The practical deployment of aqueous zinc-ion batteries (AZIBs) faces fundamental constraints from irreversible degradation and catastrophic extreme-temperature failure. Herein, tetramethyl methylene-diphosphonate (TEMDP) is introduced by a molecular engineering-designing synergistic strategy involving double P=O group (zinc-affinity and hydrophilic) and -O- group (hydrogen bond receptor). Orchestrating dual mechanisms: reconstruction of solvation sheath through preferential Zn2+-P=O coordination, which reduces de-solvation barriers and directs in-situ formation of the hybrid SEI with an organic C-F/C-O-rich outer layer (ensuring flexibility) and high ion-conductive Zn3(PO4)2-ZnF2-ZnS-ZnO inner layers (12.65 mS cm-1 under -30°C); Reprogramming of hydrogen-bond networks via competitive TEMDP-H2O bonding benefiting from the hydrophilicity and high-electronegativity of P=O and -O- groups, enabling operation at -30°C while reducing hydrogen evolution at 60°C. This molecular synergy delivers excellent electrochemical resilience across an extreme temperature, including symmetric cell for 1960 h at 30°C and 1200 h at -20°C, alongside Zn||CaV6O16·3H2O full cells maintaining 85.7% capacity after 7000 cycles at -20°C and no degradation through 1500 cycles at -30°C. Significantly, it demonstrates 80.3% capacity retention over 800 cycles at 60°C. This work establishes multifunctional synergistic molecular to unlock all-climate AZIBs for applications from North to desert energy storage.
水性锌离子电池（azib）的实际应用面临着不可逆降解和灾难性极端温度失效的基本限制。本文采用双P=O基团（亲锌亲水性）和-O基团（氢键受体）的分子工程设计协同策略，引入了四甲基亚甲基二膦酸盐（TEMDP）。协调双重机制：通过优先的Zn2+-P=O配位重建溶剂化鞘层，减少脱溶剂障碍，并指导原位形成具有有机C- f /C-O丰富的外层（确保柔韧性）和高离子导电性的Zn3(PO4)2-ZnF2-ZnS-ZnO内层（-30℃下12.65 mS cm-1）的杂化SEI；利用P=O和-O-基团的亲水性和高电负性，通过竞争性的TEMDP-H2O键对氢键网络进行重编程，使其能够在-30°C下运行，同时减少60°C下的析氢。这种分子协同作用在极端温度下提供了出色的电化学弹性，包括对称电池在30°C下的1960小时和在-20°C下的1200小时，以及Zn||CaV6O16·3H2O充满电池在-20°C下循环7000次后保持85.7%的容量，并且在-30°C下循环1500次不会降解。值得注意的是，在60°C的800次循环中，它的容量保持率为80.3%。这项工作建立了多功能协同分子，以解锁从北方到沙漠能源储存的全气候azib应用。
{"title":"Dual P=O Molecule Engineering for All-Climate Aqueous Zinc-Ion Batteries","authors":"Jiali Wang, Helong Jiang, Jiawei Mu, Xuri Wang, Miao Yu, Xiangcun Li, Gaohong He","doi":"10.1016/j.ensm.2026.105028","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105028","url":null,"abstract":"The practical deployment of aqueous zinc-ion batteries (AZIBs) faces fundamental constraints from irreversible degradation and catastrophic extreme-temperature failure. Herein, tetramethyl methylene-diphosphonate (TEMDP) is introduced by a molecular engineering-designing synergistic strategy involving double P=O group (zinc-affinity and hydrophilic) and -O- group (hydrogen bond receptor). Orchestrating dual mechanisms: reconstruction of solvation sheath through preferential Zn<ce:sup loc=\"post\">2+</ce:sup>-P=O coordination, which reduces de-solvation barriers and directs in-situ formation of the hybrid SEI with an organic C-F/C-O-rich outer layer (ensuring flexibility) and high ion-conductive Zn<ce:inf loc=\"post\">3</ce:inf>(PO<ce:inf