In-Situ Coupled Macromolecular Bridge Enables All-Solid-State Lithium Metal Batteries Capable of Wide-Temperature Operation

In-Situ Coupled Macromolecular Bridge Enables All-Solid-State Lithium Metal Batteries Capable of Wide-Temperature Operation | Authorea try { document.documentElement.classList.add('js'); } catch (e) { } var _gaq = _gaq || []; _gaq.push(['_setAccount', 'G-8VDV14Y67G']); _gaq.push(['_trackPageview']); (function() { var ga = document.createElement('script'); ga.type = 'text/javascript'; ga.async = true; ga.src = ('https:' == document.location.protocol ? 'https://ssl' : 'http://www') + '.google-analytics.com/ga.js'; var s = document.getElementsByTagName('script')[0]; s.parentNode.insertBefore(ga, s); })(); Skip to main content Preprints Collections Wiley Open Research IET Open Research Ecological Society of Japan All Collections About About Authorea FAQs Contact Us Quick Search anywhere Search for preprint articles, keywords, etc. Search Search ADVANCED SEARCH SCROLL This is a preprint and has not been peer reviewed. Data may be preliminary. 15 July 2025 V1 Latest version Share on In-Situ Coupled Macromolecular Bridge Enables All-Solid-State Lithium Metal Batteries Capable of Wide-Temperature Operation Authors : Yin Cui , shasha Shi , Chenkai Lu , ziqi Cai , Guobin Zhang , Li Li , Tao Yang , Tao Liu 0000-0001-6017-0827 , Qingxia Liu , and Xidong Lin 0009-0006-9991-1729 [email protected] Authors Info & Affiliations https://doi.org/10.22541/au.175260278.83407712/v1 243 views 153 downloads Contents Abstract Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract Composite polymer electrolytes (CPEs) containing Li7La3Zr2Ta0.5O12 (LLZT) have focused much attention owing to their merits of both ceramic and polymer electrolytes. Nevertheless, due to air exposure, the naturally formed impurity layer on LLZT hinders lithium ion transport, reduces interficial compatibility, and ultimately causes undesirable performance degradation. Herein, a novel and effective method known as in-situ coupled macromolecular bridge is proposed and corresponding functionalized LLZT (LLZT@mPEG) is synthesised. Rigid LLZT cores and flexible ionic conductive polymer side-chains are closely combined by electrostatic interaction, thus resolving the challenge of interface compatibility between different phases. As a consequence, the prepared all-solid-state CPE (LLZT@mPEG-CPE) shows a great ionic conductivity, e.g., 4.9 × 10–4 S cm⁻¹ at 40 ℃ and 7.6 × 10⁻3 S cm⁻¹ at 120 ℃. The Li|Li cell exhibits significant cycling stability of 1750 hours without short-circuits at 120 ℃ and 0.5 mA cm–2. Remarkably, the exceptional thermal endurance is demonstrated by assembled Li|LFP cell with ultrastable performance for more than 500 cycles at extreme temperature of 160 ℃ and high rate of 5 C with a significant capacity retention rate of 94%. This work provides an innovative design principle for advanced all-solid-state electrolytes of Li metal batteries capable of wide-temperature operation. Article category: Full Paper Subcategory: Lithium Metal Batteries In-Situ Coupled Macromolecular Bridge Enables All-Solid-State Lithium Metal Batteries Capable of Wide-Temperature Operation Yin Cui # , Shasha Shi # , Chenkai Lu # , Ziqi Cai, Guobin Zhang, Li Li*, Tao Yang, Tao Liu*, Qingxia Liu*, Xidong Lin* Y. Cui, C. Lu, Z. Cai, G. Zhang, L. Li, T. Yang, Q. Liu, X. Lin Future Technology School, Shenzhen Technology University, Shenzhen 518118, P. R. China E-mail: [email protected] ; [email protected] ; [email protected] # These authors contributed to the work equally. S. Shi, T. Liu School of Chemistry and Chemical Engineering, State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures, School of Resources, Environment and Materials, Guangxi University, Nanning 530004, P. R. China E-mail: [email protected] Keywords: composite polymer electrolyte, polymer matrix, filler, high temperature, lithium metal battery Abstract Composite polymer electrolytes (CPEs) containing Li 7 La 3 Zr 2 Ta 0.5 O 12 (LLZT) have focused much attention owing to their merits of both ceramic and polymer electrolytes. Nevertheless, due to air exposure, the naturally formed impurity layer on LLZT hinders lithium ion transport, reduces interficial compatibility, and ultimately causes undesirable performance degradation. Herein, a novel and effective method known as in-situ coupled macromolecular bridge is proposed and corresponding functionalized LLZT (LLZT@mPEG) is synthesised. Rigid LLZT cores and flexible ionic conductive polymer side-chains are closely combined by electrostatic interaction, thus resolving the challenge of interface compatibility between different phases. As a consequence, the prepared all-solid-state CPE (LLZT@mPEG-CPE) shows a great ionic conductivity, e.g. , 4.9 × 10 –4 S cm⁻¹ at 40 ℃ and 7.6 × 10⁻ 3 S cm⁻¹ at 120 ℃. The Li|Li cell exhibits significant cycling stability of 1750 hours without short-circuits at 120 ℃ and 0.5 mA cm –2 . Remarkably, the exceptional thermal endurance is demonstrated by assembled Li|LFP cell with ultrastable performance for more than 500 cycles at extreme temperature of 160 ℃ and high rate of 5 C with a significant capacity retention rate of 94%. This work provides an innovative design principle for advanced all-solid-state electrolytes of Li metal batteries capable of wide-temperature operation. 