Thiourea treatment broadens the lattice structure to enhance the electrochemical stability of lithium-rich manganese-based materials

Thiourea treatment broadens the lattice structure to enhance the electrochemical stability of lithium-rich manganese-based materials | 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 Research Article Thiourea treatment broadens the lattice structure to enhance the electrochemical stability of lithium-rich manganese-based materials Zhifeng Zhao, Wangjun Feng, Wenxiao Su, Yueping Niu, Wenting Hu, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4281820/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The lithium-rich manganese-based material Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 is currently the most promising anode material due to its high capacity and low cost. However, the material still suffers from severe capacity degradation and low multiplicity performance. After thiourea treatment, the electrochemical performance of the material is improved. Through elemental and morphological characterization, the treated crystals show more dispersed particles and a small amount of Sulphur doped on the surface. Various electrochemical tests were performed on the cells and the 3wt% thiourea treated cells showed improved discharge specific capacity and cycling performance compared to the non-thiourea treated cells. Moreover, the polarity of the battery was reduced and the impedance decreased. The specific capacity of the first cycle was 274.2mAh/g at 0.1C. The specific capacity was 236mAh/g at 0.5C and the capacity retention rate was 72.46% after 100 cycles. surface treatment sulfur dopant laminar oxide lattice structure Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Introduction With the development of the new energy industry, people have put forward the demand problem of the battery industry. People are constantly striving for higher specific capacity, more stable cycle characteristics, and faster charging and discharging capabilities. [ 1 – 4 ] This has led to the urgent need for high discharge capacity and high energy dense cathode materials for Li-ion batteries. The formula for lithium-rich layered oxides is expressed simply as x Li 2 MnO 3 (1-x) LiMO 2 (where 0 < x < 1 and M = Ni, Co, Mn). It’s very high capacity (over 250mAh/g), low cost, environmental friendliness and other advantages make it the most likely next-generation lithium battery. [ 5 – 7 ] However, among the lithium-rich manganese-based materials, Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 has a high theoretical capacity, good energy density and ultra-high average charge-discharge voltage, which is favored by researchers. [ 6 , 8 – 10 ] Although there are many advantages to lithium-rich oxide cathode materials, the industrialization process has been hampered by the low-rate performance and poor cycle stability of lithium-rich manganese-based materials. [ 11 – 14 ] To this end, people continue to optimize lithium-ion batteries through doping, [ 15 – 17 ] surface treatment, [ 18 , 19 ] coating, [ 13 , 14 , 20 ] nanoparticle construction, [ 21 , 22 ] etc. Simple methods of surface treatment and anion doping have been demonstrated to be more effective in improving rate performance and cycling stability. [ 16 , 17 , 23 ] Li et al. [ 16 ] achieved boron anionomer doping by introducing boric acid into the reaction process of the sol-gel method, resulting in strong specific capacity improvement and enhanced cycling performance. It was demonstrated that the boron polyanion can mitigate changes in the electronic structure of O 2p induced during delithiation and lithiation. Other polyanions were predicted to also stabilize changes in the electronic structure of oxygen during cycling by increasing the binding energy with elemental oxygen, thus enhancing material stability. This was quickly demonstrated. While Zhang et al, [ 23 ] doped sulfur anions on the surface of the layered oxides by surface sulfurisation of the co-precipitated prepared samples, thus increasing the lattice spacing, increasing the Coulombic efficiency of the first charge/discharge and improving the cycling stability.Li et al. [ 17 ] formed a thin layer of lithium manganese sulfide spinel phase on the surface of the layered oxides by simple thiourea treatment of the co-precipitated monomers, and the introduction of the spinel phase stabilised phase can improve the conductivity of lithium ions and reduce particle cracking and phase collapse during repeated cycling.S The formation of TM-S bond configuration induced by the introduction of S can effectively accelerate the diffusion of lithium ions and inhibit the undesired oxygen redox. Thus, the cycling stability and discharge performance of the lithium-rich manganese-based materials synthesised by co-precipitation are greatly enhanced. The more complicated co-precipitation process prepares samples that are mostly spherical in shape with primary particle agglomerates, and lithium ions are gradually and slowly de-embedded by gradually starting from the surface layer to the inner layer. This synthesis method has mostly been reported to form an improved layer on its spherical surface layer. [ 17 , 20 , 23 ] The sol-gel method, on the other hand, has been popularised due to its simple reaction conditions, but suffers from the disadvantages of greater capacity degradation of the material and poorer cycling stability. [ 16 , 20 , 24 , 25 ] The use of anionic doping modification is promising to improve the electrochemical performance of dispersed cathode materials prepared by the sol-gel method. In this work, the sol-gel process was used to produce relatively dispersed primary granular layered oxides, and thiourea was used for surface treatment. To study the effects of different concentrations of thiourea on its layered oxides, The results show that after 3wt% thiourea treatment, the particle size of the primary particles becomes smaller and more dispersed. Therefore, the contact area between the lithium-ion cathode material and the electrolyte is increased, which reduces the distance of lithium-ion deintercalation. At the same time, some sulfur atoms are doped with primary particles in the sintering process, which indicates that the lattice spacing on the crystal surface is increased, which in turn promotes the deintercalation of lithium ions. After treatment with 3wt% thiourea, layered oxides showed improved discharge capacity and cycling performance. At 0.1C, the specific capacity of the first cycle discharge increased from 244.4mAh/g to 274.2mAh/g. After 100 cycles of 236mAh/g at the discharge rate of 0.5C, the capacity retention rate was 72.46%. Material preparation Preparation of precursors Lithium-rich layered oxide monomers were prepared by sol-gel method, lithium acetate, manganese acetate, nickel acetate, cobalt acetate was dissolved in an appropriate amount of ethanol solution in a molar ratio of 1.2:0.54:0.13:0.13 to make a mixed solution. Then dissolve 0.5 times the metal ion molar ratio of citric acid in an appropriate volume of ethanol solution to make a citric acid-ethanol solution. Slowly drop the mixed solution into the ethanol solution of citrate (pumped at a rate of 0.8 mL/min) and stir vigorously during this time. After dripping, it is transferred to an oil bath and stirred at 80°C until it is powdery, and then taken out and ground and sintered in air at 450°C for 8 hours. After natural cooling, grind and sieve at 200 mesh. Then annealed in air at 850°C for 5 h, the resulting material is called monomer LMR. Thiourea surface treatment As shown in Fig. 1 , 0.5 g of monomer was taken, and thiourea with different weight ratios of 2wt%, 3wt%, and 5wt% was taken and mixed in 25mL of deionized water. After stirring at room temperature for 1h, stir in an oil bath at 90°C and put in a drying oven at 90°C until completely dry. After removing the powder, air annealing at 450°C for 5 h. The powders obtained were S2-LMR, S3-LMR and S5-LMR, respectively. Materials characterization The crystal structure of the surface of the sample undergoing different treatments has been determined by X-ray diffraction (XRD). The microscopic morphology and elemental distribution of the samples were analyzed using a JSM-6700F scanning electron microscope (SEM). The measurements were further characterized using a JEM-2100F transmission electron microscope (TEM). To determine the valence state of each element, the chemical elemental analysis of the sample was performed using a PHI5702 multi-function X-ray spectrometer (XPS). Electrochemical measurements The prepared cathode material, acetylene black conductive agent and polyvinylidene fluoride (PVDF) are mixed in a ratio of 8:1:1, dropwise into the appropriate NMP solution, mixed and stirred into a slurry. Cover the aluminum foil evenly with the substance. After drying, it is cut into small discs to be used as electrodes. The CR2025 type coin cell battery is assembled in an inert gas-filled glove box. The electrolyte used is 1 M lithium phosphate solution, where the solvent is diethyl carbonate (DEC), ethylene carbonate (EC) and dimethyl carbonate (DMC) in proportion (1:1:1 vol%). The amount of electrolyte used per cell is about 50µL. The LAND-CT2001A battery tester was used to test the battery charge/discharge curves at various current densities over the 2.0V to 4.8V voltage range. An electrochemical workstation (CS350H) was used to perform cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests. The CV test is an entirely new battery made from the test specimen, scanning the first 3 turns at a scan rate of 0.2mV/s in a voltage band from 2.0V to 4.8V. The EIS test is a scan test over a frequency band from 0.01 Hz to 100,000 Hz. Result and discussion Crystalline structure analysis XRD patterns of Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 with initial LMR and different thiourea treatments. As can be seen in Fig. 2 , the higher the crystalline reflectance, the higher the crystallinity of the surface. The weak peak at 2θ = 20°~25° is the Li 2 MnO 3 phase belonging to the space group C2/m. [ 14 , 26 , 27 ] Compared with the original LMR, the corresponding peaks of Li 2 MnO 3 in the XRD pattern after thiourea treatment were more obvious, which was more beneficial for capacity increase. With thiourea treatment, it can be found that the XRD peaks are shifted to a low diffraction angle, which indicates that the lattice spacing of the sample becomes larger due to the incorporation of S elements after treatment. [ 17 , 23 ] The lattice parameters for each structure were obtained by fitting the XRD patterns, as shown in Table 1 . The appropriate concentration of thiourea treatment increases the c/a ratio of the sample lattice, indicating that Sulphur doping improves the lattice parameters and the kinetic performance of lithium-ion deintercalation. It is worth noting that the ratio of I(003)/I(104) peaks, which to some extent reflects the degree of mixing and exclusion of TM atoms and lithium atoms in the lamellar structure, and the smaller the ratio, the greater the degree of mixing and exclusion, and the lithium ion de-embedding is hindered.