Energy Storage Materials最新文献_第2页

Understanding and Mitigating Acidic Species in All-Fluorinated Electrolytes for a Stable 572 Wh/kg Lithium Metal Battery (LMB)

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2025-04-05 DOI: 10.1016/j.ensm.2025.104234

Pan Luo , Ying Zhang , Jialin Song , Xing Li , Qiu Chen , Qinghua Yang , Li Liao , Haoyi Yang , Mingshan Wang , Zhengzhong Yang , David Mitlin

Fluorine-rich electrolytes hold promise to significantly enhance the energy and the safety of lithium metal batteries (LMBs). However, they generate acidic species, especially when lithium hexafluorophosphate (LiPF₆) is used as the lithium salt. This critical issue impedes their wide-scale utilization but has to date received minimum analysis. Herein, we reveal the mechanisms behind the exacerbation of HF generation in LiPF₆-based all-fluorinated electrolytes and propose a universally applicable mitigation strategy. The screened additive Tris(trimethylsilyl)phosphate (TMSPa) reacts with HF and stabilizes PF₅, preventing its further hydrolysis and thereby effectively reducing the HF content in fluorine-rich electrolytes. TMSPa contributes to preferentially form a conductive and protective solid electrolyte interphase (SEI), suppressing interface parasitic reactions and ensuring the structural integrity of electrode materials throughout battery cycling. The all-fluorinated electrolytes developed in this work with the addition of TMSPa (AFE-TMSPa) demonstrates a wide electrochemical window (4.6 V), high-temperature stability (up to 55°C), and enhanced safety for LMBs (flame-retardant and dendrite-suppressing). A Li metal pouch cell (7.2 Ah) employing AFE-TMSPa (NCM811 double sided cathode with a mass loading of 80.72 mg/cm²), and lean electrolytes at 1.23 g Ah⁻¹, achieves an energy density of 572 Wh kg⁻¹ at a 0.1 C rate. In a Li||NCM811 coin cell with a 50 µm thick Li-metal anode and a high-loading NCM811 cathode (19.8 mg cm⁻², 3.96 mAh cm⁻²), the system supports 160 stable cycles with a capacity retention of 89% at a 0.2 C charge and 0.5 C discharge rate.

{"title":"Understanding and Mitigating Acidic Species in All-Fluorinated Electrolytes for a Stable 572 Wh/kg Lithium Metal Battery (LMB)","authors":"Pan Luo , Ying Zhang , Jialin Song , Xing Li , Qiu Chen , Qinghua Yang , Li Liao , Haoyi Yang , Mingshan Wang , Zhengzhong Yang , David Mitlin","doi":"10.1016/j.ensm.2025.104234","DOIUrl":"10.1016/j.ensm.2025.104234","url":null,"abstract":"<div><div>Fluorine-rich electrolytes hold promise to significantly enhance the energy and the safety of lithium metal batteries (LMBs). However, they generate acidic species, especially when lithium hexafluorophosphate (LiPF<sub>6</sub>) is used as the lithium salt. This critical issue impedes their wide-scale utilization but has to date received minimum analysis. Herein, we reveal the mechanisms behind the exacerbation of HF generation in LiPF<sub>6</sub>-based all-fluorinated electrolytes and propose a universally applicable mitigation strategy. The screened additive Tris(trimethylsilyl)phosphate (TMSPa) reacts with HF and stabilizes PF<sub>5</sub>, preventing its further hydrolysis and thereby effectively reducing the HF content in fluorine-rich electrolytes. TMSPa contributes to preferentially form a conductive and protective solid electrolyte interphase (SEI), suppressing interface parasitic reactions and ensuring the structural integrity of electrode materials throughout battery cycling. The all-fluorinated electrolytes developed in this work with the addition of TMSPa (AFE-TMSPa) demonstrates a wide electrochemical window (4.6 V), high-temperature stability (up to 55°C), and enhanced safety for LMBs (flame-retardant and dendrite-suppressing). A Li metal pouch cell (7.2 Ah) employing AFE-TMSPa (NCM811 double sided cathode with a mass loading of 80.72 mg/cm<sup>2</sup>), and lean electrolytes at 1.23 g Ah<sup>−1</sup>, achieves an energy density of 572 Wh kg<sup>−1</sup> at a 0.1 C rate. In a Li||NCM811 coin cell with a 50 µm thick Li-metal anode and a high-loading NCM811 cathode (19.8 mg cm<sup>−2</sup>, 3.96 mAh cm<sup>−2</sup>), the system supports 160 stable cycles with a capacity retention of 89% at a 0.2 C charge and 0.5 C discharge rate.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"78 ","pages":"Article 104234"},"PeriodicalIF":18.9,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782702","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Decoding battery aging in fast-charging electric vehicles: An advanced SOH estimation framework using real-world field data 解码快速充电电动汽车的电池老化：使用真实世界现场数据的先进 SOH 估算框架

