The broad applications of energy storage systems have brought improving demands for stable electrodes with robust tolerance to extreme environmental challenges. MXenes show promising pseudocapacitive behaviors, however, the poor thermodynamical and mechanical stability makes them unfavorable for applications under complex and harsh environments. Herein, we break these limitations by aramid nanofibers (ANF)-driven interfacial nanofilling and hydrogen-bonds effects in MXenes. Theoretical and experimental results unveil that ANF with unique polarity preferentially interacts with H2O molecules and forms hydrogen bonding networks to restrain oxidative and mechanical attack toward MXene, at the same time, the nanofilling enables interfacial mass transport intensification for increment in redox dynamics. As such, the synergistically coupled ANF-MXene microstructure (AM) unlocks superior mechanical properties for facing hash forces, i.e., tensile strength of 115.2 MPa and toughness of 1.8 MJ m-3, and an ultra-long cycling life with a capacitance retention of 90.7% after 40,000 cycles. Besides, the effective IR thermal camouflage performance (IR-emissivity: 20.9%) further renders the power supply working invisibly after fast charge/discharge-driven heat generation. Moreover, the performances can be well maintained when subjected to strong acid/alkali, high-temperature (200°C), and cryogenic (-196°C) treatments. These results highlight the key role of interfacial species synergy in accelerating versatile and robust energy applications.
{"title":"Extreme Environment-Adaptable and Ultralong-Life Energy Storage Enabled by Synergistic Manipulation of Interfacial Environment and Hydrogen Bonding","authors":"Wanbin Dang, Wei Guo, Wenting Chen, Jinxin Wang, Qiuyu Zhang","doi":"10.1016/j.ensm.2024.103915","DOIUrl":"https://doi.org/10.1016/j.ensm.2024.103915","url":null,"abstract":"The broad applications of energy storage systems have brought improving demands for stable electrodes with robust tolerance to extreme environmental challenges. MXenes show promising pseudocapacitive behaviors, however, the poor thermodynamical and mechanical stability makes them unfavorable for applications under complex and harsh environments. Herein, we break these limitations by aramid nanofibers (ANF)-driven interfacial nanofilling and hydrogen-bonds effects in MXenes. Theoretical and experimental results unveil that ANF with unique polarity preferentially interacts with H<sub>2</sub>O molecules and forms hydrogen bonding networks to restrain oxidative and mechanical attack toward MXene, at the same time, the nanofilling enables interfacial mass transport intensification for increment in redox dynamics. As such, the synergistically coupled ANF-MXene microstructure (AM) unlocks superior mechanical properties for facing hash forces, i.e., tensile strength of 115.2 MPa and toughness of 1.8 MJ m<sup>-3</sup>, and an ultra-long cycling life with a capacitance retention of 90.7% after 40,000 cycles. Besides, the effective IR thermal camouflage performance (IR-emissivity: 20.9%) further renders the power supply working invisibly after fast charge/discharge-driven heat generation. Moreover, the performances can be well maintained when subjected to strong acid/alkali, high-temperature (200°C), and cryogenic (-196°C) treatments. These results highlight the key role of interfacial species synergy in accelerating versatile and robust energy applications.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"22 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665483","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The exceptional cycling stability of lithium-ion batteries in electric vehicles and large-scale grid energy storage applications necessitates the use of accelerated aging tests for rapid assessment. Overdischarge stress is an effective approach to accelerate battery aging, whereas its impact on solid electrolyte interphase (SEI) and battery aging performance remains elusive. Herein, the whole picture of SEI evolution under different overdischarge levels was quantitatively illustrated by combining the electrochemical analysis and spectrochemical techniques. Overdischarge leads to the decomposition of the organic components within SEI, such as ROCO2Li and CH3Li, while the damaged SEI is repaired during the subsequent charging process with its composition and structure reconstructed. Under overdischarge conditions, the SEI undergoes continuous cycles of destruction and repair, which suppresses its growth and evolution to inorganic components, resulting in a thinner and more uneven morphology with higher organic components and a lower Young's modulus. The unique SEI evolution mechanism of overdischarge effectively accelerates the loss of active lithium and exhibits similar thermodynamic degradation modes to normal aging, making overdischarge a potential accelerated aging method. This study provides a deeper understanding of the mechanisms behind accelerated aging in batteries and offers new insights into the evaluation and enhancement of battery performance.
