Pub Date : 2025-12-22DOI: 10.1016/j.ensm.2025.104832
Ryusei Kunisaki , Dengyao Yang , Motonori Watanabe , Jun Tae Song , Miki Inada , Tatsumi Ishihara
High-voltage sodium dual-ion batteries (SDIBs) are important from resource, energy, and cost, and for this SDIBs, electrolytes with wide electrochemical stability windows and balanced ion transport properties are strongly required. Here, we present the first time application of a highly concentrated sodium bis(fluorosulfonyl)imide (NaFSI) electrolyte in ethyl mesylate (EM) as the non-aqueous solvent. EM shows high stability to oxidation and achieved stable charge and discharge at potential higher than 5 V vs. Na/Na+, and SDIBs using EM-based electrolytes exhibited the superior capacity (111 mAh/g) and retention (98.2% after 600 cycles) and extended cycle life compared to the conventional carbonate systems. NMR and Raman spectroscopy revealed that EM strongly solvates Na+ ions even at high concentrations, suppressing excessive ion association and resulting in nearly ideal cation and anion transference numbers. The combination of high balanced cation and anion conductivity, along with robust electrochemical stability, provides a new design strategy for dual-ion battery electrolytes. These findings underscore the potential of highly concentrated sulfonate-based electrolytes for high-voltage SDIBs for the next generation, and offer fundamental insights into the relationship between solvent structure, ion solvation, and transport properties.
{"title":"Solvation structure design of high concentration sulfonate-based electrolyte for high performance sodium dual-ion batteries","authors":"Ryusei Kunisaki , Dengyao Yang , Motonori Watanabe , Jun Tae Song , Miki Inada , Tatsumi Ishihara","doi":"10.1016/j.ensm.2025.104832","DOIUrl":"10.1016/j.ensm.2025.104832","url":null,"abstract":"<div><div>High-voltage sodium dual-ion batteries (SDIBs) are important from resource, energy, and cost, and for this SDIBs, electrolytes with wide electrochemical stability windows and balanced ion transport properties are strongly required. Here, we present the first time application of a highly concentrated sodium bis(fluorosulfonyl)imide (NaFSI) electrolyte in ethyl mesylate (EM) as the non-aqueous solvent. EM shows high stability to oxidation and achieved stable charge and discharge at potential higher than 5 V vs. Na/Na<sup>+</sup>, and SDIBs using EM-based electrolytes exhibited the superior capacity (111 mAh/g) and retention (98.2% after 600 cycles) and extended cycle life compared to the conventional carbonate systems. NMR and Raman spectroscopy revealed that EM strongly solvates Na<sup>+</sup> ions even at high concentrations, suppressing excessive ion association and resulting in nearly ideal cation and anion transference numbers. The combination of high balanced cation and anion conductivity, along with robust electrochemical stability, provides a new design strategy for dual-ion battery electrolytes. These findings underscore the potential of highly concentrated sulfonate-based electrolytes for high-voltage SDIBs for the next generation, and offer fundamental insights into the relationship between solvent structure, ion solvation, and transport properties.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104832"},"PeriodicalIF":20.2,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145824023","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 : 2025-12-22DOI: 10.1016/j.ensm.2025.104831
Muhammad K. Majeed, Rashid Iqbal, M. Zeeshan Ashfaq, Muhammad Akram, M. Umar Majeed, Adil Saleem
The growing demand for safe, high-energy-density lithium-ion batteries (LIBs) in electric vehicles and portable electronics has spurred intensive research into solid polymer electrolytes (SPEs) as promising alternatives to conventional liquid electrolytes. Liquid electrolytes, though widely used, suffer from issues such as leakage, flammability, and dendrite growth, which limit the long-term safety and reliability of LIBs. All-solid polymer electrolytes (ASPEs) address these challenges by combining intrinsic safety with excellent mechanical flexibility, scalable processability, and compatibility with lithium metal anodes (LMA). In this review, we systematically summarize the latest advances in ASPEs based on diverse polymer systems, including polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF) and its copolymers, polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene glycol (PEG), polyurethane (PU), polysulfone (PSU), polysiloxane-based electrolytes, polyphosphazenes, and poly(ionic liquids) (PILs). We highlight their structural features, electrochemical properties, and modification strategies aimed at enhancing ionic conductivity, lithium-ion (Li+) transference number (tLi+), and interfacial stability. Particular emphasis is placed on hybrid and composite approaches, functional group engineering, and interfacial regulation techniques that balance ionic transport with mechanical and thermal robustness. Finally, we present a forward-looking perspective on future research opportunities, including the integration of self-healing functionalities, scalable synthesis methods, and advanced solid-state battery architectures. This comprehensive review aims to provide a roadmap for the rational design and application of ASPEs in next-generation lithium (Li) batteries.
