Ultra-Li-rich (ULR) alloys have emerged as a widely studied anode system in recent years, exhibiting Li storage capacity and voltage comparable to those of metallic Li anodes, while featuring a solid-solution lithiation mechanism that effectively suppresses Li dendrite growth. Currently, this anode faces two key challenges: its formation mechanism remains unclear, and its reversibility after complete Li extraction requires the assistance of Ag-C nanocomposite layer (NCL). To address these, we conduct a theoretical study on the representative ULR Li-Ag alloy, focusing on the behavior of active species (Ag) in Li structures and the resultant physicochemical phenomena. The results demonstrate that both the formation and solid-solution reaction of ULR alloys are driven by the dispersion trend of their active elements within metallic Li structure. This dispersion trend stems from the electrostatic shielding effect arising from the active species under extremely low concentration. Subsequently, we further extend this mechanism to other elements and screen potential ULR alloys featuring both stability and a solid-solution reaction mechanism. Additionally, we perform an immersive simulation of Li deposition and transit through the Ag-C NCL, and observe a secondary-driving Li+ reaction after Li directly binds to the NCL. This reaction enables Li on the amorphous C surface to capture surrounding Ag, which is then pushed into the space between the NCL and the current collector by subsequent deposited Li.
{"title":"Solid-Solution Composite Lithium Anodes Based on Ultra-Li-rich Alloys: Formation and Reversibility","authors":"Mengqi Wu, Jingwei Li, Chunyu Zhao, Dongxiao Kan, Huanjuan Liu, Mingzhuang Liu, Peng Liu, Xiangyu Yao, Hongguang Piao, Yingjin Wei, Ruqian Lian","doi":"10.1016/j.ensm.2026.105037","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105037","url":null,"abstract":"Ultra-Li-rich (ULR) alloys have emerged as a widely studied anode system in recent years, exhibiting Li storage capacity and voltage comparable to those of metallic Li anodes, while featuring a solid-solution lithiation mechanism that effectively suppresses Li dendrite growth. Currently, this anode faces two key challenges: its formation mechanism remains unclear, and its reversibility after complete Li extraction requires the assistance of Ag-C nanocomposite layer (NCL). To address these, we conduct a theoretical study on the representative ULR Li-Ag alloy, focusing on the behavior of active species (Ag) in Li structures and the resultant physicochemical phenomena. The results demonstrate that both the formation and solid-solution reaction of ULR alloys are driven by the dispersion trend of their active elements within metallic Li structure. This dispersion trend stems from the electrostatic shielding effect arising from the active species under extremely low concentration. Subsequently, we further extend this mechanism to other elements and screen potential ULR alloys featuring both stability and a solid-solution reaction mechanism. Additionally, we perform an immersive simulation of Li deposition and transit through the Ag-C NCL, and observe a secondary-driving Li<sup>+</sup> reaction after Li directly binds to the NCL. This reaction enables Li on the amorphous C surface to capture surrounding Ag, which is then pushed into the space between the NCL and the current collector by subsequent deposited Li.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"5 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147440215","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}
{"title":"Unplugging the truth: an empirical analysis of 417 fires of electric vehicles and the limitations of battery safety regulations","authors":"Changyong Jin, Xuning Feng, Yuedong Sun, Xin Lai, Yuejiu Zheng, Chengshan Xu, Huaibin Wan, Li Wang, Xiangming He, Minggao Ouyang","doi":"10.1016/j.ensm.2026.105035","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105035","url":null,"abstract":"","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"189 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147448413","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}
The recycling and development of spent lithium iron phosphate (SLFP) materials face challenges due to environmental and efficiency limitations of traditional pyrometallurgical and hydrometallurgical methods. Direct regeneration avoids the complete decomposition of SLFP materials, but faces the challenges of severe degradation of surface carbon coatings and repair and regeneration of bulk lattice distortion. We propose a gradient bonding heterostructure construction strategy for efficient direct regeneration of SLFP, achieving triple effects of internal crystal element gradient embedding, interface fast ion conductor hinge, and surface carbon layer activation reconstruction. The process utilizes plasma etching to create an activated carbon layer with exposed active sites. The plasma energy drives Y3+ to anchor between the carbon layer and LFP, while enabling the Li+ to migrate through the surface activation channels to the bulk phase of LFP. During subsequent calcination, YPO4 grain boundaries form at the interface, creating a C-O-Y bonding conductive network with the functional carbon layer that enhances electronic conductivity. Simultaneously, the doping of Y3+ into the LFP lattice effectively enhances the structural stability of the material. The regenerated LFP delivers a high initial capacity of 151.1 mAh g-1 at 1 C and demonstrates a capacity retention of nearly 100% after 800 cycles.