电动汽车和大规模电网储能应用中的锂离子电池具有超强的循环稳定性，因此有必要使用加速老化试验进行快速评估。过放电应力是加速电池老化的一种有效方法，但它对固态电解质相间层（SEI）和电池老化性能的影响仍然难以捉摸。本文结合电化学分析和光谱化学技术，定量展示了不同过放电水平下 SEI 演变的全貌。过放电导致 SEI 中的有机成分（如 ROCO2Li 和 CH3Li）分解，而受损的 SEI 则在随后的充电过程中得到修复，其成分和结构得以重建。在过放电条件下，SEI 不断经历破坏和修复的循环，从而抑制了其生长和向无机成分的演化，导致其形态更薄、更不均匀，有机成分更高，杨氏模量更低。过放电的独特 SEI 演化机制有效加速了活性锂的损失，并表现出与正常老化相似的热力学降解模式，使过放电成为一种潜在的加速老化方法。这项研究加深了人们对电池加速老化背后机制的理解，并为评估和提高电池性能提供了新的见解。
{"title":"Revisiting the Overdischarge Process as a Novel Accelerated Aging Method for LiFePO4/Graphite Batteries through the Unveiling of SEI Evolution Mechanism","authors":"Shijun Tang, Yuli Liang, Cong Zhong, Yufan Peng, Yonggang Hu, Wenxuan Hu, Yiqing Liao, Jianrong Lin, Xuerui Yang, Huiyan Zhang, Ying Lin, Ke Zhang, Jinding Liang, Xuefeng Wang, Yimin Wei, Zhengliang Gong, Yong Yang","doi":"10.1016/j.ensm.2024.103916","DOIUrl":"https://doi.org/10.1016/j.ensm.2024.103916","url":null,"abstract":"The exceptional cycling stability of lithium-ion batteries in electric vehicles and large-scale grid energy storage applications necessitates the use of accelerated aging tests for rapid assessment. Overdischarge stress is an effective approach to accelerate battery aging, whereas its impact on solid electrolyte interphase (SEI) and battery aging performance remains elusive. Herein, the whole picture of SEI evolution under different overdischarge levels was quantitatively illustrated by combining the electrochemical analysis and spectrochemical techniques. Overdischarge leads to the decomposition of the organic components within SEI, such as ROCO<sub>2</sub>Li and CH<sub>3</sub>Li, while the damaged SEI is repaired during the subsequent charging process with its composition and structure reconstructed. Under overdischarge conditions, the SEI undergoes continuous cycles of destruction and repair, which suppresses its growth and evolution to inorganic components, resulting in a thinner and more uneven morphology with higher organic components and a lower Young's modulus. The unique SEI evolution mechanism of overdischarge effectively accelerates the loss of active lithium and exhibits similar thermodynamic degradation modes to normal aging, making overdischarge a potential accelerated aging method. This study provides a deeper understanding of the mechanisms behind accelerated aging in batteries and offers new insights into the evaluation and enhancement of battery performance.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"51 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665522","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 : 2024-11-18DOI: 10.1016/j.ensm.2024.103914
Xiaodong Zhang, Ersha Fan, Jiao Lin, Yi Zhao, Qingrong Huang, Su Ma, Renjie Chen, Feng Wu, Li Li
Nickel-rich layered cathodes are one of the ideal electrode materials for high-energy lithium-ion batteries, yet suffer from capacity decay and structural degradation during cycling. Although the degradation mechanisms of electrode materials are flourishing, the analysis of performance decay and physicochemical properties dynamic evolution during cycling have not been well developed. Here, we propose a coupling analysis strategy based on differential capacity that distinguishes the failure behavior of electrode materials during cycling by the characteristic evolution of the dQ dV–1 curve recorded cycle-by-cycle. By coupling in-situ electrochemical tests with differential capacity characterization and comparing them with electrochemical characteristics recorded at different aging upper cut-off voltages cycles, the capacity decay mechanism and physicochemical properties evolution of electrode materials can be dynamically analyzed. The potential failure modes include loss of active Li inventory (LALI), loss of active structure integrity (LASI), and various dominant combinations of these factors. In addition, the distinction of aging behavior can also be applied to the failure level classification of spent electrode materials. Our findings demonstrate a general strategy for analyzing the dynamic failure mechanisms of electrode materials, thereby offering valuable insights for subsequent technology route selection in terms of recycling and reuse.
