Practical sodium-ion batteries require O3-type cathodes that combine low cost with high energy yet high capacity often depends on Ni/Co-rich compositions. Reducing Ni or removing Co generally lowers capacity, while phase evolution and slow sodium transport remain. Here we report a Co-free, Fe/Mn-rich high-entropy-doped layered oxide Na0.9Ni0.225Mn0.3375Fe0.3375Zn0.075Cu0.015Ti0.010O1.97 (HE-NFM) to achieve high capacity together with structural stability. X-ray absorption spectroscopy results reveal a reversible and cooperative Ni/Fe redox process and stable local environments during cycling. Density functional theory calculations indicate a metallic electronic state near the Fermi level and a reduced Na+ migration barrier, providing a mechanistic basis for the improved kinetics. The entropy-enhanced cation disorder suppresses the O3 to O'3 transition and induces a strain-buffering OP2 phase below 4.0 V. HE-NFM achieves a reversible capacity of 160.07 mAh g−1 in coin full cells and delivers an energy density of 194 Wh kg−1 in a 3 Ah pouch cell at an upper cutoff voltage of 4.15 V. For long-life operation, the pouch cell retains 98% capacity after 1000 cycles when the cutoff is reduced to 4.05 V. These results demonstrate that the high-entropy-doping strategy provides a practical route to achieve low-cost and high-performance O3-type cathodes suitable for large-scale sodium-ion energy storage.
{"title":"High-Entropy-doped Layered Oxides Toward 200 Wh kg−¹ Sodium-Ion Batteries with Long Cycle Life","authors":"Lina Zhang, Chen Cheng, Weiwei Xu, Heli Liu, Zheng Zhou, Weidong Xu, Zhiyao Li, Lin Sun, Shengzhe Yan, Kehua Dai, Liang Zhang","doi":"10.1016/j.ensm.2026.105041","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105041","url":null,"abstract":"Practical sodium-ion batteries require O3-type cathodes that combine low cost with high energy yet high capacity often depends on Ni/Co-rich compositions. Reducing Ni or removing Co generally lowers capacity, while phase evolution and slow sodium transport remain. Here we report a Co-free, Fe/Mn-rich high-entropy-doped layered oxide Na<ce:inf loc=\"post\">0.9</ce:inf>Ni<ce:inf loc=\"post\">0.225</ce:inf>Mn<ce:inf loc=\"post\">0.3375</ce:inf>Fe<ce:inf loc=\"post\">0.3375</ce:inf>Zn<ce:inf loc=\"post\">0.075</ce:inf>Cu<ce:inf loc=\"post\">0.015</ce:inf>Ti<ce:inf loc=\"post\">0.010</ce:inf>O<ce:inf loc=\"post\">1.97</ce:inf> (HE-NFM) to achieve high capacity together with structural stability. X-ray absorption spectroscopy results reveal a reversible and cooperative Ni/Fe redox process and stable local environments during cycling. Density functional theory calculations indicate a metallic electronic state near the Fermi level and a reduced Na<ce:sup loc=\"post\">+</ce:sup> migration barrier, providing a mechanistic basis for the improved kinetics. The entropy-enhanced cation disorder suppresses the O3 to O'3 transition and induces a strain-buffering OP2 phase below 4.0 V. HE-NFM achieves a reversible capacity of 160.07 mAh g<ce:sup loc=\"post\">−1</ce:sup> in coin full cells and delivers an energy density of 194 Wh kg<ce:sup loc=\"post\">−1</ce:sup> in a 3 Ah pouch cell at an upper cutoff voltage of 4.15 V. For long-life operation, the pouch cell retains 98% capacity after 1000 cycles when the cutoff is reduced to 4.05 V. These results demonstrate that the high-entropy-doping strategy provides a practical route to achieve low-cost and high-performance O3-type cathodes suitable for large-scale sodium-ion energy storage.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"4 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147464848","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 : 2026-03-16DOI: 10.1016/j.ensm.2026.105046
Wooseok Go, Ruhul Amin, Ilias Belharouak
Saltwater batteries (SWBs) that utilize Na⁺ ions from seawater have emerged as promising candidates for low-cost and sustainable grid-scale energy storage. To date, the cathode reaction mechanism of SWBs has been predominantly described by oxygen evolution and reduction reactions (OER/ORR). However, this assumption is valid only under idealized ocean-like conditions with constant pH and continuous oxygen replenishment. In practical systems, SWBs operate in finite volumes of saltwater, where saltwater composition dynamically evolves during cycling. In this work, we systematically investigate the cathode reaction mechanisms of SWBs under finite saltwater conditions using galvanostatic cycling combined with electrochemical diagnostics and operando monitoring of dissolved oxygen and pH. Our results reveal that the cathode chemistry during SWB operation is considerably more complex than previously assumed. In addition to OER and ORR, hypochlorite formation and consumption reactions, along with pH-dependent switching of dominant reaction pathways, play critical roles. We further identify the sequence and relative contributions of these reactions throughout charge–discharge cycling. These findings provide a comprehensive and mechanistically grounded understanding of SWB cathode processes under relatively realistic cell design and operation condition. The insights presented here establish a new framework for interpreting SWB electrochemistry and offer directions for future strategies aimed at improving performance, stability, and practical viability.