[ 10 , 28 , 29 ] It can be seen that the mixed arrangement situation was improved after the treatment. Table 1 Impedance values for different materials Samples LRM S2-LMR S3-LMR S5-LMR a (nm) 0.28517 0.28519 0.28502 0.28519 c (nm) 1.42418 1.42362 1.42497 1.42361 c / a 4.9942 4.9918 4.9995 4.9917 V (nm 3 ) 0.10030 0.10028 0.10025 0.10028 I (003) / I (104) 1.21 1.63 1.57 1.36 Morphological observation SEM images of LRM and S3-LRM samples are shown in Fig. 3 . Through the SEM image, it can be seen that the two samples are 100 ~ 500nm particles. The treated surface of thiourea is more dispersed, indicating that thiourea reacts on the sample surface. This changes the sample from an otherwise irregularly agglomerated topography to a more dispersed first-order particle morphology. This increases the surface area, and the more surface area in contact with the electrolytic solution, the shorter the Li-ion pathway, promoting fast Li-ion de-intercalation. At the higher sintering temperature, the sample inevitably causes a certain degree of agglomeration, which hinders the deintercalation of lithium ions. However, the phenomenon of particle agglomeration can be effectively improved by surface treatment with thiourea. This indicates that the thiourea treatment effectively limits particle size reduction, increases the contact surface area between the solution and the primary particles, and promotes lithium ion deintercalation. [ 30 ] However, it should be noted that more dispersed primary particles increase the surface area of the sample contacting the electrolyte, which may result in faster capacity decay of the sample. [ 21 ] In order to better analyses the elemental distribution of the treated samples, EDS tests were carried out on the samples treated with 3wt% thiourea, which showed that the nickel, cobalt and manganese atoms in the sample particles were uniformly distributed, and the proportions of the elements did not change much compared to the expected elemental proportions. It can also be seen that the distribution of S on the sample surface is relatively uniform. This is probably due to the fact that S will remain on the surface of the sample after thiourea treatment, and after sintering, S will enter the lattice on the surface of the sample to replace oxygen. The above shows that the thiourea surface treatment not only improves the surface morphology, but also has the potential to induce surface anion doping of the samples. In order to understand the changes in the chemical state of each element before and after treatment, XPS analysis was performed on the monomer LMR and S3-LMR. For example, Fig. 5 (a) analyzes the Mn 3s profile of the sample and calculates the average oxidation state (AOS) of the elements using the formula AOS = 8.956–1.126 ΔEs (eV) based on the relationship between ΔEs and the AOS proposed by Galakhov et al. [ 31 ] By converting the binding energy difference ΔEs between the two peaks into the average valence state of Mn, it is evident that the valence state of Mn in S3-LMR decreases compared to that of the monomer. This change in the valence state of Mn may be attributed to the improved proportion and structure of layered oxides. Examining the spectrum near the binding energy of O 1s, an increase in the peak value of 531.5 eV is observed, which corresponds to the oxygen vacancy in the lattice. This increase may be attributed to the reduction of Mn 4+ ions after treatment, and these changes are consistent with previous reports. [ 17 ] Additionally, a faint peak corresponding to SO 4− was detected near the binding energy of S 2p, [ 23 , 32 ] indicating that a small amount of sulfur polyanion was added to the material after treatment. Peaks of 855.3, 642.2 and 780.2 eV were detected in the binding energy ranges of Ni 2p, Mn 2p and Co 2p, respectively, which was consistent with the reported results of Ni 2+ , Mn 4+ and Co 3+ . [ 33 , 34 ] In order to get more specific crystal information of the processed samples, we performed TEM scans of the S3-LMR samples and analysed the lattice fringes and diffraction patterns using (Digital Micrograph) DM software. TEM images of 3S-LMR of the samples treated with 3wt% thiourea are shown in Fig. 6 . Using the diffraction centre as a reference point, the diffraction pattern was expanded by the software as in Fig. 6 (a). The relationship between the intensity of the diffraction spot and the distance from the centre was then determined. Three distinct diffraction rings were observed, with lattice spacings of 0.47 nm, 0.24 nm and 0.14 nm. These correspond to the (003), (101) and (110) planes of the R-3m structure of LiMO 2 (M = Co, Ni, Mn), respectively. Some areas were selected by the software for lattice streak measurements as in Fig. 6 (c, d), and some crystal images were compared with XRD. The figure shows a diffraction line spacing of approximately 0.47 nm, corresponding to the (003) crystal plane in XRD. [ 7 , 17 , 24 ] This is also an indication that there is no damage to the crystal structure of the surface after such treatment. The diffraction fringes of the peripheral crystal structure are compared with those of the internal crystal structure. It can be seen from Fig. 6 (c) that the lattice spacing of the peripheral part is slightly larger than that of the internal lattice. This indicates that the treated surface expands its lattice due to the incorporation of S anions, which is consistent with the results of XRD peak shift analysis. The treated sample did not form a significant coating on its surface due to sintering in the air. Simultaneously, the TEM image reveals that there are no additional phases present on the sample surface. This suggests that the uniformly distributed sulfur element is not covering the active material surface in the form of sulfide, but rather is doped onto it. Electrochemical behaviors In order to test the electrochemical properties of the materials and the differences between different materials during the first turn of charging and discharging, a first turn 0.1 C (1 C = 250 mA/g) charging and discharging test was carried out and Fig. 7 (a) shows the charging and discharging curves of the different samples at the rate of 0.1C under the voltage window of 2V to 4.8V. We can find that there are two obvious charging platforms in the charging curve, namely the specific capacity generated by the detachment of lithium ions from the layered phase between 3.7V and 4.45V, and the additional capacity generated by the lithium-rich phase greater than 4.45V. [ 23 ] When comparing the two charging platforms, LMR and S3-LMR, it is evident that the specific capacity of the layered phase in S3-LMR is greater than that of LMR. Specifically, the specific capacity of the S3-LMR in the 3.7V to 4.45V charging voltage range is 143mAh/g compared to 119mAh/g for the LMR. This suggests that the appropriate amount of thiourea treatment enhances the layered phase structure of the sample. [ 10 ] This is consistent with XRD findings that thiourea treatment increases lattice spacing, reduces atomic mixing, and improves lithium-ion de-insertion kinetics in the lamellar phase, resulting in a greater reversible specific capacity. However, the platform greater than 4.45V is the Li 2 MnO 3 phase, and the Li 2 MnO 3 →2Li + +Mn 4+ O 3 4− +2e − →2Li + +MnO 2 + 1/2O 2 reaction occurs at high voltage. The lithium-rich manganese-based material exhibits a higher specific capacity than other ternary cathode materials due to the additional specific capacity provided by the activated MnO 2 . However, it is important to note that some of the specific capacity in this reaction is irreversible as a result of the release of oxygen. [ 3 , 4 ] After analysis, the specific capacity of S3-LMR increased from 244.4mAh/g to 274.2mAh/g due to the improvement of the layered phase. To demonstrate the role of these reversible specific volumes in subsequent cycles, we measured a test in which different samples were cycled for 100 turns at 0.5C magnification. Figure 7 (b) shows the specific volume of different samples for the first 100 cycles of discharge at 0.5C, and it can be seen that the cycling stability of thiourea-treated samples is improved, with the sample treated with 3wt% thiourea having the best specific capacity. Thiourea-treated samples exhibit significantly higher volume retention compared to monomers. The decrease in the capacity of the monomer is due to