The stability of electrode materials in aqueous environments presents a significant challenge for the long-term performance of energy storage systems, particularly when operating at potentials that promote water electrolysis. Many electrode materials undergo spontaneous self-discharge, resulting in a gradual loss of stored charge. While previous studies have shown that metallic and inorganic electrodes in aqueous solutions can experience significant self-discharge, much less is known about this phenomenon in organic electrodes. To bridge this gap, this study investigates the self-discharge behavior of polyimide (PI)-based electrodes, focusing on 1,4,5,8-naphthalenetetracarboxylic dianhydride-derived polyimide (PNTCDA) in aqueous electrolyte solutions. Through a systematic evaluation of charge loss, we demonstrate that while water reduction primarily drives reversible self-discharge, it also indirectly contributes to irreversible capacity loss by generating reactive species and conditions that accelerate the hydrolytic degradation of the polymeric structure. These processes are particularly pronounced when the anode material is in its electrochemically reduced state at low potentials. Comparisons with nonaqueous systems reveal that even small amounts of water can significantly accelerate capacity loss, underscoring the susceptibility of organic-based electrodes to instability when operating within potential windows where water is reduced. These findings highlight the critical need for strategies to mitigate both reversible self-discharge and irreversible degradation processes in aqueous battery systems.
{"title":"Mechanisms of self-discharge and capacity loss in organic electrodes for aqueous batteries","authors":"Idan Karev , Amey Nimkar , Netanel Shpigel , Daniel Sharon","doi":"10.1016/j.ensm.2025.104215","DOIUrl":"10.1016/j.ensm.2025.104215","url":null,"abstract":"<div><div>The stability of electrode materials in aqueous environments presents a significant challenge for the long-term performance of energy storage systems, particularly when operating at potentials that promote water electrolysis. Many electrode materials undergo spontaneous self-discharge, resulting in a gradual loss of stored charge. While previous studies have shown that metallic and inorganic electrodes in aqueous solutions can experience significant self-discharge, much less is known about this phenomenon in organic electrodes. To bridge this gap, this study investigates the self-discharge behavior of polyimide (PI)-based electrodes, focusing on 1,4,5,8-naphthalenetetracarboxylic dianhydride-derived polyimide (PNTCDA) in aqueous electrolyte solutions. Through a systematic evaluation of charge loss, we demonstrate that while water reduction primarily drives reversible self-discharge, it also indirectly contributes to irreversible capacity loss by generating reactive species and conditions that accelerate the hydrolytic degradation of the polymeric structure. These processes are particularly pronounced when the anode material is in its electrochemically reduced state at low potentials. Comparisons with nonaqueous systems reveal that even small amounts of water can significantly accelerate capacity loss, underscoring the susceptibility of organic-based electrodes to instability when operating within potential windows where water is reduced. These findings highlight the critical need for strategies to mitigate both reversible self-discharge and irreversible degradation processes in aqueous battery systems.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104215"},"PeriodicalIF":18.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734484","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-01DOI: 10.1016/j.ensm.2025.104217
Yueming Wang , Mingqian Ji , Tengfei Zhu , Li Wang , Ying Zhou , Dejun Li , Hong Xu , Xiangming He
Striving to enhance the energy density of lithium metal batteries (LMBs) through the integration of Ni-rich cathodes is pivotal. However, these advanced batteries face significant challenges due to cathode degradation induced by water and the propensity for Li dendrite growth. To overcome these obstacles, we have synthesized amino-modified UIO-66 zirconium metal-organic frameworks (MOFs), U66N, which serve as a multifunctional separator layer to eliminate water and inhibit Li dendrite formation. Experimental evidence and theoretical computations collectively illustrate that U66N is highly effective in scavenging trace water from the electrolyte and facilitating the dissociation of Li salts, aided by the amino groups, thus preventing cathode degradation, improving electrochemical kinetics, and finely tuning the Li plating and stripping processes. In our testing, NCM811||Li cells equipped with the U66N separator preserve 77.1 % of their initial capacity after 200 cycles in an electrolyte contaminated with 300 ppm water, which is a markedly higher retention rate compared to cells with a conventional PP separator (24.7 %). Moreover, even in the electrolyte containing 600 ppm water, the NCM811||Li cells manage to retain 83.2 % of their capacity after 100 cycles. This study not only establishes a theoretical framework for the precise design of functionalized MOFs materials but also significantly advances the development of high-end battery systems with unparalleled energy density.