{"title":"Advancing All-Solid Polymer Electrolytes for Lithium Batteries: From Molecular Design to Device Integration","authors":"Muhammad K. Majeed, Rashid Iqbal, M. Zeeshan Ashfaq, Muhammad Akram, M. Umar Majeed, Adil Saleem","doi":"10.1016/j.ensm.2025.104831","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104831","url":null,"abstract":"The growing demand for safe, high-energy-density lithium-ion batteries (LIBs) in electric vehicles and portable electronics has spurred intensive research into solid polymer electrolytes (SPEs) as promising alternatives to conventional liquid electrolytes. Liquid electrolytes, though widely used, suffer from issues such as leakage, flammability, and dendrite growth, which limit the long-term safety and reliability of LIBs. All-solid polymer electrolytes (ASPEs) address these challenges by combining intrinsic safety with excellent mechanical flexibility, scalable processability, and compatibility with lithium metal anodes (LMA). In this review, we systematically summarize the latest advances in ASPEs based on diverse polymer systems, including polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF) and its copolymers, polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene glycol (PEG), polyurethane (PU), polysulfone (PSU), polysiloxane-based electrolytes, polyphosphazenes, and poly(ionic liquids) (PILs). We highlight their structural features, electrochemical properties, and modification strategies aimed at enhancing ionic conductivity, lithium-ion (Li<sup>+</sup>) transference number (<em>t<sub>Li+</sub></em>), and interfacial stability. Particular emphasis is placed on hybrid and composite approaches, functional group engineering, and interfacial regulation techniques that balance ionic transport with mechanical and thermal robustness. Finally, we present a forward-looking perspective on future research opportunities, including the integration of self-healing functionalities, scalable synthesis methods, and advanced solid-state battery architectures. This comprehensive review aims to provide a roadmap for the rational design and application of ASPEs in next-generation lithium (Li) batteries.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"94 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813607","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 : 2025-12-21DOI: 10.1016/j.ensm.2025.104823
Ning Cao , Yang Zhang , Longfei Du , Xin Gu , Mingbo Wu
The rapid growth of electric vehicles (EVs) has greatly increased the demand for lithium-ion batteries (LIBs), leading to a rising volume of spent LIBs. Due to their valuable resources and potential environmental risks, managing spent LIBs has become a key focus. This review offers a thorough assessment of current end-of-life management strategies, with an emphasis on cascade utilization and recycling/regeneration methods. First, recent advancements in battery assessment and testing techniques related to cascade utilization are systematically summarized. Then, recycling and regeneration technologies are discussed, including pretreatment, pyrometallurgy, hydrometallurgy, and direct regeneration technology. Particular attention is given to how pretreatment impacts recycling efficiency, especially concerning emerging pretreatment strategy. Although most research has centered on recovering high-value metals like cobalt, recycling lithium—an essential yet less-explored component of LIBs—deserves more focus. Additionally, the practical application of recycling methods in industrial settings is examined. Finally, the review addresses major challenges and future directions for sustainable spent LIB management. The aim is to offer both theoretical insights and practical guidance to enhance LIBs recycling and support the development of a circular economy for metal resources.
{"title":"Sustainable management strategies for spent Li-ion batteries: cascade utilization, recycling, and regeneration","authors":"Ning Cao , Yang Zhang , Longfei Du , Xin Gu , Mingbo Wu","doi":"10.1016/j.ensm.2025.104823","DOIUrl":"10.1016/j.ensm.2025.104823","url":null,"abstract":"<div><div>The rapid growth of electric vehicles (EVs) has greatly increased the demand for lithium-ion batteries (LIBs), leading to a rising volume of spent LIBs. Due to their valuable resources and potential environmental risks, managing spent LIBs has become a key focus. This review offers a thorough assessment of current end-of-life management strategies, with an emphasis on cascade utilization and recycling/regeneration methods. First, recent advancements in battery assessment and testing techniques related to cascade utilization are systematically summarized. Then, recycling and regeneration technologies are discussed, including pretreatment, pyrometallurgy, hydrometallurgy, and direct regeneration technology. Particular attention is given to how pretreatment impacts recycling efficiency, especially concerning emerging pretreatment strategy. Although most research has centered on recovering high-value metals like cobalt, recycling lithium—an essential yet less-explored component of LIBs—deserves more focus. Additionally, the practical application of recycling methods in industrial settings is examined. Finally, the review addresses major challenges and future directions for sustainable spent LIB management. The aim is to offer both theoretical insights and practical guidance to enhance LIBs recycling and support the development of a circular economy for metal resources.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104823"},"PeriodicalIF":20.2,"publicationDate":"2025-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796166","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 : 2025-12-21DOI: 10.1016/j.ensm.2025.104829
Ming Jiang , Chengxiang Tian , Donghua Wang , Xiaochao Wu , Wensheng Yan , Chunguang Chen
Ni-rich layered cathodes suffer severe structural degradation and interfacial instability at high voltages (> 4.3 V), limiting their deployment in high-energy lithium-ion batteries. Herein, we design a mechanically stabilized Ni-rich cathode (MS-NCM) via a niobium-integrated architecture engineering strategy combining with particle refinement. This design synergistically mitigates structural degradation from three aspects: i) Mechanical reinforcement by elevating Young's modulus of MS-NCM particles suppresses anisotropic lattice strain during deep delithiation at high-voltage; ii) Concurrent surface Nb-doping expands the cathode lattice volume that accelerates Li⁺ diffusion, and thus enabling 20 C fast-charging; iii) Complementary interfacial stabilization via forming LiF-dominated CEI maintains minimal charge-transfer resistance fluctuation (ΔRct < 9 % over 100 cycles). Consequently, the MS-NCM exhibits 80.4 % capacity retention after 300 cycles at 4.6 V and 64.5 % retention under an extreme 20 C charge. In situ electrochemical EIS and XRD validates suppressed strain accumulation and impedance increase. This work establishes a multifunctional stabilization paradigm for Ni-rich cathodes under extreme conditions and offers mechanistic insights into structural evolution during deep delithiation at high-rate cycling.
