Pub Date : 2025-04-22DOI: 10.1016/j.ensm.2025.104274
Cheng Lu, Liangming Wei, Jinjin Li
In the current era, against the backdrop of a vast array of energy storage batteries emerging in the historical stream, as we look back upon the evolution of aluminum-ion batteries (AIBs) over the past decade, a fundamental query emerges: Are they truly capable of carving out a substantial niche within the realm of energy storage? We present a comprehensive and systematic review of the development process, basic physical and chemical properties, electrochemistry, and failure mechanisms of electrolytes and negative electrode materials for non-aqueous aluminum ion batteries (NAAIBs) and aqueous aluminum ion batteries (AAIBs). We believe that AAIBs hold a more promising future through comparing the advantages and disadvantages of the two battery types. We focus on reviewing hydrated eutectic electrolytes, aluminum-zinc alloy negative electrodes, and negative electrode-free energy storage schemes of AAIBs. We aim to anticipate future inhibition strategies for anodic parasitic reactions (including hydrogen evolution reactions, dendrite growth, and surface passivation) to develop advanced AIBs with high energy density, long cycle life, and cost effectiveness.
{"title":"Aluminum Ion Batteries: Electrolyte and Anode Innovations and Outlook","authors":"Cheng Lu, Liangming Wei, Jinjin Li","doi":"10.1016/j.ensm.2025.104274","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104274","url":null,"abstract":"In the current era, against the backdrop of a vast array of energy storage batteries emerging in the historical stream, as we look back upon the evolution of aluminum-ion batteries (AIBs) over the past decade, a fundamental query emerges: Are they truly capable of carving out a substantial niche within the realm of energy storage? We present a comprehensive and systematic review of the development process, basic physical and chemical properties, electrochemistry, and failure mechanisms of electrolytes and negative electrode materials for non-aqueous aluminum ion batteries (NAAIBs) and aqueous aluminum ion batteries (AAIBs). We believe that AAIBs hold a more promising future through comparing the advantages and disadvantages of the two battery types. We focus on reviewing hydrated eutectic electrolytes, aluminum-zinc alloy negative electrodes, and negative electrode-free energy storage schemes of AAIBs. We aim to anticipate future inhibition strategies for anodic parasitic reactions (including hydrogen evolution reactions, dendrite growth, and surface passivation) to develop advanced AIBs with high energy density, long cycle life, and cost effectiveness.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"7 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858174","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 : 2025-04-21DOI: 10.1016/j.ensm.2025.104273
Lei Zhao, Congcong Zhu, Jiale Ji, Mengyuan Li, Zhongyi Kou, Wenzhu Li, Fengshi Cai, Libei Yuan
Air self-charging aqueous Zn-ion batteries (AZBs) integrating advantages of aqueous batteries and self-charging have attracted significant attention. However, they suffer from the time-consuming cathodic self-charging process and low capacity, limiting their real application. Herein, we report a donor-acceptor typed covalent organic framework incorporating naphthalenediimide and triphenylamine units (NT-COF) as an advanced cathode for self-charging AZBs. NT-COF features a porous structure with abundant redox-active sites and a narrow bandgap, which significantly boosts electron/ion transport properties and O2 diffusion. Upon exposure to air, the OCV of Zn//NT-COF battery rapidly increases from 0.2 to 1.03 V within 1 min, followed by a gradual rise to 1.25 V within 1 h. The battery also shows a 100% self-charging efficiency even under a low current density of 0.5 A g−1, while maintaining a stable average discharge capacity of 109.4 mAh g−1 at 0.2 A g−1 after 1 h of self-charging upon cycling. Despite self-charging and galvanostatic charging modes, Zn//NT-COF batteries exhibit high performance in hybrid configurations. Experimental and stimulation results reveal the NT-COF cathode experiences the co-insertion of Zn2+/H+ with H+ ions playing a dominant role. The rapid kinetics of H+ removal during the air-oxidation process are critical in enabling the ultrafast air self-charging capability of Zn//NT-COF batteries. This study advances the development of sustainable and efficient self-powered devices.
