Pub Date : 2025-03-22DOI: 10.1016/j.ensm.2025.104200
Xuri Wang , Bo Zhao , Xiangcun Li , Xinhong Qi , Yan Dai , Tiantian Li , Gaohong He , Fangyi Chu , Xiaobin Jiang
Nonuniform Li-ion gradient and electric fields in conventional host lead to uncontrollable Li top-growth behavior and Li dendrite, impeding the practical application of lithium metal anodes (LMAs). Herein, we design a 3D hierarchical flexible membrane host with gradient lithiophilic properties (GFC@PVDF) to regulate bottom-up growth of the spherical Li within host, by optimizing the electric field and Li-ion flux. The membrane networks with CNT as cores and β-PVDF as linking shells enabling fast electron transfer and low Li-ion migration energy barriers. Gradient Fe2O3 particles in the membrane by layer-by-layer bottom-up attenuating could induce Li-ion dredging and pumps towards the bottom for bottom-up deposition regime, reducing ion concentration gradient via lithiophilic gradient properties. Meanwhile, the Fe2O3 is converted into hybrid electron/ion conductor Fe/Li2O during cycling, which acts as charge decoupling and fast transport path that enhances the bottom transport of Li-ions. Consequently, stable symmetric cells over 500 cycles with Li spherical uniform deposition are obtained under an ultrahigh current density of 50 mA cm-2. The full cell paired with LiFePO4 cathode exhibits remarkable cycling stability at a low N/P ratio of 1.7. This study provides new insights into dendrite-free Li metal anodes, paving the way for high-energy, fast-charging LMAs.
常规基质中锂离子梯度和电场的不均匀性导致锂的顶生长行为和枝晶不可控，阻碍了锂金属阳极的实际应用。本文设计了一种具有梯度亲锂特性的三维分层柔性膜宿主（GFC@PVDF），通过优化电场和锂离子通量来调节宿主体内球形锂的自下而上生长。以碳纳米管为核心，β-PVDF为连接壳层的膜网络能够实现快速电子转移和低锂离子迁移能垒。膜中的梯度Fe2O3颗粒通过逐层自底向上衰减，诱导li离子疏通并向底部泵入，形成自底向上沉积机制，通过亲锂梯度特性降低离子浓度梯度。同时，Fe2O3在循环过程中转变为杂化电子/离子导体Fe/Li2O，起到电荷去耦和快速输运的作用，增强了锂离子的底输运。因此，在50 mA cm-2的超高电流密度下，在500次循环中获得了稳定的对称电池，并获得了Li球形均匀沉积。在低N/P比为1.7的情况下，与LiFePO4阴极配对的电池具有显著的循环稳定性。这项研究为无枝晶锂金属阳极提供了新的见解，为高能、快速充电的lma铺平了道路。
{"title":"Inducing spherical lithium deposition via simultaneously optimized electric field and ionic flux for fast-charging lithium metal batteries","authors":"Xuri Wang , Bo Zhao , Xiangcun Li , Xinhong Qi , Yan Dai , Tiantian Li , Gaohong He , Fangyi Chu , Xiaobin Jiang","doi":"10.1016/j.ensm.2025.104200","DOIUrl":"10.1016/j.ensm.2025.104200","url":null,"abstract":"<div><div>Nonuniform Li-ion gradient and electric fields in conventional host lead to uncontrollable Li top-growth behavior and Li dendrite, impeding the practical application of lithium metal anodes (LMAs). Herein, we design a 3D hierarchical flexible membrane host with gradient lithiophilic properties (GFC@PVDF) to regulate bottom-up growth of the spherical Li within host, by optimizing the electric field and Li-ion flux. The membrane networks with CNT as cores and β-PVDF as linking shells enabling fast electron transfer and low Li-ion migration energy barriers. Gradient Fe<sub>2</sub>O<sub>3</sub> particles in the membrane by layer-by-layer bottom-up attenuating could induce Li-ion dredging and pumps towards the bottom for bottom-up deposition regime, reducing ion concentration gradient via lithiophilic gradient properties. Meanwhile, the Fe<sub>2</sub>O<sub>3</sub> is converted into hybrid electron/ion conductor Fe/Li<sub>2</sub>O during cycling, which acts as charge decoupling and fast transport path that enhances the bottom transport of Li-ions. Consequently, stable symmetric cells over 500 cycles with Li spherical uniform deposition are obtained under an ultrahigh current density of 50 mA cm<sup>-2</sup>. The full cell paired with LiFePO<sub>4</sub> cathode exhibits remarkable cycling stability at a low N/P ratio of 1.7. This study provides new insights into dendrite-free Li metal anodes, paving the way for high-energy, fast-charging LMAs.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104200"},"PeriodicalIF":18.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675330","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}
Sodium-ion batteries (SIBs) have emerged as promising alternatives to lithium-ion batteries due to the advantages of low cost, abundant resources, and superior low-temperature performance. However, research on the thermal runaway (TR) behavior of large-format prismatic SIBs remains limited. To address this research gap, this work investigates the TR behavior of 185 Ah SIBs at different states of charges (SOCs). In contrast to prior research, the primary contribution of this work is the investigation of heat generation, gas production, and mechanical changes in SIBs during TR. Two significant conclusions are obtained: 1) The proportion of H2 increases significantly with SOC, reaching as high as 42% at 100% SOC, with an explosion range of 6.5%∼69.0%, suggesting substantial combustion and explosion hazards associated with SIBs; 2) SIBs release a large amount of heat during TR, resulting in the ejection of internal hot particles as sparks. However, the intense gas production behavior during TR process effectively dissipates heat from SIBs while isolating the combustible gases from the sparks and oxygen, leading to a self-extinguishing phenomenon. This study highlights the influence of SOC on TR and gas production behavior in SIBs, providing critical insights for the advancement of electrochemical energy storage systems.