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2025-04-05 DOI: 10.1016/j.ensm.2025.104236

Caiping Zhang , Jinyu Wang , Linjing Zhang , Weige Zhang , Tao Zhu , Xiao-Guang Yang , Andrew Cruden

Accurately estimating the state of health (SOH) of in-vehicle batteries is critical for advancing electric vehicle (EV) technology. However, higher charging rates and more complex driving conditions have posed major challenges, with significant variations from vehicle-to-vehicle and cycle-to-cycle. In this study, we developed a SOH estimation framework to monitor battery capacity degradation, in EVs with multi-step constant-current fast charging and voltage balancing technology. The framework employs a customized data window approach, informed by a thorough analysis of EV charging behavior, and extracts hierarchical features from vehicle-, pack- and cell-levels for tracking battery aging. We collected real-world charging data from 300 pure EVs over 1.5 years, resulting in 193,180 samples for validation. The best-performing machine learning models achieved an absolute error of less than 2 % for 93.7 % of samples, a root mean square error (RMSE) of 1.05 %, and a maximum error of only 3.73 % whilst using only 30 % data for training. Our analysis indicates that the proposed model can be effectively developed without the need to pre-select vehicles based on specific driving habits or operating conditions. Notably, reliable and accurate estimations were produced using data from just one vehicle, achieving an RMSE of 1.82 %. Our results highlight the potential of user behavior-assisted feature engineering to decode battery pack aging under dynamically changing vehicle profiles. This work underscores the promise of developing accurate SOH estimation modules for battery management systems using minimal vehicle data.

{"title":"Decoding battery aging in fast-charging electric vehicles: An advanced SOH estimation framework using real-world field data","authors":"Caiping Zhang , Jinyu Wang , Linjing Zhang , Weige Zhang , Tao Zhu , Xiao-Guang Yang , Andrew Cruden","doi":"10.1016/j.ensm.2025.104236","DOIUrl":"10.1016/j.ensm.2025.104236","url":null,"abstract":"<div><div>Accurately estimating the state of health (SOH) of in-vehicle batteries is critical for advancing electric vehicle (EV) technology. However, higher charging rates and more complex driving conditions have posed major challenges, with significant variations from vehicle-to-vehicle and cycle-to-cycle. In this study, we developed a SOH estimation framework to monitor battery capacity degradation, in EVs with multi-step constant-current fast charging and voltage balancing technology. The framework employs a customized data window approach, informed by a thorough analysis of EV charging behavior, and extracts hierarchical features from vehicle-, pack- and cell-levels for tracking battery aging. We collected real-world charging data from 300 pure EVs over 1.5 years, resulting in 193,180 samples for validation. The best-performing machine learning models achieved an absolute error of less than 2 % for 93.7 % of samples, a root mean square error (RMSE) of 1.05 %, and a maximum error of only 3.73 % whilst using only 30 % data for training. Our analysis indicates that the proposed model can be effectively developed without the need to pre-select vehicles based on specific driving habits or operating conditions. Notably, reliable and accurate estimations were produced using data from just one vehicle, achieving an RMSE of 1.82 %. Our results highlight the potential of user behavior-assisted feature engineering to decode battery pack aging under dynamically changing vehicle profiles. This work underscores the promise of developing accurate SOH estimation modules for battery management systems using minimal vehicle data.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"78 ","pages":"Article 104236"},"PeriodicalIF":18.9,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782699","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Delithiation Coupling with Surface Reconstruction during Capacity Degradation in Ni-Rich Layered Cathodes