loc=\"post\">4</ce:inf>)<ce:inf loc=\"post\">2</ce:inf>-ZnF<ce:inf loc=\"post\">2</ce:inf>-ZnS-ZnO inner layers (12.65 mS cm<ce:sup loc=\"post\">-1</ce:sup> under -30°C); Reprogramming of hydrogen-bond networks via competitive TEMDP-H<ce:inf loc=\"post\">2</ce:inf>O bonding benefiting from the hydrophilicity and high-electronegativity of P=O and -O- groups, enabling operation at -30°C while reducing hydrogen evolution at 60°C. This molecular synergy delivers excellent electrochemical resilience across an extreme temperature, including symmetric cell for 1960 h at 30°C and 1200 h at -20°C, alongside Zn||CaV<ce:inf loc=\"post\">6</ce:inf>O<ce:inf loc=\"post\">16</ce:inf>·3H<ce:inf loc=\"post\">2</ce:inf>O full cells maintaining 85.7% capacity after 7000 cycles at -20°C and no degradation through 1500 cycles at -30°C. Significantly, it demonstrates 80.3% capacity retention over 800 cycles at 60°C. This work establishes multifunctional synergistic molecular to unlock all-climate AZIBs for applications from North to desert energy storage.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"33 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147393166","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}
Olivine-type LiMnxFe1-xPO4 (LMFP) cathodes are attractive for lithium-ion batteries (LIBs) because of their intrinsic safety and low cost, yet their practical performance is limited by poor electronic conductivity and structural instability associated with Mn-induced Jahn–Teller (J–T) distortion. In this work, Al incorporation is shown to simultaneously improve charge transport and structural reversibility in LMFP. Density functional theory calculations combined with advanced structural characterizations indicate that Al3+ reduces the bandgap of LMFP and, more importantly, modifies the Mn 3d electronic configuration by lowering dz2 orbital occupancy and weakening eg orbital splitting. Such orbital-level modulation alleviates J–T distortion and reduces Mn–O bond-length variation during repeated lithiation and delithiation, leading to mitigated local lattice strain and suppressed Mn dissolution. As a result, the optimized LMFP/C-1Al cathode delivers a high specific capacity of 164.5 mAh g⁻1 at 0.1 C, a rate capability of 101.5 mAh g⁻1 at 10 C, and retains 98.7% of its capacity after 1000 cycles at 1 C. These results highlight orbital regulation as an effective route to stabilizing Mn-based olivine cathodes and provide mechanistic guidance for the design of durable phosphate cathode materials.
橄榄石型LiMnxFe1-xPO4 （LMFP）阴极由于其固有的安全性和低成本而对锂离子电池（LIBs）具有吸引力，但其实际性能受到电子导电性差和与mn诱导的Jahn-Teller （J-T）畸变相关的结构不稳定性的限制。在这项工作中，Al的加入被证明可以同时改善LMFP中的电荷传输和结构可逆性。密度泛函理论计算结合先进的结构表征表明，Al3+降低了LMFP的带隙，更重要的是通过降低dz2轨道占用率和减弱eg轨道分裂来改变Mn的三维电子构型。这种轨道级调制减轻了J-T畸变，减少了重复锂化和锂蚀过程中Mn - o键长度的变化，从而减轻了局部晶格应变，抑制了Mn的溶解。结果表明，优化后的LMFP/C- 1al阴极在0.1℃时的比容量为164.5 mAh g⁻1，在10℃时的比容量为101.5 mAh g⁻1，在1℃下循环1000次后仍能保持98.7%的容量。这些结果突出了轨道调节是稳定锰基橄榄石阴极的有效途径，并为设计耐用的磷酸盐阴极材料提供了机制指导。