{"title":"Advanced Self-Charging Aqueous Battery with Rapid Charging Capability and a High Open-Circuit Voltage","authors":"Lei Zhao, Congcong Zhu, Jiale Ji, Mengyuan Li, Zhongyi Kou, Wenzhu Li, Fengshi Cai, Libei Yuan","doi":"10.1016/j.ensm.2025.104273","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104273","url":null,"abstract":"Air self-charging aqueous Zn-ion batteries (AZBs) integrating advantages of aqueous batteries and self-charging have attracted significant attention. However, they suffer from the time-consuming cathodic self-charging process and low capacity, limiting their real application. Herein, we report a donor-acceptor typed covalent organic framework incorporating naphthalenediimide and triphenylamine units (NT-COF) as an advanced cathode for self-charging AZBs. NT-COF features a porous structure with abundant redox-active sites and a narrow bandgap, which significantly boosts electron/ion transport properties and O<sub>2</sub> diffusion. Upon exposure to air, the OCV of Zn//NT-COF battery rapidly increases from 0.2 to 1.03 V within 1 min, followed by a gradual rise to 1.25 V within 1 h. The battery also shows a 100% self-charging efficiency even under a low current density of 0.5 A g<sup>−1</sup>, while maintaining a stable average discharge capacity of 109.4 mAh g<sup>−1</sup> at 0.2 A g<sup>−1</sup> after 1 h of self-charging upon cycling. Despite self-charging and galvanostatic charging modes, Zn//NT-COF batteries exhibit high performance in hybrid configurations. Experimental and stimulation results reveal the NT-COF cathode experiences the co-insertion of Zn<sup>2+</sup>/H<sup>+</sup> with H<sup>+</sup> ions playing a dominant role. The rapid kinetics of H<sup>+</sup> removal during the air-oxidation process are critical in enabling the ultrafast air self-charging capability of Zn//NT-COF batteries. This study advances the development of sustainable and efficient self-powered devices.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"219 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858175","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}
Surface chemistry instability of Ni-rich layered oxides triggers rapid performance degradation and severe safety concerns of Li-ion batteries. Herein we report a transformative approach using free-radical reaction to in-situ build protective conductive carbon frameworks within the surface intergranular of layered oxide cathodes. Typically, a mild reaction between carbon tetrachloride (CCl4) and N,N-dimethylformamide (DMF) at 200°C achieves the direct deposition of amorphous carbon within surface intergranular of LiNi0.8Co0.1Mn0.1O2, forming dense protective layers and conductive highways, and also eliminating surface residual alkalis and other impurities. With the enhancement in the surface phase purity, chemistry stability and electrical properties, this cathode surface architecture enables much improved electrochemical performance, exhibiting high cycling retention of 87.7% after 100 cycles at 0.1 C and 82.5% after 150 cycles at 1.0 C in 2.80-4.35 V. Notably, the present synthetic methodology provides an efficient carbonaceous modification method for Ni-rich layered oxides, overcoming major constraints of traditional thermal carbonization coating technologies. It may shift the design paradigm of carbothermic sensitive metal oxide materials. Moreover, this facile and scalable fabrication strategy makes them potentially viable for commercialization in Li-ion batteries.
富镍层状氧化物的表面化学性质不稳定会导致锂离子电池性能迅速下降，并引发严重的安全问题。在此，我们报告了一种利用自由基反应在层状氧化物阴极表面晶间原位构建保护性导电碳框架的变革性方法。通常情况下，四氯化碳（CCl4）和 N,N-二甲基甲酰胺（DMF）在 200°C 温度下发生温和反应，在 LiNi0.8Co0.1Mn0.1O2 表面晶间直接沉积无定形碳，形成致密的保护层和导电高速公路，同时消除表面残留的碱和其他杂质。随着表面相纯度、化学稳定性和电性能的提高，这种阴极表面结构大大改善了电化学性能，在 2.80-4.35 V 的电压下，0.1 C 条件下循环 100 次后的循环保持率高达 87.7%，1.0 C 条件下循环 150 次后的循环保持率高达 82.5%。值得注意的是，本合成方法为富镍层状氧化物提供了一种高效的碳质改性方法，克服了传统热碳化涂层技术的主要限制。它可能会改变对碳化热敏感的金属氧化物材料的设计模式。此外，这种简便且可扩展的制造策略使它们有可能在锂离子电池中实现商业化。