由于传统火法和湿法的环境和效率限制，废磷酸铁锂（SLFP）材料的回收和开发面临挑战。直接再生避免了SLFP材料的完全分解，但面临着表面碳涂层严重降解和体晶格畸变修复再生的挑战。我们提出了一种梯度键合异质结构构建策略，用于SLFP的高效直接再生，实现了内部晶元梯度嵌入、界面快速离子导体铰接和表面碳层活化重建的三重效果。该工艺利用等离子体蚀刻产生具有暴露活性位点的活性炭层。等离子体能量驱动Y3+锚定在碳层和LFP之间，同时使Li+通过表面活化通道迁移到LFP的体相。在随后的煅烧过程中，YPO4在界面处形成晶界，与功能碳层形成C-O-Y键合导电网络，增强了电子导电性。同时，在LFP晶格中掺杂Y3+，有效地提高了材料的结构稳定性。再生的LFP在1c下提供151.1 mAh g-1的高初始容量，并且在800次循环后容量保持率接近100%。
{"title":"Efficient direct regeneration of spent LiFePO4 materials via gradient bonding heterostructure construction strategy","authors":"Yuyun Li, Yuan Ping, Fanbin Hu, Changjiang Li, Qingfeng Liu, Haigang Dong, Qi Meng, Peng Dong","doi":"10.1016/j.ensm.2026.105032","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105032","url":null,"abstract":"The recycling and development of spent lithium iron phosphate (SLFP) materials face challenges due to environmental and efficiency limitations of traditional pyrometallurgical and hydrometallurgical methods. Direct regeneration avoids the complete decomposition of SLFP materials, but faces the challenges of severe degradation of surface carbon coatings and repair and regeneration of bulk lattice distortion. We propose a gradient bonding heterostructure construction strategy for efficient direct regeneration of SLFP, achieving triple effects of internal crystal element gradient embedding, interface fast ion conductor hinge, and surface carbon layer activation reconstruction. The process utilizes plasma etching to create an activated carbon layer with exposed active sites. The plasma energy drives Y<sup>3+</sup> to anchor between the carbon layer and LFP, while enabling the Li<sup>+</sup> to migrate through the surface activation channels to the bulk phase of LFP. During subsequent calcination, YPO<sub>4</sub> grain boundaries form at the interface, creating a C-O-Y bonding conductive network with the functional carbon layer that enhances electronic conductivity. Simultaneously, the doping of Y<sup>3+</sup> into the LFP lattice effectively enhances the structural stability of the material. The regenerated LFP delivers a high initial capacity of 151.1 mAh g<sup>-1</sup> at 1 C and demonstrates a capacity retention of nearly 100% after 800 cycles.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"6 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383924","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 : 2026-03-10DOI: 10.1016/j.ensm.2026.105031
Changwei Xiao, Houjun Zhang, Yixuan Qiao, Yao Nian, Tiantian Wang, Asad Abbas, Yang Wang, You Han, Jieshan Qiu
The development of efficient and sustainable lithium extraction from low-grade brines is critical to meet the rising demand for lithium-driven clean energy technologies. While electrochemical lithium extraction shows promise, challenges remain in terms of selectivity, stability, and energy efficiency. In this work, we present a novel strategy of Ti doping in LiNi0.35Co0.37Mn0.28O2 (LNCM) to simultaneously expand the lithium interlayer spacing and stabilize the transition metal framework. The LNCM-Ti was synthesized via hydrothermal and solid-state sintering, resulting in improved structural stability, reduced Li+/Ni2+ cation mixing, and enhanced Li+ diffusion. To validate these structural advantages, a series of electrochemical tests were conducted and repeated systematically in a single cell. Compared to pristine LNCM (1.24 mmol g-1, 70.8%), the LNCM-0.5%Ti exhibited superior lithium extraction capacity (1.43 mmol g-1) and stability, with 89.5% retention after 20 cycles. Furthermore, the optimized material achieved high selectivity in Qarhan brine (Li+/Mg2+ = 31.3; Li+/Na+ = 23.8) with a high capacity of 4.99 mmol g⁻¹ and a low energy consumption of 1.14 Wh mol-1. Notably, this capacity is the highest reported to date for electrochemical lithium extraction systems tested in real high Mg/Li ratio brines under comparable conditions. Density functional theory calculations revealed that Ti doping reduced the energy barrier for Li+ intercalation due to the expanded interlayer spacing and stabilized transition metal framework, enhancing the overall electrochemical performance. This work introduces a promising approach for efficient and selective electrochemical lithium extraction from low-grade brines, with significant implications for the development of sustainable lithium recovery technologies.