{"title":"Orbital Regulation–Enabled Suppression of Jahn–Teller Distortion for Structurally Robust LiMnFePO4 Cathodes","authors":"Chao Ye, Wenqin Ling, Xiao Huang, Shan Fang, Xiaowei Huang, Naigen Zhou","doi":"10.1016/j.ensm.2026.105030","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105030","url":null,"abstract":"Olivine-type LiMn<ce:inf loc=\"post\">x</ce:inf>Fe<ce:inf loc=\"post\">1-x</ce:inf>PO<ce:inf loc=\"post\">4</ce:inf> (LMFP) cathodes are attractive for lithium-ion batteries (LIBs) because of their intrinsic safety and low cost, yet their practical performance is limited by poor electronic conductivity and structural instability associated with Mn-induced Jahn–Teller (J–T) distortion. In this work, Al incorporation is shown to simultaneously improve charge transport and structural reversibility in LMFP. Density functional theory calculations combined with advanced structural characterizations indicate that Al<ce:sup loc=\"post\">3+</ce:sup> reduces the bandgap of LMFP and, more importantly, modifies the Mn 3d electronic configuration by lowering dz<ce:sup loc=\"post\">2</ce:sup> orbital occupancy and weakening eg orbital splitting. Such orbital-level modulation alleviates J–T distortion and reduces Mn–O bond-length variation during repeated lithiation and delithiation, leading to mitigated local lattice strain and suppressed Mn dissolution. As a result, the optimized LMFP/C-1Al cathode delivers a high specific capacity of 164.5 mAh g⁻<ce:sup loc=\"post\">1</ce:sup> at 0.1 C, a rate capability of 101.5 mAh g⁻<ce:sup loc=\"post\">1</ce:sup> at 10 C, and retains 98.7% of its capacity after 1000 cycles at 1 C. These results highlight orbital regulation as an effective route to stabilizing Mn-based olivine cathodes and provide mechanistic guidance for the design of durable phosphate cathode materials.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"14 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147393163","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 : 2026-03-08DOI: 10.1016/j.ensm.2026.105027
Kyu Moon Kwon, Minji Lee, Dae Ho Kim, Hyo Rang Kang, Tae Joo Park
Ultra-thin lithium niobium oxide (LNO) protective layers were conformally deposited onto LiNi0.8Co0.1Mn0.1O2 via a powder-atomic layer deposition process, and their thickness-dependent effects on sulfide-based all-solid-state batteries (ASSBs) performance are systematically examined under a 4.5 V vs Li/Li+ cut-off condition. The cells with 2.5 and 5 nm-thick LNO protective layers exhibit comparable cycling stability. In contrast, the cell with a 1 nm-thick LNO layer shows approximately 28% shorter cycle life and ∼59% higher interfacial resistance after 80 cycles compared to the cell with a 2.5 nm-thick LNO layer. The uncoated cell exhibits more severe degradation, with a 43% shorter cycle life and ∼145% higher interfacial resistance relative to the same reference. These results indicate that a 2.5 nm-thick LNO layer represents the minimum effective thickness required to mitigate interfacial degradation, thereby establishing a quantitative thickness criterion for cathode active materials protection in sulfide-based ASSBs.