{"title":"Multifunctional amino-functionalized Zr-based metal-organic frameworks: A breakthrough in enhancing the stability and performance of Ni-rich cathode Li metal batteries in water-prone environments","authors":"Yueming Wang , Mingqian Ji , Tengfei Zhu , Li Wang , Ying Zhou , Dejun Li , Hong Xu , Xiangming He","doi":"10.1016/j.ensm.2025.104217","DOIUrl":"10.1016/j.ensm.2025.104217","url":null,"abstract":"<div><div>Striving to enhance the energy density of lithium metal batteries (LMBs) through the integration of Ni-rich cathodes is pivotal. However, these advanced batteries face significant challenges due to cathode degradation induced by water and the propensity for Li dendrite growth. To overcome these obstacles, we have synthesized amino-modified UIO-66 zirconium metal-organic frameworks (MOFs), U66N, which serve as a multifunctional separator layer to eliminate water and inhibit Li dendrite formation. Experimental evidence and theoretical computations collectively illustrate that U66N is highly effective in scavenging trace water from the electrolyte and facilitating the dissociation of Li salts, aided by the amino groups, thus preventing cathode degradation, improving electrochemical kinetics, and finely tuning the Li plating and stripping processes. In our testing, NCM811||Li cells equipped with the U66N separator preserve 77.1 % of their initial capacity after 200 cycles in an electrolyte contaminated with 300 ppm water, which is a markedly higher retention rate compared to cells with a conventional PP separator (24.7 %). Moreover, even in the electrolyte containing 600 ppm water, the NCM811||Li cells manage to retain 83.2 % of their capacity after 100 cycles. This study not only establishes a theoretical framework for the precise design of functionalized MOFs materials but also significantly advances the development of high-end battery systems with unparalleled energy density.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104217"},"PeriodicalIF":18.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734483","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}
Zinc-ion capacitors (ZICs) are viewed as a promising energy storage solution for portable electronics and biocompatible devices. Nevertheless, current ZICs technology faces challenges such as restricted specific capacitance, suboptimal cycling performance, and ongoing validation efforts regarding their biocompatibility. Herein, hierarchical porous carbon materials were prepared through a two-step carbonization-activation method using kapok fiber biomass as the precursor. The kapok fibers-based cathodes contain abundant micropores and mesopores, which provide abundant active sites for Zn2+ storage and optimize reaction kinetics. The ZICs demonstrate an ultra-high cycling life exceeding 240,000 cycles. Meanwhile, theoretical calculations verify that large micropores exhibit a reduced diffusion energy barrier for [Zn(H2O)6]2+, which accelerates [Zn(H2O)6]2+ adsorption/desorption and increases the available reversible capacitance. Furthermore, the ZICs exhibit excellent biodegradability in soil, simulated human body fluids and real seawater, and low cytotoxicity to human cells and minimal tissue damage in animal. This research presents a potential pathway for the advancement and verification of biocompatible ZICs, thereby contributing to their prospective practical utilization in biomedical and environmental field.
{"title":"Hierarchical porous carbon derived from kapok fibers for biocompatible and ultralong cycling zinc-ion capacitors","authors":"Qi Song, Ling Jiang, Hongming Chen, Huifu Li, Yaxu Yang, Shuo Huang, Lijie Luo, Yongjun Chen","doi":"10.1016/j.ensm.2025.104219","DOIUrl":"10.1016/j.ensm.2025.104219","url":null,"abstract":"<div><div>Zinc-ion capacitors (ZICs) are viewed as a promising energy storage solution for portable electronics and biocompatible devices. Nevertheless, current ZICs technology faces challenges such as restricted specific capacitance, suboptimal cycling performance, and ongoing validation efforts regarding their biocompatibility. Herein, hierarchical porous carbon materials were prepared through a two-step carbonization-activation method using kapok fiber biomass as the precursor. The kapok fibers-based cathodes contain abundant micropores and mesopores, which provide abundant active sites for Zn<sup>2+</sup> storage and optimize reaction kinetics. The ZICs demonstrate an ultra-high cycling life exceeding 240,000 cycles. Meanwhile, theoretical calculations verify that large micropores exhibit a reduced diffusion energy barrier for [Zn(H<sub>2</sub>O)<sub>6</sub>]<sup>2+</sup>, which accelerates [Zn(H<sub>2</sub>O)<sub>6</sub>]<sup>2+</sup> adsorption/desorption and increases the available reversible capacitance. Furthermore, the ZICs exhibit excellent biodegradability in soil, simulated human body fluids and real seawater, and low cytotoxicity to human cells and minimal tissue damage in animal. This research presents a potential pathway for the advancement and verification of biocompatible ZICs, thereby contributing to their prospective practical utilization in biomedical and environmental field.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104219"},"PeriodicalIF":18.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737278","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-01DOI: 10.1016/j.ensm.2025.104232
