Pub Date : 2025-02-01DOI: 10.1016/j.ensm.2025.104055
Jianyong Zhang , Jingyuan Yu , Qin Liu , Chunhua Han , Ahmed Eissa Abdelmaoula , Lin Xu
Aqueous batteries hold promising prospects as the next generation of batteries due to their high safety level, low cost, and environmental friendliness. However, for decades, aqueous batteries have been plagued by electrode dissolution issues, which are attributed to the formation of hydrogen bonds, particularly in acidic-type aqueous proton batteries. Herein, this work reveals that symmetrically polarized structural materials effectively solve the dissolution issue of electrodes, owing to an anti-hydrogen bond framework that hinders the formation of hydrogen bonds between the carbonyl (C=O) group and water molecules. As a result, these symmetrically polarized effect-induced electrodes exhibit no electrode-dissolution phenomenon after being immersed in 1 M H2SO4 solution for 500 days and achieve stable cycling for 40,000 ultra-long cycles at 10 A g−1. Therefore, this study presents a compelling analysis of the ultra-stable electrode design in proton batteries, thereby demonstrating new opportunities for electrode construction in highly corrosive environments.
{"title":"Inhibition of quinone dissolution via symmetrically polarized effect for ultra-stable proton batteries","authors":"Jianyong Zhang , Jingyuan Yu , Qin Liu , Chunhua Han , Ahmed Eissa Abdelmaoula , Lin Xu","doi":"10.1016/j.ensm.2025.104055","DOIUrl":"10.1016/j.ensm.2025.104055","url":null,"abstract":"<div><div>Aqueous batteries hold promising prospects as the next generation of batteries due to their high safety level, low cost, and environmental friendliness. However, for decades, aqueous batteries have been plagued by electrode dissolution issues, which are attributed to the formation of hydrogen bonds, particularly in acidic-type aqueous proton batteries. Herein, this work reveals that symmetrically polarized structural materials effectively solve the dissolution issue of electrodes, owing to an anti-hydrogen bond framework that hinders the formation of hydrogen bonds between the carbonyl (C=O) group and water molecules. As a result, these symmetrically polarized effect-induced electrodes exhibit no electrode-dissolution phenomenon after being immersed in 1 M H<sub>2</sub>SO<sub>4</sub> solution for 500 days and achieve stable cycling for 40,000 ultra-long cycles at 10 A g<sup>−1</sup>. Therefore, this study presents a compelling analysis of the ultra-stable electrode design in proton batteries, thereby demonstrating new opportunities for electrode construction in highly corrosive environments.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"75 ","pages":"Article 104055"},"PeriodicalIF":18.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143035041","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 : 2025-02-01DOI: 10.1016/j.ensm.2025.104069
Minjian Li , Lianzhan Huang , Boyong Wu , Jinhui Liang , Jiahao Xiang , Tong Yan , Mengli Tao , Li Du , Zhiming Cui , Huiyu Song , Zhenxing Liang
The unexpected depletion of anions and the restricted diffusion of Li+ on the Li anode lead to uncontrolled dendrite growth in Li metal batteries. Solid electrolyte interphase (SEI) engineering has been proven to be an effective method for solving these issues. Herein, a novel SEI layer with Lewis acid/base dual-site is constructed with triisopropanolamine cyclic borate (BON) and LiTFSI (defined as TFBN) to regulate the transport behavior of anions and Li+. The electron-deficient boron atom in BON can serve as the Lewis acid site, which anchors the anion to prevent its depletion at the interface. Meanwhile, the electron-rich nitrogen atom can serve as the Lewis base site, which accelerates the transport of Li+ to facilitate smooth Li deposition. As a result, BON can effectively dissociate lithium salts and regulate the migration behavior of anions and Li+. Using this novel SEI layer, Li||Li symmetric batteries can achieve stable cycling for over 1200 h at 1.0 mA cm−². Furthermore, the Li||LFP full cells show 93.7 % capacity retention after 2000 cycles at an ultrahigh current of 10 C.