{"title":"Revealing the Coupled Oxygen and Hypochlorite Chemistry in Saltwater Batteries through Operando pH and Oxygen Monitoring","authors":"Wooseok Go, Ruhul Amin, Ilias Belharouak","doi":"10.1016/j.ensm.2026.105046","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105046","url":null,"abstract":"Saltwater batteries (SWBs) that utilize Na⁺ ions from seawater have emerged as promising candidates for low-cost and sustainable grid-scale energy storage. To date, the cathode reaction mechanism of SWBs has been predominantly described by oxygen evolution and reduction reactions (OER/ORR). However, this assumption is valid only under idealized ocean-like conditions with constant pH and continuous oxygen replenishment. In practical systems, SWBs operate in finite volumes of saltwater, where saltwater composition dynamically evolves during cycling. In this work, we systematically investigate the cathode reaction mechanisms of SWBs under finite saltwater conditions using galvanostatic cycling combined with electrochemical diagnostics and <ce:italic>operando</ce:italic> monitoring of dissolved oxygen and pH. Our results reveal that the cathode chemistry during SWB operation is considerably more complex than previously assumed. In addition to OER and ORR, hypochlorite formation and consumption reactions, along with pH-dependent switching of dominant reaction pathways, play critical roles. We further identify the sequence and relative contributions of these reactions throughout charge–discharge cycling. These findings provide a comprehensive and mechanistically grounded understanding of SWB cathode processes under relatively realistic cell design and operation condition. The insights presented here establish a new framework for interpreting SWB electrochemistry and offer directions for future strategies aimed at improving performance, stability, and practical viability.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"11 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147464845","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 : 2026-03-15DOI: 10.1016/j.ensm.2026.105040
Leah Rynearson, Haoyu Liu, Stefan Ilic, Milena Martins, Pedro Farinazzo Bergamo Dias Martins, Jens Niklas, Justin G. Connell, Dusan Strmcnik, Jordi Cabana, Baris Key
Raising the upper cutoff voltage of lithium-ion batteries (LIBs) to increase energy density often exceeds the electrolyte’s anodic stability limit, accelerating degradation and creating a major durability tradeoff. Designing electrolytes that can sustain long-term high-voltage cycling requires a clearer understanding of the fundamental mechanisms occurring when commercial carbonate solvents oxidize. To this end, simplified single-salt, single-solvent formulations of LiClO4 and LiPF6 in dimethyl carbonate (DMC), ethylene carbonate (EC), or ethyl methyl carbonate (EMC) were anodically electrolyzed on inert electrodes and monitored for extended periods of time using 1H, 13C, 19F, and 35Cl nuclear magnetic resonance (NMR) spectroscopy. The controlled environment of the experiments, coupled to the unique sensitivity of NMR, unveiled novel metastable intermediates and the formation of branching networks of products with temporal evolution. Oxidation of the pristine solvent primarily proceeds through a radical pathway that also produces highly reactive protons but faces competition from a second pathway involving a radical carbocation intermediate. In all cases, the intermediates follow a variety of downstream pathways that can intersect with each other. The concomitant network of reactions represents a significant increase in complexity compared to common descriptions in the literature, yet, critically, it helps explain the wide range of products typically identified in electrolyte oxidation in complete cells. The results highlight the need for refocusing fundamental research on anodic stability to analysis of the hierarchy of reaction networks to better inform efforts to mitigate the detrimental effects on battery performance, including prevention and harvesting of proton and radical products.