{"title":"Thermal runaway and gas venting behaviors of large-format prismatic sodium-ion battery","authors":"Zhiyuan Li, Yin Yu, Junjie Wang, Chengdong Wang, Xiaofang He, Zhixiang Cheng, Huang Li, Wenxin Mei, Qingsong Wang","doi":"10.1016/j.ensm.2025.104197","DOIUrl":"10.1016/j.ensm.2025.104197","url":null,"abstract":"<div><div>Sodium-ion batteries (SIBs) have emerged as promising alternatives to lithium-ion batteries due to the advantages of low cost, abundant resources, and superior low-temperature performance. However, research on the thermal runaway (TR) behavior of large-format prismatic SIBs remains limited. To address this research gap, this work investigates the TR behavior of 185 Ah SIBs at different states of charges (SOCs). In contrast to prior research, the primary contribution of this work is the investigation of heat generation, gas production, and mechanical changes in SIBs during TR. Two significant conclusions are obtained: 1) The proportion of H<sub>2</sub> increases significantly with SOC, reaching as high as 42% at 100% SOC, with an explosion range of 6.5%∼69.0%, suggesting substantial combustion and explosion hazards associated with SIBs; 2) SIBs release a large amount of heat during TR, resulting in the ejection of internal hot particles as sparks. However, the intense gas production behavior during TR process effectively dissipates heat from SIBs while isolating the combustible gases from the sparks and oxygen, leading to a self-extinguishing phenomenon. This study highlights the influence of SOC on TR and gas production behavior in SIBs, providing critical insights for the advancement of electrochemical energy storage systems.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104197"},"PeriodicalIF":18.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675281","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}
Pub Date : 2025-03-20DOI: 10.1016/j.ensm.2025.104192
Tianxing Kang , Haoyuan Liu , Jian Cai , Xingyi Feng , Zhongqiu Tong , Hanbo Zou , Wei Yang , Junmin Nan , Shengzhou Chen
Solid-state sodium batteries present a high potential for future energy technology due to their high safety and energy density. However, sluggish Na+ transportation of solid-state electrolytes and serious Na dendrites hinder their further development. Herein, we propose a negatively charged-modified covalent organic framework (COF) with -SO3Na as a Na-ion quasi-solid-state electrolyte (QSSE-COF-SO3Na) for the first time to enhance the Na+ transportation. Density functional theory calculations and molecular dynamics simulations prove that the nano-scale ion channels of the COF-SO3Na and the interaction between the -SO3- and the anion PF6- effectively enhance the Na+ diffusion kinetics. The QSSE-COF-SO3Na exhibits a high ionic conductivity of 4.1 × 10–4 S cm-1 at room temperature and a high transference number of 0.89. Particularly, Na|QSSE-COF-SO3Na|Na symmetric cells show a stable Na plating/stripping process without Na dendrites over 1000 h and 800 h at 0.05 and 0.2 mA cm-2, respectively. Additionally, the QSSE-COF-SO3Na supports full cells, which respectively use NaTi2(PO4)3, Na3V2(PO4)3, and NaFePO4 as cathodes, to display good cycling stability and rate performance. This work highlights the novel strategy to develop the Na-ion quasi-solid-state devices.