Shunlong Ju , Xiaoyue Zhang , Chaoqun Li , Yingxue Li , Panyu Gao , Sihan Yin , Tengfei Zhang , Guanglin Xia , Baozhong Liu , Xuebin Yu
The uncontrolled deposition behavior, sluggish reaction kinetics and inefficient utilization of Al derived from unstable anode/electrolyte interface have severely impeded the development of aluminum-ion batteries. Here, we discuss the impact of interfacial electron/ion transfer on the electrochemical performance, and as an illustration, propose the construction of Cu@MXene as anodic current collector through work function engineering to simultaneously achieve homogeneous deposition morphology and rapid plating/stripping rate. The difference in work function between Cu nanoparticles and Ti3C2 MXene facilitates charge redistribution in the anode/electrolyte interface and enhances the electron availability, optimizing the interfacial electron/ion transfer behavior. This, in turn, endows Cu@MXene with elevated catalytic efficiency for desolvation reactions and robust reduction ability for the Al plating process. As a result, Cu@MXene enables a high coulombic efficiency of 99.87 % even at a high current density of 10 mA cm−2, and sustains reversible Al plating/stripping cycles for over 3200 h at a typical current density of 1 mA cm−2. Notably, by coupling graphite cathode and Cu@MXene-Al anode under a limited N/P ratio of 2.2, the full cell exhibits durable lifetime for 2000 cycles with an impressive energy density of 119.6 Wh kg−1 (based on the total mass of cathode and anode). This work highlights a fundamental understanding of interfacial interactions in the Al deposition process and offer sustainability motivations in designing highly reversible anodes for high-energy-density aluminum-ion batteries.
{"title":"Dendrite-free aluminum metal anode enabled by work function engineering","authors":"Shunlong Ju , Xiaoyue Zhang , Chaoqun Li , Yingxue Li , Panyu Gao , Sihan Yin , Tengfei Zhang , Guanglin Xia , Baozhong Liu , Xuebin Yu","doi":"10.1016/j.ensm.2025.104232","DOIUrl":"10.1016/j.ensm.2025.104232","url":null,"abstract":"<div><div>The uncontrolled deposition behavior, sluggish reaction kinetics and inefficient utilization of Al derived from unstable anode/electrolyte interface have severely impeded the development of aluminum-ion batteries. Here, we discuss the impact of interfacial electron/ion transfer on the electrochemical performance, and as an illustration, propose the construction of Cu@MXene as anodic current collector through work function engineering to simultaneously achieve homogeneous deposition morphology and rapid plating/stripping rate. The difference in work function between Cu nanoparticles and Ti<sub>3</sub>C<sub>2</sub> MXene facilitates charge redistribution in the anode/electrolyte interface and enhances the electron availability, optimizing the interfacial electron/ion transfer behavior. This, in turn, endows Cu@MXene with elevated catalytic efficiency for desolvation reactions and robust reduction ability for the Al plating process. As a result, Cu@MXene enables a high coulombic efficiency of 99.87 % even at a high current density of 10 mA cm<sup>−2</sup>, and sustains reversible Al plating/stripping cycles for over 3200 h at a typical current density of 1 mA cm<sup>−2</sup>. Notably, by coupling graphite cathode and Cu@MXene-Al anode under a limited N/P ratio of 2.2, the full cell exhibits durable lifetime for 2000 cycles with an impressive energy density of 119.6 Wh kg<sup>−1</sup> (based on the total mass of cathode and anode). This work highlights a fundamental understanding of interfacial interactions in the Al deposition process and offer sustainability motivations in designing highly reversible anodes for high-energy-density aluminum-ion batteries.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104232"},"PeriodicalIF":18.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776215","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-01DOI: 10.1016/j.ensm.2025.104229
Junye Zhang , Linlin Wang , Yuping Liao , Chen Huang , Hangtian Zhu , Juan Wang , Linying Yuan , Tianchen Shen , Shigang Lu , Luyang Chen
