Pub Date : 2024-10-06DOI: 10.1016/j.ensm.2024.103819
Guannan Qian , Saravana Kuppan , Alessandro Gallo , Jigang Zhou , Zhao Liu , Yijin Liu
The continuous advancement of battery technology necessitates innovative approaches in both research and manufacturing to ensure improved performance, reliability, and safety. This article explores the critical role of advanced imaging characterization techniques, spanning from in-situ experimentation to in-line metrology, in the development and production of lithium-ion batteries. By integrating real-time imaging and diagnostic tools, researchers and manufacturers can gain unprecedented insights into the electrochemical processes, material behaviors, structural defects and their evolutions in commercial-grade batteries. This comprehensive characterization enables the optimization of material compositions, electrode designs, and manufacturing processes, ultimately enhancing the efficiency and longevity of batteries. The synergy between in-situ experimentation and in-line metrology provides a robust framework for addressing the complex challenges in battery research and manufacturing, paving the way for innovations that will meet the growing demands of energy storage systems.
{"title":"From in-situ experimentation to in-line metrology: Advanced imaging characterization for battery research and manufacturing","authors":"Guannan Qian , Saravana Kuppan , Alessandro Gallo , Jigang Zhou , Zhao Liu , Yijin Liu","doi":"10.1016/j.ensm.2024.103819","DOIUrl":"10.1016/j.ensm.2024.103819","url":null,"abstract":"<div><div>The continuous advancement of battery technology necessitates innovative approaches in both research and manufacturing to ensure improved performance, reliability, and safety. This article explores the critical role of advanced imaging characterization techniques, spanning from in-situ experimentation to in-line metrology, in the development and production of lithium-ion batteries. By integrating real-time imaging and diagnostic tools, researchers and manufacturers can gain unprecedented insights into the electrochemical processes, material behaviors, structural defects and their evolutions in commercial-grade batteries. This comprehensive characterization enables the optimization of material compositions, electrode designs, and manufacturing processes, ultimately enhancing the efficiency and longevity of batteries. The synergy between in-situ experimentation and in-line metrology provides a robust framework for addressing the complex challenges in battery research and manufacturing, paving the way for innovations that will meet the growing demands of energy storage systems.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"73 ","pages":"Article 103819"},"PeriodicalIF":18.9,"publicationDate":"2024-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142379284","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 : 2024-10-05DOI: 10.1016/j.ensm.2024.103826
Jeong-A. Lee , Haneul Kang , Saehun Kim , Kyungho Lee , Jeong Hwan Byun , Eunji Kwon , Samuel Seo , Kyuju Kwak , Kyoung Han Ryu , Nam-Soon Choi
Anode-free Li-metal batteries (AFLMBs), in which Li+ ions from the cathode are deposited on a Cu substrate and the deposited Li-metal serves as the anode, exhibit higher energy density compared to Li-metal batteries (LMBs). However, achieving stable cycle performance, even at moderate operating conditions, is difficult and has so far hindered their practical uses. In AFLMBs, the homogeneity of solid electrolyte interphase (SEI), initially created by electrolyte reduction on Cu substrate, is not maintained during Li-metal deposition, leading to uncontrolled electrolyte decomposition. The SEI is therefore not conserved, and uneven Li deposition morphology is induced on the Cu substrate and the eventual instability of SEI leads to the overall degradation of AFLMBs. Here, we report on the failure mechanisms of AFLMBs through a comparative study with LMBs using 3 M lithium bis(fluorosulfonyl)imide (LiFSI) dissolved in N,N-dimethylsulfamoyl fluoride. Our investigation reveals that the SEI inhomogeneity in AFLMBs makes Li+ transport through SEI sluggish and non-uniform, triggering local compositional changes of the initially formed SEI on the Cu substrate and unwanted consumption of FSI− anion from the electrolyte. This work provides clear understanding to the interfacial engineering and important roles of Li-metal on the Cu substrate in AFLMBs, promising the creation of stable SEI, reversible electrochemical reaction of Li-metal, and interfacial stability of the cathode in LMBs.