the structural collapse of the material sample. When the original particle structure of the active material is exposed to the charge-discharge cycle of the electrolyte, the layered phase gradually transforms from the surface inward to the defective spinel phase. [ 7 ] Although the thiourea-treated primary particles have a more dispersed morphological structure and a larger specific surface area in contact with the electrolyte, their electrochemical stability is shown to be more stable. This is due to the improved structural stability of the samples treated with thiourea and the good improvement of the degree of mixing. Combined with XPS and SEM analysis, it may be that the lattice structure of the material was stabilized during thiourea treatment, the valence state of the elements was improved, the degree of mixing was reduced, and the considerable reversible specific capacity brought by the layered phase was increased. At the same time, it is possible that some sulfur elements are incorporated into the crystal surface, which also improves the structural stability and slows down the unfavorable phase transformation process. [ 16 , 17 , 23 ] Figure 7 (c) shows the schematic diagram of the discharge specific capacity of different samples at different magnifications, and it can be found that the performance of S2-LRM and S5-LRM is similar to that of the monomer, while the performance of S3-LRM sample is improved at different magnifications. This is due to the fact that the appropriate amount of thiourea treatment can make the samples more dispersed and improve the ionic mixing arrangement, which improves the stability of the crystal structure. Meanwhile, through the sintering treatment, the sulfur atoms produced by the reaction of thiourea on the surface of the active material can be doped into the lattice, thus enlarging the lattice spacing. All these reasons increase the lithium-ion de-insertion and improve the rate performance. In order to explore the rate performance of different samples, we performed charge-discharge tests on the samples at different current densities. Figure 7 (d) shows the average discharge voltage and coulombic efficiency for the first 100 turns of the LRM and S3-LRM. It can be seen that the attenuation of the average discharge voltage of thiourea treatment is mitigated compared to LMR. This may be due to the fact that the S element has a stronger binding energy to the metal, which improves its structural stability, thereby slowing down its capacity and voltage decay. [ 17 , 23 ] In order to observe more clearly the capacity degradation during the long cycling process, the charge/discharge curves of different samples from the 10th to the 100th cycle at 0.5C magnification are shown in Fig. 8 . This shows that the thiourea-treated specimen has a more stable charge-discharge curve and less capacity loss. Figure 9 shows the CV discharge curve of each sample in the first three cycles, and it can be found that the absorption oxidation peak corresponds to the voltage plateau of the charge-discharge curve. The oxidation voltages of the first turn peak at 3.9V and 4.6V, which correspond to the 4.0V of the charge-discharge curve and the discharge plateau around 4.5V. The 3.9V peak is attributed to the oxidation of Co 3+ and Ni 2+ , whereas the 4.6V oxidation peak is caused by the release of O during the conversion of the Li 2 MnO 3 phase to MnO 2 and the detachment of Li + . Simultaneously, two distinct reduction peaks were observed at approximately 3.3V and 3.7V, corresponding to the reduction of Mn 4+ and Ni 3+ respectively. When we compare the CV of the treated sample with the LMR sample, we can see a small oxidation peak around 2.9V and a reduction peak near 2.6V in the low-voltage fraction. These two peaks may be due to the very small fraction of the spinel phase produced by thiourea treatment and sintering. Compared to other treated samples, the reduction peak at 2.6V in the S3-LMR was smaller. [ 35 , 36 ] The difference between these phases is well reflected in the charge-discharge curve, S2-LMR and S5-LMR can see very small plateau changes in the discharge platform, while S3-LMR, although the presence of spinel is reflected in the CV, is too small to affect the charge-discharge curve. At the same time, the TEM pattern of S3-LMR was not found from the surface lattice, which indicates that the proportion of this spinel phase is very small, and the influence on the overall charge and discharge is very small. A comparative analysis of the oxidation peak portion of the first cycle can reveal subtle differences in the activation process of the Li 2 MnO 3 phase. Figure 9 (a) compares the CVs of the first cycle of each sample, and it is clear that the ratio of the S3-LMR sample is much smaller than that of the LMR sample when comparing the peak ratios of I (4.6V) /I (3.9V) . The ratio reflects the stability of the structure during the activation process to a certain extent, and the smaller the ratio is, that is to say, the oxidation reaction of the oxygen element of the Li2MnO3 phase during the activation process of the material in the first lap discharge process is alleviated, which makes the lattice oxygen oxidation reaction in the activation process to oxygen reaction is suppressed, which not only suppresses the generation of irreversible capacity but also improves the structural stability. [ 37 , 38 ] At the same time, we found that the two oxidation peaks correspond to the voltage values, and we can find that the potential difference of the redox peaks is reduced due to the slight shift of the peaks to the middle after appropriate thiourea treatment, which may be that the appropriate thiourea treatment can improve the elemental valence state of the layered structure, which indicates that the polarization of the battery has been well improved. [ 26 ] These phenomena indicate that the structure is more stable after thiourea treatment, and appropriate adjustment of the amount of thiourea treatment can effectively reduce the polarization of the cell. This may be due to the fact that the surface S doping improves the binding energy with the TM elements, which inhibits the oxygen release and enhances the structural stability, and at the same time optimizes the valence states of the TM elements and reduces the polarization of the battery, thus improving the reversible specific capacity of the battery, increasing its specific capacity, and improving its cycling stability. Finally, we analyses the impedance of the cells. Figure 10 shows the EIS curves of each of the sample cells, and Table 2 shows the impedance values of each of the impedances after fitting the corresponding EIS curve to the analogue circuit. It can be found that the impedance R ct of the S3-LRM battery is the smallest. The results indicated that appropriate thiourea treatment could reduce the impedance of the battery and improve the electrochemical performance. [ 30 , 39 ] Table 2 Impedance values for different materials Samples LRM S2-LMR S3-LMR S5-LMR R s (±Ω) 1.811 4.013 1.518 6.294 R ct (±Ω) 264.9 474.1 113.6 860.5 Conclusion The aim of this study is to solve the problems such as rapid capacity decay of lithium-rich manganese-based materials prepared by sol-gel method using thiourea surface treatment and sulfur anion doping. The results show that the surface modification of thiourea can disperse the crystal particles and improve the valence state of TM elements in the crystals, thus reducing the cell polarisation and increasing the reversible capacity of sheet phase release. Meanwhile, doping S elements on the crystal surface can reduce the release of O during the activation process and widen the surface lattice spacing, thus improving the stability. The specific capacity of the specimen was improved from 244.2mAh/g to 274.2mAh/g for the first charge at a current density of 0.1 C. At a discharge rate of 0.5 C, the capacity was 236mAh/g, and the capacity retention rate was 72.46% after 100 cycles. We hope that this work will play an active role in the development of manganese-based lithium-rich materials. Declarations Conflict of interest The authors declare no competing interests. Author Contribution Zhifeng Zhao: Conceptualization, Writing-original draft preparation. Wangjun Feng: Writing-review & editing, Validation, Funding Acquisition. Wenxiao Su: Data curation, Software. Yueping Niu: Visualization. Wenting Hu：Software, Methodology. Xiaoping Zheng: Resources, Investigation, Supervision. 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Wang, D., Zhang, X., Xiao, R., Lu, X., Li, Y., Xu, T., Pan, D., Hu, Y.-S., & Bai, Y. (2018). Electrochemical performance of Li-rich Li[Li 0.2 Mn 0.56 Ni 0.17 Co 0.07 ]O 2 cathode stabilized by metastable Li 2 SiO 3 surface modification for advanced Li-ion batteries. Electrochimica Acta, 265 , 244–253. Penki, T. R., Shanmughasundaram, D., & Munichandraiah, N. (2014). Porous lithium rich Li 1.2 Mn 0.54 Ni 0.22 Fe 0.04 O 2 prepared by microemulsion route as a high capacity and high rate capability positive electrode material. Electrochimica Acta, 143 , 152–160. Xiang, Y., Sun, Z., Li, J., Wu, X., Liu, Z., Xiong, L., He, Z., Long, B., Yang, C., & Yin, Z. (2017). Improved electrochemical performance of Li 1.2 Ni 0.2 Mn 0.6 O 2 cathode material for lithium-ion batteries synthesized by the polyvinyl alcohol assisted sol-gel method. Ceramics International, 43 (2), 2320–2324. Yi, T.-F., Tao, W., Chen, B., Zhu, Y.-R., Yang, S.