{"title":"Mechanically stabilized Ni-rich cathode via niobium-integrated architecture engineering for high-voltage fast-charging lithium-ion batteries","authors":"Ming Jiang , Chengxiang Tian , Donghua Wang , Xiaochao Wu , Wensheng Yan , Chunguang Chen","doi":"10.1016/j.ensm.2025.104829","DOIUrl":"10.1016/j.ensm.2025.104829","url":null,"abstract":"<div><div>Ni-rich layered cathodes suffer severe structural degradation and interfacial instability at high voltages (> 4.3 V), limiting their deployment in high-energy lithium-ion batteries. Herein, we design a mechanically stabilized Ni-rich cathode (MS-NCM) via a niobium-integrated architecture engineering strategy combining with particle refinement. This design synergistically mitigates structural degradation from three aspects: i) Mechanical reinforcement by elevating Young's modulus of MS-NCM particles suppresses anisotropic lattice strain during deep delithiation at high-voltage; ii) Concurrent surface Nb-doping expands the cathode lattice volume that accelerates Li⁺ diffusion, and thus enabling 20 C fast-charging; iii) Complementary interfacial stabilization via forming LiF-dominated CEI maintains minimal charge-transfer resistance fluctuation (ΔR<sub>ct</sub> < 9 % over 100 cycles). Consequently, the MS-NCM exhibits 80.4 % capacity retention after 300 cycles at 4.6 V and 64.5 % retention under an extreme 20 C charge. In situ electrochemical EIS and XRD validates suppressed strain accumulation and impedance increase. This work establishes a multifunctional stabilization paradigm for Ni-rich cathodes under extreme conditions and offers mechanistic insights into structural evolution during deep delithiation at high-rate cycling.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104829"},"PeriodicalIF":20.2,"publicationDate":"2025-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813794","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 : 2025-12-20DOI: 10.1016/j.ensm.2025.104830
Fuming Wang , Huanyu Liang , Lei Shi , Dongqing Kong , Zhen Li , Hanrui Liu , Longlong Geng
Nickel-rich layered oxides are among the most promising cathode materials for high-energy lithium-ion batteries, yet their practical deployment is hindered by severe structural degradation and interfacial instability under high-voltage cycling. In this study, a synergistic cathode–electrolyte engineering (SCEE) strategy is proposed, integrating aluminum doping in the bulk lattice with a multicomponent electrolyte containing fluoroethylene carbonate (FEC), lithium difluoro(oxalato)borate (LiDFOB), and lithium tris(tert‑butoxy)aluminate (LTBA). The Al incorporation reduces cation mixing, stabilizes the layered framework, and enhances lithium-ion transport pathways. Meanwhile, the electrolyte additives undergo preferential decomposition at the cathode surface to construct a compact and inorganic-rich cathode–electrolyte interphase (CEI). This interphase effectively suppresses oxygen-related parasitic reactions, mitigates electrolyte breakdown, and relieves mechanical strain. Electrochemical testing demonstrates that the SCEE-modified system achieves superior cycling stability, higher capacity retention, and reduced polarization compared with the unmodified counterpart. In situ and ex situ characterizations reveal thinner reconstructed layers, fewer microcracks, and improved surface integrity after extended cycling. Complementary kinetic analyses confirm enhanced lithium-ion diffusion and diminished gas evolution. Theoretical calculations further show that Al doping raises oxygen vacancy formation energy, while finite-element simulations confirm more uniform lithium distribution and lower stress gradients. These results demonstrate that SCEE provides a rational and integrated pathway to balance high capacity with structural durability, offering valuable insights for the design of next-generation high-energy cathodes.
{"title":"One plus one can be greater than two: Synergistic cathode–electrolyte engineering for high-voltage Ni-Rich cathodes","authors":"Fuming Wang , Huanyu Liang , Lei Shi , Dongqing Kong , Zhen Li , Hanrui Liu , Longlong Geng","doi":"10.1016/j.ensm.2025.104830","DOIUrl":"10.1016/j.ensm.2025.104830","url":null,"abstract":"<div><div>Nickel-rich layered oxides are among the most promising cathode materials for high-energy lithium-ion batteries, yet their practical deployment is hindered by severe structural degradation and interfacial instability under high-voltage cycling. In this study, a synergistic cathode–electrolyte engineering (SCEE) strategy is proposed, integrating aluminum doping in the bulk lattice with a multicomponent electrolyte containing fluoroethylene carbonate (FEC), lithium difluoro(oxalato)borate (LiDFOB), and lithium tris(tert‑butoxy)aluminate (LTBA). The Al incorporation reduces cation mixing, stabilizes the layered framework, and enhances lithium-ion transport pathways. Meanwhile, the electrolyte additives undergo preferential decomposition at the cathode surface to construct a compact and inorganic-rich cathode–electrolyte interphase (CEI). This interphase effectively suppresses oxygen-related parasitic reactions, mitigates electrolyte breakdown, and relieves mechanical strain. Electrochemical testing demonstrates that the SCEE-modified system achieves superior cycling stability, higher capacity retention, and reduced polarization compared with the unmodified counterpart. In situ and ex situ characterizations reveal thinner reconstructed layers, fewer microcracks, and improved surface integrity after extended cycling. Complementary kinetic analyses confirm enhanced lithium-ion diffusion and diminished gas evolution. Theoretical calculations further show that Al doping raises oxygen vacancy formation energy, while finite-element simulations confirm more uniform lithium distribution and lower stress gradients. These results demonstrate that SCEE provides a rational and integrated pathway to balance high capacity with structural durability, offering valuable insights for the design of next-generation high-energy cathodes.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104830"},"PeriodicalIF":20.2,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796083","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 : 2025-12-19DOI: 10.1016/j.ensm.2025.104825