与锂金属电池（LMB）相比，无阳极锂金属电池（AFLMB）具有更高的能量密度，在这种电池中，阴极的锂离子沉积在铜基板上，沉积的锂金属作为阳极。然而，即使在中等工作条件下也很难实现稳定的循环性能，这阻碍了它们的实际应用。在 AFLMB 中，最初通过在铜基板上还原电解质而形成的固体电解质相（SEI）在锂金属沉积过程中无法保持均匀性，从而导致电解质分解失控。因此，SEI 无法保持，锂沉积形态在铜基板上不均匀，SEI 的最终不稳定性导致了 AFLMB 的整体降解。在此，我们使用溶解在 N,N-二甲基氨基磺酰氟中的 3 M 双（氟磺酰）亚胺锂（LiFSI），通过与 LMB 的比较研究报告了 AFLMB 的失效机制。我们的研究发现，AFLMB 中 SEI 的不均匀性使得 Li+ 通过 SEI 的传输变得迟缓和不均匀，引发了铜基底上最初形成的 SEI 的局部成分变化以及电解液中 FSI- 阴离子的不必要消耗。这项研究清楚地揭示了 AFLMBs 中 Cu 基底上的界面工程和锂金属的重要作用，有望在 LMBs 中形成稳定的 SEI、锂金属的可逆电化学反应和阴极的界面稳定性。
{"title":"Unveiling degradation mechanisms of anode-free Li-metal batteries","authors":"Jeong-A. Lee , Haneul Kang , Saehun Kim , Kyungho Lee , Jeong Hwan Byun , Eunji Kwon , Samuel Seo , Kyuju Kwak , Kyoung Han Ryu , Nam-Soon Choi","doi":"10.1016/j.ensm.2024.103826","DOIUrl":"10.1016/j.ensm.2024.103826","url":null,"abstract":"<div><div>Anode-free Li-metal batteries (AFLMBs), in which Li<sup>+</sup> ions from the cathode are deposited on a Cu substrate and the deposited Li-metal serves as the anode, exhibit higher energy density compared to Li-metal batteries (LMBs). However, achieving stable cycle performance, even at moderate operating conditions, is difficult and has so far hindered their practical uses. In AFLMBs, the homogeneity of solid electrolyte interphase (SEI), initially created by electrolyte reduction on Cu substrate, is not maintained during Li-metal deposition, leading to uncontrolled electrolyte decomposition. The SEI is therefore not conserved, and uneven Li deposition morphology is induced on the Cu substrate and the eventual instability of SEI leads to the overall degradation of AFLMBs. Here, we report on the failure mechanisms of AFLMBs through a comparative study with LMBs using 3 M lithium <em>bis</em>(fluorosulfonyl)imide (LiFSI) dissolved in <em>N,N</em>-dimethylsulfamoyl fluoride. Our investigation reveals that the SEI inhomogeneity in AFLMBs makes Li<sup>+</sup> transport through SEI sluggish and non-uniform, triggering local compositional changes of the initially formed SEI on the Cu substrate and unwanted consumption of FSI<sup>−</sup> anion from the electrolyte. This work provides clear understanding to the interfacial engineering and important roles of Li-metal on the Cu substrate in AFLMBs, promising the creation of stable SEI, reversible electrochemical reaction of Li-metal, and interfacial stability of the cathode in LMBs.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"73 ","pages":"Article 103826"},"PeriodicalIF":18.9,"publicationDate":"2024-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142377747","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 : 2024-10-04DOI: 10.1016/j.ensm.2024.103823
Jianwen Yu , Zhongxi Zhao , Zhuojun Zhang , Kai Sun , Peng Tan
Aqueous zinc-based batteries offer high safety, abundant resources, low cost, and environmental friendliness, making them a promising alternative to lithium-ion batteries for large-scale energy storage markets. However, the natural convection in the electrolyte during operation, which can greatly affect the battery performance, is overlooked for a long time. Through particle tracing experiments, this study demonstrates that in the vertical placement of the battery, natural convection occurs due to the variation of electrolyte density, whereas it does not happen when the cathode is on top. Besides, there is a significant difference in electrochemical performance between these two configurations, with a voltage difference of up to 0.25 V at 10 mA cm⁻² and a peak current difference of up to 3.4 mA in linear sweep voltammetry. Simulation results show that convective mass transfer can be up to 100 times greater than diffusive mass transfer in a bulk solution. This highlights the importance of considering natural convection to improve model accuracy. Further, to increase energy density, batteries are scaled up in practical applications to reduce the weight of the casing. This work simulates mass transfer conditions under various scenarios, illustrating the trade-off between current density and battery size, and offering new guidance for the design of aqueous zinc-based batteries.