-Y., & Xie, Y. (2016). High-performance xLi 2 MnO 3 ·(1-x)LiMn 1/3 Co 1/3 Ni 1/3 O 2 (0.1 ≤ x ≤ 0.5) as Cathode Material for Lithium-ion Battery. Electrochimica Acta, 188 , 686–695. Song, C., Feng, W., Wang, X., & Shi, Z. (2020). Enhanced electrochemical performance of Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 cathode material with bamboo essential oil. Ionics, 26 (2), 661–672. Galakhov, V. R., Demeter, M., Bartkowski, S., Neumann, M., Ovechkina, N. A., Kurmaev, E. Z., Lobachevskaya, N. I., Mukovskii, Ya. M., Mitchell, J., & Ederer, D. L. (2002). Mn 3s exchange splitting in mixed-valence manganites. Physical Review B, 65 (11), 113102. Zhang, S. S., Chen, J., & Wang, C. (2019). Elemental Sulfur as a Cathode Additive for Enhanced Rate Capability of Layered Lithium Transition Metal Oxides. Journal of The Electrochemical Society, 166 (4), A487–A492. Wu, F., Liu, J., Li, L., Zhang, X., Luo, R., Ye, Y., & Chen, R. (2016). Surface Modification of Li-Rich Cathode Materials for Lithium-Ion Batteries with a PEDOT: PSS Conducting Polymer. ACS Applied Materials & Interfaces, 8 (35), 23095–23104. Zhao, E., Liu, X., Zhao, H., Xiao, X., & Hu, Z. (2015). Ion conducting Li 2 SiO 3 -coated lithium-rich layered oxide exhibiting high-rate capability and low polarization. Chemical Communications, 51 (44), 9093–9096. Zhang, J., Gao, R., Sun, L., Li, Z., Zhang, H., Hu, Z., & Liu, X. (2016). Understanding the effect of an in situ generated and integrated spinel phase on a layered Li-rich cathode material using a non-stoichiometric strategy. Physical Chemistry Chemical Physics, 18 (36), 25711–25720. Yu, R., Zhang, X., Liu, T., Yang, L., Liu, L., Wang, Y., Wang, X., Shu, H., & Yang, X. (2017). Spinel/Layered Heterostructured Lithium-Rich Oxide Nanowires as Cathode Material for High-Energy Lithium-Ion Batteries. ACS Applied Materials & Interfaces, 9 (47), 41210–41223. Liu, Y., Ning, D., Zheng, L., Zhang, Q., Gu, L., Gao, R., Zhang, J., Franz, A., Schumacher, G., & Liu, X. (2018). Improving the electrochemical performances of Li-rich Li 1.20 Mn 0.54 Ni 0.13 Co 0.13 O 2 through a cooperative doping of Na + and PO 4 3– with Na 3 PO 4 . Journal of Power Sources, 375 , 1–10. Wang, Y. X., Shang, K. H., He, W., Ai, X. P., Cao, Y. L., & Yang, H. X. (2015). Magnesium-Doped Li 1.2 [Co 0.13 Ni 0.13 Mn 0.54 ]O 2 for Lithium-Ion Battery Cathode with Enhanced Cycling Stability and Rate Capability. ACS Applied Materials & Interfaces, 7 (23), 13014–13021. Feng, W., Huang, Z., & Li, W. (2022). Improving the performance of Li-rich Mn-based cathode materials via combined surface modification with glacial acetic acid and Li 3 PO 4 Journal of Electroanalytical Chemistry, 917 , 116250. Additional Declarations No competing interests reported. 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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-4281820","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":293481179,"identity":"e66ea139-dbaa-4acc-b074-02c8e577f78f","order_by":0,"name":"Zhifeng Zhao","email":"","orcid":"","institution":"Lanzhou University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Zhifeng","middleName":"","lastName":"Zhao","suffix":""},{"id":293481180,"identity":"45f0a435-402a-4659-a13c-1e202023169d","order_by":1,"name":"Wangjun Feng","email":"","orcid":"","institution":"Lanzhou University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Wangjun","middleName":"","lastName":"Feng","suffix":""},{"id":293481181,"identity":"35c6b768-0fb8-4b4f-8bc4-a6474305c571","order_by":2,"name":"Wenxiao Su","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAwklEQVRIiWNgGAWjYLCCDwY2dvzMzIcfEK2DcUZFWrJkO1uaAdFamHnOHGbccJ5HQYIo5QY30p9JzmxjZjY+zMNgwFBjE01Yy5kzZhIf29j4zA7zHnjAcCwtt4GQFrPjPWxAW3iYzQ7zJRgwNhwmQsth9mfSvG0SjJubeQwkiNNyvMFMmueMAeMGZmK12J85Y2w5oyIhWeIwMJATiPGL5Iz0hzc+GPy34+8/fPjBhxobwlpQQQJpykfBKBgFo2AU4AIAxO8+RZGZp4cAAAAASUVORK5CYII=","orcid":"","institution":"Lanzhou University of Technology","correspondingAuthor":true,"prefix":"","firstName":"Wenxiao","middleName":"","lastName":"Su","suffix":""},{"id":293481182,"identity":"e7bed0ef-f3ad-4a54-abe3-1ac5750c89c6","order_by":3,"name":"Yueping Niu","email":"","orcid":"","institution":"Lanzhou University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Yueping","middleName":"","lastName":"Niu","suffix":""},{"id":293481183,"identity":"f5071b6f-a7b9-4c95-93d7-f7de27db61d6","order_by":4,"name":"Wenting Hu","email":"","orcid":"","institution":"Lanzhou University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Wenting","middleName":"","lastName":"Hu","suffix":""},{"id":293481184,"identity":"8b6012bb-84f0-4253-96b2-ea2d45c8d82f","order_by":5,"name":"Xiaoping Zheng","email":"","orcid":"","institution":"Lanzhou University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Xiaoping","middleName":"","lastName":"Zheng","suffix":""}],"badges":[],"createdAt":"2024-04-17 12:15:14","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4281820/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4281820/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":55158506,"identity":"a5f7eb93-04d0-4db5-b964-a43f18c6f2f6","added_by":"auto","created_at":"2024-04-23 12:26:44","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":193622,"visible":true,"origin":"","legend":"\u003cp\u003eProcess flow diagram of thiourea surface treatment\u003c/p\u003e","description":"","filename":"image1.png","url":"https://assets-eu.researchsquare.com/files/rs-4281820/v1/97bd044a0a303fbbedd8153a.png"},{"id":55158027,"identity":"3d2e07eb-0d1e-4d37-acef-353d97480b21","added_by":"auto","created_at":"2024-04-23 12:18:44","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":43822,"visible":true,"origin":"","legend":"\u003cp\u003eXRD curves of monomer and thiourea-treated samples with different contents\u003c/p\u003e","description":"","filename":"image2.png","url":"https://assets-eu.researchsquare.com/files/rs-4281820/v1/4f5adb0f09f95d933e74d545.png"},{"id":55157523,"identity":"af5fd343-7ef1-4537-8f28-55d7f1644c1b","added_by":"auto","created_at":"2024-04-23 12:10:44","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":626001,"visible":true,"origin":"","legend":"\u003cp\u003eSEM and magnification of the sample and diameter particle distribution LMR(a)(b)(e), S3-LMR(c)(d)(f).\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-4281820/v1/87452d3eadfe0baf65bfad59.png"},{"id":55157520,"identity":"e387d698-1143-43f1-9025-b02ccbe0eea7","added_by":"auto","created_at":"2024-04-23 12:10:44","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":671488,"visible":true,"origin":"","legend":"\u003cp\u003eEDS map of S3-LMR sample, distribution and proportion of each element\u003c/p\u003e","description":"","filename":"image4.png","url":"https://assets-eu.researchsquare.com/files/rs-4281820/v1/f2c0a1bf2c111b664ef0f195.png"},{"id":55158029,"identity":"177d1ccc-bf19-4732-8fe4-49b1a2805377","added_by":"auto","created_at":"2024-04-23 12:18:44","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":109547,"visible":true,"origin":"","legend":"\u003cp\u003eXPS profile of the S3-LMR sample. Which corresponds to the XPS profile near the binding energy of Mn 3s (a), O 1s (b), S 2p (c), Mn 2p (d), Ni 2p (e), Co 2p (f).\u003c/p\u003e","description":"","filename":"image5.png","url":"https://assets-eu.researchsquare.com/files/rs-4281820/v1/d628d3740e606e2f7d7451b2.png"},{"id":55157525,"identity":"0a07de31-42c6-40e9-80b9-e0beebea559d","added_by":"auto","created_at":"2024-04-23 12:10:44","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":765351,"visible":true,"origin":"","legend":"\u003cp\u003eTEM images (b) (c) and diffraction ring (a) of sample 3S-LMR\u003c/p\u003e","description":"","filename":"image6.png","url":"https://assets-eu.researchsquare.com/files/rs-4281820/v1/264214243306af2b2d045bd6.png"},{"id":55158030,"identity":"d5227f03-0df5-4f3c-8963-93fe3ed5765b","added_by":"auto","created_at":"2024-04-23 12:18:44","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":151124,"visible":true,"origin":"","legend":"\u003cp\u003eCharge-discharge curves of the first turn of different samples (a), the specific discharge capacity of the first 100 turns at 0.5C (b), the specific discharge capacity of different magnifications (c), the variation of the average discharge voltage and Coulomb efficiency with the number of discharge cycles at 0.5C of the sample LMR and S3-LMR (d)\u003c/p\u003e","description":"","filename":"image7.png","url":"https://assets-eu.researchsquare.com/files/rs-4281820/v1/f3def867744df64add6b2b1b.png"},{"id":55157526,"identity":"2799f7c4-b1f5-49b0-a090-02216eafe073","added_by":"auto","created_at":"2024-04-23 12:10:44","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":135197,"visible":true,"origin":"","legend":"\u003cp\u003eCharge-discharge curves of 10, 25, 50, 75, 100 turns LMR(a), S2-LMR(b), S3-LMR(c), S5-LMR(d) of different materials at 0.5C magnification\u003c/p\u003e","description":"","filename":"image8.png","url":"https://assets-eu.researchsquare.com/files/rs-4281820/v1/2e106ffe2bd24ba66157b802.png"},{"id":55157529,"identity":"e0fd62e8-9c58-4b6a-91fd-9e2430a90133","added_by":"auto","created_at":"2024-04-23 12:10:45","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":113169,"visible":true,"origin":"","legend":"\u003cp\u003eFirst-lap CV curves of different materials (a) First three-lap CV curves of LRM (b), S2-LMR (c), S3-LMR (d) and S5-LMR (e)\u003c/p\u003e","description":"","filename":"image9.png","url":"https://assets-eu.researchsquare.com/files/rs-4281820/v1/cddb50c28afe435d4eb0e672.png"},{"id":55158031,"identity":"0537b51a-7ef1-441b-abac-4d800d7f2ec3","added_by":"auto","created_at":"2024-04-23 12:18:45","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":75612,"visible":true,"origin":"","legend":"\u003cp\u003eImpedance plots of different samples\u003c/p\u003e","description":"","filename":"image10.png","url":"https://assets-eu.researchsquare.com/files/rs-4281820/v1/c00e6376f576fee98d5e8823.png"},{"id":55265679,"identity":"2e76f1d7-03ad-432c-a118-303d12399fec","added_by":"auto","created_at":"2024-04-25 02:14:17","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4100198,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4281820/v1/6e184ea0-84d7-42f3-86c3-d62fd8e8020f.