{"title":"Fast charging Lithium metal battery based on Lewis Acid/Base dual-site solid electrolyte interphase","authors":"Minjian Li , Lianzhan Huang , Boyong Wu , Jinhui Liang , Jiahao Xiang , Tong Yan , Mengli Tao , Li Du , Zhiming Cui , Huiyu Song , Zhenxing Liang","doi":"10.1016/j.ensm.2025.104069","DOIUrl":"10.1016/j.ensm.2025.104069","url":null,"abstract":"<div><div>The unexpected depletion of anions and the restricted diffusion of Li<sup>+</sup> on the Li anode lead to uncontrolled dendrite growth in Li metal batteries. Solid electrolyte interphase (SEI) engineering has been proven to be an effective method for solving these issues. Herein, a novel SEI layer with Lewis acid/base dual-site is constructed with triisopropanolamine cyclic borate (BON) and LiTFSI (defined as TFBN) to regulate the transport behavior of anions and Li<sup>+</sup>. The electron-deficient boron atom in BON can serve as the Lewis acid site, which anchors the anion to prevent its depletion at the interface. Meanwhile, the electron-rich nitrogen atom can serve as the Lewis base site, which accelerates the transport of Li<sup>+</sup> to facilitate smooth Li deposition. As a result, BON can effectively dissociate lithium salts and regulate the migration behavior of anions and Li<sup>+</sup>. Using this novel SEI layer, Li||Li symmetric batteries can achieve stable cycling for over 1200 h at 1.0 mA cm<sup>−</sup>². Furthermore, the Li||LFP full cells show 93.7 % capacity retention after 2000 cycles at an ultrahigh current of 10 C.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"75 ","pages":"Article 104069"},"PeriodicalIF":18.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143056390","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 : 2025-02-01DOI: 10.1016/j.ensm.2025.104074
Yifan Xu , Zongzi Jin , Xiangkun Kong , Chi Zhang , Cui Li , Zhiwen Zhuo , Ranran Peng , Chengwei Wang
In solid-state batteries, mixed electronic and ionic conductors play a crucial role in enhancing electrode charge transfer. This study proposes a strategy for modulating the reducibility of materials to develop stable and highly conductive mixed conductors based on perovskite-type (LixLa2/3-x/3)TiO3 oxides. Traditional methods that enhance electronic conductivity through B-site doping with variable valence transition metals have limited improvement on electronic conductivity with presence of significant secondary phases. Therefore, our approach focuses on A-site doping with fixed-valence non-transition metals to affect the reducibility of (LixLa2/3-x/3)TiO3, thereby regulating its electronic conductance properties. Our findings reveal that co-doping with the alkali metal Na and the alkaline earth metal Sr at the Li-site enhances the reducibility of Ti and doubles the electronic conductivity to 2.89 × 10–3 S/cm compared to the undoped composition. Meanwhile, Na-Sr co-doping improves the reconfiguration of the crystal lattice during the reduction process, so that it exhibits high sintering activity and thermodynamic stability. These factors together contribute to its outstanding rate capability and long cycle stability, enabling it to maintain over 50% of its initial capacity at a 50 C-rate, and demonstrating over 800 stable cycles at a 2.5 C-rate. This strategy provides a new way to develop high-performance mixed-conductor electrode framework materials for improving the electrode kinetic behavior of solid-state batteries and promoting their practical applications.
{"title":"Non-transition metal modulated reducibility strategy for highly conductive mixed electronic and ionic (LixLa2/3-x/3)TiO3 perovskite","authors":"Yifan Xu , Zongzi Jin , Xiangkun Kong , Chi Zhang , Cui Li , Zhiwen Zhuo , Ranran Peng , Chengwei Wang","doi":"10.1016/j.ensm.2025.104074","DOIUrl":"10.1016/j.ensm.2025.104074","url":null,"abstract":"<div><div>In solid-state batteries, mixed electronic and ionic conductors play a crucial role in enhancing electrode charge transfer. This study proposes a strategy for modulating the reducibility of materials to develop stable and highly conductive mixed conductors based on perovskite-type (Li<sub>x</sub>La<sub>2/3-x/3</sub>)TiO<sub>3</sub> oxides. Traditional methods that enhance electronic conductivity through B-site doping with variable valence transition metals have limited improvement on electronic conductivity with presence of significant secondary phases. Therefore, our approach focuses on A-site doping with fixed-valence non-transition metals to affect the reducibility of (Li<sub>x</sub>La<sub>2/3-x/3</sub>)TiO<sub>3</sub>, thereby regulating its electronic conductance properties. Our findings reveal that co-doping with the alkali metal Na and the alkaline earth metal Sr at the Li-site enhances the reducibility of Ti and doubles the electronic conductivity to 2.89 × 10<sup>–3</sup> S/cm compared to the undoped composition. Meanwhile, Na-Sr co-doping improves the reconfiguration of the crystal lattice during the reduction process, so that it exhibits high sintering activity and thermodynamic stability. These factors together contribute to its outstanding rate capability and long cycle stability, enabling it to maintain over 50% of its initial capacity at a 50 C-rate, and demonstrating over 800 stable cycles at a 2.5 C-rate. This strategy provides a new way to develop high-performance mixed-conductor electrode framework materials for improving the electrode kinetic behavior of solid-state batteries and promoting their practical applications.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"75 ","pages":"Article 104074"},"PeriodicalIF":18.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050432","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 : 2025-02-01DOI: 10.1016/j.ensm.2025.104051