{"title":"Revealing the intricacies of natural convection: A key factor in aqueous zinc battery design","authors":"Jianwen Yu , Zhongxi Zhao , Zhuojun Zhang , Kai Sun , Peng Tan","doi":"10.1016/j.ensm.2024.103823","DOIUrl":"10.1016/j.ensm.2024.103823","url":null,"abstract":"<div><div>Aqueous zinc-based batteries offer high safety, abundant resources, low cost, and environmental friendliness, making them a promising alternative to lithium-ion batteries for large-scale energy storage markets. However, the natural convection in the electrolyte during operation, which can greatly affect the battery performance, is overlooked for a long time. Through particle tracing experiments, this study demonstrates that in the vertical placement of the battery, natural convection occurs due to the variation of electrolyte density, whereas it does not happen when the cathode is on top. Besides, there is a significant difference in electrochemical performance between these two configurations, with a voltage difference of up to 0.25 V at 10 mA cm⁻² and a peak current difference of up to 3.4 mA in linear sweep voltammetry. Simulation results show that convective mass transfer can be up to 100 times greater than diffusive mass transfer in a bulk solution. This highlights the importance of considering natural convection to improve model accuracy. Further, to increase energy density, batteries are scaled up in practical applications to reduce the weight of the casing. This work simulates mass transfer conditions under various scenarios, illustrating the trade-off between current density and battery size, and offering new guidance for the design of aqueous zinc-based batteries.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"73 ","pages":"Article 103823"},"PeriodicalIF":18.9,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142374442","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 : 2024-10-03DOI: 10.1016/j.ensm.2024.103794
Israel Temprano , Javier Carrasco , Matthieu Bugnet , Ivan T. Lucas , Jigang Zhou , Robert S. Weatherup , Christopher A. O'Keefe , Zachary Ruff , Jiahui Xu , Nicolas Folastre , Jian Wang , Antonin Gajan , Arnaud Demortière
Batteries are complex systems operating far from equilibrium, relying on intricate reactions at interfaces for performance. Understanding and optimizing these interfaces is crucial, but challenges arise due to the diverse factors influencing their development, making comprehensive characterization essential despite experimental difficulties. Recent advancements in characterization tools offer new opportunities to explore interfacial evolution, particularly in the solid electrolyte interphase (SEI).
In this perspective article, leading experts in physical-chemical characterization techniques for electrochemical systems discuss the current state-of-the-art and emerging approaches to study interfaces and their evolution in batteries. The focus here is on the capabilities, technical challenges, limitations, and requirements that these techniques must meet to advance our understanding of battery interfacial evolution. The emphasis is placed on techniques that enable probing interfaces under realistic conditions, close to commercial battery systems, and on the integration of multiple approaches within a single measurement (multimodal) to minimise variable effects.
This article focuses on the most promising techniques for characterizing all phases relevant to interfacial processes, as well as their integration with correlative analyses and computational modelling. We discuss solid phase characterization with X-ray spectroscopies and microscopies (XPS, XAS, STXM, X-PEEM & XCT), Raman spectroscopies (SERS, TERS & SHINERS), solid-state NMR and electron microscopies and spectroscopies (STEM, EDXS, EELS & 4D-STEM). The liquid phase characterization is discussed in terms of solution NMR spectroscopy, TEM and optical spectroscopies, while the gas phase can be characterized using OEMS, pressure monitoring and GCMS. Computational modelling and simulation (DFT, ReaxFF & MLIP) are also discussed