固态钠电池由于其高安全性和能量密度，在未来的能源技术中具有很高的潜力。然而，固态电解质Na+输运缓慢和Na枝晶严重阻碍了它们的进一步发展。本文首次提出了一种带负电荷修饰的-SO3Na共价有机框架（COF）作为Na离子准固态电解质（QSSE-COF-SO3Na），以增强Na+的输运。密度泛函理论计算和分子动力学模拟证明，COF-SO3Na的纳米级离子通道以及- so3 -与阴离子PF6-的相互作用有效地增强了Na+的扩散动力学。QSSE-COF-SO3Na在室温下具有4.1 × 10-4 S cm-1的高离子电导率和0.89的高转移数。特别是，Na|QSSE-COF-SO3Na|Na对称细胞在0.05 mA cm-2和0.2 mA cm-2下分别在1000 h和800 h表现出稳定的无Na树突镀/剥离过程。此外，qse - cof - so3na支持全电池，分别以NaTi2(PO4)3、Na3V2(PO4)3和NaFePO4为阴极，具有良好的循环稳定性和速率性能。这项工作突出了开发钠离子准固态器件的新策略。
{"title":"Ionic covalent organic frameworks-based electrolyte enables fast Na-ion diffusion towards quasi-solid-state sodium batteries","authors":"Tianxing Kang , Haoyuan Liu , Jian Cai , Xingyi Feng , Zhongqiu Tong , Hanbo Zou , Wei Yang , Junmin Nan , Shengzhou Chen","doi":"10.1016/j.ensm.2025.104192","DOIUrl":"10.1016/j.ensm.2025.104192","url":null,"abstract":"<div><div>Solid-state sodium batteries present a high potential for future energy technology due to their high safety and energy density. However, sluggish Na<sup>+</sup> transportation of solid-state electrolytes and serious Na dendrites hinder their further development. Herein, we propose a negatively charged-modified covalent organic framework (COF) with -SO<sub>3</sub>Na as a Na-ion quasi-solid-state electrolyte (QSSE-COF-SO<sub>3</sub>Na) for the first time to enhance the Na<sup>+</sup> transportation. Density functional theory calculations and molecular dynamics simulations prove that the nano-scale ion channels of the COF-SO<sub>3</sub>Na and the interaction between the -SO<sub>3</sub><sup>-</sup> and the anion PF<sub>6</sub><sup>-</sup> effectively enhance the Na<sup>+</sup> diffusion kinetics. The QSSE-COF-SO<sub>3</sub>Na exhibits a high ionic conductivity of 4.1 × 10<sup>–4</sup> S cm<sup>-1</sup> at room temperature and a high transference number of 0.89. Particularly, Na|QSSE-COF-SO<sub>3</sub>Na|Na symmetric cells show a stable Na plating/stripping process without Na dendrites over 1000 h and 800 h at 0.05 and 0.2 mA cm<sup>-2</sup>, respectively. Additionally, the QSSE-COF-SO<sub>3</sub>Na supports full cells, which respectively use NaTi<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, and NaFePO<sub>4</sub> as cathodes, to display good cycling stability and rate performance. This work highlights the novel strategy to develop the Na-ion quasi-solid-state devices.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104192"},"PeriodicalIF":18.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666314","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}
Pub Date : 2025-03-20DOI: 10.1016/j.ensm.2025.104191
Xiaoping Yi , Yang Yang , Junjie Song , Luyu Gan , Bitong Wang , Guoliang Jiang , Kaishan Xiao , Xuening Song , Nan Wu , Liquan Chen , Hong Li
All-solid-state lithium batteries hold tremendous potential for next-generation batteries due to their exceptional theoretical energy density and intrinsic safety advantages. The forthcoming solid-state batteries employing solid electrolytes are widely expected to adopt a separator-free design strategy. However, porous separators, distinguished by their mechanical robustness, economic viability, and manufacturing scalability, present a feasible solution to address the industrialization challenges faced by solid electrolytes. Herein, a multifunctional polyethylene separator (denoted as S7540) was rationally designed through systematic optimization of structural parameters and anisotropic characteristics. Notably, the developed S7540 separator achieves an optimal balance between ultra-high porosity and broad pore size spectrum while maintaining superior mechanical integrity, enabling seamless compatibility across both liquid and solid state battery production lines. When implemented in Li/LiCoO2 configurations, the S7540 separator shows long-term cycling stability under high rate (10C) and high areal capacity (∼6.2 mAh cm−2), significantly outperforming the traditional commercial separator. Additionally, the S7540 architecture boosts mechanical properties of polymer-oxide solid electrolytes by approximately 50 times, demonstrating excellent tensile strength (42.1 MPa) and great cyclability (>6000 h) in Li/Li symmetric cells. All-solid-state Li/LiFePO4 cells exhibit outstanding capacity retention rates of 90.7 % and 81.3 % after 500 and 700 cycles at 0.5C, respectively. Importantly, the solvent-free S7540-based electrolyte demonstrates exceptional thermal stability with negligible mass loss (<0.3 %) during prolonged 120°C exposure (6 h) and minimal decomposition below 250°C. This work emphasizes the crucial relationship between separator structure optimization and battery performance metrics, while establishing a cost-effective and scalable manufacturing pathway for practical solid electrolyte implementation across various battery systems.