IF 20.4 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2025-04-05 DOI: 10.1016/j.ensm.2025.104237

Peng Wang, Lang Qiu, Fuqiren Guo, Yuting Deng, Junbo Zhou, Shuli Zheng, Jun Zhang, Yongpeng Liu, Benhe Zhong, Yang Song, Xiaodong Guo

Surface reconstruction and mechanical failure play key roles in the capacity loss of Ni-rich cathodes, yet their intertwining influences are still not completely elucidated. Herein, this work deconvolutes the primary-secondary relationships between surface reconstruction and mechanical failure in affecting capacity decay for LiNi_xCo_yMn_1-_x_-_yO₂ (NCM) cathodes. Electrochemical performance tests show that two Ni-rich cathodes with different nickel contents including LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) and LiNi_0.9Co_0.05Mn_0.05O₂ (NCM9055) in the same delithiation state exhibit similar initial discharge specific capacities and capacity retentions after cycling, which unveils that capacity decay is directly related to the degree of delithiation. In contrast to NCM622, the deep delithiation triggers the typical H2-H3 phase transition of NCM9055, leading to higher internal strain and more severe mechanical degradation during the similar capacity fading process. Such discrepancies in structural degradations disclose that the H2-H3 phase transition and the intergranular cracking cannot be the primary causes for capacity degradation. Impressively, the resemblance in surface reconstruction evolution for two cathodes after cycling further reveals that the capacity fading is strongly dependent on the reconstruction evolving properties of the cathode particle surface layer. This work offers valuable insights and further understanding of electrochemical performance degradation, which serve to facilitate Ni-rich cathode material design improvements.

{"title":"Delithiation Coupling with Surface Reconstruction during Capacity Degradation in Ni-Rich Layered Cathodes","authors":"Peng Wang, Lang Qiu, Fuqiren Guo, Yuting Deng, Junbo Zhou, Shuli Zheng, Jun Zhang, Yongpeng Liu, Benhe Zhong, Yang Song, Xiaodong Guo","doi":"10.1016/j.ensm.2025.104237","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104237","url":null,"abstract":"Surface reconstruction and mechanical failure play key roles in the capacity loss of Ni-rich cathodes, yet their intertwining influences are still not completely elucidated. Herein, this work deconvolutes the primary-secondary relationships between surface reconstruction and mechanical failure in affecting capacity decay for LiNi<em><sub>x</sub></em>Co<em><sub>y</sub></em>Mn<sub>1-</sub><em><sub>x</sub></em><sub>-</sub><em><sub>y</sub></em>O<sub>2</sub> (NCM) cathodes. Electrochemical performance tests show that two Ni-rich cathodes with different nickel contents including LiNi<sub>0.6</sub>Co<sub>0.2</sub>Mn<sub>0.2</sub>O<sub>2</sub> (NCM622) and LiNi<sub>0.9</sub>Co<sub>0.05</sub>Mn<sub>0.05</sub>O<sub>2</sub> (NCM9055) in the same delithiation state exhibit similar initial discharge specific capacities and capacity retentions after cycling, which unveils that capacity decay is directly related to the degree of delithiation. In contrast to NCM622, the deep delithiation triggers the typical H2-H3 phase transition of NCM9055, leading to higher internal strain and more severe mechanical degradation during the similar capacity fading process. Such discrepancies in structural degradations disclose that the H2-H3 phase transition and the intergranular cracking cannot be the primary causes for capacity degradation. Impressively, the resemblance in surface reconstruction evolution for two cathodes after cycling further reveals that the capacity fading is strongly dependent on the reconstruction evolving properties of the cathode particle surface layer. This work offers valuable insights and further understanding of electrochemical performance degradation, which serve to facilitate Ni-rich cathode material design improvements.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"61 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782659","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Enhancing feature importance analysis in battery research: a statistical methods perspective on machine learning limitations 加强电池研究中的特征重要性分析：从统计方法角度看机器学习的局限性