{"title":"Looking into failure mode identification driven by differential capacity in Ni-rich layered cathodes","authors":"Xiaodong Zhang, Ersha Fan, Jiao Lin, Yi Zhao, Qingrong Huang, Su Ma, Renjie Chen, Feng Wu, Li Li","doi":"10.1016/j.ensm.2024.103914","DOIUrl":"https://doi.org/10.1016/j.ensm.2024.103914","url":null,"abstract":"Nickel-rich layered cathodes are one of the ideal electrode materials for high-energy lithium-ion batteries, yet suffer from capacity decay and structural degradation during cycling. Although the degradation mechanisms of electrode materials are flourishing, the analysis of performance decay and physicochemical properties dynamic evolution during cycling have not been well developed. Here, we propose a coupling analysis strategy based on differential capacity that distinguishes the failure behavior of electrode materials during cycling by the characteristic evolution of the d<em>Q</em> d<em>V</em><sup>–1</sup> curve recorded cycle-by-cycle. By coupling in-situ electrochemical tests with differential capacity characterization and comparing them with electrochemical characteristics recorded at different aging upper cut-off voltages cycles, the capacity decay mechanism and physicochemical properties evolution of electrode materials can be dynamically analyzed. The potential failure modes include loss of active Li inventory (LALI), loss of active structure integrity (LASI), and various dominant combinations of these factors. In addition, the distinction of aging behavior can also be applied to the failure level classification of spent electrode materials. Our findings demonstrate a general strategy for analyzing the dynamic failure mechanisms of electrode materials, thereby offering valuable insights for subsequent technology route selection in terms of recycling and reuse.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"10 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665484","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}
Irreversible Zn dendrite formation and hydrogen evolution reactions (HER) have significantly impeded the large-scale commercial deployment of aqueous zinc-metal batteries (AZMBs). Herein, we proposed an innovative interfacial strategy activated by the biomacromolecule Pullulan (Pul) on the surface of metal zinc anodes (ZMAs) within the electrolyte system. The combination of comprehensive experimental results and simulation calculations demonstrated that the spontaneous assembly of the interfacial molecular layer (IML), facilitated by the adaptive adsorption of Pul molecules, not only triggers the formation of a Zn²⁺-concentrated region and effectively balances ionic flux, but also simultaneously transforms the nucleation growth pattern of Zn2+ into an instantaneous and progressive hybridized mechanism, reconfiguring the Zn2+ transfer/deposition kinetics at the heterogeneous electrode/electrolyte interface. Moreover, the IML provides a stable shielding effect for hydrated hydrogen with high thermodynamic activity and SO42− at the solid-liquid interface. Therefore, a smooth and compact Zn deposition layer devoid of dendritic growth is achieved during subsequent plating processes. As a result, Zn||Zn symmetric cells utilizing modified electrolytes exhibit remarkable plating/stripping performance exceeding 1800 hours without significant voltage fluctuations, which contributes to the exceptional long-term durability observed in Zn||CNTs@MnO2 batteries.
{"title":"Constructing interfacial molecular layer coupled with Zn2+ transfer/deposition kinetics modulation toward deeply reversible Zn anodes","authors":"Shangqing Jiao, Yulong Gao, Weigang Zhang, Zhen Xue, Yudong Wu, Zhiqian Cao","doi":"10.1016/j.ensm.2024.103909","DOIUrl":"https://doi.org/10.1016/j.ensm.2024.103909","url":null,"abstract":"Irreversible Zn dendrite formation and hydrogen evolution reactions (HER) have significantly impeded the large-scale commercial deployment of aqueous zinc-metal batteries (AZMBs). Herein, we proposed an innovative interfacial strategy activated by the biomacromolecule Pullulan (Pul) on the surface of metal zinc anodes (ZMAs) within the electrolyte system. The combination of comprehensive experimental results and simulation calculations demonstrated that the spontaneous assembly of the interfacial molecular layer (IML), facilitated by the adaptive adsorption of Pul molecules, not only triggers the formation of a Zn²⁺-concentrated region and effectively balances ionic flux, but also simultaneously transforms the nucleation growth pattern of Zn<sup>2+</sup> into an instantaneous and progressive hybridized mechanism, reconfiguring the Zn<sup>2+</sup> transfer/deposition kinetics at the heterogeneous electrode/electrolyte interface. Moreover, the IML provides a stable shielding effect for hydrated hydrogen with high thermodynamic activity and SO<sub>4</sub><sup>2−</sup> at the solid-liquid interface. Therefore, a smooth and compact Zn deposition layer devoid of dendritic growth is achieved during subsequent plating processes. As a result, Zn||Zn symmetric cells utilizing modified electrolytes exhibit remarkable plating/stripping performance exceeding 1800 hours without significant voltage fluctuations, which contributes to the exceptional long-term durability observed in Zn||CNTs@MnO<sub>2</sub> batteries.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"8 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142645842","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The application of environmentally friendly and economical aqueous zinc (Zn) metal batteries (ZMBs) is severely limited by critical issues associated with Zn anodes, including dendrite growth, hydrogen evolution reaction and corrosion. Hence, many improvement methods, such as electrolyte additives, mainly focus on the protection of Zn anodes. Herein, owing to the abundance of zincophilic functional groups, aminoglycosides represented by amikacin are introduced as sulfates to solve these problems. The presence of zincophilic functional groups, such as amino and hydroxyl, enables amikacin to effectively replace H2O molecules, thereby altering the solvation structure of Zn2+. Additionally, amikacin preferentially adsorbs on the anode surface and facilitates the formation of solid electrolyte interphase (SEI), achieving highly conductive and uniformly deposited Zn anodes. Therefore, the Zn||Zn symmetric cell with the modified electrolyte can work stably with a long cycle lifespan of up to 3300 h at 1 mA cm−2, 1 mAh cm−2. It is worth mentioning that the symmetric cells deliver excellent cycle lifespans of 1000 h (5 mA cm−2, 5 mAh cm−2), 790 h (10 mA cm−2, 10 mAh cm−2) and 330 h (20 mA cm−2, 20 mAh cm−2). Besides, the Zn-based full cell, in conjunction with NaV3O8·1.5H2O cathode, also demonstrates exceedingly good cycling stability with a remarkable capacity retention rate of 95.92% after 3000 cycles at 5 A g-1. More encouragingly, ZMBs supplemented with the other aminoglycoside sulfates, namely gentamicin sulfate (GS) and neomycin sulfate (NS), also show excellent performance, confirming the universality of the improvement by these aminoglycosides.