采用粉末-原子层沉积方法在LiNi0.8Co0.1Mn0.1O2表面沉积了超薄铌酸锂（LNO）保护层，并在4.5 V vs Li/Li+截止条件下系统地研究了其厚度对硫化物基全固态电池（assb）性能的影响。具有2.5 nm和5nm厚LNO保护层的电池具有相当的循环稳定性。相比之下，与具有2.5 nm厚LNO层的电池相比，具有1 nm厚LNO层的电池在80次循环后的循环寿命缩短了约28%，界面电阻提高了约59%。未涂覆的电池表现出更严重的降解，相对于相同的参考材料，循环寿命缩短43%，界面电阻高~ 145%。这些结果表明，2.5 nm厚的LNO层代表了减轻界面降解所需的最小有效厚度，从而建立了硫化物基assb中阴极活性材料保护的定量厚度标准。
{"title":"Minimum Effective Thickness of Cathode Protective Layers for Sulfide-Based All-Solid-State Batteries via Powder-Atomic Layer Deposition","authors":"Kyu Moon Kwon, Minji Lee, Dae Ho Kim, Hyo Rang Kang, Tae Joo Park","doi":"10.1016/j.ensm.2026.105027","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105027","url":null,"abstract":"Ultra-thin lithium niobium oxide (LNO) protective layers were conformally deposited onto LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> via a powder-atomic layer deposition process, and their thickness-dependent effects on sulfide-based all-solid-state batteries (ASSBs) performance are systematically examined under a 4.5 V vs Li/Li<sup>+</sup> cut-off condition. The cells with 2.5 and 5 nm-thick LNO protective layers exhibit comparable cycling stability. In contrast, the cell with a 1 nm-thick LNO layer shows approximately 28% shorter cycle life and ∼59% higher interfacial resistance after 80 cycles compared to the cell with a 2.5 nm-thick LNO layer. The uncoated cell exhibits more severe degradation, with a 43% shorter cycle life and ∼145% higher interfacial resistance relative to the same reference. These results indicate that a 2.5 nm-thick LNO layer represents the minimum effective thickness required to mitigate interfacial degradation, thereby establishing a quantitative thickness criterion for cathode active materials protection in sulfide-based ASSBs.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"27 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383893","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 : 2026-03-08DOI: 10.1016/j.ensm.2026.105026
Wen-Jie Shi, Xiao-Rui Wang, Min-Peng Li, Hong-Yan Li, Ming-Hui Yang, Hong-Tao Xue, Mao-Cheng Liu, Yu-Xia Hu, Bao Liu
Anode-free sodium batteries (AFSBs) are promising candidates for next-generation high energy density and superior cost-effectiveness energy storage systems. However, their cycle stability is hindered by the uncontrolled Na dendrite formation and consequent electrolyte depletion induced by exacerbated side reactions. Herein, dendrite-free Na deposition is realized on a single-crystal Cu substrate characterized by the preferential growth of (100) facet grains (denoted as Cu(100)) with high surface energy and the extensive elimination of grain boundary. Single-crystal Cu(100) substrate reduced heterogeneous Na nucleation Gibbs free energy and homogenized Na+ flux, achieving stable cycling by inducing a Frank-van der Merwe Na deposition mode. As a result, the Na||Cu(100) asymmetric battery shows a Coulombic efficiency (CE) of 99.82% and the Cu(100)@Na||Cu(100)@Na symmetric battery maintains stable cycling for over 1200 h at 0.5 mA cm−2/0.5 mAh cm−2. The Cu(100)||Na3V2(PO4)3 anode-free battery achieves stable cycling performance for over 200 cycles with a capacity retention of 91.8%, delivering a high energy density of 302.5 Wh kg−1. Remarkably, an Ah-level AFSB delivers stable cycling and achieves an high energy density of 163.5 Wh kg−1 based on the total mass of battery. This work regulated the thermodynamic and kinetic behaviors of Na deposition through substrate facet engineering, providing novel insights into achieving dendrite-free deposition to enhance cycle stability and facilitate the practical deployment of high energy density AFSBs.