{"title":"In-Situ Constructing Surface Intergranular Carbonaceous Conductive Frameworks and Protective Layers of Ni-Rich Layered Oxide Cathodes","authors":"Mohan Yang, Silong Zhao, Penghui Guo, Mokai Cui, Hanlou Li, Meng Wang, Jing Wang, Feng Wu, Guoqiang Tan","doi":"10.1016/j.ensm.2025.104272","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104272","url":null,"abstract":"Surface chemistry instability of Ni-rich layered oxides triggers rapid performance degradation and severe safety concerns of Li-ion batteries. Herein we report a transformative approach using free-radical reaction to in-situ build protective conductive carbon frameworks within the surface intergranular of layered oxide cathodes. Typically, a mild reaction between carbon tetrachloride (CCl<sub>4</sub>) and <em>N,N</em>-dimethylformamide (DMF) at 200°C achieves the direct deposition of amorphous carbon within surface intergranular of LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub>, forming dense protective layers and conductive highways, and also eliminating surface residual alkalis and other impurities. With the enhancement in the surface phase purity, chemistry stability and electrical properties, this cathode surface architecture enables much improved electrochemical performance, exhibiting high cycling retention of 87.7% after 100 cycles at 0.1 C and 82.5% after 150 cycles at 1.0 C in 2.80-4.35 V. Notably, the present synthetic methodology provides an efficient carbonaceous modification method for Ni-rich layered oxides, overcoming major constraints of traditional thermal carbonization coating technologies. It may shift the design paradigm of carbothermic sensitive metal oxide materials. Moreover, this facile and scalable fabrication strategy makes them potentially viable for commercialization in Li-ion batteries.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"2 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853742","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 : 2025-04-19DOI: 10.1016/j.ensm.2025.104264
Lipu Sun, Nan Chen, Yifan Li, Jianing Tian, Binbin Yang, Ziyi Chen, Nuo Chen, Feng Wu, Yuejiao Li, Renjie Chen
To achieve a battery system with an high energy density, it is crucial to utilize a highly reversible lithium metal anode and a high-voltage cathode. However, conventional electrolytes usually exhibit insufficient thermodynamic stability, leading to aggressive lithium dendrites growth and severe cathode-electrolyte reactions, particularly at high voltage (≥ 4.5 V vs. Li/Li+). Herein, we propose a design strategy for a strong association electrolyte (SAE) that reduces Li+-solvent coordination number, facilitating the formation of ion pairs or ion clusters, even with conventional lithium salt concentrations (1 M). Lithium salts with high cluster formation constant (KA), such as lithium difluorophosphate (LiDFP) and lithium nitrate (LiNO3), create an SAE with anion-dominated solvation structure, which promotes the formation of aggregates (AGGs) solvate species. This unique solvation structure facilitates the formation of a dense, inorgain rich solid electrolyte interphase (SEI) on lithium metal anode. Additionally, the preferential adsorption of anion clusters at the cathode interface constructs a Li+-anions enriched double electric layer (EDL), stabilizing the LiNi0.8Co0.1Mn0.1O2 (NCM811) interface. The Li||NCM811 batteries with a 4.5 V high cut-off voltage achieved stable cycling over 1400 cycles with a capacity retention rate of 84%. Furthermore, 2.5 Ah pouch cells demonstrate superior cycle performance at 4.3 V cut-off voltage and 0.6 A/3 A charge/discharge currents. These findings present a straightforward electrolyte design strategy that contrasts with conventional approaches, which typically rely on increasing salt concentration or introducing complex additives, to promote the practical applications of high energy density lithium metal batteries (LMBs).