由于与锌阳极相关的枝晶生长、氢演化反应和腐蚀等关键问题，环保型和经济型水溶锌（Zn）金属电池（ZMB）的应用受到严重限制。因此，许多改进方法（如电解质添加剂）主要侧重于锌阳极的保护。在这里，由于亲锌官能团的丰富，以阿米卡星为代表的氨基糖苷类化合物被引入作为硫酸盐来解决这些问题。氨基和羟基等亲锌官能团的存在使阿米卡星能够有效地取代 H2O 分子，从而改变 Zn2+ 的溶解结构。此外，阿米卡星还能优先吸附在阳极表面，促进固体电解质相（SEI）的形成，实现高导电性和均匀沉积的锌阳极。因此，使用改性电解质的 Zn||Zn 对称电池可以在 1 mA cm-2 和 1 mAh cm-2 的条件下稳定工作，循环寿命长达 3300 h。值得一提的是，对称电池的循环寿命分别为 1000 小时（5 mA cm-2，5 mAh cm-2）、790 小时（10 mA cm-2，10 mAh cm-2）和 330 小时（20 mA cm-2，20 mAh cm-2）。此外，锌基全电池与 NaV3O8-1.5H2O 阴极配合使用，也表现出了极好的循环稳定性，在 5 A g-1 的条件下循环 3000 次后，容量保持率高达 95.92%。更令人鼓舞的是，添加了其他氨基糖苷硫酸盐（即硫酸庆大霉素（GS）和硫酸新霉素（NS））的 ZMB 也表现出了卓越的性能，证实了这些氨基糖苷的普遍改善作用。
{"title":"Zincophilic Group-Rich Aminoglycosides for Ultra-Long Life and High-Rate Zinc Batteries","authors":"Zhao Chen, Ruheng Jiang, Yuejiao Chen, Haipeng Zhu, Xiaowei Tang, Xiaowei Huang, Yiman Xie, Jiaxin Li, Chunxiao Zhang, Libao Chen, Weifeng Wei, Liangjun Zhou","doi":"10.1016/j.ensm.2024.103913","DOIUrl":"https://doi.org/10.1016/j.ensm.2024.103913","url":null,"abstract":"The application of environmentally friendly and economical aqueous zinc (Zn) metal batteries (ZMBs) is severely limited by critical issues associated with Zn anodes, including dendrite growth, hydrogen evolution reaction and corrosion. Hence, many improvement methods, such as electrolyte additives, mainly focus on the protection of Zn anodes. Herein, owing to the abundance of zincophilic functional groups, aminoglycosides represented by amikacin are introduced as sulfates to solve these problems. The presence of zincophilic functional groups, such as amino and hydroxyl, enables amikacin to effectively replace H<sub>2</sub>O molecules, thereby altering the solvation structure of Zn<sup>2+</sup>. Additionally, amikacin preferentially adsorbs on the anode surface and facilitates the formation of solid electrolyte interphase (SEI), achieving highly conductive and uniformly deposited Zn anodes. Therefore, the Zn||Zn symmetric cell with the modified electrolyte can work stably with a long cycle lifespan of up to 3300 h at 1 mA cm<sup>−2</sup>, 1 mAh cm<sup>−2</sup>. It is worth mentioning that the symmetric cells deliver excellent cycle lifespans of 1000 h (5 mA cm<sup>−2</sup>, 5 mAh cm<sup>−2</sup>), 790 h (10 mA cm<sup>−2</sup>, 10 mAh cm<sup>−2</sup>) and 330 h (20 mA cm<sup>−2</sup>, 20 mAh cm<sup>−2</sup>). Besides, the Zn-based full cell, in conjunction with NaV<sub>3</sub>O<sub>8</sub>·1.5H<sub>2</sub>O cathode, also demonstrates exceedingly good cycling stability with a remarkable capacity retention rate of 95.92% after 3000 cycles at 5 A g<sup>-1</sup>. More encouragingly, ZMBs supplemented with the other aminoglycoside sulfates, namely gentamicin sulfate (GS) and neomycin sulfate (NS), also show excellent performance, confirming the universality of the improvement by these aminoglycosides.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"13 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665517","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 : 2024-11-16DOI: 10.1016/j.ensm.2024.103905
Umair Nisar, Florian Klein, Claudia Pfeifer, Margret Wohlfahrt-Mehrens, Markus Hölzle, Peter Axmann
LiNi0.5Mn1.5O4 (LNMO) is a promising next-generation cathode material for lithium-ion batteries (LIBs) due to its high-energy and high-power density. However, its commercial adoption is hindered by the unstable LNMO/electrolyte interface due to high operating voltages and structural degradation arising from Jahn-Teller distortion and metal-ion dissolution resulting in poor cycling stability. Additionally, the high-temperature calcination beyond 700°C often results in secondary phases such as rock salt NiO, Li1-xNixO, Ni6MnO8 or Li2MnO3, whose precise chemical compositions and their influence on electrochemical performance remain unclear. Traditional analytical techniques such as X-ray diffraction (XRD) or neutron diffraction face challenges in resolving these secondary phases due to low phase fractions and overlapping reflections with the LNMO phase. Here, we address these challenges using correlative Raman-Scanning electron microscopy (Raman-SEM) to characterize secondary phases in LNMO materials that were synthesized under various synthesis conditions and evaluate their impact on the electrochemical performance. Our results reveal the synthesis-dependent emergence of three distinct secondary phases in LNMO materials synthesized at 1000°C, a phenomenon that, to our knowledge, has not been previously reported. Specifically, LNMO synthesized at 900°C shows the coexistence of Ni6MnO8 and Li2MnO3 phases, while synthesized at 1000°C also exhibits a Mn3O4 phase. Furthermore, an increased amount of these secondary phases in LNMO led to a lower discharge capacity due to their electrochemical inactive nature. However, these phases do not affect the rate capability or the long-term cycling performance of the LNMO materials. These insights are crucial for advancing the development of LNMO cathode materials for next-generation LIBs.