1. Introduction Li metal batteries (LMBs) have recently gained significant attention as a high-energy-density energy storage solution to replace commercial Li-ion batteries. [1,2] However, conventional liquid electrolytes (LEs) are volatile and flammable, posing significant safety risks including fire and explosion hazards. Furthermore, their high reactivity with Li metal leads to unstable solid electrolyte interphase (SEI) formation and detrimental Li dendrite growth. [3-9] To address safety concerns associated with LEs, solid-state electrolytes have been proposed as a promising alternative for LMBs. Specifically, solid polymer-based electrolytes exhibit outstanding film-forming characteristics and interfacial compatibility that effectively suppress Li-dendrite formation, while their cost-effectiveness and processability facilitate commercial viability. Nevertheless, the conventional polymer electrolyte, such as polyethylene oxide (PEO), suffers from inherent drawbacks, including low modulus and poor ionic conductivity, which will eventually compromise both electrochemical performance and safety properties. For example, polymer electrolytes generally necessitate operation at elevated temperatures ( e.g. >60 ℃), during which thermal-induced modulus degradation can lead to mechanical deformation and subsequent short-circuit risk. [10-13] Composite polymer electrolytes (CPEs), fabricated by incorporating inorganic nanofillers into polymer matrices, have demonstrated significant enhancements in mechanical robustness, thermal stability, and electrochemical properties. [14] The incorporated fillers can significantly enhance the ionic conductivity of CPEs by simultaneously suppressing polymer crystallinity and promoting Li-salt dissociation. In particular, the garnet-type Li 7 La 3 Zr 2 Ta 0.5 O 12 (LLZT) is regarded as a state-of-the-art nanofiller due to its high ionic conductivity, excellent mechanical strength and great compatibility with Li metal. Unfortunately, Li 2 CO 3 and LiOH can easily form on the LLZT surface owing to the exposure in moist air. [15] Such surface contaminants are insulating and lithiophobic, thus impairing the Li + migration at the LLZT-polymer interface. Furthermore, the insufficient interfacial compatibility between the inorganic and organic phase induces fillers agglomeration, consequently leading to non-uniform distribution of mechanical modulus and Li + flux. Thus, owing to the low ionic conductivity, high interface resistance and unstable SEI layer, it is difficult to achieve long stable cycling for LMBs with traditional LLZT-based CPEs ( Figure 1a ). [16] Recent studies have been proposing several surface engineering techniques aimed at optimizing the interfacial compatibility between LLZT fillers and polymer matrices. [17] A prominent approach involves constructing functional monolayers on LLZT surface using organic or inorganic coating ( e.g. acidic 4-chlorobenzenesulfonic acid, polydopamine, and functionalized carbon dots). [18-21] These monolayers simultaneously establish active surfaces, which optimize Li + solvation and conduction. However, the functional contact area between these thin monolayers and polymer substrate is insufficient, which fails to provide percolating networks for long-range Li⁺ migration. In contrast, constructing brush-like macromoleculars on LLZT surface reduced the surface energy and facilitate soft and large-area contact at the polymer-filler interface. The grafted macromolecules, featuring long-chain and high-density functional groups, form interconnected bridges that enable uniform and continuous Li + transport across the CPE. However, such polymer brushes are usually synthesized through the “grafting from” technique, including tedious surface modification and time-consuming polymerization processes, which limit their large-scale applications. [22-25] Hence, the realization of CPEs combining efficient ion conduction, high interfacial compatibility, and scalable processability continues to pose a major challenge. In this study, we propose a facile “grafting to” strategy to construct macromolecular ion-conducting bridges on LLZT fillers (denoted as LLZT@mPEG) using methoxy polyethylene glycol carboxylic acid (mPEG-COOH). The introduction of mPEG bridge is in-situ coupled onto the surface of LLZT through acid-base interactions between the terminal carboxyl group of mPEG-COOH and alkaline impurities (LiOH/Li 2 CO 3 ), enabling potential of large-scale production. The robust LLZT cores, synergized with the flexible mPEG brushes, effectively enhance the interfacial compatibility and tailor rapid ionic channels between filler and polymer matrices. In this way, the as-prepared CPE (LLZT@mPEG-CPE), composed of LLZT@mPEG and PEO ( Figure 1b ), regulates continuous Li + flux and uniform interfacial modulus, leading to homogeneous and dendrite-free Li deposition. As a result, the LLZT@mPEG-CPE exhibits enhanced ionic conductivity and high thermal stability ( e.g. 4.9 × 10 -4 S cm⁻¹ at 40 ℃ and 7.6 × 10⁻ 3 S cm⁻¹ at 120 ℃). The cell assembled with LLZT@mPEG-CPE demonstrates outstanding cyclic performance and operates effectively over a broad temperature range of 40-160 ℃. For instance, the Li|Li symmetric cell exhibits stable plating/stripping for over 1750 h at 120 ℃. Moreover, the Li|LiFePO 4 (LFP) cell achieves a high capacity retention rate of 94% at 5 C after 500 cycles, even under extreme condition of 160 ℃. 2. Results and Discussion Figure 2a presents the Fourier transform infrared spectroscopy (FTIR) spectra of pristine LLZT and modified LLZT@mPEG nanoparticles. In the spectrum of LLZT, the characteristic peaks at 1462 and 862 cm −1 are ascribed to the asymmetric stretching vibrations of C=O bonds and the bending out of the plane of the CO 3 2− , revealing the presence of Li 2 CO 3 on LLZT surface. [15] Meanwhile, a stretching vibrational frequency from C–O–C at 1087 cm –1 indicates the presence of the mPEG side-chains on LLZT surface. As shown in Figure 2b, the existence of mPEG side-chains in LLZT-mPEG is further verified through the difference of the thermogravimetric analysis (TGA) curves of LLZT and LLZT-mPEG. X-ray diffraction (XRD) results of LLZT and LLZT@mPEG nanoparticles suggest that surface reaction does not change the cubic garnet phase of LLZT ceramic nanoparticle, and no Li-devoid phase of La 2 Zr 2 O 7 is observed either ( Figure 2c ). To study the chemical interaction between LLZT and mPEG, X-ray photoelectron spectroscopy (XPS) measurements were performed on pristine LLZT and modified LLZT@mPEG. According to XPS C1s spectra ( Figure 2d ), the characteristic peak assigned to carbonates (289.7 eV) on LLZT surface is weakened after reacting with mPEG-COOH, demonstrating that the content of Li 2 CO 3 and LiOH on LLZT surface is significantly reduced. [18] At the same time, the surface of LLZT@mPEG exhibits much higher content of C–O (286.5 eV) than that of LLZT, indicating that mPEG side-chains are successfully grafted to LLZT surface through acid-based interaction between mPEG-COOH and alkaline groups ( e.g. LiOH and Li 2 CO 3 ). [18] The reinforced chemical connection formed between LLZT and mPEG not only promotes the migration of Li + , but also effectively prevents the local potential difference at interphase between the filler and the polymer matrix, thereby reducing the aggregation of ions and the risk of electrolyte oxidation. This effect greatly improves the environmental stability of CPE, ensuring its chemical and electrochemical stability. Scanning electron microscope (SEM) images indicate that modified LLZT@mPEG shows a similar nanoparticle morphology to pristine LLZT ( Figures 2e , f ). Mechanical properties of nanoparticles are evaluated by atomic force microscopy (AFM) test. As shown in Figures 2g , h , AFM Young’s modulus topographies reveal that LLZT@mPEG still maintains a high Young’s modulus of 1.89 GPa after surface modification, which is almost the same as that of rigid LLZT (1.92 GPa). From transmission electron microscope (TEM) images ( Figure 2i ), LLZT@mPEG demonstrates a core-shell nanostructure, featuring a LLZT core with a lattice spacing of 0.32 nm, which corresponds to the (400) crystal plane, and an amorphous mPEG coating with a thickness of 3.1 nm. [26] LLZT@mPEG and residual mPEG-COOH are dispersed uniformly into a slurry containing PEO and Li bis(trifluoromethane)sulfonimide (LiTFSI), and all-solid-state CPE (LLZT@mPEG-CPE) is then obtained through a facile blade-coating method on thermotolerant polyethylene terephthalate (PET) membrane. Figures 2j , k show the good flexibility of as-prepared LLZT@mPEG-CPE, which can be rolled and folded arbitrarily. At the same time, due to the reduced crystallinity of PEO, LLZT@mPEG-CPE without PET membrane exhibits low Young’s modulus of 1.20 MPa, which is roughly the same as that of LLZT-CPE without PET membrane (1.07 MPa) ( Figures S2 , S3 ). Unsurprisingly, the soft surface may siginificantly improve interfacial compatibility between all-solid-state CPEs and electrodes. As displayed in Figure 2l , the surface of LLZT@mPEG-CPE is smooth and dense. The enlarged energy dispersive X-ray spectroscopy (EDS) mappings of LLZT@mPEG-CPE clearly indicate that La, O, S, C, and Zr elements are evenly distributed, therefore confirming the