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Thiourea treatment broadens the lattice structure to enhance the electrochemical stability of lithium-rich manganese-based materials","fulltext":[{"header":"Introduction","content":"\u003cp\u003eWith the development of the new energy industry, people have put forward the demand problem of the battery industry. People are constantly striving for higher specific capacity, more stable cycle characteristics, and faster charging and discharging capabilities. [\u003cspan additionalcitationids=\"CR2 CR3\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e] This has led to the urgent need for high discharge capacity and high energy dense cathode materials for Li-ion batteries. The formula for lithium-rich layered oxides is expressed simply as x Li\u003csub\u003e2\u003c/sub\u003eMnO\u003csub\u003e3\u003c/sub\u003e (1-x) LiMO\u003csub\u003e2\u003c/sub\u003e (where 0\u0026thinsp;\u0026lt;\u0026thinsp;x\u0026thinsp;\u0026lt;\u0026thinsp;1 and M\u0026thinsp;=\u0026thinsp;Ni, Co, Mn). It\u0026rsquo;s very high capacity (over 250mAh/g), low cost, environmental friendliness and other advantages make it the most likely next-generation lithium battery. [\u003cspan additionalcitationids=\"CR6\" citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e] However, among the lithium-rich manganese-based materials, Li\u003csub\u003e1.2\u003c/sub\u003eMn\u003csub\u003e0.54\u003c/sub\u003eNi\u003csub\u003e0.13\u003c/sub\u003eCo\u003csub\u003e0.13\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e has a high theoretical capacity, good energy density and ultra-high average charge-discharge voltage, which is favored by researchers. [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan additionalcitationids=\"CR9\" citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]\u003c/p\u003e \u003cp\u003eAlthough there are many advantages to lithium-rich oxide cathode materials, the industrialization process has been hampered by the low-rate performance and poor cycle stability of lithium-rich manganese-based materials. [\u003cspan additionalcitationids=\"CR12 CR13\" citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e] To this end, people continue to optimize lithium-ion batteries through doping, [\u003cspan additionalcitationids=\"CR16\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e] surface treatment, [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e] coating, [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e] nanoparticle construction, [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e, \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e] etc. Simple methods of surface treatment and anion doping have been demonstrated to be more effective in improving rate performance and cycling stability. [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e, \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e] Li et al. [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e] achieved boron anionomer doping by introducing boric acid into the reaction process of the sol-gel method, resulting in strong specific capacity improvement and enhanced cycling performance. It was demonstrated that the boron polyanion can mitigate changes in the electronic structure of O 2p induced during delithiation and lithiation. Other polyanions were predicted to also stabilize changes in the electronic structure of oxygen during cycling by increasing the binding energy with elemental oxygen, thus enhancing material stability. This was quickly demonstrated. While Zhang et al, [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e] doped sulfur anions on the surface of the layered oxides by surface sulfurisation of the co-precipitated prepared samples, thus increasing the lattice spacing, increasing the Coulombic efficiency of the first charge/discharge and improving the cycling stability.Li et al. [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e] formed a thin layer of lithium manganese sulfide spinel phase on the surface of the layered oxides by simple thiourea treatment of the co-precipitated monomers, and the introduction of the spinel phase stabilised phase can improve the conductivity of lithium ions and reduce particle cracking and phase collapse during repeated cycling.S The formation of TM-S bond configuration induced by the introduction of S can effectively accelerate the diffusion of lithium ions and inhibit the undesired oxygen redox. Thus, the cycling stability and discharge performance of the lithium-rich manganese-based materials synthesised by co-precipitation are greatly enhanced. The more complicated co-precipitation process prepares samples that are mostly spherical in shape with primary particle agglomerates, and lithium ions are gradually and slowly de-embedded by gradually starting from the surface layer to the inner layer. This synthesis method has mostly been reported to form an improved layer on its spherical surface layer. [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e] The sol-gel method, on the other hand, has been popularised due to its simple reaction conditions, but suffers from the disadvantages of greater capacity degradation of the material and poorer cycling stability. [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e, \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e] The use of anionic doping modification is promising to improve the electrochemical performance of dispersed cathode materials prepared by the sol-gel method.\u003c/p\u003e \u003cp\u003eIn this work, the sol-gel process was used to produce relatively dispersed primary granular layered oxides, and thiourea was used for surface treatment. To study the effects of different concentrations of thiourea on its layered oxides, The results show that after 3wt% thiourea treatment, the particle size of the primary particles becomes smaller and more dispersed. Therefore, the contact area between the lithium-ion cathode material and the electrolyte is increased, which reduces the distance of lithium-ion deintercalation. At the same time, some sulfur atoms are doped with primary particles in the sintering process, which indicates that the lattice spacing on the crystal surface is increased, which in turn promotes the deintercalation of lithium ions. After treatment with 3wt% thiourea, layered oxides showed improved discharge capacity and cycling performance. At 0.1C, the specific capacity of the first cycle discharge increased from 244.4mAh/g to 274.2mAh/g. After 100 cycles of 236mAh/g at the discharge rate of 0.5C, the capacity retention rate was 72.46%.\u003c/p\u003e"},{"header":"Material preparation","content":"\u003cp\u003e \u003cb\u003ePreparation of precursors\u003c/b\u003e \u003c/p\u003e \u003cp\u003eLithium-rich layered oxide monomers were prepared by sol-gel method, lithium acetate, manganese acetate, nickel acetate, cobalt acetate was dissolved in an appropriate amount of ethanol solution in a molar ratio of 1.2:0.54:0.13:0.13 to make a mixed solution. Then dissolve 0.5 times the metal ion molar ratio of citric acid in an appropriate volume of ethanol solution to make a citric acid-ethanol solution. Slowly drop the mixed solution into the ethanol solution of citrate (pumped at a rate of 0.8 mL/min) and stir vigorously during this time. After dripping, it is transferred to an oil bath and stirred at 80\u0026deg;C until it is powdery, and then taken out and ground and sintered in air at 450\u0026deg;C for 8 hours. After natural cooling, grind and sieve at 200 mesh. Then annealed in air at 850\u0026deg;C for 5 h, the resulting material is called monomer LMR.\u003c/p\u003e \u003cp\u003e \u003cb\u003eThiourea surface treatment\u003c/b\u003e \u003c/p\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, \u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e0.5\u003c/span\u003eg of monomer was taken, and thiourea with different weight ratios of 2wt%, 3wt%, and 5wt% was taken and mixed in 25mL of deionized water. After stirring at room temperature for 1h, stir in an oil bath at 90\u0026deg;C and put in a drying oven at 90\u0026deg;C until completely dry. After removing the powder, air annealing at 450\u0026deg;C for 5 h. The powders obtained were S2-LMR, S3-LMR and S5-LMR, respectively.\u003c/p\u003e \u003cp\u003e \u003cb\u003eMaterials characterization\u003c/b\u003e \u003c/p\u003e \u003cp\u003eThe crystal structure of the surface of the sample undergoing different treatments has been determined by X-ray diffraction (XRD). The microscopic morphology and elemental distribution of the samples were analyzed using a JSM-6700F scanning electron microscope (SEM). The measurements were further characterized using a JEM-2100F transmission electron microscope (TEM). To determine the valence state of each element, the chemical elemental analysis of the sample was performed using a PHI5702 multi-function X-ray spectrometer (XPS).\u003c/p\u003e \u003cp\u003e \u003cb\u003eElectrochemical measurements\u003c/b\u003e \u003c/p\u003e \u003cp\u003eThe prepared cathode material, acetylene black conductive agent and polyvinylidene fluoride (PVDF) are mixed in a ratio of 8:1:1, dropwise into the appropriate NMP solution, mixed and stirred into a slurry. Cover the aluminum foil evenly with the substance. After drying, it is cut into small discs to be used as electrodes. The CR2025 type coin cell battery is assembled in an inert gas-filled glove box. The electrolyte used is 1 M lithium phosphate solution, where the solvent is diethyl carbonate (DEC), ethylene carbonate (EC) and dimethyl carbonate (DMC) in proportion (1:1:1 vol%). The amount of electrolyte used per cell is about 50\u0026micro;L. The LAND-CT2001A battery tester was used to test the battery charge/discharge curves at various current densities over the 2.0V to 4.8V voltage range. An electrochemical workstation (CS350H) was used to perform cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests. The CV test is an entirely new battery made from the test specimen, scanning the first 3 turns at a scan rate of 0.2mV/s in a voltage band from 2.0V to 4.8V. The EIS test is a scan test over a frequency band from 0.01 Hz to 100,000 Hz.