Yuru Zhao , Bingbing Wang , Que Huang , Changcheng Liu , Yuelei Pan , Li Guo , Yanjun Chen
Currently, the regulation of charge rearrangement is significant for the heterogenous dual-phase electrodes. This study introduces a perovskite SrTiO3 (STO) coating layer interfacially couples with Na3V2(PO4)3 (NVP) at atomic level. Notably, STO acts as an electron trap, capturing and localizing electrons from electrolyte and NVP, driving charge rearrangement and optimizing the distribution of electrons. DFT calculations verifies NVP/STO heterostructure behaves metallic DOS state. Meanwhile, the electron capturing effects promotes the gradient distribution of electrons. Based on the difference of work function and band structure of NVP and STO, a built-in electric field (BIEF) is established, further elevating the ionic migration, which has been expounded by DFT and experimental measurements. Benefiting from BIEF, the vanadium d-band center upshift towards Fermi level, indicating optimized electronic construction. Moreover, XAFS demonstrates vanadium possesses stronger activity with lower valence, and the length of V-O bond gets elongated to construct a bigger framework for Na+ transportation. In depth, ex-situ XPS and XPS etching explore the dynamic evolution process of CEI membrane, confirming STO effectively inhibits the oxidative decomposition of electrolyte and boosts the formation of inorganic phase to regulate the CEI component. The improved interfacial charge transfer property has been verified by in-situ EIS and DRT.
{"title":"Interfacial coupling constructs electronic trap regulating charge rearrangement in cathode bulk and CEI membrane for sodium ion batteries","authors":"Yuru Zhao , Bingbing Wang , Que Huang , Changcheng Liu , Yuelei Pan , Li Guo , Yanjun Chen","doi":"10.1016/j.ensm.2025.104825","DOIUrl":"10.1016/j.ensm.2025.104825","url":null,"abstract":"<div><div>Currently, the regulation of charge rearrangement is significant for the heterogenous dual-phase electrodes. This study introduces a perovskite SrTiO<sub>3</sub> (STO) coating layer interfacially couples with Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> (NVP) at atomic level. Notably, STO acts as an electron trap, capturing and localizing electrons from electrolyte and NVP, driving charge rearrangement and optimizing the distribution of electrons. DFT calculations verifies NVP/STO heterostructure behaves metallic DOS state. Meanwhile, the electron capturing effects promotes the gradient distribution of electrons. Based on the difference of work function and band structure of NVP and STO, a built-in electric field (BIEF) is established, further elevating the ionic migration, which has been expounded by DFT and experimental measurements. Benefiting from BIEF, the vanadium <span>d</span>-band center upshift towards Fermi level, indicating optimized electronic construction. Moreover, XAFS demonstrates vanadium possesses stronger activity with lower valence, and the length of V-O bond gets elongated to construct a bigger framework for Na<sup>+</sup> transportation. In depth, ex-situ XPS and XPS etching explore the dynamic evolution process of CEI membrane, confirming STO effectively inhibits the oxidative decomposition of electrolyte and boosts the formation of inorganic phase to regulate the CEI component. The improved interfacial charge transfer property has been verified by in-situ EIS and DRT.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104825"},"PeriodicalIF":20.2,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145785911","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 : 2025-12-19DOI: 10.1016/j.ensm.2025.104822
Tao Long , Ruotong Li , Chunyang Wu , Qinqin Yu , Shuigen Li , Wenwen Liu , Bowen Huang , Yuan-Li Ding
Manganese-containing NASICON-type phosphate cathodes have shown a great potential for sodium ion batteries (SIBs) due to robust structure, 3D ion transport channels, and relatively low toxicity. However, their practical applications are limited owing to poor electron/ion transportation kinetics and large structural strain upon Na+ extraction/insertion processes. Herein, taking Na3.5V1.5Mn0.5(PO4)3 as an example, a Mn vacancy (VMn) regulation strategy has been developed for constructing VMn -containing Na3.5V1.5Mn0.5-x□x(PO4)3 in which VMn can not only efficiently alter the coordination environments of transition metals (TMs) in Na3.5V1.5Mn0.5(PO4)3 for facilitating Na+ migration and charge distribution, but also provide more flexible VO6/MnO6 octahedra environments for guaranteeing robust structural stability upon cycling. Based on theoretical calculation and characterizations, the optimized Na3.5V1.5Mn0.4□0.1(PO4)3 shows the optimized sodium storage performance than those of Na3.5V1.5Mn0.5(PO4)3 without VMn, and Na3.5V1.5Mn0.45□0.05(PO4)3, Na3.5V1.5Mn0.35□0.15(PO4)3. X-ray absorption near-edge structure and density functional theory calculations reveal that the introduction of VMn can not only reduce the band gap from 0.89 eV to 0.53 eV, but also weaken the interaction of Na2-TM and lower the sodium ion diffusion energy barrier near VMn, thus leading to enhanced intrinsic electron/ion conductivity. Importantly, Na3.5V1.5Mn0.4□0.1(PO4)3 exhibits smaller distortions of TMO6 octahedra with VO6 reduced by 21.7% and MnO6 reduced by 47.1% compared to the counterpart without VMn. When evaluated as cathode for SIBs, such cathode delivers a reversible capacity of 119.7 at 0.1 C, a rate capability of 96.6 mAh g−1 at 20 C, and a capacity retention of 88% after 5000 cycles at 20 C.