homegeneous distribution of LLZT@mPEG fillers in the PEO matrix ( Figure 2m ). In order to investigate the thermal stability, a crucial factor for the applications of solid-state electrolytes, LLZT@mPEG-CPE is subjected to heating at different temperatures to observe its structural shrinkage. Obviously, as shown in Figure S4 , LLZT@mPEG-CPE exhibits a well-maintained film morphology even at 160 ℃, thus demonstrating its capability to withstand high operating temperatures. In sharp contrast, it is observed that the commercial polypropylene (PP) separator undergoes obvious structural curling starting at 80 o C. Raman spectra analysis demonstrates that the addition of LLZT@mPEG or LLZT can significantly reduce the crystallinity of PEO matrix, which is manifested in the attenuation of the C–H bending vibration (861 cm –1 ) of LLZT@mPEG-CPE and LLZT-CPE ( Figure 3a ). [27] To investigate the relevant phase transition behavior and the chain motion in electrolytes, differential scanning calorimetry (DSC) measurements of various all-solid-state electrolytes without PET membranes are performed. Since Li + mobility is restricted by the highly organized and densely packed polymer chains, crystalline regions typically hinder ionic conduction. By increasing the fraction of amorphous regions and creating more conduction pathways, the decrease of the crystallinity of polymer electrolytes will improve Li + conductivity and interfacial stability, which eventually contributes to enhanced electrochemical properties and prolonged battery lifespans. [28] As exhibited in Figure 3b , the glass transition ( T g ) of the SPE (w/o PET) is found to be −37.3 ℃, which is high than the LLZT-CPE (w/o PET) of −42.4 ℃. Notably, when adding LLZT@mPEG, the LLZT@mPEG-CPE (w/o PET) displays a distinct reduced crystallinity with a T g of −48.3 ℃. These results show that the motion of polymer segments in the amorphous region of LLZT@mPEG-CPE is better than that of SPE and LLZT-CPE, which is more conducive to facilitate Li + migration. In order to investigate the effect of LLZT@mPEG filler on the mechanical strength of LLZT@mPEG-CPE, we test tensile mechanical performance of LLZT@mPEG-CPE and LLZT-CPE. Due to the strong interaction between LLZT@mPEG and PEO, the LLZT@mPEG-CPE exhibits a high tensile strength of 9.3 Mpa and toughness of 658.8 kJ m −3 , which is much better than those of LLZT-CPE (6.9 Mpa and 442.4 kJ m −3 ) ( Figure 3c ). The practical application of electrolyte in Li battery is governed by its electrochemical stability window, and the electrochemical stability window of LLZT@mPEG-CPE is further investigated by linear sweeping voltammetry (LSV) on Li | stainless-steel cells. Owing to the excellent ionic conductivity, which reduces the Li + accumulation at the electrode/electrolyte interface, LLZT@mPEG-CPE exhibits superior electrochemical stability. As shown in Figure 3d , LLZT@mPEG-CPE delivers a higher oxidation voltage (5.0 V) than LLZT-CPE (4.3 V) and SPE (4.2 V). Materials with elevated oxidation potentials typically present superior antioxidant property and enhanced corrosion resistance, which can sustain stability throughout extended usage, thereby prolonging Li battery lifespan. [29-31] We employed electrochemical impedance spectroscopy (EIS) to explore the ionic conductivity of LLZT@mPEG-CPE and SPE, which is a crucial characteristic for assessing Li + transport capacity in electrolytes. Notably, as exhibited in Figures 3e and S5 , LLZT@mPEG-CPE displays great ionic conductivities of 4.9 × 10 −4 S cm −1 at 40 ℃ and 7.6 × 10⁻ 3 S cm⁻¹ at 120 ℃, respectively, which are higher than SPE (3.4 × 10 −5 S cm −1 at 40 ℃ and 8.5 × 10⁻ 4 S cm⁻¹ at 120 ℃). As presented in the Arrhenius plots of Figure 3f , the relationship between ionic conductivity and temperature of LLZT@mPEG-CPE fits the typical Arrhenius linear equation. Particularly, the activation energy of LLZT@mPEG-CPE is as low as 0.36 eV. This result is attributed to the uniform distribution of the LLZT@mPEG filler into the PEO matrix, which provides a continuous Li-ion conducting pathway within LLZT@mPEG-CPE. LLZT-CPE tends to have phase separation phenomenon at high temperature, which reduces the overall conductivity by impeding Li + conduction pathways and weakening the interfacial contact between PEO and LLZT. In contrast, by grafting the mPEG side-chains on the LLZT surface, we achieve a tighter interface bond between the PEO matrix and the LLZT@mPEG filler. This modification not only significantly enhances the compatibility between both systems, but also effectively inhibits the phase separation phenomenon. In order to further clarify the role of mPEG coating in LLZT@mPEG-CPE, the density functional theory (DFT) calculations were performed to determine the interface bonding energy of LLZT–PEO and LLZT@mPEG systems. As illustrated in Figure 3g , the LLZT@mPEG system exhibits a