{"title":"Networks of Electrochemical Oxidation of Common Lithium-Ion Battery Solvents Revealed by NMR Spectroscopy","authors":"Leah Rynearson, Haoyu Liu, Stefan Ilic, Milena Martins, Pedro Farinazzo Bergamo Dias Martins, Jens Niklas, Justin G. Connell, Dusan Strmcnik, Jordi Cabana, Baris Key","doi":"10.1016/j.ensm.2026.105040","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105040","url":null,"abstract":"Raising the upper cutoff voltage of lithium-ion batteries (LIBs) to increase energy density often exceeds the electrolyte’s anodic stability limit, accelerating degradation and creating a major durability tradeoff. Designing electrolytes that can sustain long-term high-voltage cycling requires a clearer understanding of the fundamental mechanisms occurring when commercial carbonate solvents oxidize. To this end, simplified single-salt, single-solvent formulations of LiClO<sub>4</sub> and LiPF<sub>6</sub> in dimethyl carbonate (DMC), ethylene carbonate (EC), or ethyl methyl carbonate (EMC) were anodically electrolyzed on inert electrodes and monitored for extended periods of time using <sup>1</sup>H, <sup>13</sup>C, <sup>19</sup>F, and <sup>35</sup>Cl nuclear magnetic resonance (NMR) spectroscopy. The controlled environment of the experiments, coupled to the unique sensitivity of NMR, unveiled novel metastable intermediates and the formation of branching networks of products with temporal evolution. Oxidation of the pristine solvent primarily proceeds through a radical pathway that also produces highly reactive protons but faces competition from a second pathway involving a radical carbocation intermediate. In all cases, the intermediates follow a variety of downstream pathways that can intersect with each other. The concomitant network of reactions represents a significant increase in complexity compared to common descriptions in the literature, yet, critically, it helps explain the wide range of products typically identified in electrolyte oxidation in complete cells. The results highlight the need for refocusing fundamental research on anodic stability to analysis of the hierarchy of reaction networks to better inform efforts to mitigate the detrimental effects on battery performance, including prevention and harvesting of proton and radical products.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"3 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461876","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}
Alkali-metal-ion batteries based on Li⁺, Na⁺, and K⁺ underpin electrified transport and are increasingly attractive for grid-scale storage, yet their performance and durability emerge from tightly coupled variables spanning composition, crystal chemistry, microstructure, interphase reactions, and operating protocols. When paired with physically meaningful representations and leakage-resistant evaluation, machine learning (ML) can complement experiments and first-principles calculations by providing fast, decision-oriented surrogates for property prediction, candidate ranking, and iterative optimization under constrained budgets. This review summarizes ML-enabled paradigms that are reshaping metal-ion battery research. We first distill practical workflow elements, including data generation and curation, domain-informed representations and descriptor design (from composition statistics to structure-aware graphs and electrochemical signals), model training and validation under realistic split strategies, and tools for uncertainty quantification and interpretability. We then survey representative advances across cathodes, anodes, electrolytes, and interfaces, highlighting high-throughput down-selection, structure-property-processing mapping, and multi-objective optimization across Li-, Na-, and K-ion chemistries. Finally, we discuss persistent challenges in data quality, transferability, and mechanistic trust, and outline emerging opportunities in closed-loop experimentation, manufacturing-process optimization, and intelligent battery management toward more reproducible and increasingly autonomous discovery pipelines.