{"title":"Framework Stabilization and Interlayer Expansion in LNCM for Highly Selective Lithium Recovery from Low-Grade Brine","authors":"Changwei Xiao, Houjun Zhang, Yixuan Qiao, Yao Nian, Tiantian Wang, Asad Abbas, Yang Wang, You Han, Jieshan Qiu","doi":"10.1016/j.ensm.2026.105031","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105031","url":null,"abstract":"The development of efficient and sustainable lithium extraction from low-grade brines is critical to meet the rising demand for lithium-driven clean energy technologies. While electrochemical lithium extraction shows promise, challenges remain in terms of selectivity, stability, and energy efficiency. In this work, we present a novel strategy of Ti doping in LiNi<ce:inf loc=\"post\">0.35</ce:inf>Co<ce:inf loc=\"post\">0.37</ce:inf>Mn<ce:inf loc=\"post\">0.28</ce:inf>O<ce:inf loc=\"post\">2</ce:inf> (LNCM) to simultaneously expand the lithium interlayer spacing and stabilize the transition metal framework. The LNCM-Ti was synthesized via hydrothermal and solid-state sintering, resulting in improved structural stability, reduced Li<ce:sup loc=\"post\">+</ce:sup>/Ni<ce:sup loc=\"post\">2+</ce:sup> cation mixing, and enhanced Li<ce:sup loc=\"post\">+</ce:sup> diffusion. To validate these structural advantages, a series of electrochemical tests were conducted and repeated systematically in a single cell. Compared to pristine LNCM (1.24 mmol g<ce:sup loc=\"post\">-1</ce:sup>, 70.8%), the LNCM-0.5%Ti exhibited superior lithium extraction capacity (1.43 mmol g<ce:sup loc=\"post\">-1</ce:sup>) and stability, with 89.5% retention after 20 cycles. Furthermore, the optimized material achieved high selectivity in Qarhan brine (Li<ce:sup loc=\"post\">+</ce:sup>/Mg<ce:sup loc=\"post\">2+</ce:sup> = 31.3; Li<ce:sup loc=\"post\">+</ce:sup>/Na<ce:sup loc=\"post\">+</ce:sup> = 23.8) with a high capacity of 4.99 mmol g⁻¹ and a low energy consumption of 1.14 Wh mol<ce:sup loc=\"post\">-1</ce:sup>. Notably, this capacity is the highest reported to date for electrochemical lithium extraction systems tested in real high Mg/Li ratio brines under comparable conditions. Density functional theory calculations revealed that Ti doping reduced the energy barrier for Li<ce:sup loc=\"post\">+</ce:sup> intercalation due to the expanded interlayer spacing and stabilized transition metal framework, enhancing the overall electrochemical performance. This work introduces a promising approach for efficient and selective electrochemical lithium extraction from low-grade brines, with significant implications for the development of sustainable lithium recovery technologies.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"52 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147393161","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}
Aqueous zinc-ion batteries offer compelling advantages for grid storage, but their wider commercialization is hindered by irreversible Zn anodes due to dendritic growth, anion-related side reactions, and water-induced corrosion. To overcome this, we design a conjugated supramolecular framework through π-π stacking assembly of Subphthalocyanine (SubPc) into a “head-to-head” architecture. This multifunctional interphase selectively guides Zn(101) deposition to reduce concentration polarization, establish “S-shaped” ion channels for uniform Zn2+ flux dispersion, topologically confine SO42- migration, and immobilize water molecules via integrated H-bond networks. The MnO2//SubPc@Zn battery delivers an initial capacity 174.3 mAh g-1 at 1.5 A g-1 with 83% retention after 4000 cycles. Pouch cells retain 93.19% capacity over 350 cycles while maintaining 1.7 V open-circuit voltage post-cutting, confirming mechanical safety. Integrated pouch cell validation includes sustained power delivery to miniaturized electronics, demonstrating practical viability for stable zinc electrochemistry.