more negative binding energy of –7.068 eV, compared to the LLZT–PEO system (–0.612 eV). This indicates that the successful grafting of the mPEG layer onto the LLZT interface significantly enhances the interface compatibility relative to LLZT–PEO. Moreover, by calculating the binding energies between LiTFSI and PEO/mPEG ( Figure 3h ), the interactions of Li + –mPEG (–63.67 kcal mol −1 ) and TFSI − –mPEG (–14.42 kcal mol −1 ) are stronger than those of Li + –PEO (–48.48 kcal mol −1 ) and TFSI − –PEO (–10.11 kcal mol −1 ), respectively, indicating that mPEG side-chains interact more strongly with LiTFSI than PEO/LiTFSI. This stronger connection can weaken the interaction between cation and anion pairs and thus promote the dissociation of Li salts, which is conducive to increasing the concentration of free Li + and better conducting Li + . One of the most important metrics for assessing the performance of solid-state electrolytes is their capacity to prevent Li dendrites formation during the repetitive Li plating/stripping processes. [32,33] Due to the excellent high-temperature stability and ionic conductivity, we attempt to assemble Li | Li symmetric cells with LLZT@mPEG-CPE and control samples to investigate their long-term cycling stability the long-term cycling stability under the exceptionally harsh conditions. As displayed in Figure 4a , under high temperature of 120 ℃, the Li | Li symmetric cell with LLZT@mPEG-CPE shows greatly smooth and stable voltage profiles during ultralong cycle life of 1750 hours at 0.5 mA cm −2 and 0.1 mAh cm −2 . In sharp contrast, the cells with SPE and LLZT-CPE display much larger voltage hysteresis with significant fluctuations, and fail within on various CPEs ( Figure 4b and Table S1 ), Li | Li symmetric cell based on LLZT@mPEG-CPE still delivers a considerable merit in cycle life at high temperature. The rate performance of Li | Li symmetric cells with SPE, LLZT-CPE and LLZT@mPEG-CPE is shown in Figure 4c . Particularly, compared with Li | SPE | Li and Li | LLZT-CPE | Li cells, Li | LLZT@mPEG-CPE | Li cell shows lower and reversible polarization LLZT@mPEG-CPE exhibits little degradation or side reactions, and successfully inhibits dendritic development while maintaining excellent equilibrium during charging and discharging. [34,35] As exhibited in Figure 4d , the symmetric cell with LLZT@mPEG-CPE demonstrates a considerably lower interfacial charge transfer resistance than those of cells with SPE and LLZT-CPE. Significantly, with the number of cycles increases, the impedance of symmetric cells with LLZT@mPEG-CPE and control samples also increase, while Li|LLZT@mPEG-CPE|Li cell always maintains the lowest charge transfer resistance, suggestive of superior interface stability and enhanced Li + diffusion kinetics ( Figure S6 ). Moreover, the SEM images of the Li electrode after 50 cycles at 0.5 mA cm −2 and 0.1 mAh cm −2 are demonstrated in Figures 4e-g . It can be seen that the Li foils disassembled from cycled Li|SPE|Li and Li|LLZT-CPE|Li cells exhibit a rough and uneven surface with obvious delamination and cracks, indicating that the SEI layer formed during the cycling is unstable and produce a large amount of “dead Li”. In contrast, the one retrieved from the cycled Li|LLZT@mPEG-CPE|Li cell presents a flat and relatively dense surface. As a result, LLZT@mPEG-CPE can provide a more unobstructive Li + conduction path even at high temperature, thus showing significant application potential at high temperature. As presented in Figures 5a-c , XPS was used to analyze the Li electrode surface after the charge/discharge cycle. There is a peak at 289.4 eV in the C 1s spectrum corresponding to Li 2 CO 3 , and a peak at 685.3 eV in the F 1s spectrum corresponding to LiF, manifesting the presence of small amounts of Li 2 CO 3 and LiF in the SEI layer of Li|LLZT@mPEG-CPE|Li. [18,36] Among them, Li 2 CO 3 may originate from surface contaminants of LLZT, and LiF is formed by the reaction between Li metal and fluorine-containing anion TFSI − . Although both Li 2 CO 3 and LiF possess high Young’s moduli, and have a significant impact on the physicochemical stability of SEI layer on the Li surface. [37] Additionally, the presence of Li 3 N is detected in the SEI layer obtained from cycled Li|LLZT@mPEG-CPE|Li, corresponding to peaks at 399.4 eV in the N 1s spectrum, which may result from the decomposition products TFSI − . [39] Noteworthily, as a fast Li conductor, Li 3 N can decrease interface impedance and improve the stability and electrical conductivity of SEI layer. [39] Of note, the SEI layer on the Li metal surface of cycled Li|LLZT@mPEG-CPE|Li cell contains abundant Li 3 N, indicating that LLZT@mPEG helps to form a dense, chemically stable, and Li 3 N-containing SEI layer, which is more conductive and facilitates interfacial Li + diffusion, guaranteeing homogeneous plating/stripping and considerable