无阳极钠电池（AFSBs）是下一代高能量密度和高成本效益的储能系统的有希望的候选者。然而，它们的循环稳定性受到不受控制的Na枝晶形成和随之而来的由加剧的副反应引起的电解质消耗的阻碍。本文在单晶Cu衬底上实现了无枝晶Na沉积，其特征是（100）面晶（表示为Cu(100)）优先生长，具有高表面能和广泛消除晶界。单晶Cu（100）衬底降低了非均相Na成核吉布斯自由能和均质Na+通量，通过诱导Frank-van der Merwe Na沉积模式实现稳定循环。结果表明，Na||Cu（100）非对称电池的库仑效率（CE）为99.82%,Cu(100)@Na||Cu(100)@Na对称电池在0.5 mA cm−2/0.5 mAh cm−2下可保持1200 h以上的稳定循环。Cu(100)||Na3V2(PO4)3无阳极电池的循环性能稳定，循环次数超过200次，容量保持率为91.8%，能量密度高达302.5 Wh kg−1。值得注意的是，ah级AFSB提供了稳定的循环，并实现了基于电池总质量的163.5 Wh kg−1的高能量密度。这项工作通过衬底面工程调节了Na沉积的热力学和动力学行为，为实现无枝晶沉积提供了新的见解，以提高循环稳定性并促进高能量密度AFSBs的实际部署。
{"title":"Single-Crystal Copper Foils with Exposed (100) Facet for Dendrite-Free Sodium Deposition Enables Ah-Level Anode-Free Sodium Batteries","authors":"Wen-Jie Shi, Xiao-Rui Wang, Min-Peng Li, Hong-Yan Li, Ming-Hui Yang, Hong-Tao Xue, Mao-Cheng Liu, Yu-Xia Hu, Bao Liu","doi":"10.1016/j.ensm.2026.105026","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105026","url":null,"abstract":"Anode-free sodium batteries (AFSBs) are promising candidates for next-generation high energy density and superior cost-effectiveness energy storage systems. However, their cycle stability is hindered by the uncontrolled Na dendrite formation and consequent electrolyte depletion induced by exacerbated side reactions. Herein, dendrite-free Na deposition is realized on a single-crystal Cu substrate characterized by the preferential growth of (100) facet grains (denoted as Cu(100)) with high surface energy and the extensive elimination of grain boundary. Single-crystal Cu(100) substrate reduced heterogeneous Na nucleation Gibbs free energy and homogenized Na<sup>+</sup> flux, achieving stable cycling by inducing a Frank-van der Merwe Na deposition mode. As a result, the Na||Cu(100) asymmetric battery shows a Coulombic efficiency (CE) of 99.82% and the Cu(100)@Na||Cu(100)@Na symmetric battery maintains stable cycling for over 1200 h at 0.5 mA cm<sup>−2</sup>/0.5 mAh cm<sup>−2</sup>. The Cu(100)||Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> anode-free battery achieves stable cycling performance for over 200 cycles with a capacity retention of 91.8%, delivering a high energy density of 302.5 Wh kg<sup>−1</sup>. Remarkably, an Ah-level AFSB delivers stable cycling and achieves an high energy density of 163.5 Wh kg<sup>−1</sup> based on the total mass of battery. This work regulated the thermodynamic and kinetic behaviors of Na deposition through substrate facet engineering, providing novel insights into achieving dendrite-free deposition to enhance cycle stability and facilitate the practical deployment of high energy density AFSBs.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"81 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371270","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 : 2026-03-06DOI: 10.1016/j.ensm.2026.105020
Huiquan Che, Yuefeng Su, Jinyang Dong, Yun Lu, Jianan Hao, Yiya Wang, Teng Yang, Xinbai He, Yujia Wu, Ning Li, Xulai Yang, Tinglu Song, Lai Chen, Feng Wu
Stabilizing lithium-rich manganese-based layered oxides (LRMOs) during high-voltage cycling remains difficult for high-energy lithium-ion batteries because oxygen-redox reactions trigger severe surface reconstruction, dissolution of transition-metal ions, electrolyte breakdown, and the development of an unstable cathode-electrolyte interphase (CEI). These degradation routes become even more pronounced at elevated temperatures, where reactive oxygen species and electrolyte-generated fragments accelerate structural deterioration and promote rapid voltage fading. Achieving long-term LRMO stability, therefore, requires an interphase that provides both mechanical strength and chemical tolerance. Here, we propose a composite‑electrolyte strategy that integrates a mechanically robust inorganic framework (Al2O3) with a reactive film‑forming agent (lithium tri(tert‑butoxy)hydroaluminate, LTBA) to construct a rigid‑adaptive CEI on LRMO cathodes. This hybrid interphase synergistically combines the structural durability of Al2O3 with the chemical flexibility of LTBA, resulting in a uniform, continuous, and aluminum‑rich CEI that effectively suppresses oxygen‑driven side reactions, mitigates transition‑metal dissolution, and inhibits lattice distortion. Electrochemical evaluations demonstrate that the composite electrolyte significantly enhances the initial Coulombic efficiency, improves capacity retention, and reduces the average voltage decay rate by approximately 50%. Multiscale post‑cycling characterizations confirm attenuated surface reconstruction, preserved lattice ordering, and a more stable interfacial chemical environment. These findings establish an interphase design paradigm that integrates structural resilience with chemical responsiveness and highlights its potential for enabling stable operation of high-voltage, high-energy lithium-ion batteries.