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"Result and discussion","content":"\u003cp\u003e \u003cb\u003eCrystalline structure analysis\u003c/b\u003e \u003c/p\u003e \u003cp\u003eXRD patterns of Li\u003csub\u003e1.2\u003c/sub\u003eMn\u003csub\u003e0.54\u003c/sub\u003eNi\u003csub\u003e0.13\u003c/sub\u003eCo\u003csub\u003e0.13\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e with initial LMR and different thiourea treatments. As can be seen in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, the higher the crystalline reflectance, the higher the crystallinity of the surface. The weak peak at 2θ\u0026thinsp;=\u0026thinsp;20\u0026deg;~25\u0026deg; is the Li\u003csub\u003e2\u003c/sub\u003eMnO\u003csub\u003e3\u003c/sub\u003e phase belonging to the space group C2/m. [\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e, \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e] Compared with the original LMR, the corresponding peaks of Li\u003csub\u003e2\u003c/sub\u003eMnO\u003csub\u003e3\u003c/sub\u003e in the XRD pattern after thiourea treatment were more obvious, which was more beneficial for capacity increase. With thiourea treatment, it can be found that the XRD peaks are shifted to a low diffraction angle, which indicates that the lattice spacing of the sample becomes larger due to the incorporation of S elements after treatment. [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e, \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e] The lattice parameters for each structure were obtained by fitting the XRD patterns, as shown in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. The appropriate concentration of thiourea treatment increases the c/a ratio of the sample lattice, indicating that Sulphur doping improves the lattice parameters and the kinetic performance of lithium-ion deintercalation. It is worth noting that the ratio of I(003)/I(104) peaks, which to some extent reflects the degree of mixing and exclusion of TM atoms and lithium atoms in the lamellar structure, and the smaller the ratio, the greater the degree of mixing and exclusion, and the lithium ion de-embedding is hindered.[\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e, \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e] It can be seen that the mixed arrangement situation was improved after the treatment.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eImpedance values for different materials\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"5\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSamples\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eLRM\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eS2-LMR\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eS3-LMR\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eS5-LMR\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ea\u003c/b\u003e(nm)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.28517\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.28519\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.28502\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.28519\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ec\u003c/b\u003e(nm)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1.42418\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e1.42362\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.42497\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e1.42361\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ec\u003c/b\u003e/\u003cb\u003ea\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e4.9942\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e4.9918\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e4.9995\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e4.9917\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eV\u003c/b\u003e(nm\u003csup\u003e3\u003c/sup\u003e)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.10030\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.10028\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.10025\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.10028\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eI\u003c/b\u003e\u003csub\u003e(003)\u003c/sub\u003e/\u003cb\u003eI\u003c/b\u003e\u003csub\u003e(104)\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1.21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e1.63\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.57\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e1.36\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003cb\u003eMorphological observation\u003c/b\u003e \u003c/p\u003e \u003cp\u003eSEM images of LRM and S3-LRM samples are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. Through the SEM image, it can be seen that the two samples are 100\u0026thinsp;~\u0026thinsp;500nm particles. The treated surface of thiourea is more dispersed, indicating that thiourea reacts on the sample surface. This changes the sample from an otherwise irregularly agglomerated topography to a more dispersed first-order particle morphology. This increases the surface area, and the more surface area in contact with the electrolytic solution, the shorter the Li-ion pathway, promoting fast Li-ion de-intercalation. At the higher sintering temperature, the sample inevitably causes a certain degree of agglomeration, which hinders the deintercalation of lithium ions. However, the phenomenon of particle agglomeration can be effectively improved by surface treatment with thiourea. This indicates that the thiourea treatment effectively limits particle size reduction, increases the contact surface area between the solution and the primary particles, and promotes lithium ion deintercalation. [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e] However, it should be noted that more dispersed primary particles increase the surface area of the sample contacting the electrolyte, which may result in faster capacity decay of the sample. [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]\u003c/p\u003e \u003cp\u003eIn order to better analyses the elemental distribution of the treated samples, EDS tests were carried out on the samples treated with 3wt% thiourea, which showed that the nickel, cobalt and manganese atoms in the sample particles were uniformly distributed, and the proportions of the elements did not change much compared to the expected elemental proportions. It can also be seen that the distribution of S on the sample surface is relatively uniform. This is probably due to the fact that S will remain on the surface of the sample after thiourea treatment, and after sintering, S will enter the lattice on the surface of the sample to replace oxygen. The above shows that the thiourea surface treatment not only improves the surface morphology, but also has the potential to induce surface anion doping of the samples.\u003c/p\u003e \u003cp\u003eIn order to understand the changes in the chemical state of each element before and after treatment, XPS analysis was performed on the monomer LMR and S3-LMR. For example, Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(a) analyzes the Mn 3s profile of the sample and calculates the average oxidation state (AOS) of the elements using the formula AOS\u0026thinsp;=\u0026thinsp;8.956\u0026ndash;1.126 ΔEs (eV) based on the relationship between ΔEs and the AOS proposed by Galakhov et al. [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e] By converting the binding energy difference ΔEs between the two peaks into the average valence state of Mn, it is evident that the valence state of Mn in S3-LMR decreases compared to that of the monomer. This change in the valence state of Mn may be attributed to the improved proportion and structure of layered oxides. Examining the spectrum near the binding energy of O 1s, an increase in the peak value of 531.5 eV is observed, which corresponds to the oxygen vacancy in the lattice. This increase may be attributed to the reduction of Mn\u003csup\u003e4+\u003c/sup\u003e ions after treatment, and these changes are consistent with previous reports. [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e] Additionally, a faint peak corresponding to SO\u003csup\u003e4\u0026minus;\u003c/sup\u003e was detected near the binding energy of S 2p, [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e, \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e] indicating that a small amount of sulfur polyanion was added to the material after treatment. Peaks of 855.3, 642.2 and 780.2 eV were detected in the binding energy ranges of Ni 2p, Mn 2p and Co 2p, respectively, which was consistent with the reported results of Ni\u003csup\u003e2+\u003c/sup\u003e, Mn\u003csup\u003e4+\u003c/sup\u003e and Co\u003csup\u003e3+\u003c/sup\u003e. [\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e, \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e]\u003c/p\u003e \u003cp\u003eIn order to get more specific crystal information of the processed samples, we performed TEM scans of the S3-LMR samples and analysed the lattice fringes and diffraction patterns using (Digital Micrograph) DM software. TEM images of 3S-LMR of the samples treated with 3wt% thiourea are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e. Using the diffraction centre as a reference point, the