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2025-04-05 DOI: 10.1016/j.ensm.2025.104242

Yoshiyasu Takefuji

This paper addresses critical concerns related to feature importance analysis in battery research, specifically examining the limitations of machine learning-derived feature importances as reported by Yuan et al. While recent studies have achieved impressive prediction accuracy in battery modeling, this paper underscores that such accuracy does not necessarily ensure the trustworthy interpretation of feature importances. This paper advocates for the adoption of robust statistical methods as a superior alternative to model-derived feature importances, emphasizing three key advantages: the provision of directional information (ranging from -1 to +1), standardized comparison scales, and statistical validation through p-values. To enhance the reliability and interpretability of feature importance analysis, this paper introduces a comprehensive framework that incorporates five nonlinear, nonparametric statistical methods. This approach is designed to enhance the rigor and clarity of feature importance assessments in battery research and related fields.

引用次数: 0

Failure mechanism of sulfurized polyacrylonitrile (SPAN) cathode induced by boron-contained lithium salt

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2025-04-05 DOI: 10.1016/j.ensm.2025.104243

Zuohang Li, Yijia Xu, Chenchen Zhang, Chen Li, Su Wang, Zhaokun Wang, Yue Ma, Xixi Shi, Hongzhou Zhang, Dawei Song, Lianqi Zhang

Sulfurized polyacrylonitrile (SPAN) is deemed as the most promising lithium-sulfur (Li-S) batteries cathode owing to high sulfur utilization degree and stable cycling performance. However, abnormal high initial capacity of 2683.2 mA h g^-1 and severe degradation (100.5 mA h g^-1, 100 cycles) induced by LiDFOB salt are observed in our work. To conduct in-depth research on related mechanism, LiPF₆ and LiTFSI based batteries are tested as fair comparisons and relatively cycling performances are exhibited. The electrochemical performance of electrolyte and the interfacial properties of cycled Li anode are compared, then the impact of Li ion transfer and parasitic interface reactions are excluded. Synchrotron-based pair distribution function (PDF) and Raman spectroscopy tests indicate that new B-S bonds are generated on SPAN during the first discharge process in LiDFOB based battery, while the insertion of Li ions on S sites are greatly suppressed. Density functional theory method suggests that active S sites after S-S bond cleavage will be attacked and bonded by B from DFOB^-, which is hard to break and continuously inhibit effective reactions between Li ions and S, leading to serious irreversible battery degradation. The failure mechanism of SPAN cathode induced by boron-contained lithium salt are further verified by LiBOB.