Xiaojie Guo, Yi Yang, Chenwu Shi, Mingjian Xu, Yifan Liu, Deqiu Zou
Compared to external temperature monitoring and control of batteries, internal temperature monitoring and control can more realistically and directly display the temperature field inside the battery, and can perform thermal management more timely and effectively to prevent battery overheating or thermal runaway. Herein, a comprehensive review of the latest research advancements in internal temperature monitoring and control for batteries is provided. The thermal characteristics and temperature sensitivity of batteries are introduced first, followed by a detailed discussion of various internal temperature monitoring technologies, including Fiber Bragg Grating (FBG) sensors, embedded thermocouples, and thermal resistive temperature sensing devices, alongside other indirect methods. Real-time, accurate temperature data is provided by these technologies, assisting in the monitoring of the thermal state during battery operation. Building on this, different temperature control strategies are emphasized, such as active liquid cooling systems, the use of internal passive control methods, and various advanced low-temperature heating technologies. These strategies aim to effectively manage internal temperatures. Finally, the challenges currently faced by these strategies and future research directions were also discussed, including the improvement of the battery's intelligence to further enhance operational safety. This provides new insights for the future design and application of power batteries.
{"title":"Monitoring and control of internal temperature in power batteries: A comprehensive review","authors":"Xiaojie Guo, Yi Yang, Chenwu Shi, Mingjian Xu, Yifan Liu, Deqiu Zou","doi":"10.1016/j.ensm.2025.104051","DOIUrl":"10.1016/j.ensm.2025.104051","url":null,"abstract":"<div><div>Compared to external temperature monitoring and control of batteries, internal temperature monitoring and control can more realistically and directly display the temperature field inside the battery, and can perform thermal management more timely and effectively to prevent battery overheating or thermal runaway. Herein, a comprehensive review of the latest research advancements in internal temperature monitoring and control for batteries is provided. The thermal characteristics and temperature sensitivity of batteries are introduced first, followed by a detailed discussion of various internal temperature monitoring technologies, including Fiber Bragg Grating (FBG) sensors, embedded thermocouples, and thermal resistive temperature sensing devices, alongside other indirect methods. Real-time, accurate temperature data is provided by these technologies, assisting in the monitoring of the thermal state during battery operation. Building on this, different temperature control strategies are emphasized, such as active liquid cooling systems, the use of internal passive control methods, and various advanced low-temperature heating technologies. These strategies aim to effectively manage internal temperatures. Finally, the challenges currently faced by these strategies and future research directions were also discussed, including the improvement of the battery's intelligence to further enhance operational safety. This provides new insights for the future design and application of power batteries.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"75 ","pages":"Article 104051"},"PeriodicalIF":18.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143071678","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 : 2025-02-01DOI: 10.1016/j.ensm.2025.104093
Xiaowen Zhao , Chuanchao Sheng , Zhi Chang , Lei Cheng , Ping Wu , Lin Xu , Yiming Zhou , Ping He , Yawen Tang , Xin Cao , Haoshen Zhou
Single-crystal (SC) Li-rich cathodes have demonstrated superior structural and electrochemical stability compared to their polycrystal (PC) counterparts. However, the principles governing the solid-state synthesis of SC Li-rich oxides remain elusive, and the growth mechanisms of SC cathodes are still poorly understood. Herein, a prototype Li-rich layered oxide, Li1.2Ni0.13Co0.13Mn0.54O2, was synthesized with well-dispersed SC morphology through the regulation of Li excess content during solid-state reactions. This approach facilitated a solid-state exfoliation growth process, transforming spherical secondary particles into monodisperse primary SC oxides. Furthermore, two diffusion pathways of Li source—boundary diffusion and grain diffusion—were proposed to elucidate the underlying mechanisms driving SC exfoliation during solid-state reactions. This understanding enables the flexible synthesis of both PC and SC Li-rich cathodes. Compared to traditional PC counterparts, severe irreversible oxygen release, crack formation, and the transition from layered to spinel phases were effectively suppressed within the exfoliated SC cathode, resulting in an extended battery lifespan with a capacity retention of 93.6 % over 500 cycles at 1 C. These findings provide practical methodology and mechanism insights for the synthesis and design of high-energy-density and high-stability Li-rich cathodes.