{"title":"A Whole Greater Than the Sum of Its Parts: Composite-Electrolyte-Induced Rigid-Adaptive Interphase for Stabilizing a Lithium-Rich Cathode","authors":"Huiquan Che, Yuefeng Su, Jinyang Dong, Yun Lu, Jianan Hao, Yiya Wang, Teng Yang, Xinbai He, Yujia Wu, Ning Li, Xulai Yang, Tinglu Song, Lai Chen, Feng Wu","doi":"10.1016/j.ensm.2026.105020","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105020","url":null,"abstract":"Stabilizing lithium-rich manganese-based layered oxides (LRMOs) during high-voltage cycling remains difficult for high-energy lithium-ion batteries because oxygen-redox reactions trigger severe surface reconstruction, dissolution of transition-metal ions, electrolyte breakdown, and the development of an unstable cathode-electrolyte interphase (CEI). These degradation routes become even more pronounced at elevated temperatures, where reactive oxygen species and electrolyte-generated fragments accelerate structural deterioration and promote rapid voltage fading. Achieving long-term LRMO stability, therefore, requires an interphase that provides both mechanical strength and chemical tolerance. Here, we propose a composite‑electrolyte strategy that integrates a mechanically robust inorganic framework (Al<sub>2</sub>O<sub>3</sub>) with a reactive film‑forming agent (lithium tri(tert‑butoxy)hydroaluminate, LTBA) to construct a rigid‑adaptive CEI on LRMO cathodes. This hybrid interphase synergistically combines the structural durability of Al<sub>2</sub>O<sub>3</sub> with the chemical flexibility of LTBA, resulting in a uniform, continuous, and aluminum‑rich CEI that effectively suppresses oxygen‑driven side reactions, mitigates transition‑metal dissolution, and inhibits lattice distortion. Electrochemical evaluations demonstrate that the composite electrolyte significantly enhances the initial Coulombic efficiency, improves capacity retention, and reduces the average voltage decay rate by approximately 50%. Multiscale post‑cycling characterizations confirm attenuated surface reconstruction, preserved lattice ordering, and a more stable interfacial chemical environment. These findings establish an interphase design paradigm that integrates structural resilience with chemical responsiveness and highlights its potential for enabling stable operation of high-voltage, high-energy lithium-ion batteries.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"4 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147359738","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 : 2026-03-04DOI: 10.1016/j.ensm.2026.105024
Shuoshuo Cheng, Chenchen Song, Miaorui Yang, Fan Li, Zhiyu Song, Shiyu Li, Peng Lv, Ying Bai
NASICON-type fluorophosphates are attractive cathode candidates for sodium-ion batteries due to their rigid frameworks and accessible multi-electron transition metal redox chemistry. Nevertheless, reconciling high operating voltage with long-term structural durability remains challenging. Here, a Na3V2(PO4)2F3/Na2MnPO4F (NVPF/NMPF) heterostructure is constructed to modulate interfacial electronic states and promote stable high-voltage operation. Density functional theory calculations reveal pronounced interfacial charge redistribution, in which electron transfer from NMPF to NVPF strengthens the interfacial Mn-O-V covalency and stabilizes the high-potential V3+/V4+ redox transitions (∼3.7 and 4.2 V). This electronically coupled interface enhances structural robustness while accelerating both electronic conduction and Na+ transport. Benefiting from these synergistic effects, the NVPF/NMPF heterostructure delivers outstanding durability, retaining 82.7% of its capacity after 1000 cycles at 1 C and sustaining highly stable operation for over 10000 cycles at 50 C. These findings highlight the effectiveness of interfacial electronic engineering in designing heterostructure fluorophosphate cathodes with elevated energy output and extended cycling life.