水锌离子电池为电网存储提供了令人信服的优势，但由于树突生长、阴离子相关的副反应和水腐蚀等原因，不可逆的锌阳极阻碍了其更广泛的商业化。为了克服这一问题，我们通过亚酞菁（SubPc）的π-π堆叠组装设计了一个共轭超分子框架，形成了“头对头”结构。这种多功能界面相选择性地引导Zn（101）沉积以减少浓度极化，建立“s形”离子通道以实现均匀的Zn2+通量分散，在拓扑上限制SO42-迁移，并通过集成的氢键网络固定水分子。MnO2//SubPc@Zn电池在1.5 A g-1时提供174.3 mAh g-1的初始容量，在4000次循环后保持83%的保留率。袋状电池在350次循环中保持93.19%的容量，同时在切割后保持1.7 V的开路电压，确认了机械安全性。集成袋电池验证包括持续的电力输送到小型化电子设备，展示了稳定锌电化学的实际可行性。
{"title":"Conquering Coupled Failure Modes in Aqueous Zn Anodes via a Functional Subphthalocyanine Supramolecular Architecture","authors":"Xingxing Zhang, Xinbo Ai, Zemin He, Bing Wang, Cheng Ma, Zongcheng Miao, Wenhuan Huang","doi":"10.1016/j.ensm.2026.105025","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105025","url":null,"abstract":"Aqueous zinc-ion batteries offer compelling advantages for grid storage, but their wider commercialization is hindered by irreversible Zn anodes due to dendritic growth, anion-related side reactions, and water-induced corrosion. To overcome this, we design a conjugated supramolecular framework through π-π stacking assembly of Subphthalocyanine (SubPc) into a “head-to-head” architecture. This multifunctional interphase selectively guides Zn(101) deposition to reduce concentration polarization, establish “S-shaped” ion channels for uniform Zn<sup>2+</sup> flux dispersion, topologically confine SO<sub>4</sub><sup>2-</sup> migration, and immobilize water molecules via integrated H-bond networks. The MnO<sub>2</sub>//SubPc@Zn battery delivers an initial capacity 174.3 mAh g<sup>-1</sup> at 1.5 A g<sup>-1</sup> with 83% retention after 4000 cycles. Pouch cells retain 93.19% capacity over 350 cycles while maintaining 1.7 V open-circuit voltage post-cutting, confirming mechanical safety. Integrated pouch cell validation includes sustained power delivery to miniaturized electronics, demonstrating practical viability for stable zinc electrochemistry.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"16 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147440218","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}
The development of sustainable and efficient energy storage systems based on abundant and environmentally friendly charge carriers is paramount to achieving global net-zero goals. Ammonium (NH4+)-ion-based systems present a promising non-metallic alternative owing to their atomic structure that enhances the kinetics, assisting charge storage. However, the identification of suitable host materials for reversible NH4⁺ storage remains a significant challenge. Herein, we report the use of manganese oxide (Mn3O4) as a novel electrode material for aqueous ammonium-ion storage. Tetragonal-shaped Mn3O4 nanoparticles were synthesised directly on carbon cloth (Mn3O4@CC) using a controlled layer-by-layer assembly method. These electrodes exhibit an excellent specific capacity of 322.8 mAh/g at a current density of 0.5 A/g, with impressive rate capability and 77.7 mAh/g capacity retention over 3000 cycles. The charge storage kinetics analysed using ex-situ characterisations confirm the reversible insertion and extraction mechanism of the NH4+-ion in the Mn3O4 structure. DFT calculations reveal the superior electronic conductivity and the interaction of the NH4+ ion with Mn3O4, by which the material could achieve a high capacity. Furthermore, an ammonium-ion supercapacitor (AISC) was constructed using the Mn3O4@CC as the positive and activated carbon (AC) as the negative electrode material. The device delivered a maximum specific energy of 47.9 Wh/kg and a specific power of 8000 W/kg, with excellent cycling stability. This investigation highlights Mn3O4 as a promising material for NH4⁺ ion storage and paves the way for the exploration of other electrode materials synthesised using the layer-by-layer method for next-generation, environmentally friendly energy storage systems.