{"title":"Solid-state exfoliation growth mechanism of single-crystal Li-rich layered cathode materials","authors":"Xiaowen Zhao , Chuanchao Sheng , Zhi Chang , Lei Cheng , Ping Wu , Lin Xu , Yiming Zhou , Ping He , Yawen Tang , Xin Cao , Haoshen Zhou","doi":"10.1016/j.ensm.2025.104093","DOIUrl":"10.1016/j.ensm.2025.104093","url":null,"abstract":"<div><div>Single-crystal (SC) Li-rich cathodes have demonstrated superior structural and electrochemical stability compared to their polycrystal (PC) counterparts. However, the principles governing the solid-state synthesis of SC Li-rich oxides remain elusive, and the growth mechanisms of SC cathodes are still poorly understood. Herein, a prototype Li-rich layered oxide, Li<sub>1.2</sub>Ni<sub>0.13</sub>Co<sub>0.13</sub>Mn<sub>0.54</sub>O<sub>2</sub>, was synthesized with well-dispersed SC morphology through the regulation of Li excess content during solid-state reactions. This approach facilitated a solid-state exfoliation growth process, transforming spherical secondary particles into monodisperse primary SC oxides. Furthermore, two diffusion pathways of Li source—boundary diffusion and grain diffusion—were proposed to elucidate the underlying mechanisms driving SC exfoliation during solid-state reactions. This understanding enables the flexible synthesis of both PC and SC Li-rich cathodes. Compared to traditional PC counterparts, severe irreversible oxygen release, crack formation, and the transition from layered to spinel phases were effectively suppressed within the exfoliated SC cathode, resulting in an extended battery lifespan with a capacity retention of 93.6 % over 500 cycles at 1 C. These findings provide practical methodology and mechanism insights for the synthesis and design of high-energy-density and high-stability Li-rich cathodes.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"75 ","pages":"Article 104093"},"PeriodicalIF":18.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143083877","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 : 2025-02-01DOI: 10.1016/j.ensm.2024.103883
Utkarsh Vijay , Diego E. Galvez-Aranda , Franco M. Zanotto , Tan Le-Dinh , Mohammed Alabdali , Mark Asch , Alejandro A. Franco
Lithium-ion battery (LIB) performance is significantly influenced by its manufacturing process. Manufacturing of an optimized electrode can incur high production costs such as high energy consumption, high scrap rates and emissions. This is due to the process that consists of a series of manufacturing steps presenting a complex interrelationship, thus limiting the understanding of performance as a function of manufacturing parameters. While several empirical and computational methods are employed for optimization, they are demanding in terms of resources such as materials or computational effort. By leveraging Deep Learning (DL), we can enhance our understanding of the complex manufacturing processes and accelerate its optimization. We propose a data-driven supervised DL methodology to complement physics-based LIB cathode manufacturing simulations. The trained DL-based predictive model integrates well into a manufacturing simulation framework to forecast cathode slurry microstructures. The DL model demonstrates robust predictive performance for LIB NMC-111 and LiFePO4–based slurries and slurries for a solid-state battery NMC-622/argyrodite composite electrode preparation. While the current work is focused on the electrode slurry preparation process, the proposed methodology has potential for application to drying and calendering steps. This approach will be helpful in streamlining lab-scale electrode manufacturing, and reducing errors, waste and resource consumption.