全固态锂电池由于其卓越的理论能量密度和固有的安全性优势，在下一代电池中具有巨大的潜力。人们普遍认为，未来使用固体电解质的固态电池将采用无分离器的设计策略。然而，多孔分离器以其机械稳健性、经济可行性和制造可扩展性而闻名，为解决固体电解质面临的工业化挑战提供了可行的解决方案。本文通过对结构参数和各向异性特性的系统优化，合理设计了多功能聚乙烯分离器S7540。值得注意的是，开发的S7540分离器在超高孔隙率和宽孔径光谱之间实现了最佳平衡，同时保持了卓越的机械完整性，实现了液体和固态电池生产线的无缝兼容性。当在Li/LiCoO2配置中实现时，S7540分离器在高倍率（10C）和高面积容量（~ 6.2 mAh cm−2）下表现出长期循环稳定性，显著优于传统的商用分离器。此外，S7540结构将聚合物-氧化物固体电解质的机械性能提高了约50倍，在Li/Li对称电池中表现出优异的抗拉强度（42.1 MPa）和良好的循环性能（>；6000小时）。在0.5℃下循环500次和700次后，全固态锂/LiFePO4电池的容量保持率分别为90.7%和81.3%。重要的是，无溶剂s7540基电解质表现出优异的热稳定性，质量损失可以忽略不计(<；0.3%)在120°C长时间暴露（6h）和250°C以下的最小分解。这项工作强调了隔膜结构优化与电池性能指标之间的重要关系，同时为各种电池系统的实际固体电解质实现建立了一种具有成本效益和可扩展的制造途径。
{"title":"Strategically tailored polyethylene separator parameters enable cost-effective, facile, and scalable development of ultra-stable liquid and all-solid-state lithium batteries","authors":"Xiaoping Yi , Yang Yang , Junjie Song , Luyu Gan , Bitong Wang , Guoliang Jiang , Kaishan Xiao , Xuening Song , Nan Wu , Liquan Chen , Hong Li","doi":"10.1016/j.ensm.2025.104191","DOIUrl":"10.1016/j.ensm.2025.104191","url":null,"abstract":"<div><div>All-solid-state lithium batteries hold tremendous potential for next-generation batteries due to their exceptional theoretical energy density and intrinsic safety advantages. The forthcoming solid-state batteries employing solid electrolytes are widely expected to adopt a separator-free design strategy. However, porous separators, distinguished by their mechanical robustness, economic viability, and manufacturing scalability, present a feasible solution to address the industrialization challenges faced by solid electrolytes. Herein, a multifunctional polyethylene separator (denoted as S7540) was rationally designed through systematic optimization of structural parameters and anisotropic characteristics. Notably, the developed S7540 separator achieves an optimal balance between ultra-high porosity and broad pore size spectrum while maintaining superior mechanical integrity, enabling seamless compatibility across both liquid and solid state battery production lines. When implemented in Li/LiCoO<sub>2</sub> configurations, the S7540 separator shows long-term cycling stability under high rate (10C) and high areal capacity (∼6.2 mAh cm<sup>−2</sup>), significantly outperforming the traditional commercial separator. Additionally, the S7540 architecture boosts mechanical properties of polymer-oxide solid electrolytes by approximately 50 times, demonstrating excellent tensile strength (42.1 MPa) and great cyclability (>6000 h) in Li/Li symmetric cells. All-solid-state Li/LiFePO<sub>4</sub> cells exhibit outstanding capacity retention rates of 90.7 % and 81.3 % after 500 and 700 cycles at 0.5C, respectively. Importantly, the solvent-free S7540-based electrolyte demonstrates exceptional thermal stability with negligible mass loss (<0.3 %) during prolonged 120°C exposure (6 h) and minimal decomposition below 250°C. This work emphasizes the crucial relationship between separator structure optimization and battery performance metrics, while establishing a cost-effective and scalable manufacturing pathway for practical solid electrolyte implementation across various battery systems.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104191"},"PeriodicalIF":18.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660513","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}
Pub Date : 2025-03-19DOI: 10.1016/j.ensm.2025.104178
Yiju Song, Hao Cui, Yixiu Gan, Wei Gao
Sodium-ion batteries (SIBs), as a promising energy storage technology, offer the advantages of cost-effectiveness and abundance of source materials. However, insufficient thermal stability at elevated temperatures remains a significant challenge for their commercialization. This study aims to enhance the high-temperature thermal stability of SIBs cathode materials through rational structural design and ion doping strategies. The gradient-directed diffusion technique optimizes the calcination process, adjusting the concentration gradient distribution within the material. This approach increases sodium layer spacing and cell volume, improving thermal stability and electrode kinetics under high-rate cycling conditions. On this basis, a copper-iron dual doping strategy is applied further to enhance the cathode's crystal structure and electrical conductivity, reducing side reactions with the electrolyte. Experimental results show that the optimized and doped P2-Na0.67Mn0.55Ni0.30Fe0.05Cu0.10O2 materials exhibit excellent capacity retention at high temperatures, with 87.8% retention after 200 cycles at 10 C and 60°C in half-cell tests. In full-cell configurations, the materials retain 81.7% of their initial capacity after 100 cycles at 5 C and 60°C, while exhibiting near-zero strain characteristics (0.86%). The first principle calculations reveal that NMNCF-2 enhances electrical conductivity, sodium-ion migration rate, and cycling stability by narrowing the band gaps and reducing the migration energy barrier. These findings provide a robust solution for the high-temperature applications of SIBs, demonstrating the potential of structural optimization and ion doping to improve performance and safety significantly.