{"title":"Strong association dual lithium salts for ether-based electrolyte enable 4.5 V high-voltage lithium metal battery","authors":"Lipu Sun, Nan Chen, Yifan Li, Jianing Tian, Binbin Yang, Ziyi Chen, Nuo Chen, Feng Wu, Yuejiao Li, Renjie Chen","doi":"10.1016/j.ensm.2025.104264","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104264","url":null,"abstract":"To achieve a battery system with an high energy density, it is crucial to utilize a highly reversible lithium metal anode and a high-voltage cathode. However, conventional electrolytes usually exhibit insufficient thermodynamic stability, leading to aggressive lithium dendrites growth and severe cathode-electrolyte reactions, particularly at high voltage (≥ 4.5 V vs. Li/Li<sup>+</sup>). Herein, we propose a design strategy for a strong association electrolyte (SAE) that reduces Li<sup>+</sup>-solvent coordination number, facilitating the formation of ion pairs or ion clusters, even with conventional lithium salt concentrations (1 M). Lithium salts with high cluster formation constant (K<sub>A</sub>), such as lithium difluorophosphate (LiDFP) and lithium nitrate (LiNO<sub>3</sub>), create an SAE with anion-dominated solvation structure, which promotes the formation of aggregates (AGGs) solvate species. This unique solvation structure facilitates the formation of a dense, inorgain rich solid electrolyte interphase (SEI) on lithium metal anode. Additionally, the preferential adsorption of anion clusters at the cathode interface constructs a Li<sup>+</sup>-anions enriched double electric layer (EDL), stabilizing the LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> (NCM811) interface. The Li||NCM811 batteries with a 4.5 V high cut-off voltage achieved stable cycling over 1400 cycles with a capacity retention rate of 84%. Furthermore, 2.5 Ah pouch cells demonstrate superior cycle performance at 4.3 V cut-off voltage and 0.6 A/3 A charge/discharge currents. These findings present a straightforward electrolyte design strategy that contrasts with conventional approaches, which typically rely on increasing salt concentration or introducing complex additives, to promote the practical applications of high energy density lithium metal batteries (LMBs).","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"41 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849417","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 : 2025-04-19DOI: 10.1016/j.ensm.2025.104269
Yifan Gao, Weiyin Chen, Jin-Sung Park, Hui Xu, Tao Dai, Xia Huang, Ju Li
The growing use of lithium iron phosphate (LiFePO4, LFP) batteries in electric vehicles and energy storage systems highlights the urgent need for efficient and sustainable recycling methods. Direct recovery technologies show promise but often require supplementary lithium chemicals. This study introduces a novel thick electrode system for the electrochemical relithiation of spent LFP battery powder, utilizing residual lithium from low-grade Black Mass. Unlike previous regeneration techniques, this method eliminates the need for external lithium sources beyond the spent battery powder and the minimal amount of aqueous electrolyte. Our approach overcomes the limitations of traditional electrochemical relithiation by directly processing the spent battery powder without binder, enhancing both industrial scalability and processing capacity. The thick electrode system significantly improves powder recovery capacity, achieving 405 g h−1 m−2 with low energy consumption (9.3 kWh t−1), and demonstrates excellent performance under constant current relithiation. Ecological and economic assessments reveal considerable reductions in the recycling cost and environmental impact.
{"title":"Thick electrodes for electrochemical relithiation to regenerate spent battery powder","authors":"Yifan Gao, Weiyin Chen, Jin-Sung Park, Hui Xu, Tao Dai, Xia Huang, Ju Li","doi":"10.1016/j.ensm.2025.104269","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104269","url":null,"abstract":"The growing use of lithium iron phosphate (LiFePO<sub>4</sub>, LFP) batteries in electric vehicles and energy storage systems highlights the urgent need for efficient and sustainable recycling methods. Direct recovery technologies show promise but often require supplementary lithium chemicals. This study introduces a novel thick electrode system for the electrochemical relithiation of spent LFP battery powder, utilizing residual lithium from low-grade Black Mass. Unlike previous regeneration techniques, this method eliminates the need for external lithium sources beyond the spent battery powder and the minimal amount of aqueous electrolyte. Our approach overcomes the limitations of traditional electrochemical relithiation by directly processing the spent battery powder without binder, enhancing both industrial scalability and processing capacity. The thick electrode system significantly improves powder recovery capacity, achieving 405 g h<sup>−1</sup> m<sup>−2</sup> with low energy consumption (9.3 kWh t<sup>−1</sup>), and demonstrates excellent performance under constant current relithiation. Ecological and economic assessments reveal considerable reductions in the recycling cost and environmental impact.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"17 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849419","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 : 2025-04-19DOI: 10.1016/j.ensm.2025.104271
Eunbin Park, Young-Hoon Lee, Sung-Ho Huh, June Huh, Yung-Eun Sung, Seung-Ho Yu
Lithium metal batteries are regarded as one of the most promising candidates for next-generation energy storage systems due to their high energy density. However, challenges such as lithium dendrite growth and poor cycling stability limit their practical application. Recent efforts focus on electrolyte additives to stabilize interphases and improve battery performance. In this study, we investigate the effect of a bifunctional additive, trimethylsilyl 2,2-difluoro-2-(fluorosulfonyl)acetate (TDFA), on lithium metal batteries, with a focus on its role in promoting uniform lithium deposition and enhancing interfacial stability. Surface analysis shows that the additive forms a LiF-rich solid-electrolyte interphase (SEI) layer, which is chemically stable and mechanically robust. Li/Li symmetric cells demonstrate that TDFA significantly reduces nucleation overpotential, suppresses dendrite formation, and extends cycling life over 500 hours at 1 mA cm-2 for 1 mAh cm-2. In Li/LFP cells, TDFA improves capacity retention to 89.4% after 300 cycles, with reduced polarization and enhanced rate performance. Additionally, XPS depth profiling confirms an F-rich cathode-electrolyte interphase (CEI) layer that mitigates crack formation on cathode and enhances cell durability. These findings suggest TDFA could play a critical role in advancing lithium metal batteries, offering enhanced electrochemical performance and long-term stability through improved SEI and CEI layer formation.