含锰的nasicon型磷酸盐阴极具有坚固的结构、三维离子传输通道和相对较低的毒性，在钠离子电池（SIBs）中显示出巨大的潜力。然而，由于Na+提取/插入过程中电子/离子传输动力学差和结构应变大，它们的实际应用受到限制。本文以Na3.5V1.5Mn0.5(PO4)3为例，构建了含Na3.5V1.5Mn0.5-x□x(PO4)3的Mn空位调节策略，该策略不仅可以有效改变Na3.5V1.5Mn0.5(PO4)3中过渡金属（TMs）的配位环境，促进Na+的迁移和电荷分布，还可以提供更灵活的VO6/MnO6八面体环境，保证循环时结构的稳定性。通过理论计算和表征，优化后的Na3.5V1.5Mn0.4□0.1(PO4)3的储钠性能优于无VMn的Na3.5V1.5Mn0.5(PO4)3、Na3.5V1.5Mn0.45□0.05(PO4)3、Na3.5V1.5Mn0.35□0.15(PO4)3。x射线吸收近边结构和密度泛函理论计算表明，VMn的引入不仅可以将带隙从0.89 eV减小到0.53 eV，还可以减弱Na2-TM的相互作用，降低VMn附近钠离子的扩散能垒，从而提高本征电子/离子电导率。重要的是，Na3.5V1.5Mn0.4□0.1(PO4)3表现出较小的TMO6八面体畸变，与未添加VMn的对偶物相比，VO6减少了21.7%，MnO6减少了47.1%。作为sib的阴极，这种阴极在0.1 C时的可逆容量为119.7，在20 C时的倍率容量为96.6 mAh g - 1，在20 C下循环5000次后的容量保持率为88%。
{"title":"Mn vacancies-induced electronic and structural regulation of NASICON phosphate cathodes toward highly stable sodium ion batteries","authors":"Tao Long , Ruotong Li , Chunyang Wu , Qinqin Yu , Shuigen Li , Wenwen Liu , Bowen Huang , Yuan-Li Ding","doi":"10.1016/j.ensm.2025.104822","DOIUrl":"10.1016/j.ensm.2025.104822","url":null,"abstract":"<div><div>Manganese-containing NASICON-type phosphate cathodes have shown a great potential for sodium ion batteries (SIBs) due to robust structure, 3D ion transport channels, and relatively low toxicity. However, their practical applications are limited owing to poor electron/ion transportation kinetics and large structural strain upon Na<sup>+</sup> extraction/insertion processes. Herein, taking Na<sub>3.5</sub>V<sub>1.5</sub>Mn<sub>0.5</sub>(PO<sub>4</sub>)<sub>3</sub> as an example, a Mn vacancy (V<sub>Mn</sub>) regulation strategy has been developed for constructing V<sub>Mn</sub> -containing Na<sub>3.5</sub>V<sub>1.5</sub>Mn<sub>0.5-x</sub>□<sub>x</sub>(PO<sub>4</sub>)<sub>3</sub> in which V<sub>Mn</sub> can not only efficiently alter the coordination environments of transition metals (TMs) in Na<sub>3.5</sub>V<sub>1.5</sub>Mn<sub>0.5</sub>(PO<sub>4</sub>)<sub>3</sub> for facilitating Na<sup>+</sup> migration and charge distribution, but also provide more flexible VO<sub>6</sub>/MnO<sub>6</sub> octahedra environments for guaranteeing robust structural stability upon cycling. Based on theoretical calculation and characterizations, the optimized Na<sub>3.5</sub>V<sub>1.5</sub>Mn<sub>0.4</sub>□<sub>0.1</sub>(PO<sub>4</sub>)<sub>3</sub> shows the optimized sodium storage performance than those of Na<sub>3.5</sub>V<sub>1.5</sub>Mn<sub>0.5</sub>(PO<sub>4</sub>)<sub>3</sub> without V<sub>Mn</sub>, and Na<sub>3.5</sub>V<sub>1.5</sub>Mn<sub>0.45</sub>□<sub>0.05</sub>(PO<sub>4</sub>)<sub>3</sub>, Na<sub>3.5</sub>V<sub>1.5</sub>Mn<sub>0.35</sub>□<sub>0.15</sub>(PO<sub>4</sub>)<sub>3</sub>. X-ray absorption near-edge structure and density functional theory calculations reveal that the introduction of V<sub>Mn</sub> can not only reduce the band gap from 0.89 eV to 0.53 eV, but also weaken the interaction of Na2-TM and lower the sodium ion diffusion energy barrier near V<sub>Mn</sub>, thus leading to enhanced intrinsic electron/ion conductivity. Importantly, Na<sub>3.5</sub>V<sub>1.5</sub>Mn<sub>0.4</sub>□<sub>0.1</sub>(PO<sub>4</sub>)<sub>3</sub> exhibits smaller distortions of TMO<sub>6</sub> octahedra with VO<sub>6</sub> reduced by 21.7% and MnO<sub>6</sub> reduced by 47.1% compared to the counterpart without V<sub>Mn</sub>. When evaluated as cathode for SIBs, such cathode delivers a reversible capacity of 119.7 at 0.1 C, a rate capability of 96.6 mAh g<sup>−1</sup> at 20 C, and a capacity retention of 88% after 5000 cycles at 20 C.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104822"},"PeriodicalIF":20.2,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145785914","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 : 2025-12-18DOI: 10.1016/j.ensm.2025.104820
Chencheng Sun , Jiran Chen , Haihong Hou , Fanjun Kong , Dajun Wu , Peixin Cui , Liang Zhang , Shi Tao
