003e. The visualization was generated via the VMD package. The binding energy of Li\u003csup\u003e+\u003c/sup\u003e containing internal term (ΔE\u003csub\u003eint\u003c/sub\u003e), van der Waals (ΔE\u003csub\u003evdW\u003c/sub\u003e) and electrostatic (ΔE\u003csub\u003eele\u003c/sub\u003e) energies was calculated with Generalized Born model by gmx_MMPBSA\u003csup\u003e\u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e57\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003c/div\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAcknowledgements\u003c/h2\u003e \u003cp\u003eThis work was supported by National Natural Science Foundation of China (22479094, 22075174), the Science and Technology Commission of Shanghai Municipality (20520740900 and 19DZ2271100), and International Joint Laboratory on Resource Chemistry.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eZhou, G., Chen, H. \u0026amp; Cui, Y. 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Theory Comput\u0026nbsp;\u003c/em\u003e\u003cstrong\u003e17\u003c/strong\u003e, 6281-6291(2021).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Wide temperature, Thermoresponsive electrolyte, Interfacial chemistry, Li-metal batteries","lastPublishedDoi":"10.21203/rs.3.rs-5101221/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5101221/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eDeveloping wide-temperature range and safety electrolytes for lithium metal batteries (LMBs) is expected to possess high redox interfacial stability, rapid kinetics and intrinsic safety. However, \u003ca href=\"file:///D:/%E7%99%BE%E5%BA%A6%E7%BF%BB%E8%AF%91/baidu-translate-client/resources/app.asar/app.html\"\u003etraditional\u003c/a\u003e electrolytes are rarely able to satisfy all of these characteristics simultaneously, often exhibiting preference for one over the other. Herein, we present a novel ether-based thermoresponsive electrolyte, that are designed by temperature-dependent Li\u003csup\u003e+\u003c/sup\u003e solvation structure and forming polycrystalline electrode/electrolyte interface, can achieve the above characteristics at conventional salt concentration. The solvation sheath in the novel electrolyte is reconstructed by 1,3,5-trioxane (TO), accelerating the dissociation and charge transfer kinetics of anions. TO also induces cationic-ring-opening polymerization of tetrahydrofuran solvent molecules at 60 \u003csup\u003eo\u003c/sup\u003eC to produce oxidation-resistant ether-based polymers, which enhances the high-temperature performance and safety of LMBs. Consequently, the Li||LiNi\u003csub\u003e0.8\u003c/sub\u003eCo\u003csub\u003e0.1\u003c/sub\u003eMn\u003csub\u003e0.1\u003c/sub\u003eO\u003csub\u003e2 \u003c/sub\u003e(NCM811) cells using this thermoresponsive electrolyte operate well over a wide temperature range (from −60 to 60 \u003csup\u003eo\u003c/sup\u003eC). Besides, the Li||NCM811 pouch cell (1.5 Ah) achieve a high capacity-retention of 74.7% after 60 cycles at −40 °C, accompanied by an impressive energy density of 317.1 Wh kg\u003csup\u003e−1\u003c/sup\u003e.\u003c/p\u003e","manuscriptTitle":"Novel thermoresponsive ether-based electrolyte for wide-temperature operating lithium metal batteries","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-09-27 09:17:22","doi":"10.21203/rs.3.rs-5101221/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"445df869-132d-45c6-85c7-6270215d32a6","owner":[],"postedDate":"September 27th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":38222140,"name":"Physical sciences/Chemistry/Energy"},{"id":38222141,"name":"Physical sciences/Energy science and technology/Energy storage/Batteries"}],"tags":[],"updatedAt":"2025-07-02T07:11:39+00:00","versionOfRecord":{"articleIdentity":"rs-5101221","link":"https://doi.org/10.1038/s41467-025-60524-8","journal":{"identity":"nature-communications","isVorOnly":false,"title":"Nature Communications"},"publishedOn":"2025-07-01 04:00:00","publishedOnDateReadable":"July 1st, 2025"},"versionCreatedAt":"2024-09-27 09:17:22","video":"","vorDoi":"10.1038/s41467-025-60524-8","vorDoiUrl":"https://doi.org/10.1038/s41467-025-60524-8","workflowStages":[]},"version":"v1","identity":"rs-5101221","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5101221","identity":"rs-5101221","version":["v1"]},"buildId":"WrCJVZZCHTDjtuVLN7oU0","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}