diffraction pattern was expanded by the software as in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e(a). The relationship between the intensity of the diffraction spot and the distance from the centre was then determined. Three distinct diffraction rings were observed, with lattice spacings of 0.47 nm, 0.24 nm and 0.14 nm. These correspond to the (003), (101) and (110) planes of the R-3m structure of LiMO\u003csub\u003e2\u003c/sub\u003e (M\u0026thinsp;=\u0026thinsp;Co, Ni, Mn), respectively. Some areas were selected by the software for lattice streak measurements as in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e(c, d), and some crystal images were compared with XRD. The figure shows a diffraction line spacing of approximately 0.47 nm, corresponding to the (003) crystal plane in XRD. [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e, \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e] This is also an indication that there is no damage to the crystal structure of the surface after such treatment. The diffraction fringes of the peripheral crystal structure are compared with those of the internal crystal structure. It can be seen from Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e(c) that the lattice spacing of the peripheral part is slightly larger than that of the internal lattice. This indicates that the treated surface expands its lattice due to the incorporation of S anions, which is consistent with the results of XRD peak shift analysis. The treated sample did not form a significant coating on its surface due to sintering in the air. Simultaneously, the TEM image reveals that there are no additional phases present on the sample surface. This suggests that the uniformly distributed sulfur element is not covering the active material surface in the form of sulfide, but rather is doped onto it.\u003c/p\u003e \u003cp\u003e \u003cb\u003eElectrochemical behaviors\u003c/b\u003e \u003c/p\u003e \u003cp\u003eIn order to test the electrochemical properties of the materials and the differences between different materials during the first turn of charging and discharging, a first turn 0.1 C (1 C\u0026thinsp;=\u0026thinsp;250 mA/g) charging and discharging test was carried out and Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e(a) shows the charging and discharging curves of the different samples at the rate of 0.1C under the voltage window of 2V to 4.8V. We can find that there are two obvious charging platforms in the charging curve, namely the specific capacity generated by the detachment of lithium ions from the layered phase between 3.7V and 4.45V, and the additional capacity generated by the lithium-rich phase greater than 4.45V. [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e] When comparing the two charging platforms, LMR and S3-LMR, it is evident that the specific capacity of the layered phase in S3-LMR is greater than that of LMR. Specifically, the specific capacity of the S3-LMR in the 3.7V to 4.45V charging voltage range is 143mAh/g compared to 119mAh/g for the LMR. This suggests that the appropriate amount of thiourea treatment enhances the layered phase structure of the sample. [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e] This is consistent with XRD findings that thiourea treatment increases lattice spacing, reduces atomic mixing, and improves lithium-ion de-insertion kinetics in the lamellar phase, resulting in a greater reversible specific capacity. However, the platform greater than 4.45V is the Li\u003csub\u003e2\u003c/sub\u003eMnO\u003csub\u003e3\u003c/sub\u003e phase, and the Li\u003csub\u003e2\u003c/sub\u003eMnO\u003csub\u003e3\u003c/sub\u003e\u0026rarr;2Li\u003csup\u003e+\u003c/sup\u003e+Mn\u003csup\u003e4+\u003c/sup\u003eO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e4\u0026minus;\u003c/sup\u003e+2e\u003csup\u003e\u0026minus;\u003c/sup\u003e\u0026rarr;2Li\u003csup\u003e+\u003c/sup\u003e+MnO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;1/2O\u003csub\u003e2\u003c/sub\u003e reaction occurs at high voltage. The lithium-rich manganese-based material exhibits a higher specific capacity than other ternary cathode materials due to the additional specific capacity provided by the activated MnO\u003csub\u003e2\u003c/sub\u003e. However, it is important to note that some of the specific capacity in this reaction is irreversible as a result of the release of oxygen. [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e] After analysis, the specific capacity of S3-LMR increased from 244.4mAh/g to 274.2mAh/g due to the improvement of the layered phase.\u003c/p\u003e \u003cp\u003eTo demonstrate the role of these reversible specific volumes in subsequent cycles, we measured a test in which different samples were cycled for 100 turns at 0.5C magnification. Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e(b) shows the specific volume of different samples for the first 100 cycles of discharge at 0.5C, and it can be seen that the cycling stability of thiourea-treated samples is improved, with the sample treated with 3wt% thiourea having the best specific capacity. Thiourea-treated samples exhibit significantly higher volume retention compared to monomers. The decrease in the capacity of the monomer is due to the structural collapse of the material sample. When the original particle structure of the active material is exposed to the charge-discharge cycle of the electrolyte, the layered phase gradually transforms from the surface inward to the defective spinel phase. [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e] Although the thiourea-treated primary particles have a more dispersed morphological structure and a larger specific surface area in contact with the electrolyte, their electrochemical stability is shown to be more stable. This is due to the improved structural stability of the samples treated with thiourea and the good improvement of the degree of mixing. Combined with XPS and SEM analysis, it may be that the lattice structure of the material was stabilized during thiourea treatment, the valence state of the elements was improved, the degree of mixing was reduced, and the considerable reversible specific capacity brought by the layered phase was increased. At the same time, it is possible that some sulfur elements are incorporated into the crystal surface, which also improves the structural stability and slows down the unfavorable phase transformation process. [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e, \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]\u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e(c) shows the schematic diagram of the discharge specific capacity of different samples at different magnifications, and it can be found that the performance of S2-LRM and S5-LRM is similar to that of the monomer, while the performance of S3-LRM sample is improved at different magnifications. This is due to the fact that the appropriate amount of thiourea treatment can make the samples more dispersed and improve the ionic mixing arrangement, which improves the stability of the crystal structure. Meanwhile, through the sintering treatment, the sulfur atoms produced by the reaction of thiourea on the surface of the active material can be doped into the lattice, thus enlarging the lattice spacing. All these reasons increase the lithium-ion de-insertion and improve the rate performance.\u003c/p\u003e\u003cp\u003eIn order to explore the rate performance of different samples, we performed charge-discharge tests on the samples at different current densities. Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e(d) shows the average discharge voltage and coulombic efficiency for the first 100 turns of the LRM and S3-LRM. It can be seen that the attenuation of the average discharge voltage of thiourea treatment is mitigated compared to LMR. This may be due to the fact that the S element has a stronger binding energy to the metal, which improves its structural stability, thereby slowing down its capacity and voltage decay. [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e, \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]\u003c/p\u003e \u003cp\u003eIn order to observe more clearly the capacity degradation during the long cycling process, the charge/discharge curves of different samples from the 10th to the 100th cycle at 0.5C magnification are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e. This shows that the thiourea-treated specimen has a more stable charge-discharge curve and less capacity loss. Figure\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e shows the CV discharge curve of each sample in the first three cycles, and it can be found that the absorption oxidation peak corresponds to the voltage plateau of the charge-discharge curve. The oxidation voltages of the first turn peak at 3.9V and 4.6V, which correspond to the 4.0V of the charge-discharge curve and the discharge plateau around 4.5V. The 3.9V peak is attributed to the oxidation of Co\u003csup\u003e3+\u003c/sup\u003e and Ni\u003csup\u003e2+\u003c/sup\u003e, whereas the 4.6V oxidation peak is caused by the release of O during the conversion of the Li\u003csub\u003e2\u003c/sub\u003eMnO\u003csub\u003e3\u003c/sub\u003e phase to MnO\u003csub\u003e2\u003c/sub\u003e and the detachment of Li\u003csup\u003e+\u003c/sup\u003e. Simultaneously, two distinct reduction peaks were observed at approximately 3.3V and 3.7V, corresponding to the reduction of Mn\u003csup\u003e4+\u003c/sup\u003e and Ni\u003csup\u003e3+\u003c/sup\u003e respectively. When we compare the CV of the treated sample with the LMR sample, we can see a small oxidation peak around 2.9V and a reduction peak near 2.6V in the low-voltage fraction. These two peaks may be due to the very small fraction of the spinel