{"title":"Enhancing high-rate cycling capability of sodium-ion batteries at high temperatures through cathode structural design and modulation","authors":"Yiju Song, Hao Cui, Yixiu Gan, Wei Gao","doi":"10.1016/j.ensm.2025.104178","DOIUrl":"10.1016/j.ensm.2025.104178","url":null,"abstract":"<div><div>Sodium-ion batteries (SIBs), as a promising energy storage technology, offer the advantages of cost-effectiveness and abundance of source materials. However, insufficient thermal stability at elevated temperatures remains a significant challenge for their commercialization. This study aims to enhance the high-temperature thermal stability of SIBs cathode materials through rational structural design and ion doping strategies. The gradient-directed diffusion technique optimizes the calcination process, adjusting the concentration gradient distribution within the material. This approach increases sodium layer spacing and cell volume, improving thermal stability and electrode kinetics under high-rate cycling conditions. On this basis, a copper-iron dual doping strategy is applied further to enhance the cathode's crystal structure and electrical conductivity, reducing side reactions with the electrolyte. Experimental results show that the optimized and doped P2-Na<sub>0.67</sub>Mn<sub>0.55</sub>Ni<sub>0.30</sub>Fe<sub>0.05</sub>Cu<sub>0.10</sub>O<sub>2</sub> materials exhibit excellent capacity retention at high temperatures, with 87.8% retention after 200 cycles at 10 C and 60°C in half-cell tests. In full-cell configurations, the materials retain 81.7% of their initial capacity after 100 cycles at 5 C and 60°C, while exhibiting near-zero strain characteristics (0.86%). The first principle calculations reveal that NMNCF-2 enhances electrical conductivity, sodium-ion migration rate, and cycling stability by narrowing the band gaps and reducing the migration energy barrier. These findings provide a robust solution for the high-temperature applications of SIBs, demonstrating the potential of structural optimization and ion doping to improve performance and safety significantly.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104178"},"PeriodicalIF":18.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660514","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}
Pub Date : 2025-03-18DOI: 10.1016/j.ensm.2025.104183
Haoruo Xiao, Chenrui Zeng, Fengxia Fan, Xinxiang Wang, Guilei Tian, Pengfei Liu, Shuhan Wang, Chuan Wang, Yan Huang, Yang Zhang, Chaozhu Shu
Recycling spent lithium-ion batteries through direct methods provides significant environmental and economic advantages compared to pyrometallurgical and hydrometallurgical approaches. In this research, we introduce a one-step, closed-loop approach for the direct regeneration of severely degraded lithium iron phosphate (LiFePO4, LFP) black mass, employing a low-temperature molten salt system. The binary molten lithium salts system of lithium iodide and lithium hydroxide enables Li+ to fully interact with delithiated LFP particles, thus overcoming the uneven repair issues associated with solid-state sintering methods. The reduction environment caused by the oxidation of I- to I2 significantly lowers the Li+ migration energy barrier to lithium vacancies and boosts the repair of Li/Fe anti-site defects at reduced temperature of 450 °C. In addition, a closed-loop regeneration system is established because the produced iodine can be collected through condensation for reuse in production. The regenerated LFP material exhibits a retention rate of 95.7 % in terms of capacity after 300 cycles at 1C. The regenerated LFP-based pouch cell (1Ah) demonstrates a capacity retention rate of 96.84 % after 300 charge-discharge cycles at 0.5C rate. Technical and economic evaluations reveal that this innovative regeneration approach holds significant potential for industrial implementation.