{"title":"Elucidating the Nature of Secondary Phases in LiNi0.5Mn1.5O4 Cathode Materials using Correlative Raman-SEM Microscopy","authors":"Umair Nisar, Florian Klein, Claudia Pfeifer, Margret Wohlfahrt-Mehrens, Markus Hölzle, Peter Axmann","doi":"10.1016/j.ensm.2024.103905","DOIUrl":"https://doi.org/10.1016/j.ensm.2024.103905","url":null,"abstract":"LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> (LNMO) is a promising next-generation cathode material for lithium-ion batteries (LIBs) due to its high-energy and high-power density. However, its commercial adoption is hindered by the unstable LNMO/electrolyte interface due to high operating voltages and structural degradation arising from Jahn-Teller distortion and metal-ion dissolution resulting in poor cycling stability. Additionally, the high-temperature calcination beyond 700°C often results in secondary phases such as rock salt NiO, Li<sub>1-x</sub>Ni<sub>x</sub>O, Ni<sub>6</sub>MnO<sub>8</sub> or Li<sub>2</sub>MnO<sub>3</sub>, whose precise chemical compositions and their influence on electrochemical performance remain unclear. Traditional analytical techniques such as X-ray diffraction (XRD) or neutron diffraction face challenges in resolving these secondary phases due to low phase fractions and overlapping reflections with the LNMO phase. Here, we address these challenges using correlative Raman-Scanning electron microscopy (Raman-SEM) to characterize secondary phases in LNMO materials that were synthesized under various synthesis conditions and evaluate their impact on the electrochemical performance. Our results reveal the synthesis-dependent emergence of three distinct secondary phases in LNMO materials synthesized at 1000°C, a phenomenon that, to our knowledge, has not been previously reported. Specifically, LNMO synthesized at 900°C shows the coexistence of Ni<sub>6</sub>MnO<sub>8</sub> and Li<sub>2</sub>MnO<sub>3</sub> phases, while synthesized at 1000°C also exhibits a Mn<sub>3</sub>O<sub>4</sub> phase. Furthermore, an increased amount of these secondary phases in LNMO led to a lower discharge capacity due to their electrochemical inactive nature. However, these phases do not affect the rate capability or the long-term cycling performance of the LNMO materials. These insights are crucial for advancing the development of LNMO cathode materials for next-generation LIBs.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"5 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642731","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The instable Zn/electrolyte interface due to severe corrosion, especially at high utilization of Zn anode, strongly hindered the practical application of aqueous zinc metal battery. Herein, we report a voltage-driven molecular switch through a reversible transition of the nicotinic molecules between zwitterion and anion to enable deep cycled zinc metal battery. In light of in-situ Raman, the switching mechanism of nicotinic molecules in the electrical double layer is unveiled: during plating, nicotinic molecules switches to zwitterion mode (ON state) with periodical pyridine-ring-substrate adlayer while during stripping, shifts to anion mode with periodical carbonyl group-substrate adlayer (OFF state). The transition of NA molecules enables molecular flipping on the substrate due to the electrostatic force and in this way, in both ON and OFF state, the zinc anode is protected by the adlayer to avoid the zinc corrosion on the anode side. Furthermore, the OTF‒ decomposition is accompanied by the open ring reaction of N‒heterocyclic from nicotinic acid molecules to form highly elastic solid electrolyte interface layer. Benefiting from both the molecular switch function and solid electrolyte interface layer formation, the nicotinic molecules-based electrolyte enables practical zinc metal battery of high energy density (100 Wh/kgelectrode) for over 800 cycles with a cumulative capacity of 2.71 Ah cm−2 at practical condition of low N/P ratio of 2, and lean electrolyte of 10 μL mAh−1, representing the state-of-the-art performance. These findings highlight the utilization of molecular switch and its interfacial protection of the deep cycled zinc anode, and provide a new tactic for the development of high energy metal battery.