{"title":"Bifunctional trimethylsilyl-modified fluorinated ester additive for LiF-rich solid electrolyte interphase in lithium metal batteries","authors":"Eunbin Park, Young-Hoon Lee, Sung-Ho Huh, June Huh, Yung-Eun Sung, Seung-Ho Yu","doi":"10.1016/j.ensm.2025.104271","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104271","url":null,"abstract":"Lithium metal batteries are regarded as one of the most promising candidates for next-generation energy storage systems due to their high energy density. However, challenges such as lithium dendrite growth and poor cycling stability limit their practical application. Recent efforts focus on electrolyte additives to stabilize interphases and improve battery performance. In this study, we investigate the effect of a bifunctional additive, trimethylsilyl 2,2-difluoro-2-(fluorosulfonyl)acetate (TDFA), on lithium metal batteries, with a focus on its role in promoting uniform lithium deposition and enhancing interfacial stability. Surface analysis shows that the additive forms a LiF-rich solid-electrolyte interphase (SEI) layer, which is chemically stable and mechanically robust. Li/Li symmetric cells demonstrate that TDFA significantly reduces nucleation overpotential, suppresses dendrite formation, and extends cycling life over 500 hours at 1 mA cm<sup>-2</sup> for 1 mAh cm<sup>-2</sup>. In Li/LFP cells, TDFA improves capacity retention to 89.4% after 300 cycles, with reduced polarization and enhanced rate performance. Additionally, XPS depth profiling confirms an F-rich cathode-electrolyte interphase (CEI) layer that mitigates crack formation on cathode and enhances cell durability. These findings suggest TDFA could play a critical role in advancing lithium metal batteries, offering enhanced electrochemical performance and long-term stability through improved SEI and CEI layer formation.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"31 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849497","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}
Electrolyte engineering has emerged as a facile and efficient strategy to solve side reactions in aqueous Zn-I2 batteries. However, most of these solutions usually ignore the simultaneous modulation of the cathode and anode. Here, a multifunctional electrolyte additive, pyridoxine (VB6), enables simultaneous regulation of the anode and cathode in Zn-I2 batteries. For the cathode, VB6 preferentially coordinates with ions through Lewis acid-base effect, thereby suppressing the generation of polyiodides and the shuttle effect. For the anode, VB6 can not only significantly restrain the hydrogen evolution reaction (HER) and the pH fluctuation of the electrolyte through protonation, but also promote the fast de-solvation of Zn2+ and regulate the Zn deposition benefitting from its structure with multi-hydroxyl groups. Due to the synergistic effect of VB6, the modified symmetric Zn||Zn cell achieves a remarkable Coulombic efficiency (99.7%) over 1600 h and excellent cycling stability (2100 h). Most intriguingly, the Zn-I2 cell exhibits an ultra-long lifespan of 50000 cycles (> 6 months) at 2 A g-1 with an exceptional capacity retention of 84.3%. Even without pressurized equipment, the Zn-I2 pouch cell with VB6 still maintains prominent performance (76.5% capacity after 450 cycles) without swelling.