基于丰富、环保的电荷载体开发可持续、高效的储能系统对于实现全球净零目标至关重要。铵（NH4+）离子基体系由于其原子结构增强了动力学，有助于电荷储存，因此是一种很有前途的非金属替代品。然而，确定适合NH4 +可逆存储的宿主材料仍然是一个重大挑战。在这里，我们报道了使用氧化锰（Mn3O4）作为一种新的电极材料用于水铵离子存储。采用一种受控的逐层组装方法，在碳布（Mn3O4@CC）上直接合成了四角形的Mn3O4纳米颗粒。这些电极在电流密度为0.5 a /g时表现出322.8 mAh/g的优异比容量，具有令人印象深刻的倍率能力和超过3000次循环的77.7 mAh/g容量保持。利用非原位表征分析电荷存储动力学，证实了NH4+离子在Mn3O4结构中的可逆插入和萃取机制。DFT计算表明，Mn3O4具有优异的电子导电性和NH4+离子与Mn3O4的相互作用，从而使材料具有较高的容量。以Mn3O4@CC为正极，活性炭（AC）为负极材料，构建了氨离子超级电容器（AISC）。该装置的最大比能量为47.9 Wh/kg，比功率为8000 W/kg，具有出色的循环稳定性。这项研究强调了Mn3O4是一种很有前途的NH4 +离子存储材料，并为探索使用逐层方法合成的下一代环保储能系统的其他电极材料铺平了道路。
{"title":"Spinel-Structured Tetragonal Mn3O4 Nanocrystals as Promising Electrode for Aqueous Ammonium-Ion Storage","authors":"Abhishek Kulkarni, Ankit Dandriyal, Shubham Patil, Niroshan Manoharan, Digambar Sawant, Mahesh Chougale, Gaurav Lohar, Jennifer MacLeod, Prashant Sonar, Deepak Dubal","doi":"10.1016/j.ensm.2026.105029","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105029","url":null,"abstract":"The development of sustainable and efficient energy storage systems based on abundant and environmentally friendly charge carriers is paramount to achieving global net-zero goals. Ammonium (NH<ce:inf loc=\"post\">4</ce:inf><ce:sup loc=\"post\">+</ce:sup>)-ion-based systems present a promising non-metallic alternative owing to their atomic structure that enhances the kinetics, assisting charge storage. However, the identification of suitable host materials for reversible NH<ce:inf loc=\"post\">4</ce:inf>⁺ storage remains a significant challenge. Herein, we report the use of manganese oxide (Mn<ce:inf loc=\"post\">3</ce:inf>O<ce:inf loc=\"post\">4</ce:inf>) as a novel electrode material for aqueous ammonium-ion storage. Tetragonal-shaped Mn<ce:inf loc=\"post\">3</ce:inf>O<ce:inf loc=\"post\">4</ce:inf> nanoparticles were synthesised directly on carbon cloth (Mn<ce:inf loc=\"post\">3</ce:inf>O<ce:inf loc=\"post\">4</ce:inf>@CC) using a controlled layer-by-layer assembly method. These electrodes exhibit an excellent specific capacity of 322.8 mAh/g at a current density of 0.5 A/g, with impressive rate capability and 77.7 mAh/g capacity retention over 3000 cycles. The charge storage kinetics analysed using ex-situ characterisations confirm the reversible insertion and extraction mechanism of the NH<ce:inf loc=\"post\">4</ce:inf><ce:sup loc=\"post\">+</ce:sup>-ion in the Mn<ce:inf loc=\"post\">3</ce:inf>O<ce:inf loc=\"post\">4</ce:inf> structure. DFT calculations reveal the superior electronic conductivity and the interaction of the NH<ce:inf loc=\"post\">4</ce:inf><ce:sup loc=\"post\">+</ce:sup> ion with Mn<ce:inf loc=\"post\">3</ce:inf>O<ce:inf loc=\"post\">4</ce:inf>, by which the material could achieve a high capacity. Furthermore, an ammonium-ion supercapacitor (AISC) was constructed using the Mn<ce:inf loc=\"post\">3</ce:inf>O<ce:inf loc=\"post\">4</ce:inf>@CC as the positive and activated carbon (AC) as the negative electrode material. The device delivered a maximum specific energy of 47.9 Wh/kg and a specific power of 8000 W/kg, with excellent cycling stability. This investigation highlights Mn<ce:inf loc=\"post\">3</ce:inf>O<ce:inf loc=\"post\">4</ce:inf> as a promising material for NH<ce:inf loc=\"post\">4</ce:inf>⁺ ion storage and paves the way for the exploration of other electrode materials synthesised using the layer-by-layer method for next-generation, environmentally friendly energy storage systems.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"80 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147393164","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}
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}
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