Despite their environmental friendliness, security and high volumetric energy density of zinc anodes, aqueous Zinc-ion batteries (AZIBs) still face poor reversibility of Zn anodes, especially under high current density, originating from various parasitic reactions induced by high activity of water. The hydrated deep eutectic electrolyte (HDEE) effectively suppresses parasitic reactions, but the electrochemical performance still needs to be optimized. Here, our research emphasized the importance of balancing enhanced reversibility and fast Zn2+ transfer kinetics. A new green and low-cost HDEE (Zn(ClO4)2·6H2O/Glycerol) is developed, and then an optimized solvation structure [Zn(H2O)2.0(Gl)1.3(ClO4)2.7]²⁺ can be formed by adding glycerol (Gl), which not only maintains a high Zn2+ diffusion coefficient (1.2 × 10−7 cm2 s−1), but also disrupts the bulk water network via strong H-bonding with ClO₄− and water, significantly lowering the freezing point (−65 °C) and inhibiting the parasitic reactions/cathode dissolution. Furthermore, the evolution of the HDEEs solvation chemistry and its impact on the electrode/electrolyte interfacial stabilities can be understood through precise adjustments of the molar ratios of Zn(ClO4)2·6H2O and Gl, molecular dynamics and COMSOL simulation. The Zn//Zn with the HDEE (Zn|HDEE|Zn cells) can cycle for ∼5000 h without short-circuiting at 1 mA cm−2, which is roughly 12.5 times more stable than ordinary aqueous electrolyte, indicating effective suppression of parasitic reactions. The Zn//NH4V4O10 with HDEE (Zn|HDEE|NH4V4O10 cells) can stably cycle 3500 cycles with 120 mAh g−1 at 10 A g−1 at room temperature and 1000 cycles with 95 mAh g−1 at 5 A g−1 at a low temperature of -20 °C. This study provides a path toward the development of HDEE electrolyte and a thorough comprehension of the influence of Zn2+ solvation structure on reversibility.
{"title":"Trade-off between reversibility and fast Zn2+ kinetics: Toward ultra-stable low-temperature aqueous zinc-ion batteries","authors":"Junye Zhang , Linlin Wang , Yuping Liao , Chen Huang , Hangtian Zhu , Juan Wang , Linying Yuan , Tianchen Shen , Shigang Lu , Luyang Chen","doi":"10.1016/j.ensm.2025.104229","DOIUrl":"10.1016/j.ensm.2025.104229","url":null,"abstract":"<div><div>Despite their environmental friendliness, security and high volumetric energy density of zinc anodes, aqueous Zinc-ion batteries (AZIBs) still face poor reversibility of Zn anodes, especially under high current density, originating from various parasitic reactions induced by high activity of water. The hydrated deep eutectic electrolyte (HDEE) effectively suppresses parasitic reactions, but the electrochemical performance still needs to be optimized. Here, our research emphasized the importance of balancing enhanced reversibility and fast Zn<sup>2+</sup> transfer kinetics. A new green and low-cost HDEE (Zn(ClO<sub>4</sub>)<sub>2</sub>·6H<sub>2</sub>O/Glycerol) is developed, and then an optimized solvation structure [Zn(H<sub>2</sub>O)<sub>2.0</sub>(Gl)<sub>1.3</sub>(ClO<sub>4</sub>)<sub>2.7</sub>]²⁺ can be formed by adding glycerol (Gl), which not only maintains a high Zn<sup>2+</sup> diffusion coefficient (1.2 × 10<sup>−7</sup> cm<sup>2</sup> s<sup>−1</sup>), but also disrupts the bulk water network via strong H-bonding with ClO₄<sup>−</sup> and water, significantly lowering the freezing point (−65 °C) and inhibiting the parasitic reactions/cathode dissolution. Furthermore, the evolution of the HDEEs solvation chemistry and its impact on the electrode/electrolyte interfacial stabilities can be understood through precise adjustments of the molar ratios of Zn(ClO<sub>4</sub>)<sub>2</sub>·6H<sub>2</sub>O and Gl, molecular dynamics and COMSOL simulation. The Zn//Zn with the HDEE (Zn|HDEE|Zn cells) can cycle for ∼5000 h without short-circuiting at 1 mA cm<sup>−2</sup>, which is roughly 12.5 times more stable than ordinary aqueous electrolyte, indicating effective suppression of parasitic reactions. The Zn//NH<sub>4</sub>V<sub>4</sub>O<sub>10</sub> with HDEE (Zn|HDEE|NH<sub>4</sub>V<sub>4</sub>O<sub>10</sub> cells) can stably cycle 3500 cycles with 120 mAh <em>g</em><sup>−1</sup> at 10 A <em>g</em><sup>−1</sup> at room temperature and 1000 cycles with 95 mAh <em>g</em><sup>−1</sup> at 5 A <em>g</em><sup>−1</sup> at a low temperature of -20 °C. This study provides a path toward the development of HDEE electrolyte and a thorough comprehension of the influence of Zn<sup>2+</sup> solvation structure on reversibility.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104229"},"PeriodicalIF":18.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766696","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-01DOI: 10.1016/j.ensm.2025.104193