{"title":"Voltage-driven Molecular Switch of Highly Periodically N‒heterocyclic Adlayer Enabled Deep Cycled Zinc Metal Battery","authors":"Weina Xu, Bomian Zhang, Wangwang Xu, Guang Yao, Lei Zhang, Sitian Lian, Qi Liu, Chaozheng Liu, Ronghua Yuan, Wenzhou Chen, Xiaochang Qiao, Kangning Zhao","doi":"10.1016/j.ensm.2024.103910","DOIUrl":"https://doi.org/10.1016/j.ensm.2024.103910","url":null,"abstract":"The instable Zn/electrolyte interface due to severe corrosion, especially at high utilization of Zn anode, strongly hindered the practical application of aqueous zinc metal battery. Herein, we report a voltage-driven molecular switch through a reversible transition of the nicotinic molecules between zwitterion and anion to enable deep cycled zinc metal battery. In light of <em>in-situ</em> Raman, the switching mechanism of nicotinic molecules in the electrical double layer is unveiled: during plating, nicotinic molecules switches to zwitterion mode (ON state) with periodical pyridine-ring-substrate adlayer while during stripping, shifts to anion mode with periodical carbonyl group-substrate adlayer (OFF state). The transition of NA molecules enables molecular flipping on the substrate due to the electrostatic force and in this way, in both ON and OFF state, the zinc anode is protected by the adlayer to avoid the zinc corrosion on the anode side. Furthermore, the OTF<sup>‒</sup> decomposition is accompanied by the open ring reaction of N‒heterocyclic from nicotinic acid molecules to form highly elastic solid electrolyte interface layer. Benefiting from both the molecular switch function and solid electrolyte interface layer formation, the nicotinic molecules-based electrolyte enables practical zinc metal battery of high energy density (100 Wh/kg<sub>electrode</sub>) for over 800 cycles with a cumulative capacity of 2.71 Ah cm<sup>−2</sup> at practical condition of low N/P ratio of 2, and lean electrolyte of 10 μL mAh<sup>−1</sup>, representing the state-of-the-art performance. These findings highlight the utilization of molecular switch and its interfacial protection of the deep cycled zinc anode, and provide a new tactic for the development of high energy metal battery.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"11 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642697","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 : 2024-11-16DOI: 10.1016/j.ensm.2024.103912
Fangchao Han, Shichao Zhang, Jun Xia, Dezhi Yan, Yalan Xing, Xianggang Guan, Qianfan Zhang
Sodium-based dual-ion batteries (SDIBs) have received widespread attention due to their high voltage, low cost, safety, and eco-friendliness. Nevertheless, the irregular spherical graphite cathodes are limited by the mass transfer non-uniformity and sluggish reaction kinetics due to uneven anion migration through the highly tortuous pathways and the inductive anisotropic electric fields. Herein, we report a facile dissolution-precipitation-carbonation optimized modification strategy to synthesize a series of nano-Li2TiO3/C-modified graphite flake (GF-LTx, x=1, 2.5, and 5) as cathode for SDIBs. The Li2TiO3-C-Cathode Electrolyte Interphase (Li2TiO3-C-CEI) trinity layer by in situ reactions shows good cycling performance. The intrinsic mechanism of Li2TiO3-C-CEI was further explored by DFT molecular orbital theory and distribution relaxation time (DRT) analysis. Notably, the GF-LT2.5 achieves 10,000 stable cycles at 3-5.2 V (vs. Na/Na+) with a initial capacity of 91.1 mAh g−1 and a decay rate of only 0.00217% per cycle. Furthermore, GF-LT2.5 demonstrates an ultra-high rate performance of 100C with only 30s for a single charge and 86% capacity for low current density. Infrared thermography confirms the good thermal stability and safety of the gel-based flexible pouch cells. This work provides new insights into the design of high-rate performance, long-cycle stability, and high-safety energy storage systems.