{"title":"A one-step low-temperature closed-loop eutectic salt strategy for direct regeneration of severely degraded LiFePO4","authors":"Haoruo Xiao, Chenrui Zeng, Fengxia Fan, Xinxiang Wang, Guilei Tian, Pengfei Liu, Shuhan Wang, Chuan Wang, Yan Huang, Yang Zhang, Chaozhu Shu","doi":"10.1016/j.ensm.2025.104183","DOIUrl":"10.1016/j.ensm.2025.104183","url":null,"abstract":"<div><div>Recycling spent lithium-ion batteries through direct methods provides significant environmental and economic advantages compared to pyrometallurgical and hydrometallurgical approaches. In this research, we introduce a one-step, closed-loop approach for the direct regeneration of severely degraded lithium iron phosphate (LiFePO<sub>4</sub>, LFP) black mass, employing a low-temperature molten salt system. The binary molten lithium salts system of lithium iodide and lithium hydroxide enables Li<sup>+</sup> to fully interact with delithiated LFP particles, thus overcoming the uneven repair issues associated with solid-state sintering methods. The reduction environment caused by the oxidation of I<sup>-</sup> to I<sub>2</sub> significantly lowers the Li<sup>+</sup> migration energy barrier to lithium vacancies and boosts the repair of Li/Fe anti-site defects at reduced temperature of 450 °C. In addition, a closed-loop regeneration system is established because the produced iodine can be collected through condensation for reuse in production. The regenerated LFP material exhibits a retention rate of 95.7 % in terms of capacity after 300 cycles at 1C. The regenerated LFP-based pouch cell (1Ah) demonstrates a capacity retention rate of 96.84 % after 300 charge-discharge cycles at 0.5C rate. Technical and economic evaluations reveal that this innovative regeneration approach holds significant potential for industrial implementation.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104183"},"PeriodicalIF":18.9,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640941","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}
Pub Date : 2025-03-18DOI: 10.1016/j.ensm.2025.104176
Jianing Qi , Yang Feng , Jiangtao Yu , Huili Wang , Zhonghan Wu , Jiahua Zhao , Ying Jiang , Jing Liu , Yixin Li , Limin Zhou , Kai Zhang , Jun Chen
Anode-free lithium batteries (AFLBs) directly utilize current collectors (CCs) as the lithium-deposition substrates to achieve maximum energy density and minimum lithium redundancy. However, without Li compensation from the anode, the loss of active lithium is sharply intensified due to the generation of dead lithium and the side reactions between the electrolyte and electrode, resulting in a rapid decline in capacity and poor cycling stability. Herein, a wave-like Cu substrate with highly (100)-preferential orientation (wCu(100)-H) is proposed as the sustainable CC for AFLBs, which displays a gradient {100} texture component from valleys (96.8 %) to peaks (47.1 %). Specifically, the periodic micro-valley structure with an enlarged surface area suppresses Li dendrite growth by reducing the local current density. Moreover, the gradient distribution of the Cu(100) facet achieves a spatially oriented Li deposition pattern. As a result, the anode-free LiFePO4-based and LiNi0.8Co0.1Mn0.1O2-based full cells exhibit remarkable capacity retentions of 87 % (120 cycles) and 77 % (110 cycles), respectively. The successful construction of the wCu(100)-H provides a fresh insight into the exquisite modification of CC and a significant step toward realizing high-performance AFLBs.
{"title":"Wave-like Cu substrate with gradient {100} texture for anode-free lithium batteries","authors":"Jianing Qi , Yang Feng , Jiangtao Yu , Huili Wang , Zhonghan Wu , Jiahua Zhao , Ying Jiang , Jing Liu , Yixin Li , Limin Zhou , Kai Zhang , Jun Chen","doi":"10.1016/j.ensm.2025.104176","DOIUrl":"10.1016/j.ensm.2025.104176","url":null,"abstract":"<div><div>Anode-free lithium batteries (AFLBs) directly utilize current collectors (CCs) as the lithium-deposition substrates to achieve maximum energy density and minimum lithium redundancy. However, without Li compensation from the anode, the loss of active lithium is sharply intensified due to the generation of dead lithium and the side reactions between the electrolyte and electrode, resulting in a rapid decline in capacity and poor cycling stability. Herein, a wave-like Cu substrate with highly (100)-preferential orientation (wCu(100)-H) is proposed as the sustainable CC for AFLBs, which displays a gradient {100} texture component from valleys (96.8 %) to peaks (47.1 %). Specifically, the periodic micro-valley structure with an enlarged surface area suppresses Li dendrite growth by reducing the local current density. Moreover, the gradient distribution of the Cu(100) facet achieves a spatially oriented Li deposition pattern. As a result, the anode-free LiFePO<sub>4</sub>-based and LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub>-based full cells exhibit remarkable capacity retentions of 87 % (120 cycles) and 77 % (110 cycles), respectively. The successful construction of the wCu(100)-H provides a fresh insight into the exquisite modification of CC and a significant step toward realizing high-performance AFLBs.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104176"},"PeriodicalIF":18.9,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654117","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}
Pub Date : 2025-03-18DOI: 10.1016/j.ensm.2025.104190
Eugene Engmann, Pete Barnes, Eric J. Dufek, Abderrahman Atifi
The early detection of secondary reactions that affect the life and performance of zinc manganese oxide batteries requires a shift from conventional time-consuming and often destructive procedures to rapid lifetime-predictive techniques. In this work, an electrochemical approach is employed to elucidate independent signatures for four common types of failure mechanisms in zinc manganese dioxide (Zn||MnO2) batteries—namely, the loss of zinc inventory, the loss of active material at the cathode, electrolyte depletion, and increased cell impedance. Our findings, specific to coin cell configurations, reveal that each induced failure mechanism can be distinctively modeled and identified based on responses from the rest voltage and columbic-efficiency data for prompt detection. For instance, electrolyte depletion response manifests a distinctive abrupt (>80 %) decrease in columbic efficiency (CE) and charge-rest voltage (Vc) while the discharge-rest voltage remained constant at ∼1.3 V. Furthermore, electrolyte rejuvenation of the cell increased the CE to >95 % and restored Vc from ∼0.3 to >1.7 V. Recovery experiments and reference performance tests demonstrated consistency between electrochemical descriptors and their associated failure mechanisms. The outcomes of this work provide valuable insights and data models for some of the dominant failure mechanisms present in zinc manganese battery chemistries, which are beneficial to accelerated early-lifetime diagnosis and advancement of Zn batteries development.