long-term cycling stability. [40] Furthermore, as shown in Figure 5d , time-of-flight secondary ion mass spectrometry (TOF-SIMS) was also performed to investigate the 3D structure and surface species of various SEI layers. On the one hand, the depth profiles suggest that the SEI formed with LLZT-CPE is enriched with inorganic LiF − derived from LiF, which is almost consistent with XPS result ( Figure 5e ). [41] On the other hand, the low content of organic C 2 H 4 O − could be attributed to the great compatibility of LLZT@mPEG-CPE with the Li anode, thereby reducing the side reaction between PEO matrix and Li anode at high temperature. The 3D and 2D distribution graphs of related substances contained on the SEI layer also indicate their uniform distribution in the SEI layer, which is conducive to the homogeneous and efficient transport of Li + . ( Figure 5g ). The LMBs needs further improvement to operate effectively when exposed to high temperature for long periods of time or frequently. Electrolyte engineering with high temperature tolerance and electrode compatibility is critical to the development of high-temperature LMBs. In order to evaluate the potential practical application of LLZT@mPEG-CPE in high-temperature LMBs, the electrochemical properties of Li|LFP cells with LLZT@mPEG-CPE are investigated. Using the LLZT@mPEG-CPE, the assembled Li|LFP cells can be used in the temperature range of 40–160 °C (Figure 6a). It is worth noting that the high temperature tolerance capability of the Li|LLZT@mPEG-CPE|LFP cell is splendid compared with previously reported CPEs based LMBs (Figure 6b and Table S2). The cycling properties of the Li|LFP cells at different rates and temperatures are exhibited in Figures 6c, d and S7-S11. Specifically, as shown in Figure 6c, Li|LLZT@mPEG-CPE|LFP cell exhibits outstanding long-term cycling performance, achieving 2100 stable cycles with a capacity retention rate of 77% at 1 C and 120 ℃. In contrast, Li|SPE|LFP and Li|LLZT-CPE|LFP cells present extremely poor capacity stability, which could be attributed to the low ionic conductivity and unstable electrode–electrolyte interface of SPE and LLZT-CPE. Additionally, the charge-discharge profiles of Li|LLZT@mPEG-CPE|LFP cell with the increasing cycling number display obvious voltage plateaus, indicating that Li|LLZT@mPEG-CPE|LFP cell still has high reversibility even under the ultralong cycle life (Figure S11). Due to the good interfacial affinity and enhanced diffusion of Li + , Li|LLZT@mPEG-CPE|LFP cell delivers great advantage in terms of long-term cycling stability as compared with most reported Li|LFP cells with CPEs (Figure S12). Importantly, at a high rate of 5 C and an extreme temperature of 160 ℃, the initial discharge capacity of the Li|LLZT@mPEG-CPE|LFP cell is 104 mAh g –1 , and 99 mAh g –1 is maintained after 500 cycles, corresponding to a significant capacity retention as high as 94% ( Figure 6d ). These above results reveal that LLZT@mPEG-CPE successfully inhibit the interfacial decomposition reactions at high temperature, thus guaranteeing excellent cycle stability at extreme temperature. As displayed in Figure S13 , owing to the fast electrode reaction kinetics, the Li|LLZT@mPEG-CPE|LFP cell demonstrated exceptional rate performance, and the reversible discharge capacity can be recovered while the current density is decreased back to low rates. To further investigate the impact of the local ionic coordination environment on the dynamic behavior, we have calculated the radial distribution functions (RDF) at various temperatures to better understand the dissociation degree of the Li salt. Herein, the sites of Li salt anions (TFSI − ) and PEO chains were represented by their respective oxygen atoms. For all the studied systems, the RDFs between Li + and PEO chains, and between Li + and TFSI − , were denoted as Li + –O(PEO) and Li + –O(TFSI − ), respectively. From Figure 6e , it can be seen that regardless of temperature, the first peak and valley in the RDF profiles of Li + –O(PEO) and Li + –O(TFSI − ) appear at approximately 2.5 and 3.7 Å, respectively, and where the local minimum corresponds to the edge of the first solvation shell of Li + . Additionally, the first coordination peak heights of Li + –O(PEO) are much higher than that of Li + –O(TFSI − ), suggesting that the interaction between Li + and O atoms in the PEO polymer chain is significantly stronger than the interaction between Li + and the surrounding TFSI − . This can be attributed to the coordination structure formed by the preferential adsorption of Li + through the oxygen-rich EO units in the PEO polymer chains. The preferential solvation structure of the Li + by PEO promotes the dissociation of Li salt, and the diffusion of Li + is slower because these are captured by the EO units, resulting in faster diffusion of dissociated TFSI − . Therefore, more TFSI − will participate in the construction of the SEI layer on the Li anode surface. At the same time, the relatively higher Li 3 N content in the SEI using LLZT@mPEG-CPE suggests that more TFSI − participated in robust and dense SEI formation, effectively mitigating the interfacial side reactions between the electrolyte and the Li metal anode, and enhancing electrochemical performance of Li|LFP cells at high temperatures. Furthermore, with the increase of temperature from 40 to 160 ℃, the height of the first peak in the RDF profiles of both Li + –O(PEO) and Li + –O(TFSI − ) decreases, meaning that the coordination effect gradually weakens. This weakening of the coordination facilitates the movement of free ions and exhibits accelerated dynamic behavior. [42] To gain a deeper understanding of the dynamic transport behavior and coordination mechanism of the Li + in polymer electrolytes as a function of temperature, a series of molecular dynamics simulations were conducted. The EO/Li + ratio was fixed at 10, with the corresponding number of ion pairs for each system of EO and LiTFSI set to 800 and 80, respectively. The calculated self-diffusion coefficients (Ds) of the Li + and TFSI − as a function of temperature are shown in Figure 6f. It is clear that the Ds of TFSI − are consistently higher than those of the Li + regardless of temperature, and the Ds of both ion species increases with temperature. This trend is consistent with both reported experimental data and simulation results. These indicates that the TFSI − diffuse more freely than Li + in the PEO-based polymer electrolytes, meaning significant dissociation of the LiTFSI. [43,44] We further conduct puncture experiments on Li metal pouch cell (~1 Ah) with commercial LE and our LLZT@mPEG-CPE in this work to study the safety of LLZT@mPEG-CPE in pouch cell. As shown in Figure S14 , the liquid Li metal pouch cell catch fire after acupuncture, while the LLZT@mPEG-CPE based Li metal pouch cell do not smoke or catch fire after acupuncture. One of the most challenging issues hindering the industrialization of solid-state batteries is the difficulty of achieving mass production of the high-quality solid-state electrolytes. Our preparation method is low cost, high efficiency and scalable for the production of solid-state electrolytes ( Figure S15 ). Furthermore, this process is highly compatible with the current battery industry and delivers great potential for commercialization. Conclusion In summary, by using a novel “grafting to” strategy to build macromolecular bridges on the surface of inorganic filler, we have successfully designed and prepared an all-solid-state PEO-based electrolyte with an extended operating temperature range, exceptional thermal stability and increased ionic conductivity. The results reveal a considerable improvement in the interfacial compatibility of LLZT@mPEG and PEO, enabling for LLZT@mPEG-CPE to possess low interface resistance. Therefore, our LLZT@mPEG-CPE delivers superior ionic conductivity (4.9 × 10 –4 and 7.6 × 10 –3 S cm –1 at 40 and 120 ℃, respectively) due to the formation of rapid Li-ion conduction channels directly at the interface layer of LLZT@mPEG and the reduction of interface resistance to the electrodes. It is worth noting that owing to homogeneous Li deposition forming a chemically stable and Li 3 N-containing SEI layer, the Li|LLZT@mPEG-CPE|Li cell displays an outstanding cycling performance of 1750 hours at 120 ℃. Moreover, within a wide temperature range (from 40 to 160 ℃), our LLZT@mPEG-CPE demonstrates exceptional long-term cycling stability and safety. For example, the Li|LLZT@mPEG-CPE|LFP cell achieve high capacity retention rate of 94% over 500 cycles even at extreme temperature of 160 ℃ and high rate of 5 C. Our research offers a facile and effective method that can be used as a useful guide for practical applications involving high-safety and long-lasting solid-state batteries. Supporting Information Supporting Information is available from the Wiley Online Library or from the author. Acknowledgements Y. C., S. S. and C. L. contributed equally to this work. X. L. is thankful for support from funding of the Natural Science Foundation of Top Talent of SZTU (grant no. GDRC202315) and Guangdong Basic and Applied Basic Research Foundation (2024A1515012363). T. Y. is thankful for support from the project of the research on the electrochemical reaction mechanism of the anode of medium-low temperature direct ammonia SOFCs (2022ZDZX3024). The authors would also like to acknowledge financial support from the National Natural Science Foundation of China (52174255) and Pingshan District Innovation Platform Project of Shenzhen Hi-tech Zone Development Special Plan in 2022 (No. 29853M-KCJ-2023-002-02). This work is supported by Guangxi Science and Technology Major Program under Grant No. AA24206037, the Training Project of High-level