{"title":"Ultra-High Rate and Long Cycle Life Sodium-Based Dual-Ion Batteries Enabled by Li2TiO3-Modified Cathode-Electrolyte-Interphase","authors":"Fangchao Han, Shichao Zhang, Jun Xia, Dezhi Yan, Yalan Xing, Xianggang Guan, Qianfan Zhang","doi":"10.1016/j.ensm.2024.103912","DOIUrl":"https://doi.org/10.1016/j.ensm.2024.103912","url":null,"abstract":"Sodium-based dual-ion batteries (SDIBs) have received widespread attention due to their high voltage, low cost, safety, and eco-friendliness. Nevertheless, the irregular spherical graphite cathodes are limited by the mass transfer non-uniformity and sluggish reaction kinetics due to uneven anion migration through the highly tortuous pathways and the inductive anisotropic electric fields. Herein, we report a facile dissolution-precipitation-carbonation optimized modification strategy to synthesize a series of nano-Li<sub>2</sub>TiO<sub>3</sub>/C-modified graphite flake (GF-LTx, x=1, 2.5, and 5) as cathode for SDIBs. The Li<sub>2</sub>TiO<sub>3</sub>-C-Cathode Electrolyte Interphase (Li<sub>2</sub>TiO<sub>3</sub>-C-CEI) trinity layer by <em>in situ</em> reactions shows good cycling performance. The intrinsic mechanism of Li<sub>2</sub>TiO<sub>3</sub>-C-CEI was further explored by DFT molecular orbital theory and distribution relaxation time (DRT) analysis. Notably, the GF-LT2.5 achieves 10,000 stable cycles at 3-5.2 V (vs. Na/Na<sup>+</sup>) with a initial capacity of 91.1 mAh g<sup>−1</sup> and a decay rate of only 0.00217% per cycle. Furthermore, GF-LT2.5 demonstrates an ultra-high rate performance of 100C with only 30s for a single charge and 86% capacity for low current density. Infrared thermography confirms the good thermal stability and safety of the gel-based flexible pouch cells. This work provides new insights into the design of high-rate performance, long-cycle stability, and high-safety energy storage systems.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"75 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642698","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 : 2024-11-15DOI: 10.1016/j.ensm.2024.103911
Changhaoyue Xu, Peng Jing, Zhiwen Deng, Qingqing Liu, Ye Jia, Xuemei Zhang, Yan Deng, Yun Zhang, Wenlong Cai
Electrolyte engineering is a promising strategy to stabilize electrode structure. However, the high active material utilization of Si anode accompanied by inevitable huge volume expansion makes higher requirements than regulating Li metal deposition behaviors from dendrite growth. Herein, we rectified the solid electrolyte interphase (SEI) layer on Si surface to maintain the electrode integrity during repeated cycling. In our design, an oligomeric buffer layer (CHO2-/CH3O-) derived from FEC and an inorganic pillar (LiF/Li3N) derived from LiFSI/LiNO3 weave into organic-inorganic crosslinking SEI during the initial activation process. Leveraging COMSOL modeling reveals the small stress and strain of the Si particle under the protective effect of concrete SEI layers. Moreover, synchrotron X-ray 3D nano-computed tomography comprehensively elucidates the structural integrity of Si particles during cycling. With this merit, various silicon-based anodes show remarkable cycling stability. Notably, the Si/C || LiFePO4 full battery still affords a capacity retention ratio exceeding 95% at 1 mA cm−2 after 300 cycles. This interphase engineering design strategy provided in our work advances the understanding of how to cope with devastating volume variation by leveraging the SEI characteristic perspective.