{"title":"Failure mechanism of sulfurized polyacrylonitrile (SPAN) cathode induced by boron-contained lithium salt","authors":"Zuohang Li, Yijia Xu, Chenchen Zhang, Chen Li, Su Wang, Zhaokun Wang, Yue Ma, Xixi Shi, Hongzhou Zhang, Dawei Song, Lianqi Zhang","doi":"10.1016/j.ensm.2025.104243","DOIUrl":"10.1016/j.ensm.2025.104243","url":null,"abstract":"<div><div>Sulfurized polyacrylonitrile (SPAN) is deemed as the most promising lithium-sulfur (Li-S) batteries cathode owing to high sulfur utilization degree and stable cycling performance. However, abnormal high initial capacity of 2683.2 mA h g<sup>-1</sup> and severe degradation (100.5 mA h g<sup>-1</sup>, 100 cycles) induced by LiDFOB salt are observed in our work. To conduct in-depth research on related mechanism, LiPF<sub>6</sub> and LiTFSI based batteries are tested as fair comparisons and relatively cycling performances are exhibited. The electrochemical performance of electrolyte and the interfacial properties of cycled Li anode are compared, then the impact of Li ion transfer and parasitic interface reactions are excluded. Synchrotron-based pair distribution function (PDF) and Raman spectroscopy tests indicate that new B-S bonds are generated on SPAN during the first discharge process in LiDFOB based battery, while the insertion of Li ions on S sites are greatly suppressed. Density functional theory method suggests that active S sites after S-S bond cleavage will be attacked and bonded by B from DFOB<sup>-</sup>, which is hard to break and continuously inhibit effective reactions between Li ions and S, leading to serious irreversible battery degradation. The failure mechanism of SPAN cathode induced by boron-contained lithium salt are further verified by LiBOB.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"78 ","pages":"Article 104243"},"PeriodicalIF":18.9,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782700","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Metal-fatigue-resistant thin lithium foil with high depth of discharge for high-performance lithium metal batteries 用于高性能金属锂电池的高放电深度抗金属疲劳锂薄箔

IF 20.4 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2025-04-04 DOI: 10.1016/j.ensm.2025.104238

Xuyan Ni, Jinqiu Zhou, Kecheng Long, Shaozhen Huang, Yihuan Zhou, Zhenkang Wang, Yiwei Zheng, Tianshu Zhang, Tao Qian, Chenglin Yan, Libao Chen

In Li metal batteries, due to the inadequate resistance to metal fatigue of existing Li foil to withstand the severe strain during charge-discharge cycles, the Li anode is prone to pulverization, which can lead to short circuits or rapid capacity decay of batteries. This issue is further exacerbated in practical high-energy-density batteries that require high discharge depth conditions. To overcome it, a metal-fatigue-resistant thin Li (RMFLi) foil with a stable skeleton has been fabricated by employing a cyclic extrusion compression technique. This RMFLi possesses better metal fatigue resistance than pure Li, maintaining its integrity under cyclic stress and strain without cracking or fracturing. Both finite element simulations (FES) and microscopic morphological characterization provide evidence that the excellent mechanical properties of RMFLi, specifically its resistance to metal fatigue, play a significant role in facilitating controlled dense deposition of Li ions and ensure electrochemical stability of the anode during cycling. Impressively, thanks to its high fatigue resistance and stable skeleton, the RMFLi foil achieves long-term stable cycling even at a discharge depth of up to 90.3%. When paired with high-load lithium iron phosphate (LFP) and S cathodes in full cells, it achieves stable cycling for 1000 and 600 cycles, respectively. It's worth noting that the Li-S pouch cell utilizing this RMFLi foil exhibits high energy density of 391.4 Wh kg⁻¹ and can cycle stably for 80 cycles. This study provides a scalable mechanical preparation method with tremendous expansion possibilities for manufacturing metal-fatigue-resistant thin Li foils.