{"title":"Lewis Acid-Base Effect and Protonation in Electrolyte Engineering Enable Shuttle-Free, Dendrite-Free, and HER-Free Aqueous Zn-I2 Batteries","authors":"Xingxiu Yang, Long Zhang, Jinyao Zhu, Lequan Wang, Yixiang Zhang, Zhimin Zhai, Junming Kang, Yizhen Shao, Jiajia Zhang, Xianfu Zhang, Jia Guo, Yanglong Hou, Hongbin Lu","doi":"10.1016/j.ensm.2025.104268","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104268","url":null,"abstract":"Electrolyte engineering has emerged as a facile and efficient strategy to solve side reactions in aqueous Zn-I2 batteries. However, most of these solutions usually ignore the simultaneous modulation of the cathode and anode. Here, a multifunctional electrolyte additive, pyridoxine (VB6), enables simultaneous regulation of the anode and cathode in Zn-I2 batteries. For the cathode, VB6 preferentially coordinates with <span><span style=\"\"></span><span data-mathml='<math xmlns=\"http://www.w3.org/1998/Math/MathML\"><msup is=\"true\"><mrow is=\"true\"><mi mathvariant=\"normal\" is=\"true\">I</mi></mrow><mo is=\"true\">&#x2212;</mo></msup></math>' role=\"presentation\" style=\"font-size: 90%; display: inline-block; position: relative;\" tabindex=\"0\"><svg aria-hidden=\"true\" focusable=\"false\" height=\"2.317ex\" role=\"img\" style=\"vertical-align: -0.235ex;\" viewbox=\"0 -896.2 1012 997.6\" width=\"2.35ex\" xmlns:xlink=\"http://www.w3.org/1999/xlink\"><g fill=\"currentColor\" stroke=\"currentColor\" stroke-width=\"0\" transform=\"matrix(1 0 0 -1 0 0)\"><g is=\"true\"><g is=\"true\"><g is=\"true\"><use xlink:href=\"#MJMAIN-49\"></use></g></g><g is=\"true\" transform=\"translate(361,410)\"><use transform=\"scale(0.707)\" xlink:href=\"#MJMAIN-2212\"></use></g></g></g></svg><span role=\"presentation\"><math xmlns=\"http://www.w3.org/1998/Math/MathML\"><msup is=\"true\"><mrow is=\"true\"><mi is=\"true\" mathvariant=\"normal\">I</mi></mrow><mo is=\"true\">−</mo></msup></math></span></span><script type=\"math/mml\"><math><msup is=\"true\"><mrow is=\"true\"><mi mathvariant=\"normal\" is=\"true\">I</mi></mrow><mo is=\"true\">−</mo></msup></math></script></span> ions through Lewis acid-base effect, thereby suppressing the generation of polyiodides and the shuttle effect. For the anode, VB6 can not only significantly restrain the hydrogen evolution reaction (HER) and the pH fluctuation of the electrolyte through protonation, but also promote the fast de-solvation of Zn2+ and regulate the Zn deposition benefitting from its structure with multi-hydroxyl groups. Due to the synergistic effect of VB6, the modified symmetric Zn||Zn cell achieves a remarkable Coulombic efficiency (99.7%) over 1600 h and excellent cycling stability (2100 h). Most intriguingly, the Zn-I2 cell exhibits an ultra-long lifespan of 50000 cycles (> 6 months) at 2 A g-1 with an exceptional capacity retention of 84.3%. Even without pressurized equipment, the Zn-I2 pouch cell with VB6 still maintains prominent performance (76.5% capacity after 450 cycles) without swelling.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"11 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849418","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 : 2025-04-19DOI: 10.1016/j.ensm.2025.104270
Jin Kyo Koo, Jaejin Lim, Jeongmin Shin, Jae Kwon Seo, Chaeyeon Ha, Weerawat To A Ran, Jung-Hun Lee, Yewon Kwon, Yong Min Lee, Young-Jun Kim
As the electric vehicle market rapidly expands as an eco-friendly means of transportation, there is a growing demand for innovative manufacturing processes that achieve high energy density while being environmentally sustainable and energy-efficient. To address these challenges, we developed a cathode using a solvent-free electrode process with single-crystalline LiNi0.8Co0.15Al0.05O2 (SC-NCA), renowned for its mechanical robustness and high specific capacity. This process involves conformal layers of carbon nanotubes (CNTs) on SC-NCA particles, resulting in superior Li+/electronic conductivity along with a cathode active-material ratio of 99.6 wt.%, electrode density of 4.0 g cm−3, and volumetric capacity of 835 mAh cm−3. Furthermore, the 3D digital twin analysis of the dry electrode elucidated the key features responsible for its outstanding electrochemical performance with remarkable clarity. This novel combination of CNT wrapping with solvent-free electrode processing not only increases the energy density but also improves the industrial feasibility of solvent-free electrodes for commercial LIBs application.