{"title":"Advanced methods for characterizing battery interfaces: Towards a comprehensive understanding of interfacial evolution in modern batteries","authors":"Israel Temprano , Javier Carrasco , Matthieu Bugnet , Ivan T. Lucas , Jigang Zhou , Robert S. Weatherup , Christopher A. O'Keefe , Zachary Ruff , Jiahui Xu , Nicolas Folastre , Jian Wang , Antonin Gajan , Arnaud Demortière","doi":"10.1016/j.ensm.2024.103794","DOIUrl":"10.1016/j.ensm.2024.103794","url":null,"abstract":"<div><div>Batteries are complex systems operating far from equilibrium, relying on intricate reactions at interfaces for performance. Understanding and optimizing these interfaces is crucial, but challenges arise due to the diverse factors influencing their development, making comprehensive characterization essential despite experimental difficulties. Recent advancements in characterization tools offer new opportunities to explore interfacial evolution, particularly in the solid electrolyte interphase (SEI).</div><div>In this perspective article, leading experts in physical-chemical characterization techniques for electrochemical systems discuss the current state-of-the-art and emerging approaches to study interfaces and their evolution in batteries. The focus here is on the capabilities, technical challenges, limitations, and requirements that these techniques must meet to advance our understanding of battery interfacial evolution. The emphasis is placed on techniques that enable probing interfaces under realistic conditions, close to commercial battery systems, and on the integration of multiple approaches within a single measurement (multimodal) to minimise variable effects.</div><div>This article focuses on the most promising techniques for characterizing all phases relevant to interfacial processes, as well as their integration with correlative analyses and computational modelling. We discuss solid phase characterization with X-ray spectroscopies and microscopies (XPS, XAS, STXM, X-PEEM & XCT), Raman spectroscopies (SERS, TERS & SHINERS), solid-state NMR and electron microscopies and spectroscopies (STEM, EDXS, EELS & 4D-STEM). The liquid phase characterization is discussed in terms of solution NMR spectroscopy, TEM and optical spectroscopies, while the gas phase can be characterized using OEMS, pressure monitoring and GCMS. Computational modelling and simulation (DFT, ReaxFF & MLIP) are also discussed</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"73 ","pages":"Article 103794"},"PeriodicalIF":18.9,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142369717","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 : 2024-10-02DOI: 10.1016/j.ensm.2024.103822
Xiaoyang Wei , Zhongqin Dai , Yan Lu , Wei Shan , Wuhan Liu , Kaiying Shi , Cheng Ding , Jun Jin , Zhaoyin Wen
Lithium-sulfur (Li-S) batteries are a key area of research in energy storage due to their high theoretical energy density, low cost, and environmental friendliness. However, the shuttle effect caused by lithium polysulfides (LiPSs) intermediates often results in poor cycling stability. Therefore, constructing rational cathode structures to achieve fast reaction kinetics in adsorbing and catalyzing LiPSs is the key to obtain high-performance Li-S batteries. Metallic single-atom catalysts (SACs), known for their 100 % atomic utilization rate and low cost, have demonstrated excellent catalytic activity and selectivity in the redox reactions of Li-S batteries, positioning them as one of the most promising catalysts in this field. Rare earth metallic SACs with versatile oxidation states, diverse coordination chemistry and environmentally friendly are rarely investigated in Li-S system. Herein, we fabricate a rare earth metal-based single-atom catalyst (CeSAs) supported on a three-dimensional porous N-doped carbon (3DCeSA-N-WS), and systematically study its performance in Li-S batteries. Benefitting from the atomic dispersion and versatile oxidation states (Ce3+/Ce4+), the 3DCeSA-N-WS demonstrates excellent performance in anchoring and catalyzing LiPSs, significantly enhancing the redox reaction kinetics. Consequently, the prepared sulfur cathode exhibits exceptional electrochemical performance, with a high initial specific discharge capacity of 1225 mAh g−1 at 0.2 C and a capacity retention of 76.1 % after 160 cycles. The assembled 100 mAh-level pouch cellmaintains a high specific discharge capacity of 877 mAh g−1 after 50 cycles at 0.5 C. This work provides new insights into the design of sulfur cathode catalysts, thereby contributing to the realization of high-performance Li-S batteries.