{"title":"A hybrid modelling approach coupling physics-based simulation and deep learning for battery electrode manufacturing simulations","authors":"Utkarsh Vijay , Diego E. Galvez-Aranda , Franco M. Zanotto , Tan Le-Dinh , Mohammed Alabdali , Mark Asch , Alejandro A. Franco","doi":"10.1016/j.ensm.2024.103883","DOIUrl":"10.1016/j.ensm.2024.103883","url":null,"abstract":"<div><div>Lithium-ion battery (LIB) performance is significantly influenced by its manufacturing process. Manufacturing of an optimized electrode can incur high production costs such as high energy consumption, high scrap rates and emissions. This is due to the process that consists of a series of manufacturing steps presenting a complex interrelationship, thus limiting the understanding of performance as a function of manufacturing parameters. While several empirical and computational methods are employed for optimization, they are demanding in terms of resources such as materials or computational effort. By leveraging Deep Learning (DL), we can enhance our understanding of the complex manufacturing processes and accelerate its optimization. We propose a data-driven supervised DL methodology to complement physics-based LIB cathode manufacturing simulations. The trained DL-based predictive model integrates well into a manufacturing simulation framework to forecast cathode slurry microstructures. The DL model demonstrates robust predictive performance for LIB NMC-111 and LiFePO<sub>4</sub>–based slurries and slurries for a solid-state battery NMC-622/argyrodite composite electrode preparation. While the current work is focused on the electrode slurry preparation process, the proposed methodology has potential for application to drying and calendering steps. This approach will be helpful in streamlining lab-scale electrode manufacturing, and reducing errors, waste and resource consumption.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"75 ","pages":"Article 103883"},"PeriodicalIF":18.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142566229","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 : 2025-02-01DOI: 10.1016/j.ensm.2025.104082
Changping Zhou , Fei Yan , Zihao Zheng , Bin Yang , Tonghui Liu , Jinming Guo
Lead-free dielectric ceramic capacitors have attracted widespread attentions in the field of pulsed power systems due to their ultrafast discharge rate and ultrahigh power density. Therefore, pursuing superior energy storage density and high efficiency is a key objective for developing capacitive dielectric ceramics. In this work, La3+ ions are introduced at A-sites of relaxor ferroelectric ceramics 0.9Bi0.5-xLaxNa0.5TiO3–0.1SrAl0.5Nb0.5O3 (0.9BLxNT-0.1SAN) for optimizing energy storage properties, which are fabricated via tape-casting technique. Grain size decreases and oxygen vacancies are suppressed after La3+ partially substituting Bi3+, which effectively increases the electric breakdown strength. Atomic-scale investigations show that fractions of rhombohedral and tetragonal phases transform into cubic phase when introducing La3+ ions, and sizes of polar nanoregions are further decreased down to 2 – 3 nm because of the weaker orbital coupling of La-O bond relative to Bi-O bond, which gives rise to ultrafast polarization response and low polarization hysteresis. La3+ ions substitution effectively optimizes the trade-off between polarization and electric breakdown strength, contributing to a superior recoverable energy storage density of 11.2 J/cm3 and a high efficiency of 88 % under an electric field of 820 kV/cm. In addition, the energy storage performance exhibits excellent frequency, thermal and cycling stabilities. La3+ introduction displays an effective multiscale regulation on relaxor ferroelectrics. The 0.9BL0.09NT-0.1SAN ceramic fabricated via tape-casting technique in this work exhibits great potential for manufacturing environment-friendly high-performance capacitors.
{"title":"Achieving superior capacitive energy storage in tape-casting fabricated Bi0.5Na0.5TiO3-based relaxor ferroelectrics via multiscale regulation","authors":"Changping Zhou , Fei Yan , Zihao Zheng , Bin Yang , Tonghui Liu , Jinming Guo","doi":"10.1016/j.ensm.2025.104082","DOIUrl":"10.1016/j.ensm.2025.104082","url":null,"abstract":"<div><div>Lead-free dielectric ceramic capacitors have attracted widespread attentions in the field of pulsed power systems due to their ultrafast discharge rate and ultrahigh power density. Therefore, pursuing superior energy storage density and high efficiency is a key objective for developing capacitive dielectric ceramics. In this work, La<sup>3+</sup> ions are introduced at A-sites of relaxor ferroelectric ceramics 0.9Bi<sub>0.5-</sub><em><sub>x</sub></em>La<em><sub>x</sub></em>Na<sub>0.5</sub>TiO<sub>3</sub>–0.1SrAl<sub>0.5</sub>Nb<sub>0.5</sub>O<sub>3</sub> (0.9BL<em><sub>x</sub></em>NT-0.1SAN) for optimizing energy storage properties, which are fabricated via tape-casting technique. Grain size decreases and oxygen vacancies are suppressed after La<sup>3+</sup> partially substituting Bi<sup>3+</sup>, which effectively increases the electric breakdown strength. Atomic-scale