{"title":"Metal-fatigue-resistant thin lithium foil with high depth of discharge for high-performance lithium metal batteries","authors":"Xuyan Ni, Jinqiu Zhou, Kecheng Long, Shaozhen Huang, Yihuan Zhou, Zhenkang Wang, Yiwei Zheng, Tianshu Zhang, Tao Qian, Chenglin Yan, Libao Chen","doi":"10.1016/j.ensm.2025.104238","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104238","url":null,"abstract":"In Li metal batteries, due to the inadequate resistance to metal fatigue of existing Li foil to withstand the severe strain during charge-discharge cycles, the Li anode is prone to pulverization, which can lead to short circuits or rapid capacity decay of batteries. This issue is further exacerbated in practical high-energy-density batteries that require high discharge depth conditions. To overcome it, a metal-fatigue-resistant thin Li (RMFLi) foil with a stable skeleton has been fabricated by employing a cyclic extrusion compression technique. This RMFLi possesses better metal fatigue resistance than pure Li, maintaining its integrity under cyclic stress and strain without cracking or fracturing. Both finite element simulations (FES) and microscopic morphological characterization provide evidence that the excellent mechanical properties of RMFLi, specifically its resistance to metal fatigue, play a significant role in facilitating controlled dense deposition of Li ions and ensure electrochemical stability of the anode during cycling. Impressively, thanks to its high fatigue resistance and stable skeleton, the RMFLi foil achieves long-term stable cycling even at a discharge depth of up to 90.3%. When paired with high-load lithium iron phosphate (LFP) and S cathodes in full cells, it achieves stable cycling for 1000 and 600 cycles, respectively. It's worth noting that the Li-S pouch cell utilizing this RMFLi foil exhibits high energy density of 391.4 Wh kg<sup>−1</sup> and can cycle stably for 80 cycles. This study provides a scalable mechanical preparation method with tremendous expansion possibilities for manufacturing metal-fatigue-resistant thin Li foils.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"157 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782703","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Versatile chemical repair strategy for direct regeneration of cathode materials from retired lithium-ion battery

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2025-04-03 DOI: 10.1016/j.ensm.2025.104227

Wei Liu , Linfeng Peng , Mengchuang Liu , Jiayue Peng , Ziqi Zeng , Shijie Cheng , Jia Xie

Direct recycling of retired lithium-ion batteries offers a promising solution to address resource scarcity and environmental concerns. While existing recovery methods focused on black mass face limitations, which underscores the demand for universal and efficient strategies to regenerate degraded cathode materials. Here, we introduce a highly compatible chemical lithiation-based method for regenerating degraded LiFePO₄ materials. This process uses a multifunctional bipyridine-lithium reagent to drive spontaneous chemical reactions, followed by annealing that simultaneously restores structural integrity and introduces nitrogen doping. The regenerated material delivers a discharge capacity of 164 mAh g⁻¹ and retains 90 % of its capacity after 500 cycles at 0.5C. Additionally, this method enables in-situ regeneration of degraded electrodes, yielding a 10 % enhancement in initial capacity compared to untreated samples. This approach provides a feasible solution for the direct regeneration of cathode materials, paving the way for sustainable practices in the circular development of the battery industry.

{"title":"Versatile chemical repair strategy for direct regeneration of cathode materials from retired lithium-ion battery","authors":"Wei Liu , Linfeng Peng , Mengchuang Liu , Jiayue Peng , Ziqi Zeng , Shijie Cheng , Jia Xie","doi":"10.1016/j.ensm.2025.104227","DOIUrl":"10.1016/j.ensm.2025.104227","url":null,"abstract":"<div><div>Direct recycling of retired lithium-ion batteries offers a promising solution to address resource scarcity and environmental concerns. While existing recovery methods focused on black mass face limitations, which underscores the demand for universal and efficient strategies to regenerate degraded cathode materials. Here, we introduce a highly compatible chemical lithiation-based method for regenerating degraded LiFePO<sub>4</sub> materials. This process uses a multifunctional bipyridine-lithium reagent to drive spontaneous chemical reactions, followed by annealing that simultaneously restores structural integrity and introduces nitrogen doping. The regenerated material delivers a discharge capacity of 164 mAh g⁻¹ and retains 90 % of its capacity after 500 cycles at 0.5C. Additionally, this method enables in-situ regeneration of degraded electrodes, yielding a 10 % enhancement in initial capacity compared to untreated samples. This approach provides a feasible solution for the direct regeneration of cathode materials, paving the way for sustainable practices in the circular development of the battery industry.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"78 ","pages":"Article 104227"},"PeriodicalIF":18.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767115","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Immobilizing single atom on high-entropy oxides as separator regulators for catalyzing low-temperature lithium-sulfur battery