锂硫（Li-S）电池具有理论能量密度高、成本低和环保等优点，是储能领域的一个重要研究方向。然而，锂多硫化物（LiPSs）中间体造成的穿梭效应往往导致循环稳定性差。因此，构建合理的正极结构以实现吸附和催化 LiPSs 的快速反应动力学是获得高性能锂-S 电池的关键。金属单原子催化剂（SAC）以其 100% 的原子利用率和低成本而著称，在锂-S 电池的氧化还原反应中表现出卓越的催化活性和选择性，使其成为该领域最有前途的催化剂之一。稀土金属 SAC 具有多种氧化态、多种配位化学性质和环境友好性，但在锂-S 体系中却很少被研究。在此，我们制备了一种支撑在三维多孔 N 掺杂碳（3DCeSA-N-WS）上的稀土金属基单原子催化剂（CeSAs），并对其在锂-S 电池中的性能进行了系统研究。3DCeSA-N-WS 具有原子分散性和多种氧化态（Ce3+/Ce4+），因此在锚定和催化锂离子电池方面表现出色，显著提高了氧化还原反应的动力学性能。因此，所制备的硫阴极表现出卓越的电化学性能，在 0.2 C 条件下的初始比放电容量高达 1225 mAh g-1，160 次循环后的容量保持率为 76.1%。这项工作为硫阴极催化剂的设计提供了新的见解，从而有助于实现高性能锂-S 电池。
{"title":"Engineering rare earth metal Ce-N coordination as catalyst for high redox kinetics in lithium-sulfur batteries","authors":"Xiaoyang Wei , Zhongqin Dai , Yan Lu , Wei Shan , Wuhan Liu , Kaiying Shi , Cheng Ding , Jun Jin , Zhaoyin Wen","doi":"10.1016/j.ensm.2024.103822","DOIUrl":"10.1016/j.ensm.2024.103822","url":null,"abstract":"<div><div>Lithium-sulfur (Li-S) batteries are a key area of research in energy storage due to their high theoretical energy density, low cost, and environmental friendliness. However, the shuttle effect caused by lithium polysulfides (LiPSs) intermediates often results in poor cycling stability. Therefore, constructing rational cathode structures to achieve fast reaction kinetics in adsorbing and catalyzing LiPSs is the key to obtain high-performance Li-S batteries. Metallic single-atom catalysts (SACs), known for their 100 % atomic utilization rate and low cost, have demonstrated excellent catalytic activity and selectivity in the redox reactions of Li-S batteries, positioning them as one of the most promising catalysts in this field. Rare earth metallic SACs with versatile oxidation states, diverse coordination chemistry and environmentally friendly are rarely investigated in Li-S system. Herein, we fabricate a rare earth metal-based single-atom catalyst (CeSAs) supported on a three-dimensional porous N-doped carbon (3DCeSA-N-WS), and systematically study its performance in Li-S batteries. Benefitting from the atomic dispersion and versatile oxidation states (Ce<sup>3+</sup>/Ce<sup>4+</sup>), the 3DCeSA-N-WS demonstrates excellent performance in anchoring and catalyzing LiPSs, significantly enhancing the redox reaction kinetics. Consequently, the prepared sulfur cathode exhibits exceptional electrochemical performance, with a high initial specific discharge capacity of 1225 mAh <em>g</em><sup>−1</sup> at 0.2 C and a capacity retention of 76.1 % after 160 cycles. The assembled 100 mAh-level pouch cellmaintains a high specific discharge capacity of 877 mAh <em>g</em><sup>−1</sup> after 50 cycles at 0.5 C. This work provides new insights into the design of sulfur cathode catalysts, thereby contributing to the realization of high-performance Li-S batteries.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"73 ","pages":"Article 103822"},"PeriodicalIF":18.9,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142360658","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 : 2024-10-01DOI: 10.1016/j.ensm.2024.103820
Zhenyu Hu , Li Lin , Yi Jiang , Lianshan Sun , Wanqiang Liu , Qingshuang Wang , Fang Wang
In this work, we have discovered and investigated the reaction mechanism of Aqueous Hydrogen Proton Battery (AHPB), which differ from conventional rocking-chair batteries. The hydrogen protons in the battery reaction is provided by the dissociation of H2O molecules in the electrolyte. Thus, the charging and discharging processes of the battery are also accompanied by changes in electrolyte concentration. To explore this, we have designed a AHPBs with a 2 M Zn(ClO4)2 electrolyte. The experimental results demonstrate excellent performance of the AHPBs, with a discharge specific capacity of up to 700.6 mAh g−1 and a charge-discharge power conversion efficiency of 83.638 %. Both experimental and simulation results confirm that H+ in the battery is primarily provided by H2O molecules solvating Zn2+. As the electrolyte concentration increases, ClO4− replaces some of the solvating H2O molecules of Zn2+, resulting in the remaining unsaturated solvating H2O molecules having a stronger propensity for deprotonation, thus facilitating the release of H+. This elucidates the specific source of H+ in AHPBs.