investigations show that fractions of rhombohedral and tetragonal phases transform into cubic phase when introducing La<sup>3+</sup> ions, and sizes of polar nanoregions are further decreased down to 2 – 3 nm because of the weaker orbital coupling of La-O bond relative to Bi-O bond, which gives rise to ultrafast polarization response and low polarization hysteresis. La<sup>3+</sup> ions substitution effectively optimizes the trade-off between polarization and electric breakdown strength, contributing to a superior recoverable energy storage density of 11.2 J/cm<sup>3</sup> and a high efficiency of 88 % under an electric field of 820 kV/cm. In addition, the energy storage performance exhibits excellent frequency, thermal and cycling stabilities. La<sup>3+</sup> introduction displays an effective multiscale regulation on relaxor ferroelectrics. The 0.9BL<sub>0.09</sub>NT-0.1SAN ceramic fabricated via tape-casting technique in this work exhibits great potential for manufacturing environment-friendly high-performance capacitors.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"75 ","pages":"Article 104082"},"PeriodicalIF":18.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143071645","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}
Exploring metal-sulfur batteries with low cost, high safety, and capacity is the need of the hour for large storage applications. Iron (Fe) being a highly abundant and cost-effective element, provides an excellent option as an anode material which on coupling with abundant sulfur (S) in an aqueous electrolyte will be a game-changing approach. Despite a promising outlook, the stability of Fe anode due to side reactions in aqueous electrolytes and inherent corrosion tendencies limit their performance. Herein, we have explored dimethyl sulfoxide (DMSO) as an electrolyte additive in iron percholorate (Fe(ClO4)2 for aqueous Fe-S battery, which exhibited high specific capacity of 1145 mAh g-1 at 50 mA g-1 with remarkable cycling stability for 400 continuous cycles at 2.0 and 0.5 A g-1 current densities with 72 % and 98 % capacity retention respectively without replacing the Fe-anode. The addition of DMSO, suppressed parasitic hydrogen evolution reaction (HER) by 6.7 times and mitigated the corrosion rate of iron electrodes by 2.2 times as evidenced by the spectroscopic and gas chromatography techniques. The molecular dynamics (MD) simulations revealed that DMSO engages the water molecules through hydrogen bonding which reduced the fraction of free water molecules available for HER and corrosion of iron electrodes.
探索低成本、高安全性和高容量的金属硫电池是大型存储应用的当务之急。铁（Fe）是一种储量丰富且具有成本效益的元素，作为阳极材料提供了一个很好的选择，它与水电解质中丰富的硫(S)偶联将是一种改变游戏规则的方法。尽管前景看好，但由于铁阳极在水溶液中的副反应和固有的腐蚀倾向，其稳定性限制了其性能。在此，我们探索了二甲亚砜（DMSO）作为高氯酸铁（Fe(ClO4)2）水溶液中Fe- s电池的电解质添加剂，该电池在50 mA g-1时具有1145 mAh g-1的高比容量，并且在2.0和0.5 A g-1电流密度下连续循环400次，分别具有72%和98%的容量保留率，而无需更换Fe阳极。光谱和气相色谱分析结果表明，DMSO的加入抑制了寄生析氢反应（HER）的6.7倍，使铁电极的腐蚀速率降低了2.2倍。分子动力学（MD）模拟表明，DMSO通过氢键与水分子结合，减少了可用于HER和铁电极腐蚀的自由水分子的比例。
{"title":"Boosted capacity and stability of aqueous iron-sulfur battery using DMSO as an electrolyte additive","authors":"Man Singh , Sukhjot Kaur , Shivangi Mehta , Mukesh Kumar , Kush Kumar , Santosh Kumar Meena , Tharamani C. Nagaiah","doi":"10.1016/j.ensm.2024.103965","DOIUrl":"10.1016/j.ensm.2024.103965","url":null,"abstract":"<div><div>Exploring metal-sulfur batteries with low cost, high safety, and capacity is the need of the hour for large storage applications. Iron (Fe) being a highly abundant and cost-effective element, provides an excellent option as an anode material which on coupling with abundant sulfur (S) in an aqueous electrolyte will be a game-changing approach. Despite a promising outlook, the stability of Fe anode due to side reactions in aqueous electrolytes and inherent corrosion tendencies limit their performance. Herein, we have explored dimethyl sulfoxide (DMSO) as an electrolyte additive in iron percholorate (Fe(ClO<sub>4</sub>)<sub>2</sub> for aqueous Fe-S battery, which exhibited high specific capacity of 1145 mAh g<sup>-1</sup> at 50 mA g<sup>-1</sup> with remarkable cycling stability for 400 continuous cycles at 2.0 and 0.5 A g<sup>-1</sup> current densities with 72 % and 98 % capacity retention respectively without replacing the Fe-anode. The addition of DMSO, suppressed parasitic hydrogen evolution reaction (HER) by 6.7 times and mitigated the corrosion rate of iron electrodes by 2.2 times as evidenced by the spectroscopic and gas chromatography techniques. The molecular dynamics (MD) simulations revealed that DMSO engages the water molecules through hydrogen bonding which reduced the fraction of free water molecules available for HER and corrosion of iron electrodes.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"75 ","pages":"Article 103965"},"PeriodicalIF":18.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142823357","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}