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2025-04-03 DOI: 10.1016/j.ensm.2025.104228

Fei Na , Xiang Li , Jian Wang , Xiaomin Cheng , Jing Zhang , Yanli Wang , Hongzhen Lin , Liang Zhan , Licheng Ling , Yongzheng Zhang

The commercialization of lithium-sulfur batteries suffers from severe polysulfide shuttling, the sluggish kinetics of sulfur redox reaction and large desolvation barrier. Herein, an atom-dispersed Fe immobilized on high-entropy oxides (Cu-Zn-Al-Ce-ZrO) (SA-Fe/HEO@NC) is proposed via electron delocalization engineering, which serves as an efficient separator regulator for catalyzing sulfur cascade redox reactions with enhanced desolvation kinetics This design leverages electron delocalization engineering to enhance sulfur cascade redox reactions and desolvation kinetics, as confirmed by theoretical simulations and comprehensive electrochemical characterizations, including time-of-flight secondary ion mass spectroscopy (TOF-SIMS) and in-situ Raman spectroscopy. Consequently, the cell with SA-Fe/HEO@NC modified separator displays final capacity of 1035 mAh g⁻¹ at 0.2 C after 100 cycles, and stabilizes for 4.1 mAh cm⁻² when increasing areal loading to ∼6 mg cm⁻² at 0.1 C after 200 cycles. Under 0 °C, an outstanding specific capacity of 751 mAh g⁻¹ with the high capacity-retention of 78.3 % after 100 cycles is still achieved at 1 C, verifying the feasibility of integrating single atom catalyst on high-entropy compounds for rapid conversion kinetics.

{"title":"Immobilizing single atom on high-entropy oxides as separator regulators for catalyzing low-temperature lithium-sulfur battery","authors":"Fei Na , Xiang Li , Jian Wang , Xiaomin Cheng , Jing Zhang , Yanli Wang , Hongzhen Lin , Liang Zhan , Licheng Ling , Yongzheng Zhang","doi":"10.1016/j.ensm.2025.104228","DOIUrl":"10.1016/j.ensm.2025.104228","url":null,"abstract":"<div><div>The commercialization of lithium-sulfur batteries suffers from severe polysulfide shuttling, the sluggish kinetics of sulfur redox reaction and large desolvation barrier. Herein, an atom-dispersed Fe immobilized on high-entropy oxides (Cu-Zn-Al-Ce-ZrO) (SA-Fe/HEO@NC) is proposed via electron delocalization engineering, which serves as an efficient separator regulator for catalyzing sulfur cascade redox reactions with enhanced desolvation kinetics This design leverages electron delocalization engineering to enhance sulfur cascade redox reactions and desolvation kinetics, as confirmed by theoretical simulations and comprehensive electrochemical characterizations, including time-of-flight secondary ion mass spectroscopy (TOF-SIMS) and <em>in-situ</em> Raman spectroscopy. Consequently, the cell with SA-Fe/HEO@NC modified separator displays final capacity of 1035 mAh g<sup>−1</sup> at 0.2 C after 100 cycles, and stabilizes for 4.1 mAh cm<sup>−2</sup> when increasing areal loading to ∼6 mg cm<sup>−2</sup> at 0.1 C after 200 cycles. Under 0 °C, an outstanding specific capacity of 751 mAh g<sup>−1</sup> with the high capacity-retention of 78.3 % after 100 cycles is still achieved at 1 C, verifying the feasibility of integrating single atom catalyst on high-entropy compounds for rapid conversion kinetics.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"78 ","pages":"Article 104228"},"PeriodicalIF":18.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767116","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Strategies for improving ionic conductivity and mechanical stability of solid polymer electrolytes for lithium batteries via physical and chemical interlocking

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2025-04-03 DOI: 10.1016/j.ensm.2025.104233