O3-type nickel-manganese-based layered cathodes are appealing for building high-energy sodium-ion batteries (SIBs) in growing energy storage application. However, the complicated phase transitions and sluggish Na+ kinetics have largely impeded their practical applications. Herein, this work proposes a medium-entropy strategy for O3-type NaNi0.5Mn0.5O2 cathode to regulate the covalency of Ni/Mn-O bonds via reinforcing TM-O bonding strength, which leads to the contraction of d(O-TM-O) and elongation of d(O-Na-O). Experimental analysis combined with theoretical calculations verifies that the entropy regulation contributes to the retention of O3-type structure and suppressed excessive TM slab gliding and stabilizes Na+ migration pathways as well as limited precipitation of high-valent Ni ions during the cyclic process. Consequently, the designed O3-Na0.92Ni0.47Nb0.03Mn0.30Ti0.20O2 (NNNMTO) demonstrates an excellent rate capability (53 mAh g-1 at 10 C) and long-term cycling stability (70% capacity retention at 2 C after 500 cycles) under a wide working voltage range between 2.0–4.2 V, along with less moisture sensitivity. Additionally, the full battery paired with commercial hard carbon anode displays an impressive cycling stability with an energy density of 260 Wh kg-1 based on the active material mass of both electrodes, making its practical operation possible. This work provides insightful perspectives in facilitating Na+ diffusion and mitigating the undesirable phase transition for layered oxide cathode materials of high-energy SIBs.
o3型镍锰基层状阴极在构建高能钠离子电池（sib）方面具有广泛的应用前景。然而，复杂的相变和缓慢的Na+动力学在很大程度上阻碍了它们的实际应用。本文提出了一种o3型NaNi0.5Mn0.5O2阴极的中熵策略，通过增强TM-O的键合强度来调节Ni/Mn-O键的共价，从而导致d（O-TM-O）的收缩和d（O-Na-O）的伸长。实验分析与理论计算相结合，验证了在循环过程中，熵的调节有助于o3型结构的保留，抑制了TM板的过度滑动，稳定了Na+的迁移路径，限制了高价Ni离子的析出。因此，所设计的O3-Na0.92Ni0.47Nb0.03Mn0.30Ti0.20O2 （NNNMTO）在2.0-4.2 V的宽工作电压范围内表现出优异的倍率性能（10℃时53 mAh g-1）和长期循环稳定性（500次循环后2℃时容量保持70%），同时具有较低的水分敏感性。此外，与商用硬碳阳极配对的全电池显示出令人印象深刻的循环稳定性，基于两个电极的活性物质质量，能量密度为260 Wh kg-1，使其实际操作成为可能。这项工作为促进Na+扩散和减轻高能sib层状氧化物阴极材料的不良相变提供了有见地的观点。
{"title":"Covalency regulation of metal-oxygen ligand in O3-type layered cathode material for high-performance sodium-ion batteries","authors":"Chencheng Sun , Jiran Chen , Haihong Hou , Fanjun Kong , Dajun Wu , Peixin Cui , Liang Zhang , Shi Tao","doi":"10.1016/j.ensm.2025.104820","DOIUrl":"10.1016/j.ensm.2025.104820","url":null,"abstract":"<div><div>O3-type nickel-manganese-based layered cathodes are appealing for building high-energy sodium-ion batteries (SIBs) in growing energy storage application. However, the complicated phase transitions and sluggish Na<sup>+</sup> kinetics have largely impeded their practical applications. Herein, this work proposes a medium-entropy strategy for O3-type NaNi<sub>0.5</sub>Mn<sub>0.5</sub>O<sub>2</sub> cathode to regulate the covalency of Ni/Mn-O bonds via reinforcing TM-O bonding strength, which leads to the contraction of <em>d</em><sub>(O-TM-O)</sub> and elongation of <em>d</em><sub>(O</sub><sub>-Na-O)</sub>. Experimental analysis combined with theoretical calculations verifies that the entropy regulation contributes to the retention of O3-type structure and suppressed excessive TM slab gliding and stabilizes Na<sup>+</sup> migration pathways as well as limited precipitation of high-valent Ni ions during the cyclic process. Consequently, the designed O3-Na<sub>0.92</sub>Ni<sub>0.47</sub>Nb<sub>0.03</sub>Mn<sub>0.30</sub>Ti<sub>0.20</sub>O<sub>2</sub> (NNNMTO) demonstrates an excellent rate capability (53 mAh g<sup>-1</sup> at 10 C) and long-term cycling stability (70% capacity retention at 2 C after 500 cycles) under a wide working voltage range between 2.0–4.2 V, along with less moisture sensitivity. Additionally, the full battery paired with commercial hard carbon anode displays an impressive cycling stability with an energy density of 260 Wh kg<sup>-1</sup> based on the active material mass of both electrodes, making its practical operation possible. This work provides insightful perspectives in facilitating Na<sup>+</sup> diffusion and mitigating the undesirable phase transition for layered oxide cathode materials of high-energy SIBs.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104820"},"PeriodicalIF":20.2,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145785918","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 : 2025-12-18DOI: 10.1016/j.ensm.2025.104821
Yupeng Huang , Kai Lu , Jianbo Dong , Xia Wang , Jinchi Li , Ziyi Gong , Yule He , Hua Jia , Guocai Yuan , Pan Wang , Hong Tan , Lihong Huang , Dongliang Chao , Wanhai Zhou