{"title":"Reveal the source of protons in aqueous hydrogen proton battery","authors":"Zhenyu Hu , Li Lin , Yi Jiang , Lianshan Sun , Wanqiang Liu , Qingshuang Wang , Fang Wang","doi":"10.1016/j.ensm.2024.103820","DOIUrl":"10.1016/j.ensm.2024.103820","url":null,"abstract":"<div><div>In this work, we have discovered and investigated the reaction mechanism of Aqueous Hydrogen Proton Battery (AHPB), which differ from conventional rocking-chair batteries. The hydrogen protons in the battery reaction is provided by the dissociation of H<sub>2</sub>O molecules in the electrolyte. Thus, the charging and discharging processes of the battery are also accompanied by changes in electrolyte concentration. To explore this, we have designed a AHPBs with a 2 M Zn(ClO<sub>4</sub>)<sub>2</sub> electrolyte. The experimental results demonstrate excellent performance of the AHPBs, with a discharge specific capacity of up to 700.6 mAh <em>g</em><sup>−1</sup> and a charge-discharge power conversion efficiency of 83.638 %. Both experimental and simulation results confirm that <em>H</em><sup>+</sup> in the battery is primarily provided by H<sub>2</sub>O molecules solvating Zn<sup>2+</sup>. As the electrolyte concentration increases, ClO<sub>4</sub><sup>−</sup> replaces some of the solvating H<sub>2</sub>O molecules of Zn<sup>2+</sup>, resulting in the remaining unsaturated solvating H<sub>2</sub>O molecules having a stronger propensity for deprotonation, thus facilitating the release of <em>H</em><sup>+</sup>. This elucidates the specific source of <em>H</em><sup>+</sup> in AHPBs.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"73 ","pages":"Article 103820"},"PeriodicalIF":18.9,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142360657","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 : 2024-10-01DOI: 10.1016/j.ensm.2024.103817
Chang Chen , Libo Zhu , Javeed Mahmood , Zhong-Hua Xue , Xu Yu , Qin Li , Ziwei Chang , Han Tian , Fantao Kong , Haitao Huang , Cafer T. Yavuz , Xiangzhi Cui , Jianlin Shi
Electrochemical water splitting and energy storage are key for a sustainable energy future, despite the challenges related to undesirable overpotentials and high voltage requirements. Herein, we introduce a synergistic approach between a low overpotential hydrogen evolution reaction (HER) and a low voltage zinc-air/iodine battery (ZAIB) by coupling with iodide oxidation half reactions. By developing a Pt/Co3O4 electrocatalyst in two steps and with under 2% Pt loading, we achieve an unprecedented low full cell potential for hydrogen generation at 0.574 V, exhibiting an ultra-high reduction of energy consumption of 64.7%. The Pt/Co3O4 electrode also enables ZAIB to record a power density of 154 mW cm−2 at an ultra-low charging potential of 1.68 V. Mechanistic studies and DFT calculations of the novel electrode confirm an electron rich Pt-Co interface and favorable Pt-I interactions, facilitating both HER and IOR reactions. Our design provides critical technology for potential large-scale renewable energy projects.
尽管存在与不良过电位和高电压要求相关的挑战，但电化学水分离和能量存储是未来可持续能源的关键。在此，我们通过与碘氧化半反应的耦合，介绍了一种低过电位氢进化反应（HER）与低电压锌-空气/碘电池（ZAIB）之间的协同方法。通过分两步开发铂/Co3O4 电催化剂，在铂载量低于 2% 的情况下，我们实现了前所未有的 0.574 V 低全电池制氢电位，能耗降低了 64.7%。铂/Co3O4 电极还使ZAIB 在 1.68 V 的超低充电电位下达到了 154 mW cm-2 的功率密度。对这种新型电极进行的机理研究和 DFT 计算证实，富电子的铂-钴界面和有利的铂-碘相互作用可促进 HER 和 IOR 反应。我们的设计为潜在的大规模可再生能源项目提供了关键技术。
{"title":"An electrocatalytic iodine oxidations-based configuration for hydrogen and I2/I3− co-productions driven by the Zn-air/iodine battery","authors":"Chang Chen , Libo Zhu , Javeed Mahmood , Zhong-Hua Xue , Xu Yu , Qin Li , Ziwei Chang , Han Tian , Fantao Kong , Haitao Huang , Cafer T. Yavuz , Xiangzhi Cui , Jianlin Shi","doi":"10.1016/j.ensm.2024.103817","DOIUrl":"10.1016/j.ensm.2024.103817","url":null,"abstract":"<div><div>Electrochemical water splitting and energy storage are key for a sustainable energy future, despite the challenges related to undesirable overpotentials and high voltage requirements. Herein, we introduce a synergistic approach between a low overpotential hydrogen evolution reaction (HER) and a low voltage zinc-air/iodine battery (ZAIB) by coupling with iodide oxidation half reactions. By developing a Pt/Co<sub>3</sub>O<sub>4</sub> electrocatalyst in two steps and with under 2% Pt loading, we achieve an unprecedented low full cell potential for hydrogen generation at 0.574 V, exhibiting an ultra-high reduction of energy consumption of 64.7%. The Pt/Co<sub>3</sub>O<sub>4</sub> electrode also enables ZAIB to record a power density of 154 mW cm<sup>−2</sup> at an ultra-low charging potential of 1.68 V. Mechanistic studies and DFT calculations of the novel electrode confirm an electron rich Pt-Co interface and favorable Pt-I interactions, facilitating both HER and IOR reactions. Our design provides critical technology for potential large-scale renewable energy projects.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"73 ","pages":"Article 103817"},"PeriodicalIF":18.9,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142360400","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 : 2024-10-01DOI: 10.1016/j.ensm.2024.103821
Atin Pramanik , Alexis G. Manche , Fredrik Lindgren , Tore Ericsson , Lennart Häggström , David B. Cordes , A. Robert Armstrong
Recently, polyanionic compounds have received great interest as alternative cathode materials to conventional oxides due to their different advantages in cost, safety, structural stability, as well as being environmentally friendly. However, the vast majority of polyanionic materials reported so far rely exclusively upon the redox reaction of the transition metal for lithium/sodium transfer.