{"title":"Dry-processed ultra-high-energy cathodes (99.6wt%, 4.0 g cm−3) using single-crystalline Ni-rich oxides","authors":"Jin Kyo Koo, Jaejin Lim, Jeongmin Shin, Jae Kwon Seo, Chaeyeon Ha, Weerawat To A Ran, Jung-Hun Lee, Yewon Kwon, Yong Min Lee, Young-Jun Kim","doi":"10.1016/j.ensm.2025.104270","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104270","url":null,"abstract":"As the electric vehicle market rapidly expands as an eco-friendly means of transportation, there is a growing demand for innovative manufacturing processes that achieve high energy density while being environmentally sustainable and energy-efficient. To address these challenges, we developed a cathode using a solvent-free electrode process with single-crystalline LiNi<sub>0.8</sub>Co<sub>0.15</sub>Al<sub>0.05</sub>O<sub>2</sub> (SC-NCA), renowned for its mechanical robustness and high specific capacity. This process involves conformal layers of carbon nanotubes (CNTs) on SC-NCA particles, resulting in superior Li<sup>+</sup>/electronic conductivity along with a cathode active-material ratio of 99.6 wt.%, electrode density of 4.0 g cm<sup>−3</sup>, and volumetric capacity of 835 mAh cm<sup>−3</sup>. Furthermore, the 3D digital twin analysis of the dry electrode elucidated the key features responsible for its outstanding electrochemical performance with remarkable clarity. This novel combination of CNT wrapping with solvent-free electrode processing not only increases the energy density but also improves the industrial feasibility of solvent-free electrodes for commercial LIBs application.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"23 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849420","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 : 2025-04-19DOI: 10.1016/j.ensm.2025.104267
Peng Zhang, Qingjuan Ren, Zhenlei Chen, Liang He, Pan Liu, Yujia Wang, Guang Feng, Zhiqiang Shi
Supercapacitors (SCs) are considered promising next-generation energy storage devices due to their high power density, fast charge / discharge capabilities and long cycle life. However, in traditional acetonitrile (ACN) -based electrolytes, the energy density of SCs is severely limited by the decomposition of ACN and its side reactions with activated carbon electrodes at high voltages. In this work, we report a localized high-concentration electrolyte (LHCE, 2 M spiro-(1,1′)-bipyrrolidinium bis(fluorosulfonyl)imide (SBP-FSI) / (ACN and fluorobenzene (FB)), with a molality ratio of 1: 3.38), which exhibits an exceptionally wide electrochemical stability window of 5.73 V. Molecular dynamics (MD) simulations of the planar graphene and slit-pore electrode system using constant potential method (CPM) reveal strong "SBP⁺ - ACN" and "FSI⁻ - ACN" solvation, along with the extensive adsorption of "inert" FB molecules onto the electrode surface. This forms a protective electric double layer (EDL) structure, effectively isolating ACN and enhancing voltage tolerance. Cylindrical SCs retained 88.7 % of its capacitance after 15,000 cycles at 3.2 V with the LHCE-2M electrolyte, closely matching the cycling stability of commercial cylindrical SCs at 2.7 V. These results highlight the improved electrochemical performance of the novel electrolyte formulation, offering a promising solution for next-generation high-voltage SCs.