{"title":"Non-destructive electrochemical diagnosis of failure mechanisms in aqueous zinc batteries","authors":"Eugene Engmann, Pete Barnes, Eric J. Dufek, Abderrahman Atifi","doi":"10.1016/j.ensm.2025.104190","DOIUrl":"10.1016/j.ensm.2025.104190","url":null,"abstract":"<div><div>The early detection of secondary reactions that affect the life and performance of zinc manganese oxide batteries requires a shift from conventional time-consuming and often destructive procedures to rapid lifetime-predictive techniques. In this work, an electrochemical approach is employed to elucidate independent signatures for four common types of failure mechanisms in zinc manganese dioxide (Zn||MnO<sub>2</sub>) batteries—namely, the loss of zinc inventory, the loss of active material at the cathode, electrolyte depletion, and increased cell impedance. Our findings, specific to coin cell configurations, reveal that each induced failure mechanism can be distinctively modeled and identified based on responses from the rest voltage and columbic-efficiency data for prompt detection. For instance, electrolyte depletion response manifests a distinctive abrupt (>80 %) decrease in columbic efficiency (CE) and charge-rest voltage (V<sub>c</sub>) while the discharge-rest voltage remained constant at ∼1.3 V. Furthermore, electrolyte rejuvenation of the cell increased the CE to >95 % and restored V<sub>c</sub> from ∼0.3 to >1.7 V. Recovery experiments and reference performance tests demonstrated consistency between electrochemical descriptors and their associated failure mechanisms. The outcomes of this work provide valuable insights and data models for some of the dominant failure mechanisms present in zinc manganese battery chemistries, which are beneficial to accelerated early-lifetime diagnosis and advancement of Zn batteries development.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104190"},"PeriodicalIF":18.9,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654100","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}
Pub Date : 2025-03-17DOI: 10.1016/j.ensm.2025.104157
Yu Wang , Weijie Chen , Yu Du , Yan Zhao , Yulin Chen , Zhuang Lv , Liu Wang , Jingli Shi , Gan Qu
The microenvironment of nitrogen-coordinated single metal (M−Nx) sites significantly impacts the electronic properties and the kinetics of sulfur species in lithium−sulfur (Li−S) batteries. However, accurately designing the M−Nx materials remains challenging, which is crucial for investigating the structure-function relationship and developing high-performance electrocatalysts. Compared with the traditional pyrolyzed M−Nx catalysts, the single-atom metal sites with precise microenvironment can be fabricated with molecularly dispersed MPc loaded on matrix. Herein, we modulate the d-band electronic states by tailoring the molecularly dispersed iron phthalocyanine (FePc) by means of donating/withdrawing (tetraamino, TA/tetranitro, TN) groups with amino-functionalized carbon nanotube (ACNT) as matrix. The static and dynamic properties between FePc derivatives and LiPSs are investigated by in-situ Raman spectra and quasi-in-situ XPS methods. Density functional theory (DFT) calculations further reveal the enhanced orbital hybridization of 3dπ-2px/y between Fe and S for FeTNPc@ACNT, which improves the reduction of long-chain polysulfides and the dissociation of Li2S. Consequently, cells with FeTNPc@ACNT exhibit a high specific capacity of 1000.9 mA h g−1 at 2 C, along with a decay rate of 0.041% after 1000 cycles. This study uncovers that peripheral ligand structure regulation selectively steers the redox kinetics in Li−S batteries.