{"title":"Data-Driven Paradigms for Advancing Alkali-Metal-Ion Battery Technologies","authors":"Hengjia Shao, Naveen Kumar, Wei-Hong Lai, Hao Li, Xue Jia, Hua-Kun Liu, Yun-Xiao Wang","doi":"10.1016/j.ensm.2026.105044","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105044","url":null,"abstract":"Alkali-metal-ion batteries based on Li⁺, Na⁺, and K⁺ underpin electrified transport and are increasingly attractive for grid-scale storage, yet their performance and durability emerge from tightly coupled variables spanning composition, crystal chemistry, microstructure, interphase reactions, and operating protocols. When paired with physically meaningful representations and leakage-resistant evaluation, machine learning (ML) can complement experiments and first-principles calculations by providing fast, decision-oriented surrogates for property prediction, candidate ranking, and iterative optimization under constrained budgets. This review summarizes ML-enabled paradigms that are reshaping metal-ion battery research. We first distill practical workflow elements, including data generation and curation, domain-informed representations and descriptor design (from composition statistics to structure-aware graphs and electrochemical signals), model training and validation under realistic split strategies, and tools for uncertainty quantification and interpretability. We then survey representative advances across cathodes, anodes, electrolytes, and interfaces, highlighting high-throughput down-selection, structure-property-processing mapping, and multi-objective optimization across Li-, Na-, and K-ion chemistries. Finally, we discuss persistent challenges in data quality, transferability, and mechanistic trust, and outline emerging opportunities in closed-loop experimentation, manufacturing-process optimization, and intelligent battery management toward more reproducible and increasingly autonomous discovery pipelines.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"52 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147464851","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 : 2026-03-15DOI: 10.1016/j.ensm.2026.105043
Muhammad Shoaib Tahir, Muhammad Faizan, Iqra Kainat, Hammad Ghazanfar, Fahad Rehman, Minsung Kim, Young-Soo Seo
Silicon offers an unparalleled theoretical capacity for all-solid-state batteries (ASSBs); however, its pronounced volumetric expansion and the fragility of solid-solid interfaces severely limit practical implementation. Polymers have emerged as pivotal enablers capable of reconciling these mechanical and chemical incompatibilities. This review systematically analyzes polymer-mediated strategies for stabilizing silicon anodes across sulfide-, oxide-, and polymer-based electrolytes. We categorize representative systems, including conductive polymers, elastomeric networks, self-healing chemistries, and ion-conducting polymer electrolytes, and delineate their electrolyte-dependent performance priorities in regulating interfacial chemistry, sustaining Li+ transport, and accommodating mechanical strain. Comparative evaluation reveals that conductive polymers are particularly advantageous in oxide-based architectures where electronic percolation and interfacial impedance dominate, whereas elastomeric and self-healing polymers demonstrate superior efficacy in sulfide systems by mitigating chemo-mechanical mismatch and suppressing fracture evolution. In polymer-based solid electrolytes, ion-conducting matrices primarily govern lithium transport, while structural polymers stabilize electrode morphology and interphase integrity. Emphasis is placed on dynamic covalent and hydrogen-bonding networks, artificial interphase engineering, and hybrid polymer-ceramic frameworks that couple ionic conductivity with mechanical resilience. Advances in solvent-free processing and scalable roll-to-roll fabrication further highlight the translational relevance of these materials. By integrating electrochemical, interfacial, and mechanical design principles, this review establishes an electrolyte-aware framework for rationally engineering polymer-enabled silicon anodes toward durable, high-energy, and manufacturable solid-state batteries.