To achieve highly stable zinc aqueous batteries (ZnABs), inhibiting Zn corrosion and dendrite growth is crucial, relying on redox reactions and kinetics at the electrode-electrolyte interface. Herein, a chelate reconstruction strategy using pantothenic acid (PA) optimizes Zn2⁺ solvation and the inner Helmholtz plane (IHP), thereby regulating Zn deposition kinetics and stabilizing the interface. Based on experimental spectra and theoretical calculations, PA molecules chelate with Zn2+ via carboxyl and amide groups, replacing H2O in the solvation sheath, and reconstructing the IHP into a Zn-rich and H2O-poor electric double-layer structure. This special configuration suppresses water-induced corrosion, regulates Zn deposition kinetics, and induces the preferential Zn growth along the (002) plane. In addition, part of the PA decomposition at the interface forms an organic-inorganic hybrid solid-electrolyte interphase rich in C, N, O, and S species, which enhances the corrosion resistance and stability of the Zn anode. Consequently, the Zn anode achieves an average Coulombic efficiency of 99.7%, prolonged lifespan over 2500 h, fast plating kinetics of 50 mA cm–2, and 68% of Zn utilization rate. Furthermore, the Zn//MnO2 full cell exhibits improved cyclic stability with capacity retention of 89.2% after 1000 cycles and is scaled up to 1.5 Ah for practical validation. This work provides a novel design strategy of additive towards stabilization of Zn anodes for practical ZnABs.
为了获得高度稳定的锌水电池（znab），抑制锌腐蚀和枝晶生长至关重要，这取决于电极-电解质界面的氧化还原反应和动力学。本文采用泛酸（PA）的螯合重构策略优化了Zn2 +的溶剂化和内亥姆霍兹平面（IHP），从而调节了Zn沉积动力学，稳定了界面。根据实验光谱和理论计算，PA分子通过羧基和酰胺基与Zn2+螯合，取代溶剂化鞘中的H2O，将IHP重构为富锌贫氢的电双层结构。这种特殊的结构抑制了水致腐蚀，调节了Zn沉积动力学，诱导Zn沿（002）面优先生长。此外，部分PA在界面处分解形成富含C、N、O、S等物质的有机-无机杂化固-电解质界面，增强了Zn阳极的耐蚀性和稳定性。因此，锌阳极的平均库仑效率达到99.7%，寿命超过2500 h，电镀动力学达到50 mA cm-2，锌利用率达到68%。此外，Zn/ MnO2全电池表现出更好的循环稳定性，在1000次循环后容量保持率为89.2%，并且在实际验证中放大到1.5 Ah。这项工作为实际的锌纳米硼合金提供了一种新的稳定锌阳极的添加剂设计策略。
{"title":"Chelate reconstruction with a H2O-poor and zinc-rich interface toward robust anti-corrosion Ah-level zinc aqueous batteries","authors":"Yupeng Huang , Kai Lu , Jianbo Dong , Xia Wang , Jinchi Li , Ziyi Gong , Yule He , Hua Jia , Guocai Yuan , Pan Wang , Hong Tan , Lihong Huang , Dongliang Chao , Wanhai Zhou","doi":"10.1016/j.ensm.2025.104821","DOIUrl":"10.1016/j.ensm.2025.104821","url":null,"abstract":"<div><div>To achieve highly stable zinc aqueous batteries (ZnABs), inhibiting Zn corrosion and dendrite growth is crucial, relying on redox reactions and kinetics at the electrode-electrolyte interface. Herein, a chelate reconstruction strategy using pantothenic acid (PA) optimizes Zn<sup>2</sup>⁺ solvation and the inner Helmholtz plane (IHP), thereby regulating Zn deposition kinetics and stabilizing the interface. Based on experimental spectra and theoretical calculations, PA molecules chelate with Zn<sup>2+</sup> via carboxyl and amide groups, replacing H<sub>2</sub>O in the solvation sheath, and reconstructing the IHP into a Zn-rich and H<sub>2</sub>O-poor electric double-layer structure. This special configuration suppresses water-induced corrosion, regulates Zn deposition kinetics, and induces the preferential Zn growth along the (002) plane. In addition, part of the PA decomposition at the interface forms an organic-inorganic hybrid solid-electrolyte interphase rich in C, N, O, and S species, which enhances the corrosion resistance and stability of the Zn anode. Consequently, the Zn anode achieves an average Coulombic efficiency of 99.7%, prolonged lifespan over 2500 h, fast plating kinetics of 50 mA cm<sup>–2</sup>, and 68% of Zn utilization rate. Furthermore, the Zn//MnO<sub>2</sub> full cell exhibits improved cyclic stability with capacity retention of 89.2% after 1000 cycles and is scaled up to 1.5 Ah for practical validation. This work provides a novel design strategy of additive towards stabilization of Zn anodes for practical ZnABs.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104821"},"PeriodicalIF":20.2,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145785915","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 : 2025-12-17DOI: 10.1016/j.ensm.2025.104816