The development of multielectron redox-active cathode materials is a top priority for achieving high energy density with long cycle life in the next-generation secondary battery applications. Triggering anion redox activity is a promising strategy to enhance the energy density of polyanionic cathode materials for Li/Na-ion batteries. In addition to transition metal redox activity, the oxalate group also shows redox behavior enabling reversible charge/discharge and high capacity without gas evolution.
Herein, we report NaLiFe(C2O4)2 as a new positive electrode and use different characterization techniques such as Raman spectroscopy and Mössbauer analyses to characterise this dual-ion redox process experimentally. First-principles calculations also help to understand the interactions between the transition metal and the oxalate group as the main factor that modulates the cationic and polyanionic redox couples in these materials.
{"title":"NaLiFe(C2O4)2: A polyanionic Li/Na-ion battery cathode exhibiting cationic and anionic redox","authors":"Atin Pramanik , Alexis G. Manche , Fredrik Lindgren , Tore Ericsson , Lennart Häggström , David B. Cordes , A. Robert Armstrong","doi":"10.1016/j.ensm.2024.103821","DOIUrl":"10.1016/j.ensm.2024.103821","url":null,"abstract":"<div><div>Recently, polyanionic compounds have received great interest as alternative cathode materials to conventional oxides due to their different advantages in cost, safety, structural stability, as well as being environmentally friendly. However, the vast majority of polyanionic materials reported so far rely exclusively upon the redox reaction of the transition metal for lithium/sodium transfer.</div><div>The development of multielectron redox-active cathode materials is a top priority for achieving high energy density with long cycle life in the next-generation secondary battery applications. Triggering anion redox activity is a promising strategy to enhance the energy density of polyanionic cathode materials for Li/Na-ion batteries. In addition to transition metal redox activity, the oxalate group also shows redox behavior enabling reversible charge/discharge and high capacity without gas evolution.</div><div>Herein, we report NaLiFe(C<sub>2</sub>O<sub>4</sub>)<sub>2</sub> as a new positive electrode and use different characterization techniques such as Raman spectroscopy and Mössbauer analyses to characterise this dual-ion redox process experimentally. First-principles calculations also help to understand the interactions between the transition metal and the oxalate group as the main factor that modulates the cationic and polyanionic redox couples in these materials.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"73 ","pages":"Article 103821"},"PeriodicalIF":18.9,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142360656","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 : 2024-10-01DOI: 10.1016/j.ensm.2024.103813
Juntian Fan , Huimin Luo , Tao Wang , Sheng Dai
With the widespread use of lithium-ion batteries (LIBs) in portable electronics and electric vehicles (EVs), the end-of-life (EOL) LIBs are projected to reach 1336 GWh by 2040 under the sustainable development scenario. Proper recycling is urgently needed to minimize the release of hazardous waste and reduce mining activities by reintroducing critical minerals into the supply chain. Lithium nickel manganese cobalt oxide (LiNixMnyCozO2, NMCs) cathodes have become dominant in the LIB market, especially with the increasing production of EVs, which are also the most valuable components in EOL LIBs. Unlike pyrometallurgical and/or hydrometallurgical methods, which convert spent NMCs into metals or metal compounds, direct recycling technologies aim to maximize the value of spent cathodes by restoring their degraded structure and composition. This review summarizes direct recycling methods for NMC cathodes published in the last decade and provides insights into the challenges and future development of direct recycling techniques.