{"title":"Silicon-Polymer Composites in All-Solid-State Batteries: Interfacial Chemistry, Mechanical Buffering, and Scalable Design","authors":"Muhammad Shoaib Tahir, Muhammad Faizan, Iqra Kainat, Hammad Ghazanfar, Fahad Rehman, Minsung Kim, Young-Soo Seo","doi":"10.1016/j.ensm.2026.105043","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105043","url":null,"abstract":"Silicon offers an unparalleled theoretical capacity for all-solid-state batteries (ASSBs); however, its pronounced volumetric expansion and the fragility of solid-solid interfaces severely limit practical implementation. Polymers have emerged as pivotal enablers capable of reconciling these mechanical and chemical incompatibilities. This review systematically analyzes polymer-mediated strategies for stabilizing silicon anodes across sulfide-, oxide-, and polymer-based electrolytes. We categorize representative systems, including conductive polymers, elastomeric networks, self-healing chemistries, and ion-conducting polymer electrolytes, and delineate their electrolyte-dependent performance priorities in regulating interfacial chemistry, sustaining Li<ce:sup loc=\"post\">+</ce:sup> transport, and accommodating mechanical strain. Comparative evaluation reveals that conductive polymers are particularly advantageous in oxide-based architectures where electronic percolation and interfacial impedance dominate, whereas elastomeric and self-healing polymers demonstrate superior efficacy in sulfide systems by mitigating chemo-mechanical mismatch and suppressing fracture evolution. In polymer-based solid electrolytes, ion-conducting matrices primarily govern lithium transport, while structural polymers stabilize electrode morphology and interphase integrity. Emphasis is placed on dynamic covalent and hydrogen-bonding networks, artificial interphase engineering, and hybrid polymer-ceramic frameworks that couple ionic conductivity with mechanical resilience. Advances in solvent-free processing and scalable roll-to-roll fabrication further highlight the translational relevance of these materials. By integrating electrochemical, interfacial, and mechanical design principles, this review establishes an electrolyte-aware framework for rationally engineering polymer-enabled silicon anodes toward durable, high-energy, and manufacturable solid-state batteries.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"59 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147464852","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 : 2026-03-15DOI: 10.1016/j.ensm.2026.105045
Ruizhuo Zhang, Seyedhosein Payandeh, Yuan Ma, Damian Goonetilleke, Yushu Tang, Aleksandr Kondrakov, Jürgen Janek, Torsten Brezesinski
Controlling electro-chemo-mechanical effects remains a key challenge in advancing the development of solid-state batteries (SSBs) with layered Ni-rich cathode and sulfide solid electrolyte. While surface coatings suppress parasitic side reactions, mechanical failure can still be severe, and there is a relative lack of effective strategies to counteract it. To improve the integrity of the cathode, herein we propose a capacity balancing approach with Li4Ti5O12 (LTO) as a model anode in thiophosphate-based SSBs. By leveraging the tip-shaped lithiation tail of LTO with a low negative-to-positive balancing (LB), this strategy enables a reduced upper cut-off potential of the LiNi0.85Co0.10Mn0.05O2 (NCM85) cathode used, thereby mitigating mechanical stress/strain induced by the H2-H3 phase transition. As polarization increases during cycling, the potential is gradually increased, compensating for the loss of capacity without external voltage adjustment. Three-electrode measurements validate the proposed mechanism across several C-rates and corroborate this self-regulating process. Unlike high negative-to-positive balancing (HB), the LB configuration achieves improved structural integrity, reduced charge-transfer resistance, and prolonged cycle life, retaining 80% capacity after about 1300 cycles at 1C, compared to 400 cycles in HB. Overall, this work offers a simple, yet effective strategy for extending the longevity of cathodes for the development of high-performance SSBs.
{"title":"Compromise between energy density and stability: Proper capacity balancing enables high-performance solid-state batteries","authors":"Ruizhuo Zhang, Seyedhosein Payandeh, Yuan Ma, Damian Goonetilleke, Yushu Tang, Aleksandr Kondrakov, Jürgen Janek, Torsten Brezesinski","doi":"10.1016/j.ensm.2026.105045","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105045","url":null,"abstract":"Controlling electro-chemo-mechanical effects remains a key challenge in advancing the development of solid-state batteries (SSBs) with layered Ni-rich cathode and sulfide solid electrolyte. While surface coatings suppress parasitic side reactions, mechanical failure can still be severe, and there is a relative lack of effective strategies to counteract it. To improve the integrity of the cathode, herein we propose a capacity balancing approach with Li<ce:inf loc=\"post\">4</ce:inf>Ti<ce:inf loc=\"post\">5</ce:inf>O<ce:inf loc=\"post\">12</ce:inf> (LTO) as a model anode in thiophosphate-based SSBs. By leveraging the tip-shaped lithiation tail of LTO with a low negative-to-positive balancing (LB), this strategy enables a reduced upper cut-off potential of the LiNi<ce:inf loc=\"post\">0.85</ce:inf>Co<ce:inf loc=\"post\">0.10</ce:inf>Mn<ce:inf loc=\"post\">0.05</ce:inf>O<ce:inf loc=\"post\">2</ce:inf> (NCM85) cathode used, thereby mitigating mechanical stress/strain induced by the H2-H3 phase transition. As polarization increases during cycling, the potential is gradually increased, compensating for the loss of capacity without external voltage adjustment. Three-electrode measurements validate the proposed mechanism across several C-rates and corroborate this self-regulating process. Unlike high negative-to-positive balancing (HB), the LB configuration achieves improved structural integrity, reduced charge-transfer resistance, and prolonged cycle life, retaining 80% capacity after about 1300 cycles at 1C, compared to 400 cycles in HB. Overall, this work offers a simple, yet effective strategy for extending the longevity of cathodes for the development of high-performance SSBs.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"26 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147465434","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}