{"title":"Heterointerface charge reorganization enables high-voltage sodium storage in NASICON-type cathodes","authors":"Shuoshuo Cheng, Chenchen Song, Miaorui Yang, Fan Li, Zhiyu Song, Shiyu Li, Peng Lv, Ying Bai","doi":"10.1016/j.ensm.2026.105024","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105024","url":null,"abstract":"NASICON-type fluorophosphates are attractive cathode candidates for sodium-ion batteries due to their rigid frameworks and accessible multi-electron transition metal redox chemistry. Nevertheless, reconciling high operating voltage with long-term structural durability remains challenging. Here, a Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>2</sub>F<sub>3</sub>/Na<sub>2</sub>MnPO<sub>4</sub>F (NVPF/NMPF) heterostructure is constructed to modulate interfacial electronic states and promote stable high-voltage operation. Density functional theory calculations reveal pronounced interfacial charge redistribution, in which electron transfer from NMPF to NVPF strengthens the interfacial Mn-O-V covalency and stabilizes the high-potential V<sup>3+</sup>/V<sup>4+</sup> redox transitions (∼3.7 and 4.2 V). This electronically coupled interface enhances structural robustness while accelerating both electronic conduction and Na<sup>+</sup> transport. Benefiting from these synergistic effects, the NVPF/NMPF heterostructure delivers outstanding durability, retaining 82.7% of its capacity after 1000 cycles at 1 C and sustaining highly stable operation for over 10000 cycles at 50 C. These findings highlight the effectiveness of interfacial electronic engineering in designing heterostructure fluorophosphate cathodes with elevated energy output and extended cycling life.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"9 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147359739","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 : 2026-03-04DOI: 10.1016/j.ensm.2026.105023
Yang Su, Jingyuan Zhao, Dan Liu, Xinlu Wang, Jinxian Wang, Wensheng Yu, Xiangting Dong, Dongtao Liu
Zinc-iodine (Zn-I2) batteries have emerged as promising candidates for next-generation energy storage systems due to their low cost, environmental friendliness, and inherent safety. However, challenges such as Zn dendrite growth, hydrogen evolution, and the shuttle effect of polyiodides in liquid electrolytes significantly hinder their practical applications. To address these issues, we propose a novel composite polymer electrolyte (CPE) with a dual-network design, integrating a 3D porous β-cyclodextrin polymer (CDP) framework and hollow spherical TiO2 (H-TiO2) nanoparticles through synergistic covalent/non-covalent interactions. The CDP is constructed by cross-linking flexible β-cyclodextrin (β-CD) units with rigid aryl-rich polymers of intrinsic microporosity (PIM-1), forming a mechanically robust and highly porous architecture. Within this network, H-TiO2 nanoparticles are uniformly dispersed via hydrogen bonding with PEO chains and CDP functional groups, enhancing interfacial compatibility and ion transport pathways. The resulting electrolyte (PCPE-CDP-TiO2) achieves an exceptional ionic conductivity of 9.4 × 10-4 S cm-1 at room temperature, and effectively suppresses Zn dendrite growth and polyiodide shuttling. Symmetrical Zn//Zn batteries with PCPE-CDP-TiO2 exhibit reversible Zn plating/stripping for over 11000 hours at 5 mA cm-2. Solid-state Zn-I2 full batteries enables an ultra-long cycle life of 10000 cycles at 5 C. This work presents a molecular engineering strategy for designing high-performance CPEs.