Professional and Technical Talents of Guangxi University, and the Natural Science and Technology Innovation Development Multiplication Program of Guangxi University (2022BZRC006). Conflict of Interest The authors declare no conflict of interest. Data Availability Statement The data that support the findings of this study are available in the Supporting Information of this article. Received: ((will be filled in by the editorial staff)) Revised: ((will be filled in by the editorial staff)) Published online: ((will be filled in by the editorial staff)) Figure 1. Schematic illustrations of Li plating/stripping behaviors of LMBs with (a) LLZT-CPE and (b) LLZT@mPEG-CPE. For LLZT@mPEG-CPE, the LLZT@mPEG fillers integrate the rigid LLZT cores and the flexible mPEG side-chains through a facile “grafting to” strategy, significantly prompting Li + conduction and enhancing the filler/matrix interfacial compatibility, thereby improving electrochemical performance, thermal durability and mechanical strength. Figure 2. (a) FTIR spectra, (b) TGA curves, (c) XRD patterns, and (d) XPS C 1s spectra of LLZT and LLZT@mPEG. Top-view SEM images of (e) LLZT and (f) LLZT@mPEG. 3D AFM Young’s modulus images of (g) LLZT and (h) LLZT@mPEG. (i) High-resolution TEM images of LLZT@mPEG. Digital photographs of (j) rolling and (k) folding of LLZT@mPEG-CPE. (l) Top-view SEM image of LLZT@mPEG-CPE and (m) its elemental mappings showing the distribution of La, O, S, C, and Zr elements. Figure 3. (a) Raman spectra of SPE, LLZT-CPE and LLZT@mPEG-CPE. (b) DSC profiles of different electrolytes without PET membranes. (c) Stress-strain curves of LLZT-CPE and LLZT@mPEG-CPE. (d) LSV curves of SPE, LLZT-CPE and LLZT@mPEG-CPE at 120 ℃. (e) Nyquist plots of LLZT@mPEG-CPE from 40 to 160 ℃. (f) Temperature-dependent ionic conductivity of SPE and LLZT@mPEG-CPE. (g) Interface bonding energy of the LLZT-CPE and LLZT@mPEG-CPE. (h) Interaction energy between LiTFSI and PEO/mPEG. Figure 4. (a) Voltage-time curves of Li|Li symmetric cells based on SPE, LLZT-CPE and LLZT@mPEG-CPE with a current density of 0.5 mA cm −2 at 120 ℃. (b) Comparison of cycle life of Li|Li symmetric cells based on LLZT@mPEG-CPE and previously reported CPEs with various temperatures at different current densities. (c) Rate performance of Li|Li symmetric cells with SPE, LLZT-CPE and LLZT@mPEG-CPE at various current densities. (d) Nyquist plots of Li|Li symmetric cells with SPE, LLZT-CPE and LLZT@mPEG-CPE. Top-view SEM images of Li anodes with (e) SPE, (f) LLZT-CPE and (g) LLZT@mPEG-CPE after 50 cycles at 0.5 mA cm −2 . Figure 5. (a) C 1s, (b) F 1s and (c) N 1s HR-XPS data illustrate the chemical composition of SEI layers formed in cycled Li|Li symmetric cells with LLZT@mPEG-CPE. (d) Schematic diagram of TOF-SIMS sputtering. (e) TOF-SIMS depth profiles of various atom group fragments formed on the Li anodes after cycling with LLZT@mPEG-CPE. TOF-SIMS (f) 3D and (g) 2D spectra of SEI layers formed on the Li anodes after cycling with LLZT@mPEG-CPE. Figure 6. (a) Charge and discharge voltage profiles of Li|LFP cells with LLZT@mPEG-CPE at different temperatures. (b) Comparison of the operating temperature of Li|LFP cells with LLZT@mPEG-CPE and previously reported CPEs-based LMBs. (c) Cycling performance of Li|LFP cells with SPE, LLZT-CPE and LLZT@mPEG-CPE at 1 C and 120 ℃. (d) Cycling performance of Li|LFP cell with LLZT@mPEG-CPE at 5 C and 160 ℃. 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Keywords batteries electrolytes organics polymers Authors Affiliations Yin Cui Shenzhen Technology University View all articles by this author shasha Shi Shenzhen Technology University View all articles by this author Chenkai Lu Shenzhen Technology University View all articles by this author ziqi Cai Shenzhen Technology University View all articles by this author Guobin Zhang Shenzhen Technology University View all articles by this author Li Li Shenzhen Technology University View all articles by this author Tao Yang Shenzhen Technology University View all articles by this author Tao Liu 0000-0001-6017-0827 Guangxi University View all articles by this author Qingxia Liu Shenzhen Technology University View all articles by this author Xidong Lin 0009-0006-9991-1729 [email protected] Shenzhen Technology University View all articles by this author Metrics & Citations Metrics Article Usage 243 views 153 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation Yin Cui, shasha Shi, Chenkai Lu, et al. In-Situ Coupled Macromolecular Bridge Enables All-Solid-State Lithium Metal Batteries Capable of Wide-Temperature Operation. Authorea . 15 July 2025. DOI: https://doi.org/10.22541/au.175260278.83407712/v1 If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download. For more information or tips please see 'Downloading to a citation manager' in the Help menu . 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