Younghoon Jo , Hongjun Chang , Chaeyeon Ha , Hyeongjun Choi , Taesun Song , Yeonghoon Kim , Janghyuk Moon , Young-Jun Kim
Sulfide-based all-solid-state batteries (ASSBs) are promising candidates for next-generation energy storage systems owing to their notable ionic conductivity and stability against explosions. However, the low chemical stability of sulfide-based solid electrolytes (SSEs) causes problems at their interfaces with other electrode components. Among them, addressing the side reactions between conductive agents and SSEs is crucial for commercialization. Herein, a conductive agent surface-modified with Li3PO4 is employed to enhance the interfacial stability of SSEs. Density functional theory-based analysis reveals that Li3PO4, characterized by strong inter-element bonding, exhibits high ionic conductivity and stability at the interface with SSEs. Electrochemical measurements confirm that Li3PO4-coated conductive agents suppress the interfacial decomposition of SSEs, thereby securing the targeted ionic conductivity in the composite cathode. Consequently, ASSBs adopting surface-engineered conductive agents demonstrate remarkable rate capability (153.6 mAh g−1 at 2 C) and cycle performance (88.8 % retention over 1000 cycles) with a high areal capacity (4 mAh cm−2). This study provides a novel concept for conductive agents that enhance charge transport characteristics and mitigate SSE degradation, paving the way for the development of long cycle life ASSBs.
{"title":"Prolonged cycle life of composite cathodes via ionically permeable Li3PO4 surface engineering on conductive agents to suppress degradation of sulfide solid electrolytes","authors":"Younghoon Jo , Hongjun Chang , Chaeyeon Ha , Hyeongjun Choi , Taesun Song , Yeonghoon Kim , Janghyuk Moon , Young-Jun Kim","doi":"10.1016/j.ensm.2025.104193","DOIUrl":"10.1016/j.ensm.2025.104193","url":null,"abstract":"<div><div>Sulfide-based all-solid-state batteries (ASSBs) are promising candidates for next-generation energy storage systems owing to their notable ionic conductivity and stability against explosions. However, the low chemical stability of sulfide-based solid electrolytes (SSEs) causes problems at their interfaces with other electrode components. Among them, addressing the side reactions between conductive agents and SSEs is crucial for commercialization. Herein, a conductive agent surface-modified with Li<sub>3</sub>PO<sub>4</sub> is employed to enhance the interfacial stability of SSEs. Density functional theory-based analysis reveals that Li<sub>3</sub>PO<sub>4</sub>, characterized by strong inter-element bonding, exhibits high ionic conductivity and stability at the interface with SSEs. Electrochemical measurements confirm that Li<sub>3</sub>PO<sub>4</sub>-coated conductive agents suppress the interfacial decomposition of SSEs, thereby securing the targeted ionic conductivity in the composite cathode. Consequently, ASSBs adopting surface-engineered conductive agents demonstrate remarkable rate capability (153.6 mAh g<sup>−1</sup> at 2 C) and cycle performance (88.8 % retention over 1000 cycles) with a high areal capacity (4 mAh cm<sup>−2</sup>). This study provides a novel concept for conductive agents that enhance charge transport characteristics and mitigate SSE degradation, paving the way for the development of long cycle life ASSBs.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104193"},"PeriodicalIF":18.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703032","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sodium-ion batteries (SIBs) are potential candidates for next-generation grid-scale energy storage owing to their safety as well as the abundance of sodium resources. Further progress in SIB technology demands the advancement of cathode materials with outstanding performance. Among various cathode materials, layered transition metal oxides based on Ni, Fe, and Mn (NaNFM) have recently received great attention by combining the positive features of each of them. This review focuses on the most current developments in the study and design of NaNFM (NaxNiyFezMn1−(y+z)O2) as a cathode material for SIBs, including synthesis methods, crystal structure/structural evolution during charge–discharging, and the effect of different molar ratios. Adjusting the transition elements enables formation in several phases that promote Na-ion diffusion, resulting in high-rate capability and cycle stability. Moreover, key strategies to improve the electrochemical performance through doping and surface modifications are discussed. Future optimization of these materials shows potential for enormous opportunities for implementing cost-effective and high-performance energy -storage technologies.