锌碘（Zn-I2）电池因其低成本、环保和固有的安全性而成为下一代储能系统的有希望的候选者。然而，诸如锌枝晶生长、析氢和多碘化物在液体电解质中的穿梭效应等挑战极大地阻碍了它们的实际应用。为了解决这些问题，我们提出了一种具有双网络设计的新型复合聚合物电解质（CPE），通过协同共价/非共价相互作用将3D多孔β-环糊精聚合物（CDP）框架和空心球形TiO2 （H-TiO2）纳米粒子集成在一起。CDP是由柔性β-环糊精（β-CD）单元与具有固有微孔性的刚性富芳基聚合物（PIM-1）交联而成，形成机械坚固的高多孔结构。在这个网络中，H-TiO2纳米粒子通过氢键与PEO链和CDP官能团均匀分散，增强了界面相容性和离子传输途径。制备的电解质（ppe - cdp - tio2）室温离子电导率为9.4 × 10-4 S cm-1，有效抑制了Zn枝晶的生长和多碘化物的穿梭。ppe - cdp - tio2对称锌/锌电池在5 mA cm-2下可可逆镀锌/剥离11000小时以上。固态锌- i2全电池在5℃下可实现10000次的超长循环寿命。本研究提出了一种设计高性能cpe的分子工程策略。
{"title":"Highly Stable Composite Polymer Electrolyte with Covalent/Non-Covalent Network for Solid-State Zinc-Iodine Battery","authors":"Yang Su, Jingyuan Zhao, Dan Liu, Xinlu Wang, Jinxian Wang, Wensheng Yu, Xiangting Dong, Dongtao Liu","doi":"10.1016/j.ensm.2026.105023","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105023","url":null,"abstract":"Zinc-iodine (Zn-I<sub>2</sub>) batteries have emerged as promising candidates for next-generation energy storage systems due to their low cost, environmental friendliness, and inherent safety. However, challenges such as Zn dendrite growth, hydrogen evolution, and the shuttle effect of polyiodides in liquid electrolytes significantly hinder their practical applications. To address these issues, we propose a novel composite polymer electrolyte (CPE) with a dual-network design, integrating a 3D porous <em>β</em>-cyclodextrin polymer (CDP) framework and hollow spherical TiO<sub>2</sub> (H-TiO<sub>2</sub>) nanoparticles through synergistic covalent/non-covalent interactions. The CDP is constructed by cross-linking flexible <em>β</em>-cyclodextrin (<em>β</em>-CD) units with rigid aryl-rich polymers of intrinsic microporosity (PIM-1), forming a mechanically robust and highly porous architecture. Within this network, H-TiO<sub>2</sub> nanoparticles are uniformly dispersed via hydrogen bonding with PEO chains and CDP functional groups, enhancing interfacial compatibility and ion transport pathways. The resulting electrolyte (PCPE-CDP-TiO<sub>2</sub>) achieves an exceptional ionic conductivity of 9.4 × 10<sup>-4</sup> S cm<sup>-1</sup> at room temperature, and effectively suppresses Zn dendrite growth and polyiodide shuttling. Symmetrical Zn//Zn batteries with PCPE-CDP-TiO<sub>2</sub> exhibit reversible Zn plating/stripping for over 11000 hours at 5 mA cm<sup>-2</sup>. Solid-state Zn-I<sub>2</sub> full batteries enables an ultra-long cycle life of 10000 cycles at 5 C. This work presents a molecular engineering strategy for designing high-performance CPEs.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"31 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147359773","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 : 2026-03-04DOI: 10.1016/j.ensm.2026.105022
Shuguo Sun, Bo Rui, Saurabh Bahuguna, Jun Zhou, Faisal Sayeed, Jun Xu
{"title":"Electrochemo-Mechanical-Thermal Dynamics of Internal Short Circuits in Batteries","authors":"Shuguo Sun, Bo Rui, Saurabh Bahuguna, Jun Zhou, Faisal Sayeed, Jun Xu","doi":"10.1016/j.ensm.2026.105022","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105022","url":null,"abstract":"","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"5 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147360245","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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