phase produced by thiourea treatment and sintering. Compared to other treated samples, the reduction peak at 2.6V in the S3-LMR was smaller. [\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e, \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e] The difference between these phases is well reflected in the charge-discharge curve, S2-LMR and S5-LMR can see very small plateau changes in the discharge platform, while S3-LMR, although the presence of spinel is reflected in the CV, is too small to affect the charge-discharge curve. At the same time, the TEM pattern of S3-LMR was not found from the surface lattice, which indicates that the proportion of this spinel phase is very small, and the influence on the overall charge and discharge is very small. A comparative analysis of the oxidation peak portion of the first cycle can reveal subtle differences in the activation process of the Li\u003csub\u003e2\u003c/sub\u003eMnO\u003csub\u003e3\u003c/sub\u003e phase. Figure\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e(a) compares the CVs of the first cycle of each sample, and it is clear that the ratio of the S3-LMR sample is much smaller than that of the LMR sample when comparing the peak ratios of I \u003csub\u003e(4.6V)\u003c/sub\u003e/I \u003csub\u003e(3.9V)\u003c/sub\u003e. The ratio reflects the stability of the structure during the activation process to a certain extent, and the smaller the ratio is, that is to say, the oxidation reaction of the oxygen element of the Li2MnO3 phase during the activation process of the material in the first lap discharge process is alleviated, which makes the lattice oxygen oxidation reaction in the activation process to oxygen reaction is suppressed, which not only suppresses the generation of irreversible capacity but also improves the structural stability. [\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e, \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e] At the same time, we found that the two oxidation peaks correspond to the voltage values, and we can find that the potential difference of the redox peaks is reduced due to the slight shift of the peaks to the middle after appropriate thiourea treatment, which may be that the appropriate thiourea treatment can improve the elemental valence state of the layered structure, which indicates that the polarization of the battery has been well improved. [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e] These phenomena indicate that the structure is more stable after thiourea treatment, and appropriate adjustment of the amount of thiourea treatment can effectively reduce the polarization of the cell. This may be due to the fact that the surface S doping improves the binding energy with the TM elements, which inhibits the oxygen release and enhances the structural stability, and at the same time optimizes the valence states of the TM elements and reduces the polarization of the battery, thus improving the reversible specific capacity of the battery, increasing its specific capacity, and improving its cycling stability.\u003c/p\u003e \u003cp\u003eFinally, we analyses the impedance of the cells. Figure\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e shows the EIS curves of each of the sample cells, and Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e shows the impedance values of each of the impedances after fitting the corresponding EIS curve to the analogue circuit. It can be found that the impedance \u003cem\u003eR\u003c/em\u003ect of the S3-LRM battery is the smallest. The results indicated that appropriate thiourea treatment could reduce the impedance of the battery and improve the electrochemical performance. [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e, \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e]\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eImpedance values for different materials\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"5\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSamples\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eLRM\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eS2-LMR\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eS3-LMR\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eS5-LMR\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eR\u003c/em\u003es (\u0026plusmn;Ω)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1.811\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e4.013\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.518\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e6.294\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eR\u003c/em\u003ect (\u0026plusmn;Ω)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e264.9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e474.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e113.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e860.5\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eThe aim of this study is to solve the problems such as rapid capacity decay of lithium-rich manganese-based materials prepared by sol-gel method using thiourea surface treatment and sulfur anion doping. The results show that the surface modification of thiourea can disperse the crystal particles and improve the valence state of TM elements in the crystals, thus reducing the cell polarisation and increasing the reversible capacity of sheet phase release. Meanwhile, doping S elements on the crystal surface can reduce the release of O during the activation process and widen the surface lattice spacing, thus improving the stability. The specific capacity of the specimen was improved from 244.2mAh/g to 274.2mAh/g for the first charge at a current density of 0.1 C. At a discharge rate of 0.5 C, the capacity was 236mAh/g, and the capacity retention rate was 72.46% after 100 cycles. We hope that this work will play an active role in the development of manganese-based lithium-rich materials.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eConflict of interest\u003c/h2\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\n\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\n\u003cp\u003eZhifeng Zhao: Conceptualization, Writing-original draft preparation. Wangjun Feng: Writing-review \u0026amp; editing, Validation, Funding Acquisition. Wenxiao Su: Data curation, Software. Yueping Niu: Visualization. Wenting Hu：Software, Methodology. Xiaoping Zheng: Resources, Investigation, Supervision.\u003c/p\u003e\n\u003ch2\u003eAcknowledgements\u003c/h2\u003e\n\u003cp\u003eThis work was supported by the National Natural Science Foundation of China (No. 21965019); HongLiu First-class Disciplines Development Program of Lanzhou University of Technology; the Lanzhou Talent Innovation and Entrepreneurship Project (Approval No.114); the First Batch of Lanzhou Science and Technology Planning Projects in 2019 (2019-1-46); Gansu College Innovation Fund Project of Gansu Provincial Department of Education (No.2022A-169).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eNgoepe, N., Gutierrez, A., Barai, P., Chen, J., Ngoepe, P. E., \u0026amp; Croy, J. R. (2021). The effects of process parameters on the properties of manganese-rich carbonate precursors: A study of co-precipitation synthesis using semi-batch reactors. 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Improving the performance of Li-rich Mn-based cathode materials via combined surface modification with glacial acetic acid and Li\u003csub\u003e3\u003c/sub\u003ePO\u003csub\u003e4\u003c/sub\u003e Journal of Electroanalytical Chemistry, \u003cem\u003e917\u003c/em\u003e, 116250.\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"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":"surface treatment, sulfur dopant, laminar oxide, lattice structure","lastPublishedDoi":"10.21203/rs.3.rs-4281820/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4281820/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe lithium-rich manganese-based material Li\u003csub\u003e1.2\u003c/sub\u003eMn\u003csub\u003e0.54\u003c/sub\u003eNi\u003csub\u003e0.13\u003c/sub\u003eCo\u003csub\u003e0.13\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e is currently the most promising anode material due to its high capacity and low cost. However, the material still suffers from severe capacity degradation and low multiplicity performance. After thiourea treatment, the electrochemical performance of the material is improved. Through elemental and morphological characterization, the treated crystals show more dispersed particles and a small amount of Sulphur doped on the surface. Various electrochemical tests were performed on the cells and the 3wt% thiourea treated cells showed improved discharge specific capacity and cycling performance compared to the non-thiourea treated cells. Moreover, the polarity of the battery was reduced and the impedance decreased. The specific capacity of the first cycle was 274.2mAh/g at 0.1C. The specific capacity was 236mAh/g at 0.5C and the capacity retention rate was 72.46% after 100 cycles.\u003c/p\u003e","manuscriptTitle":"Thiourea treatment broadens the lattice structure to enhance the electrochemical stability of lithium-rich manganese-based materials","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-04-23 12:10:39","doi":"10.21203/rs.3.rs-4281820/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":"3ef599d1-ee41-4eef-babe-b396128e2794","owner":[],"postedDate":"April 23rd, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2024-04-23T23:42:01+00:00","versionOfRecord":[],"versionCreatedAt":"2024-04-23 12:10:39","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-4281820","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4281820","identity":"rs-4281820","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}