电解质工程是稳定电极结构的一种可行策略。然而，硅阳极的高活性材料利用率伴随着不可避免的巨大体积膨胀，这就对调节枝晶生长的锂金属沉积行为提出了更高的要求。在此，我们对硅表面的固体电解质相间层（SEI）进行了整流，以在反复循环过程中保持电极的完整性。在我们的设计中，源自 FEC 的低聚缓冲层（CHO2-/CH3O-）和源自 LiFSI/LiNO3 的无机支柱（LiF/Li3N）在初始活化过程中交织成有机-无机交联 SEI。利用 COMSOL 建模揭示了硅粒子在混凝土 SEI 层保护作用下的微小应力和应变。此外，同步辐射 X 射线三维纳米计算机断层扫描全面阐明了硅颗粒在循环过程中的结构完整性。凭借这一优点，各种硅基阳极都表现出了显著的循环稳定性。值得注意的是，Si/C || LiFePO4 全电池在 1 mA cm-2 循环 300 次后，容量保持率仍超过 95%。我们工作中提供的这种相间工程设计方案，有助于人们理解如何利用 SEI 特性来应对破坏性的体积变化。
{"title":"Rectifying solid electrolyte interphase structure for stable multi-dimensional silicon anodes","authors":"Changhaoyue Xu, Peng Jing, Zhiwen Deng, Qingqing Liu, Ye Jia, Xuemei Zhang, Yan Deng, Yun Zhang, Wenlong Cai","doi":"10.1016/j.ensm.2024.103911","DOIUrl":"https://doi.org/10.1016/j.ensm.2024.103911","url":null,"abstract":"Electrolyte engineering is a promising strategy to stabilize electrode structure. However, the high active material utilization of Si anode accompanied by inevitable huge volume expansion makes higher requirements than regulating Li metal deposition behaviors from dendrite growth. Herein, we rectified the solid electrolyte interphase (SEI) layer on Si surface to maintain the electrode integrity during repeated cycling. In our design, an oligomeric buffer layer (CHO<sub>2</sub><sup>-</sup>/CH<sub>3</sub>O<sup>-</sup>) derived from FEC and an inorganic pillar (LiF/Li<sub>3</sub>N) derived from LiFSI/LiNO<sub>3</sub> weave into organic-inorganic crosslinking SEI during the initial activation process. Leveraging COMSOL modeling reveals the small stress and strain of the Si particle under the protective effect of concrete SEI layers. Moreover, synchrotron X-ray 3D nano-computed tomography comprehensively elucidates the structural integrity of Si particles during cycling. With this merit, various silicon-based anodes show remarkable cycling stability. Notably, the Si/C || LiFePO<sub>4</sub> full battery still affords a capacity retention ratio exceeding 95% at 1 mA cm<sup>−2</sup> after 300 cycles. This interphase engineering design strategy provided in our work advances the understanding of how to cope with devastating volume variation by leveraging the SEI characteristic perspective.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"5 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637570","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 : 2024-11-14DOI: 10.1016/j.ensm.2024.103907
Hongpeng Li , Shumei Ding , Jiabao Ding , Junhao Luo , Shuiren Liu , Haibo Huang
Integrated sensing systems are playing increasingly important roles in health monitoring as a spearhead of artificial intelligence. Rationally integrating the two key components of microsystems, that is, power sources and sensors, has become a desperate requirement. Micro-supercapacitors (MSCs) with high power delivery and long operating life have emerged as the next generation of microscale power supplies. MXenes, a novel growing family of two-dimensional transition metal carbides/nitrides, show great potential in MSCs due to their metallic conductivity, tunable surface chemistry, and redox capability. Herein, the state of-the-art of MXene-based MSCs and their integrated sensing systems are briefly reviewed from the perspective of structures and functions. Firstly, the working mechanism and performance evaluation metrics of MXene are investigated. Secondly, typical fabrication technologies of MXene-based MSCs are thoroughly summarized and examined. Then, the application of MSC-powered integrated sensing systems in smart electronics is reviewed. Finally, current challenges and future perspectives in fabricating MXene-based MSCs and their self-powered integrated sensing microsystems are proposed.
{"title":"MXene-based micro-supercapacitors powered integrated sensing system: Progress and prospects","authors":"Hongpeng Li , Shumei Ding , Jiabao Ding , Junhao Luo , Shuiren Liu , Haibo Huang","doi":"10.1016/j.ensm.2024.103907","DOIUrl":"10.1016/j.ensm.2024.103907","url":null,"abstract":"<div><div>Integrated sensing systems are playing increasingly important roles in health monitoring as a spearhead of artificial intelligence. Rationally integrating the two key components of microsystems, that is, power sources and sensors, has become a desperate requirement. Micro-supercapacitors (MSCs) with high power delivery and long operating life have emerged as the next generation of microscale power supplies. MXenes, a novel growing family of two-dimensional transition metal carbides/nitrides, show great potential in MSCs due to their metallic conductivity, tunable surface chemistry, and redox capability. Herein, the state of-the-art of MXene-based MSCs and their integrated sensing systems are briefly reviewed from the perspective of structures and functions. Firstly, the working mechanism and performance evaluation metrics of MXene are investigated. Secondly, typical fabrication technologies of MXene-based MSCs are thoroughly summarized and examined. Then, the application of MSC-powered integrated sensing systems in smart electronics is reviewed. Finally, current challenges and future perspectives in fabricating MXene-based MSCs and their self-powered integrated sensing microsystems are proposed.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"74 ","pages":"Article 103907"},"PeriodicalIF":18.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610397","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：