{"title":"Towards high-performance sodium-ion batteries: A comprehensive review on NaxNiyFezMn1−(y+z)O2 cathode materials","authors":"Alibi Namazbay , Maksat Karlykan , Lunara Rakhymbay , Zhumabay Bakenov , Natalia Voronina , Seung-Taek Myung , Aishuak Konarov","doi":"10.1016/j.ensm.2025.104212","DOIUrl":"10.1016/j.ensm.2025.104212","url":null,"abstract":"<div><div>Sodium-ion batteries (SIBs) are potential candidates for next-generation grid-scale energy storage owing to their safety as well as the abundance of sodium resources. Further progress in SIB technology demands the advancement of cathode materials with outstanding performance. Among various cathode materials, layered transition metal oxides based on Ni, Fe, and Mn (NaNFM) have recently received great attention by combining the positive features of each of them. This review focuses on the most current developments in the study and design of NaNFM (Na<em><sub>x</sub></em>Ni<em><sub>y</sub></em>Fe<em><sub>z</sub></em>Mn<sub>1−(<em><sub>y</sub></em>+</sub><em><sub>z</sub></em><sub>)</sub>O<sub>2</sub>) as a cathode material for SIBs, including synthesis methods, crystal structure/structural evolution during charge–discharging, and the effect of different molar ratios. Adjusting the transition elements enables formation in several phases that promote Na-ion diffusion, resulting in high-rate capability and cycle stability. Moreover, key strategies to improve the electrochemical performance through doping and surface modifications are discussed. Future optimization of these materials shows potential for enormous opportunities for implementing cost-effective and high-performance energy -storage technologies.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104212"},"PeriodicalIF":18.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723843","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-01DOI: 10.1016/j.ensm.2025.104213
Peng Yin , Li Lei , Qingyang Tang , Davoud Dastan , Yao Liu , Hong Wang , Zhicheng Shi
Polymer dielectrics suffer from significant degradation in energy density and charge–discharge efficiency at high temperatures, and incorporating inorganic nanofillers into polymer is the most straightforward and effective approach to ameliorate this behavior. However, the nanofillers are prone to form aggregated state driven by surface energy and electrostatic forces, compromising high-temperature energy storage performance of dielectrics. Here, we propose a unique non-contiguous granular intercalation strategy to solve the nanofiller aggregation problem. Specifically, an intercalation consisting of non-contiguous distributed aluminum@alumina (Al@AlOx) core–shell nanoparticles is introduced into polyetherimide (PEI) matrix via sputtering reaction. It should be noted that the non-contiguous distribution of nanoparticles within the intercalation ensures discontinuous charge transport, which prevents the formation of conductive network within the nanocomposite. Additionally, benefiting from charge trap induced by wide-bandgap AlOx shell and Coulomb blockade effect of Al core, the charge transport is significantly suppressed. The nanocomposite achieves ultrahigh energy densities of 9.0 J cm⁻3 at 150 °C and 6.2 J cm⁻3 at 200 °C, with charge–discharge efficiencies ≥ 90 %. This work offers a promising pathway for the design of high-temperature energy storage dielectrics and holds huge potential for scalable fabrication.