All-solid-state sodium batteries (ASSSBs) have emerged as promising options for next-generation energy storage systems owing to high energy density, superior safety, rich sodium resources, and low cost. To promote the practical application of ASSSBs, advanced solid electrolytes (SEs) that are well matched with metallic sodium anode and high-voltage cathodes are of urgently needed to be developed. Sodium halides, which rationally combine the merits of high ionic conductivity, wide electrochemical window, and excellent mechanical flexibility, show great promise as ideal SEs for use in ASSSBs. However, due to the nature of sodium halides, several bottlenecks still need to be overcome, such as high sensitivity to moisture, limited methods for efficient production, unideal interface stability with electrodes, and complex assembly process for full batteries. In this review, the characteristics of sodium halides SEs, including crystal structure, ionic transport mechanism, and synthesis routes are well summarized. Meanwhile, the issues of high moisture sensitivity and unstable interface are focused, and associated optimization strategies are overviewed. In addition, the assembly and electrochemical performance of ASSSBs are outlined. For future research directions, several constructive suggestions are proposed. This work may provide a relatively comprehensive understanding of promising sodium halides SEs, helping to the exploration of innovative electrolyte design and utilization solutions for advanced ASSSBs.
{"title":"Sodium halide solid electrolytes for all-solid-state sodium batteries: advances, challenges, strategies, and prospects","authors":"Bing Yan, Hyokyeong Kang, Rongkang Zhou, Heesung Shin, Yameng Fan, Fanqin Yue, Busheng Zhang, Biwei Xiao, Jang-Yeon Hwang, Dan Zhou","doi":"10.1016/j.ensm.2026.105042","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105042","url":null,"abstract":"All-solid-state sodium batteries (ASSSBs) have emerged as promising options for next-generation energy storage systems owing to high energy density, superior safety, rich sodium resources, and low cost. To promote the practical application of ASSSBs, advanced solid electrolytes (SEs) that are well matched with metallic sodium anode and high-voltage cathodes are of urgently needed to be developed. Sodium halides, which rationally combine the merits of high ionic conductivity, wide electrochemical window, and excellent mechanical flexibility, show great promise as ideal SEs for use in ASSSBs. However, due to the nature of sodium halides, several bottlenecks still need to be overcome, such as high sensitivity to moisture, limited methods for efficient production, unideal interface stability with electrodes, and complex assembly process for full batteries. In this review, the characteristics of sodium halides SEs, including crystal structure, ionic transport mechanism, and synthesis routes are well summarized. Meanwhile, the issues of high moisture sensitivity and unstable interface are focused, and associated optimization strategies are overviewed. In addition, the assembly and electrochemical performance of ASSSBs are outlined. For future research directions, several constructive suggestions are proposed. This work may provide a relatively comprehensive understanding of promising sodium halides SEs, helping to the exploration of innovative electrolyte design and utilization solutions for advanced ASSSBs.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"190 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147465735","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 : 2026-03-13DOI: 10.1016/j.ensm.2026.105033
Tao Ren, Yu Bai, Xin Li, Jiaxin Jing, Zhenhua Wang, Kening Sun
The development of high-voltage lithium metal batteries is constrained by the instability of the electrode-electrolyte interphase (EEI). This study proposes a novel multifunctional additive,3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(trifluoromethyl)pyridine (TDBTFP), which helps to restructure the Li+ solvation structure, so as to reduce the Li+ desolvation energy barrier and improve Li+ transport kinetics. The introduction of TDBTFP enables the construction of a solid electrolyte interphase (SEI) enriched with LiF, LiBxOy and Li3N on the Li anode, thereby suppressing dendrite growth. Simultaneously, a cathode electrolyte interphase (CEI) with a gradient composition is formed on the NCM811. The CEI structure features LiF residing predominantly in the inner layer and Li3N/LiBxOy concentrated mainly in the outer layer, which collectively enhances Li+ conductivity and inhibits phase transition and transition metals dissolution for the NCM811. Furthermore, TDBTFP acts as an efficient HF scavenger. Consequently, Li||NCM811 battery with TDBTFP-contained electrolyte delivers a high initial discharge capacity of 214.4 mAh g-1 and retains 88.8% of its initial capacity after 200 cycles at a high cut-off voltage of 4.6 V, along with 86.5% retention at 4.7 V and 72.3% at 60°C after 200 cycles of its initial capacity respectively.