Precise control of defect distribution through conventional methods remains challenging, while spatial heterogeneity of defects within materials plays critical roles on their performance. Guided by density functional theory (DFT) predictions, we regulate the crystal defects in the solution-based synthesis of cation disordered rocksalt (DRX) cathodes through chelator optimization. A cluster analysis categorizes typical chelators into “soft” and “hard” groups. Combining a wide range of (in-situ) characterization techniques, we unambiguously demonstrate that soft chelators induce shallow surface defects, leading to enhanced crystallinity, uniform morphology and elevated electrochemical properties of high capacity, enhanced Li ion transport and cycling stability. In contrast, hard chelators produce deeper bulk defects, resulting in unsatisfactory electrochemical performance with low capacity, slower Li ion transport and worse cyclability. Critically, in-situ temperature-dependent high-resolution transmission electron microscopy observations reveal that hard chelators, such as acetic acid, are buried deeply inside the bulk of the gel and leave behind bulk defects upon removal at high temperature. The healing of these bulk defects requires prolonged high temperature annealing, inevitably increasing the energy cost. Our findings highlight the pivotal role of chelator physicochemical properties in defect engineering for DRX cathodes, underscoring the strategic importance of chelator optimization as a valuable approach for enhancing the performance of cathodes synthesized by solution-based methods.
{"title":"Chelator optimization enabled defect engineering for cation disordered rocksalt cathodes via solution-based synthesis method","authors":"Hao Chen , Yuchen Zhang , Yongjian Zhao , Junhong Liao , Jia He , Runze Yu , Shendong Tan , Runjie Zhang , Tingzheng Hou , Xianhu Sun , Zhengyan Lun","doi":"10.1016/j.ensm.2024.103990","DOIUrl":"10.1016/j.ensm.2024.103990","url":null,"abstract":"<div><div>Precise control of defect distribution through conventional methods remains challenging, while spatial heterogeneity of defects within materials plays critical roles on their performance. Guided by density functional theory (DFT) predictions, we regulate the crystal defects in the solution-based synthesis of cation disordered rocksalt (DRX) cathodes through chelator optimization. A cluster analysis categorizes typical chelators into “soft” and “hard” groups. Combining a wide range of (<em>in-situ</em>) characterization techniques, we unambiguously demonstrate that soft chelators induce shallow surface defects, leading to enhanced crystallinity, uniform morphology and elevated electrochemical properties of high capacity, enhanced Li ion transport and cycling stability. In contrast, hard chelators produce deeper bulk defects, resulting in unsatisfactory electrochemical performance with low capacity, slower Li ion transport and worse cyclability. Critically, <em>in-situ</em> temperature-dependent high-resolution transmission electron microscopy observations reveal that hard chelators, such as acetic acid, are buried deeply inside the bulk of the gel and leave behind bulk defects upon removal at high temperature. The healing of these bulk defects requires prolonged high temperature annealing, inevitably increasing the energy cost. Our findings highlight the pivotal role of chelator physicochemical properties in defect engineering for DRX cathodes, underscoring the strategic importance of chelator optimization as a valuable approach for enhancing the performance of cathodes synthesized by solution-based methods.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"75 ","pages":"Article 103990"},"PeriodicalIF":18.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888761","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 : 2025-02-01DOI: 10.1016/j.ensm.2024.103994
Zitong Zhu , Dan Luo , Lu Wei, Jianxiong Chen, Tianqi Jia, Xiaodong Chi, Xin Guo
Aqueous zinc-iodine batteries (AZIBs) are promising for cost-effective energy storage. However, some critical problems related to the slow reaction kinetics of iodine conversion, polyiodide shuttle effect and polyiodide corrosion greatly hinder their practical applications. Herein, a novel bipyridine-based nonporous covalent-organic cage (Bpd-COC) is developed as a high-performance cathode for AZIBs with active electrolyte containing I–/I3– redox couple. The rapid I–/I3– conversion mechanism involved in the Bpd-COC cathode and the strong intermolecular host-guest interactions between Bpd-COC and I3– are revealed by comprehensive in-situ/ex-situ experimental characterizations and theoretical calculations. The Bpd-COC selectively captures I3– ions through electron-pair interactions between the framework nitrogen atoms and the adsorbed I3– ions, thus the shuttle of I3– is effectively suppressed. Consequently, the AZIB with Bpd-COC cathode achieves a high specific capacity of 197.3 mAh g-1 at 0.3 A g-1, excellent rate capability (110.9 mAh g-1 retained at 5 A g-1), and superior cycling stability (over 40,000 cycles with 93.5 % capacity retention). Moreover, the corrosion of the Zn metal anode normally triggered by the polyiodide shuttling is significantly alleviated. This work paves a promising avenue for the development of intrinsically safe, high-rate and long-lifespan AZIBs.