Sumana Bandyopadhyay, Bhanu Nandan

Solid polymer electrolytes (SPEs) are essential for the advancement of high-energy density, safe, solid-state lithium batteries. However, traditional SPEs encounter difficulties such as inadequate ionic conductivity, poor mechanical stability, and high interfacial impedance. Incorporating inorganic fillers or polymer-reinforced structures can improve the electrochemical performance and physical qualities of the SPEs. Inorganic fillers frequently have compatibility issues with the polymer matrix and result in poor ionic conductivity due to their uneven distribution in the matrix. Conversely, continuous fiber-based three-dimensional frameworks, whether inorganic or polymeric, facilitate physical interlocking of the polymer matrix, limit filler aggregation, and improve ion transport, resulting in increased ionic conductivity and mechanical strength. Electrospinning is the most widely adopted approach for fabricating oriented fibrous frameworks with uniform thickness. Cross-linking also improves ionic conductivity by chemically interlocking the polymer matrix, inhibiting crystallization and allowing for steady battery performance across a wide temperature range. This review emphasizes the dual-interlocking strategies employed in SPEs, where electrospun fibrous networks provide physical interlocking and cross-linking offers chemical interlocking of the polymer matrices simultaneously. The synergy between fiber-based networks and cross-linking results in SPEs with balanced electro-chemo-mechanical properties which is crucial for the development of next-generation solid-state lithium batteries.

固体聚合物电解质（SPE）对于高能量密度、安全的固态锂电池的发展至关重要。然而，传统的固态聚合物电解质存在离子导电性不足、机械稳定性差和界面阻抗高等问题。加入无机填料或聚合物增强结构可以改善固相锂离子电解质的电化学性能和物理特性。无机填料经常与聚合物基体存在兼容性问题，并且由于在基体中分布不均而导致离子传导性较差。相反，以连续纤维为基础的三维框架，无论是无机还是聚合物，都能促进聚合物基体的物理互锁，限制填料聚集，改善离子传输，从而提高离子导电性和机械强度。电纺丝是制造厚度均匀的定向纤维框架最广泛采用的方法。交联还能通过化学交联聚合物基体、抑制结晶并使电池在宽温度范围内保持稳定性能，从而提高离子传导性。本综述强调了 SPE 中采用的双重互锁策略，即电纺纤维网络提供物理互锁，交联同时提供聚合物基质的化学互锁。纤维网络和交联之间的协同作用使 SPE 具有均衡的电化学机械性能，这对下一代固态锂电池的开发至关重要。

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引用次数: 0

Membrane contamination-driven sulfonate structuring for enhanced stability in all-iron redox flow batteries

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2025-04-03 DOI: 10.1016/j.ensm.2025.104226

Xusheng Cheng , Tao Xuan , Jianchi Wang , Haoran Hu , Duoyong Zhang , Jiantao Zai , Liwei Wang

All-soluble all-iron redox flow batteries are considered a promising long-duration, large-scale energy storage technology due to their fully decoupled energy and power design and low-cost active materials. However, the anode requires chelating ligands with electron-donating capabilities to establish a potential difference with ferrocyanide, but ligand crossover results in their oxidation, which subsequently causes failure and restricts stable operation. This work proposes a method based on K⁺-induced aggregation of sulfonate groups in perfluorosulfonic acid membranes, eliminating the need for additional additives. By cycling the membrane through the flow battery process, the barrier effect against anode ligands is enhanced, enabling stable cycling for 3227 cycles at 80 mA/cm² and ensuring long-term stability. Molecular dynamics simulations and cross-membrane diffusion experiments reveal the impact of different metal cations on the morphology of water channels in the membranes. A Na⁺-exchange membrane treated with K⁺ from the electrolyte achieves a high average energy efficiency of 73.4 %, maintaining battery stability. This work provides a simple yet effective strategy to improve the stability of all-soluble all-iron redox flow batteries. By uncovering the underlying microscopic mechanisms through simulations, it paves the way for the practical implementation of this technology in large-scale energy storage systems.

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引用次数: 0