氮配位单金属（M-Nx）位点的微环境对锂硫（Li-S）电池中硫物种的电子特性和动力学有重大影响。然而，精确设计 M-Nx 材料仍然具有挑战性，这对于研究结构-功能关系和开发高性能电催化剂至关重要。与传统的热解 M-Nx 催化剂相比，在基质上负载分子分散的 MPc 可以制造出具有精确微环境的单原子金属位点。在此，我们以氨基功能化碳纳米管（ACNT）为基质，通过捐献/抽取（四氨基 TA/四硝基 TN）基团来定制分子分散的铁酞菁（FePc），从而调节 d 波段电子状态。通过原位拉曼光谱和准原位 XPS 方法研究了 FePc 衍生物与 LiPS 之间的静态和动态特性。密度泛函理论（DFT）计算进一步揭示了 FeTNPc@ACNT 中 Fe 和 S 之间 3dπ-2px/y 的轨道杂化增强，从而改善了长链多硫化物的还原和 Li2S 的解离。因此，含有 FeTNPc@ACNT 的电池在 2 C 条件下显示出 1000.9 mA h g-1 的高比容量，1000 次循环后的衰减率为 0.041%。这项研究发现，外围配体结构调节可选择性地引导锂-S 电池的氧化还原动力学。
{"title":"Fundamental mechanistic insights on the peripherally substituted iron phthalocyanine selectively catalyzing the sulfur redox reactions","authors":"Yu Wang , Weijie Chen , Yu Du , Yan Zhao , Yulin Chen , Zhuang Lv , Liu Wang , Jingli Shi , Gan Qu","doi":"10.1016/j.ensm.2025.104157","DOIUrl":"10.1016/j.ensm.2025.104157","url":null,"abstract":"<div><div>The microenvironment of nitrogen-coordinated single metal (M−N<sub>x</sub>) sites significantly impacts the electronic properties and the kinetics of sulfur species in lithium−sulfur (Li−S) batteries. However, accurately designing the M−N<sub>x</sub> materials remains challenging, which is crucial for investigating the structure-function relationship and developing high-performance electrocatalysts. Compared with the traditional pyrolyzed M−N<sub>x</sub> catalysts, the single-atom metal sites with precise microenvironment can be fabricated with molecularly dispersed MPc loaded on matrix. Herein, we modulate the d-band electronic states by tailoring the molecularly dispersed iron phthalocyanine (FePc) by means of donating/withdrawing (tetraamino, TA/tetranitro, TN) groups with amino-functionalized carbon nanotube (ACNT) as matrix. The static and dynamic properties between FePc derivatives and LiPSs are investigated by in-situ Raman spectra and quasi-in-situ XPS methods. Density functional theory (DFT) calculations further reveal the enhanced orbital hybridization of 3d<sub>π</sub>-2p<sub>x/y</sub> between Fe and S for FeTNPc@ACNT, which improves the reduction of long-chain polysulfides and the dissociation of Li<sub>2</sub>S. Consequently, cells with FeTNPc@ACNT exhibit a high specific capacity of 1000.9 mA h g<sup>−1</sup> at 2 C, along with a decay rate of 0.041% after 1000 cycles. This study uncovers that peripheral ligand structure regulation selectively steers the redox kinetics in Li−S <em>bat</em>teries.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104157"},"PeriodicalIF":18.9,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635648","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}
Pub Date : 2025-03-17DOI: 10.1016/j.ensm.2025.104189
Zhibin Xu , Bo Liu , Xuanwei Yin , Xin Lei , Ya Zhou , Hongge Pan , Daping He , Gongming Wang
Aqueous Zn metal batteries (AZBs) hold significant promise for grid-level energy storage, yet their commercial viability is hindered by surface passivation of Zn anodes in humid air and aqueous electrolytes. Aiming at this issue, we present a novel self-deprotonation electrolyte additive, pyridinium (PyH+), which resolves passivation issues through gradually releasing protons and creating a H₂O-lean microenvironment through adsorption. With the PyH+ additive, commercial Zn anodes without pretreatment achieve lifespans exceeding 4600 h in Zn//Zn coin cells and 800 h in 25 cm² Zn//Zn pouch cells at 1 mA cm−2, compared to only 360 h and 100 h in PyH+-free electrolyte, respectively. Attractively, we demonstrate that such self-deprotonation strategy can be extended to other protonated N-containing heterocyclic compounds, which display universial anti-passivation effects as electrolyte additives. This work provides a promising approach for the anti-passivation of commercial Zn anodes to achieve long-lasting and large-scale AZBs.
{"title":"Anti-passivation of commercial Zn anodes by self-deprotonation additives for aqueous Zn metal batteries","authors":"Zhibin Xu , Bo Liu , Xuanwei Yin , Xin Lei , Ya Zhou , Hongge Pan , Daping He , Gongming Wang","doi":"10.1016/j.ensm.2025.104189","DOIUrl":"10.1016/j.ensm.2025.104189","url":null,"abstract":"<div><div>Aqueous Zn metal batteries (AZBs) hold significant promise for grid-level energy storage, yet their commercial viability is hindered by surface passivation of Zn anodes in humid air and aqueous electrolytes. Aiming at this issue, we present a novel self-deprotonation electrolyte additive, pyridinium (PyH<sup>+</sup>), which resolves passivation issues through gradually releasing protons and creating a H₂O-lean microenvironment through adsorption. With the PyH<sup>+</sup> additive, commercial Zn anodes without pretreatment achieve lifespans exceeding 4600 h in Zn//Zn coin cells and 800 h in 25 cm² Zn//Zn pouch cells at 1 mA cm<sup>−2</sup>, compared to only 360 h and 100 h in PyH<sup>+</sup>-free electrolyte, respectively. Attractively, we demonstrate that such self-deprotonation strategy can be extended to other protonated N-containing heterocyclic compounds, which display universial anti-passivation effects as electrolyte additives. This work provides a promising approach for the anti-passivation of commercial Zn anodes to achieve long-lasting and large-scale AZBs.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104189"},"PeriodicalIF":18.9,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640939","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}
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