{"title":"Polymer dielectrics intercalated with a non-contiguous granular nanolayer for high-temperature pulsed energy storage","authors":"Peng Yin , Li Lei , Qingyang Tang , Davoud Dastan , Yao Liu , Hong Wang , Zhicheng Shi","doi":"10.1016/j.ensm.2025.104213","DOIUrl":"10.1016/j.ensm.2025.104213","url":null,"abstract":"<div><div>Polymer dielectrics suffer from significant degradation in energy density and charge–discharge efficiency at high temperatures, and incorporating inorganic nanofillers into polymer is the most straightforward and effective approach to ameliorate this behavior. However, the nanofillers are prone to form aggregated state driven by surface energy and electrostatic forces, compromising high-temperature energy storage performance of dielectrics. Here, we propose a unique non-contiguous granular intercalation strategy to solve the nanofiller aggregation problem. Specifically, an intercalation consisting of non-contiguous distributed aluminum@alumina (Al@AlO<sub>x</sub>) core–shell nanoparticles is introduced into polyetherimide (PEI) matrix via sputtering reaction. It should be noted that the non-contiguous distribution of nanoparticles within the intercalation ensures discontinuous charge transport, which prevents the formation of conductive network within the nanocomposite. Additionally, benefiting from charge trap induced by wide-bandgap AlO<sub>x</sub> shell and Coulomb blockade effect of Al core, the charge transport is significantly suppressed. The nanocomposite achieves ultrahigh energy densities of 9.0 J cm⁻<sup>3</sup> at 150 °C and 6.2 J cm⁻<sup>3</sup> at 200 °C, with charge–discharge efficiencies ≥ 90 %. This work offers a promising pathway for the design of high-temperature energy storage dielectrics and holds huge potential for scalable fabrication.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104213"},"PeriodicalIF":18.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767710","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-01DOI: 10.1016/j.ensm.2025.104216
Hao Ge , Bei Huang , Chaoyue Wang , Longhui Xie , Ruicong Pan , Xiaoman Cao , Zhijia Sun
The global market share of electric vehicles has rapidly grown from ∼10 % in 2022 to ∼18 % in 2024. However, safety issue is a crucial obstacle hindering the commercialization of high-energy lithium-ion batteries. The inferior thermal stability exhibited by high-energy Ni-rich cathodes has severely affected their practical application in LIBs. Particularly, Co in Ni-rich cathodes promotes lattice oxygen release, leading to reduced structural and thermal stability. Therefore, the development of Ni-rich Co-free cathode materials (NRCFs) is promising. Herein, the detrimental effects of Co on the thermal stability of Ni-rich layered oxides are demonstrated. Thereafter, we summarize in detail the popular modification strategies and mechanisms for enhancing the thermal stability of NRCFs. Finally, conclusions and future challenges and prospects for boosting the thermal stability of NRCFs are presented. Notably, synergistic modification strategies combining high-entropy doping and surface coating in single-crystal cathode materials is an efficient approach to significantly improve the thermal stability. Understanding the thermal stability of NRCFs has become urgent for the large-scale application of high-energy LIBs. More effective thermal safety strategies will be aroused to promote the development of next-generation power LIBs. This review aims to inspire further exploration of safer NRCFs featuring higher reversible capacity, attracting interest from both academic and industrial communities to accelerate the commercialization of NRCFs and promote the sustainable development of high-energy LIBs.
{"title":"Advanced design strategies for enhancing the thermal stability of Ni-rich co-free cathodes towards high-energy power lithium-ion batteries","authors":"Hao Ge , Bei Huang , Chaoyue Wang , Longhui Xie , Ruicong Pan , Xiaoman Cao , Zhijia Sun","doi":"10.1016/j.ensm.2025.104216","DOIUrl":"10.1016/j.ensm.2025.104216","url":null,"abstract":"<div><div>The global market share of electric vehicles has rapidly grown from ∼10 % in 2022 to ∼18 % in 2024. However, safety issue is a crucial obstacle hindering the commercialization of high-energy lithium-ion batteries. The inferior thermal stability exhibited by high-energy Ni-rich cathodes has severely affected their practical application in LIBs. Particularly, Co in Ni-rich cathodes promotes lattice oxygen release, leading to reduced structural and thermal stability. Therefore, the development of Ni-rich Co-free cathode materials (NRCFs) is promising. Herein, the detrimental effects of Co on the thermal stability of Ni-rich layered oxides are demonstrated. Thereafter, we summarize in detail the popular modification strategies and mechanisms for enhancing the thermal stability of NRCFs. Finally, conclusions and future challenges and prospects for boosting the thermal stability of NRCFs are presented. Notably, synergistic modification strategies combining high-entropy doping and surface coating in single-crystal cathode materials is an efficient approach to significantly improve the thermal stability. Understanding the thermal stability of NRCFs has become urgent for the large-scale application of high-energy LIBs. More effective thermal safety strategies will be aroused to promote the development of next-generation power LIBs. This review aims to inspire further exploration of safer NRCFs featuring higher reversible capacity, attracting interest from both academic and industrial communities to accelerate the commercialization of NRCFs and promote the sustainable development of high-energy LIBs.