Wenjie Huang , Hui Wang , Xuerong Zheng , Yida Deng , Liuzhang Ouyang , Lichun Yang , Min Zhu
Layered α-MoO3 shows potential as an anode for aqueous proton batteries. However, the irreversible phase transition during the first cycle leads to entrapment of 30 % protons within the lattice, resulting in a low initial coulombic efficiency (ICE) below 70 % and poor cycling stability. To overcome these limitations, the interlayer engineering via H2O molecule intercalation and oxygen vacancy introduction is exploited to design MoO3-x·H2O with a high interlayer spacing of 7.80 Å. We establish the structure-property relationship among interlayer structure, proton storage mechanism, and ICE, confirming that the interlayer expansion shifts the proton intercalation/de-intercalation behavior from multiphase transition to solid-solution evolution, thereby enhancing the structural reversibility and stability. We also reveal that this interlayer structure weakens the bonding strength between intercalated protons and terminal oxygen atoms of [MoO6] octahedra of the MoO3-x·H2O interlayer, thus improving proton storage kinetics. MoO3-x·H2O demonstrates excellent compatibility with MnO2@CF cathode of deposition/dissolution mechanism, in an acidic electrolyte containing BF4−. The MoO3-x·H2O//MnO2@CF achieves an excellent ICE of 97.9 %, delivering 84.6 mA h g−1 at 50 A g−1, with durability over 20,000 cycles. Furthermore, this battery reaches low-temperature performance with 137.5 mA h g−1 at −30 °C.
层状α-MoO3表现出作为水溶液质子电池阳极的潜力。然而，在第一个循环期间的不可逆相变导致30%的质子被困在晶格内，导致初始库仑效率（ICE）低于70%，循环稳定性差。为了克服这些限制，利用H2O分子嵌入和引入氧空位的层间工程设计了具有7.80 Å高层间间距的MoO3-x·H2O。我们建立了层间结构、质子储存机制和ICE之间的结构-性能关系，证实了层间膨胀使质子的插/脱插行为从多相转变为固溶演化，从而增强了结构的可逆性和稳定性。我们还发现，这种层间结构削弱了嵌入质子与MoO3-x·H2O层[MoO6]八面体末端氧原子之间的键合强度，从而提高了质子存储动力学。在含有BF4−的酸性电解质中，MoO3-x·H2O与MnO2@CF阴极的沉积/溶解机制具有良好的相容性。MoO3-x·H2O//MnO2@CF实现了97.9%的优异ICE，在50 A g−1时输出84.6 mA h g−1，耐用性超过20,000次。此外，该电池在−30°C时达到137.5 mA h g−1的低温性能。
{"title":"Activating the solid-solution transformation mechanism of MoO3 to boost initial coulombic efficiency and cyclic stability of aqueous MoO3-x·H2O//MnO2 battery","authors":"Wenjie Huang , Hui Wang , Xuerong Zheng , Yida Deng , Liuzhang Ouyang , Lichun Yang , Min Zhu","doi":"10.1016/j.ensm.2025.104816","DOIUrl":"10.1016/j.ensm.2025.104816","url":null,"abstract":"<div><div>Layered α-MoO<sub>3</sub> shows potential as an anode for aqueous proton batteries. However, the irreversible phase transition during the first cycle leads to entrapment of 30 % protons within the lattice, resulting in a low initial coulombic efficiency (ICE) below 70 % and poor cycling stability. To overcome these limitations, the interlayer engineering via H<sub>2</sub>O molecule intercalation and oxygen vacancy introduction is exploited to design MoO<sub>3-x</sub>·H<sub>2</sub>O with a high interlayer spacing of 7.80 Å. We establish the structure-property relationship among interlayer structure, proton storage mechanism, and ICE, confirming that the interlayer expansion shifts the proton intercalation/de-intercalation behavior from multiphase transition to solid-solution evolution, thereby enhancing the structural reversibility and stability. We also reveal that this interlayer structure weakens the bonding strength between intercalated protons and terminal oxygen atoms of [MoO<sub>6</sub>] octahedra of the MoO<sub>3-x</sub>·H<sub>2</sub>O interlayer, thus improving proton storage kinetics. MoO<sub>3-x</sub>·H<sub>2</sub>O demonstrates excellent compatibility with MnO<sub>2</sub>@CF cathode of deposition/dissolution mechanism, in an acidic electrolyte containing BF<sub>4</sub><sup>−</sup>. The MoO<sub>3-x</sub>·H<sub>2</sub>O//MnO<sub>2</sub>@CF achieves an excellent ICE of 97.9 %, delivering 84.6 mA h g<sup>−1</sup> at 50 A g<sup>−1</sup>, with durability over 20,000 cycles. Furthermore, this battery reaches low-temperature performance with 137.5 mA h g<sup>−1</sup> at −30 °C.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"84 ","pages":"Article 104816"},"PeriodicalIF":20.2,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145785925","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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