高压锂金属电池的发展受到电极-电解质界面不稳定性的制约。本研究提出了一种新的多功能添加剂3-（4,4,5,5-四甲基-1,3,2-二恶硼酸-2-基）-5-（三氟甲基）吡啶（TDBTFP），它有助于重构Li+的溶剂化结构，从而降低Li+的脱溶能垒，改善Li+的转运动力学。引入TDBTFP可以在锂阳极上构建富含LiF、LiBxOy和Li3N的固体电解质界面（SEI），从而抑制枝晶生长。同时，在NCM811上形成具有梯度组成的阴极电解质界面相（CEI）。CEI结构的特点是LiF主要分布在内层，Li3N/LiBxOy主要集中在外层，这两种结构共同增强了NCM811的Li+电导率，抑制了相变和过渡金属的溶解。此外，TDBTFP作为一个有效的HF清除剂。因此，含tdbtfp电解质的Li||NCM811电池具有214.4 mAh g-1的高初始放电容量，在4.6 V的高截止电压下循环200次后保持88.8%的初始容量，在4.7 V和60℃循环200次后分别保持86.5%和72.3%的初始容量。
{"title":"A B/F/N-Contained Additive: Synchronous Regulation of Bilateral Electrode-Electrolyte Interphases and Elimination of HF Enables High-Voltage and High-Temperature Lithium Metal Batteries","authors":"Tao Ren, Yu Bai, Xin Li, Jiaxin Jing, Zhenhua Wang, Kening Sun","doi":"10.1016/j.ensm.2026.105033","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105033","url":null,"abstract":"The development of high-voltage lithium metal batteries is constrained by the instability of the electrode-electrolyte interphase (EEI). This study proposes a novel multifunctional additive,3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(trifluoromethyl)pyridine (TDBTFP), which helps to restructure the Li<sup>+</sup> solvation structure, so as to reduce the Li<sup>+</sup> desolvation energy barrier and improve Li<sup>+</sup> transport kinetics. The introduction of TDBTFP enables the construction of a solid electrolyte interphase (SEI) enriched with LiF, LiB<sub>x</sub>O<sub>y</sub> and Li<sub>3</sub>N on the Li anode, thereby suppressing dendrite growth. Simultaneously, a cathode electrolyte interphase (CEI) with a gradient composition is formed on the NCM811. The CEI structure features LiF residing predominantly in the inner layer and Li<sub>3</sub>N/LiB<sub>x</sub>O<sub>y</sub> concentrated mainly in the outer layer, which collectively enhances Li<sup>+</sup> conductivity and inhibits phase transition and transition metals dissolution for the NCM811. Furthermore, TDBTFP acts as an efficient HF scavenger. Consequently, Li||NCM811 battery with TDBTFP-contained electrolyte delivers a high initial discharge capacity of 214.4 mAh g<sup>-1</sup> and retains 88.8% of its initial capacity after 200 cycles at a high cut-off voltage of 4.6 V, along with 86.5% retention at 4.7 V and 72.3% at 60°C after 200 cycles of its initial capacity respectively.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"17 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147440216","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：