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104216"},"PeriodicalIF":18.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734486","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-01DOI: 10.1016/j.ensm.2025.104221
Yang Li , Gang Wu , Xiaomeng Fan , Dabing Li , Hong Liu , Xiaoxue Zhao , Wanqing Ren , Peng Lei , Xianyi Zhao , Xun Wang , Guoxu Wang , Lei Gao , Ce-Wen Nan , Li-Zhen Fan
Solid-state electrolytes (SSEs) play a crucial role in the operation of all-solid-state lithium metal batteries (ASSLMBs). Among them, sulfide SSEs have attracted particular attention due to their high ionic conductivity. However, the incompatibility of sulfide SSEs with lithium anodes and the inherent air instability severely impact battery cycling performance. Here, we successfully synthesize halogen-rich lithium argyrodites with the general formula Li5.5+3xP1−xCuxS4.5Cl1.5−2xBr2x. The incorporation of Cu and Br alter the spatial arrangement and electronic distribution of structure. Given that the anion disorder positively affects Li-ion dynamics, the ultrahigh ionic conductivity of 10.3 mS cm−1 at room temperature has been achieved in Li5.8P0.9Cu0.1S4.5Cl1.3Br0.2 (LPSC-CB). Importantly, benefiting from the robust and stable interlayer, the lithium symmetric batteries deliver prolonged plating/stripping over 3000 h at 0.2 mA cm−2. Furthermore, the density functional theory calculations were used to prove the mechanisms of high chemical stability. Notably, the LPSC-CB electrolyte has remarkable applicability in ASSLMBs. The full batteries of FeS2/LPSC-CB/Li deliver outstanding discharge-specific capacities of 788.9 mAh g−1 and robust cycling stability (>4.02 mAh cm−2 after 200 cycles). The versatile CuBr2 substitution in the most promising argyrodite electrolytes is considered as a valid strategy to realize high ionic conductivity and air-stabilized sulfide SSEs for large-scale applications.
{"title":"Engineering high-performance argyrodite sulfide electrolytes via metal halide doping for all-solid-state lithium metal batteries","authors":"Yang Li , Gang Wu , Xiaomeng Fan , Dabing Li , Hong Liu , Xiaoxue Zhao , Wanqing Ren , Peng Lei , Xianyi Zhao , Xun Wang , Guoxu Wang , Lei Gao , Ce-Wen Nan , Li-Zhen Fan","doi":"10.1016/j.ensm.2025.104221","DOIUrl":"10.1016/j.ensm.2025.104221","url":null,"abstract":"<div><div>Solid-state electrolytes (SSEs) play a crucial role in the operation of all-solid-state lithium metal batteries (ASSLMBs). Among them, sulfide SSEs have attracted particular attention due to their high ionic conductivity. However, the incompatibility of sulfide SSEs with lithium anodes and the inherent air instability severely impact battery cycling performance. Here, we successfully synthesize halogen-rich lithium argyrodites with the general formula Li<sub>5.5</sub> <sub>+</sub> <sub>3x</sub>P<sub>1−x</sub>Cu<sub>x</sub>S<sub>4.5</sub>Cl<sub>1.5</sub> <sub>−</sub> <sub>2x</sub>Br<sub>2x</sub>. The incorporation of Cu and Br alter the spatial arrangement and electronic distribution of structure. Given that the anion disorder positively affects Li-ion dynamics, the ultrahigh ionic conductivity of 10.3 mS cm<sup>−1</sup> at room temperature has been achieved in Li<sub>5.8</sub>P<sub>0.9</sub>Cu<sub>0.1</sub>S<sub>4.5</sub>Cl<sub>1.3</sub>Br<sub>0.2</sub> (LPSC-CB). Importantly, benefiting from the robust and stable interlayer, the lithium symmetric batteries deliver prolonged plating/stripping over 3000 h at 0.2 mA cm<sup>−2</sup>. Furthermore, the density functional theory calculations were used to prove the mechanisms of high chemical stability. Notably, the LPSC-CB electrolyte has remarkable applicability in ASSLMBs. The full batteries of FeS<sub>2</sub>/LPSC-CB/Li deliver outstanding discharge-specific capacities of 788.9 mAh g<sup>−1</sup> and robust cycling stability (>4.02 mAh cm<sup>−2</sup> after 200 cycles). The versatile CuBr<sub>2</sub> substitution in the most promising argyrodite electrolytes is considered as a valid strategy to realize high ionic conductivity and air-stabilized sulfide SSEs for large-scale applications.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104221"},"PeriodicalIF":18.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737274","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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