{"title":"Modulating Solvation and Electric Double-Layer Configuration for High-Voltage Supercapacitors","authors":"Peng Zhang, Qingjuan Ren, Zhenlei Chen, Liang He, Pan Liu, Yujia Wang, Guang Feng, Zhiqiang Shi","doi":"10.1016/j.ensm.2025.104267","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104267","url":null,"abstract":"Supercapacitors (SCs) are considered promising next-generation energy storage devices due to their high power density, fast charge / discharge capabilities and long cycle life. However, in traditional acetonitrile (ACN) -based electrolytes, the energy density of SCs is severely limited by the decomposition of ACN and its side reactions with activated carbon electrodes at high voltages. In this work, we report a localized high-concentration electrolyte (LHCE, 2 M spiro-(1,1′)-bipyrrolidinium bis(fluorosulfonyl)imide (SBP-FSI) / (ACN and fluorobenzene (FB)), with a molality ratio of 1: 3.38), which exhibits an exceptionally wide electrochemical stability window of 5.73 V. Molecular dynamics (MD) simulations of the planar graphene and slit-pore electrode system using constant potential method (CPM) reveal strong \"SBP⁺ - ACN\" and \"FSI⁻ - ACN\" solvation, along with the extensive adsorption of \"inert\" FB molecules onto the electrode surface. This forms a protective electric double layer (EDL) structure, effectively isolating ACN and enhancing voltage tolerance. Cylindrical SCs retained 88.7 % of its capacitance after 15,000 cycles at 3.2 V with the LHCE-2M electrolyte, closely matching the cycling stability of commercial cylindrical SCs at 2.7 V. These results highlight the improved electrochemical performance of the novel electrolyte formulation, offering a promising solution for next-generation high-voltage SCs.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"17 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849454","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 : 2025-04-18DOI: 10.1016/j.ensm.2025.104266
Chao-Fan Wan , Zhong-Hui Shen , Jian-Yong Jiang , Jie Shen , Yang Shen , Ce-Wen Nan
Molecular engineering of polyimide (PI) has been an effective method for achieving high-performance polymer dielectrics with both good energy storage capability and enhanced thermal stability. However, the rational design of PI derivatives on demand remains a great challenge due to the complex and nonlinear structure-property relationships. To address this challenge, we developed an integrated framework that combines theoretical calculations, advanced molecular descriptors, and machine learning models to study the effect of molecular structures on five key properties of energy gap (Eg), lowest unoccupied molecular orbital (LUMO), dielectric constant (Dk), fractional free volume (FFV) and glass transition temperature (Tg). By employing Artificial Neural Network (ANN), the framework captured nonlinear dependencies between molecular structures and five properties, achieving the prediction accuracy of R2 > 0.90, far surpassing traditional linear models. Using a multi-objective optimization strategy to screen over 200,000 polyimide derivatives, eight optimal molecules with superior properties (e.g., Eg > 4.0 eV, Tg > 300 °C, and Dk > 3.3) were discovered with great potential for applications in high-temperature electrostatic energy storage. This study provides a robust, data-driven approach for multi-property optimization, bridging theoretical insights with machine learning to accelerate the design of advanced polymer dielectrics.
{"title":"Machine learning-accelerated discovery of polyimide derivatives for high-temperature electrostatic energy storage","authors":"Chao-Fan Wan , Zhong-Hui Shen , Jian-Yong Jiang , Jie Shen , Yang Shen , Ce-Wen Nan","doi":"10.1016/j.ensm.2025.104266","DOIUrl":"10.1016/j.ensm.2025.104266","url":null,"abstract":"<div><div>Molecular engineering of polyimide (PI) has been an effective method for achieving high-performance polymer dielectrics with both good energy storage capability and enhanced thermal stability. However, the rational design of PI derivatives on demand remains a great challenge due to the complex and nonlinear structure-property relationships. To address this challenge, we developed an integrated framework that combines theoretical calculations, advanced molecular descriptors, and machine learning models to study the effect of molecular structures on five key properties of energy gap (<em>E</em><sub>g</sub>), lowest unoccupied molecular orbital (LUMO), dielectric constant (<em>D</em><sub>k</sub>), fractional free volume (FFV) and glass transition temperature (<em>T</em><sub>g</sub>). By employing Artificial Neural Network (ANN), the framework captured nonlinear dependencies between molecular structures and five properties, achieving the prediction accuracy of <em>R</em><sup>2</sup> > 0.90, far surpassing traditional linear models. Using a multi-objective optimization strategy to screen over 200,000 polyimide derivatives, eight optimal molecules with superior properties (e.g., <em>E</em><sub>g</sub> > 4.0 eV, <em>T</em><sub>g</sub> > 300 °C, and <em>D</em><sub>k</sub> > 3.3) were discovered with great potential for applications in high-temperature electrostatic energy storage. This study provides a robust, data-driven approach for multi-property optimization, bridging theoretical insights with machine learning to accelerate the design of advanced polymer dielectrics.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"78 ","pages":"Article 104266"},"PeriodicalIF":18.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849455","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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