水锌碘电池（AZIBs）是一种极具成本效益的储能技术。然而，碘转化的慢反应动力学、多碘化物穿梭效应和多碘化物腐蚀等关键问题极大地阻碍了其实际应用。本文研制了一种新型的联吡啶基无孔共价有机笼（Bpd-COC），作为活性电解质中含有I - /I3 -氧化还原偶对的azib的高性能阴极。通过原位/非原位实验表征和理论计算，揭示了Bpd-COC阴极中I - /I3 -的快速转化机制，以及Bpd-COC与I3 -之间强烈的分子间主客体相互作用。Bpd-COC通过框架氮原子与吸附的I3 -离子之间的电子对相互作用选择性捕获I3 -离子，从而有效抑制I3 -的穿梭。因此，具有Bpd-COC阴极的AZIB在0.3 a g-1时具有197.3 mAh g-1的高比容量，优异的倍率容量（在5 a g-1时保持110.9 mAh g-1），以及优异的循环稳定性（超过40,000次循环，容量保持率为93.5%）。此外，明显减轻了通常由多碘化物穿梭引起的锌金属阳极的腐蚀。这项工作为开发本质安全、高速率和长寿命的azib铺平了一条有希望的道路。
{"title":"Long-life aqueous zinc-iodine batteries enabled by selective adsorption of polyiodide anions in nonporous adaptive organic cages","authors":"Zitong Zhu , Dan Luo , Lu Wei, Jianxiong Chen, Tianqi Jia, Xiaodong Chi, Xin Guo","doi":"10.1016/j.ensm.2024.103994","DOIUrl":"10.1016/j.ensm.2024.103994","url":null,"abstract":"<div><div>Aqueous zinc-iodine batteries (AZIBs) are promising for cost-effective energy storage. However, some critical problems related to the slow reaction kinetics of iodine conversion, polyiodide shuttle effect and polyiodide corrosion greatly hinder their practical applications. Herein, a novel bipyridine-based nonporous covalent-organic cage (Bpd-COC) is developed as a high-performance cathode for AZIBs with active electrolyte containing I<sup>–</sup>/I<sub>3</sub><sup>–</sup> redox couple. The rapid I<sup>–</sup>/I<sub>3</sub><sup>–</sup> conversion mechanism involved in the Bpd-COC cathode and the strong intermolecular host-guest interactions between Bpd-COC and I<sub>3</sub><sup>–</sup> are revealed by comprehensive in-situ/ex-situ experimental characterizations and theoretical calculations. The Bpd-COC selectively captures I<sub>3</sub><sup>–</sup> ions through electron-pair interactions between the framework nitrogen atoms and the adsorbed I<sub>3</sub><sup>–</sup> ions, thus the shuttle of I<sub>3</sub><sup>–</sup> is effectively suppressed. Consequently, the AZIB with Bpd-COC cathode achieves a high specific capacity of 197.3 mAh g<sup>-1</sup> at 0.3 A g<sup>-1</sup>, excellent rate capability (110.9 mAh g<sup>-1</sup> retained at 5 A g<sup>-1</sup>), and superior cycling stability (over 40,000 cycles with 93.5 % capacity retention). Moreover, the corrosion of the Zn metal anode normally triggered by the polyiodide shuttling is significantly alleviated. This work paves a promising avenue for the development of intrinsically safe, high-rate and long-lifespan AZIBs.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"75 ","pages":"Article 103994"},"PeriodicalIF":18.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905377","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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