{"title":"Progress in direct recycling of spent lithium nickel manganese cobalt oxide (NMC) cathodes","authors":"Juntian Fan , Huimin Luo , Tao Wang , Sheng Dai","doi":"10.1016/j.ensm.2024.103813","DOIUrl":"10.1016/j.ensm.2024.103813","url":null,"abstract":"<div><div>With the widespread use of lithium-ion batteries (LIBs) in portable electronics and electric vehicles (EVs), the end-of-life (EOL) LIBs are projected to reach 1336 GWh by 2040 under the sustainable development scenario. Proper recycling is urgently needed to minimize the release of hazardous waste and reduce mining activities by reintroducing critical minerals into the supply chain. Lithium nickel manganese cobalt oxide (LiNi<sub>x</sub>Mn<sub>y</sub>Co<sub>z</sub>O<sub>2</sub>, NMCs) cathodes have become dominant in the LIB market, especially with the increasing production of EVs, which are also the most valuable components in EOL LIBs. Unlike pyrometallurgical and/or hydrometallurgical methods, which convert spent NMCs into metals or metal compounds, direct recycling technologies aim to maximize the value of spent cathodes by restoring their degraded structure and composition. This review summarizes direct recycling methods for NMC cathodes published in the last decade and provides insights into the challenges and future development of direct recycling techniques.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"73 ","pages":"Article 103813"},"PeriodicalIF":18.9,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142360659","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 : 2024-09-30DOI: 10.1016/j.ensm.2024.103816
Pin Du , Jiale Wan , Baolong Qiu , Hongwei Xie , Qiushi Song , Dihua Wang , Huayi Yin
Electrolytes play a vital role in determining the performances of lithium-ion batteries (LIBs), especially the high-voltage LiNi0.6Co0.2Mn0.2O2 (NCM622) cathode in LiTFSI-based electrolytes. Herein, we report a high-capacity and stable NCM622 cathode that can be realized in LiTFSI-based (named T) carbonate electrolytes by tuning the intermolecular interactions using the added LiDFOB (named D). In the 1 M dual-salt electrolyte, the cathode failure and Al corrosion are suppressed in the 4.5 V-NCM622||Li batteries, because a uniform interfacial layer and weaker Li+-solvent interactions are built to inhibit the parasitic reactions. As a result, the capacity retention reaches 94.68% after 200 cycles and the 10 C-rate capacity is about 160 mA h g-1 in the 1 M T + D dual-salt electrolyte. Unlike the commonly used electrolyte, the FEC additive increases the de-solvation barrier and disturbs the cycle stability in (T + D) dual-salt systems. Density functional theory (DFT) calculation and nuclear magnetic resonance (NMR) spectra reveal that the additive FEC changes the solvent-solvent and solvent-anion interactions in the presence of T + D, which weakens the electrolyte-cathode compatibility. This work indicates that regulating the solvation structure and interfacial chemistry from solvent-solvent/anion interactions is promising for designing high-performance LIBs by using dual‐salt electrolytes.
电解质在决定锂离子电池（LIB）性能方面起着至关重要的作用，尤其是在基于 LiTFSI 的电解质中的高压 LiNi0.6Co0.2Mn0.2O2 (NCM622) 正极。在此，我们报告了一种高容量、稳定的 NCM622 阴极，它可以在基于 LiTFSI（命名为 T）的碳酸盐电解质中实现，方法是使用添加的 LiDFOB（命名为 D）调整分子间的相互作用。在 1 M 双盐电解质中，4.5 V-NCM622||Li 电池的阴极失效和铝腐蚀得到了抑制，这是因为建立了均匀的界面层和较弱的 Li+-溶剂相互作用，从而抑制了寄生反应。因此，在 1 M T+D 双盐电解液中，200 次循环后的容量保持率达到 94.68%，10 C 速率容量约为 160 mA h g-1。与常用电解液不同的是，FEC 添加剂增加了（T+D）双盐体系中的脱溶障碍，干扰了循环稳定性。密度泛函理论（DFT）计算和核磁共振（NMR）光谱显示，添加剂 FEC 改变了 T+D 存在时溶剂-溶剂和溶剂-阴离子之间的相互作用，从而削弱了电解质-阴极的相容性。这项工作表明，从溶剂-溶剂/阴离子相互作用中调节溶解结构和界面化学性质，对于利用双盐电解质设计高性能锂离子电池大有可为。
{"title":"Engineering the solvent-anion interactions of LiTFSI-based dual-salt electrolytes to sustain high-performance NCM622 cathodes","authors":"Pin Du , Jiale Wan , Baolong Qiu , Hongwei Xie , Qiushi Song , Dihua Wang , Huayi Yin","doi":"10.1016/j.ensm.2024.103816","DOIUrl":"10.1016/j.ensm.2024.103816","url":null,"abstract":"<div><div>Electrolytes play a vital role in determining the performances of lithium-ion batteries (LIBs), especially the high-voltage LiNi<sub>0.6</sub>Co<sub>0.2</sub>Mn<sub>0.2</sub>O<sub>2</sub> (NCM622) cathode in LiTFSI-based electrolytes. Herein, we report a high-capacity and stable NCM622 cathode that can be realized in LiTFSI-based (named T) carbonate electrolytes by tuning the intermolecular interactions using the added LiDFOB (named D). In the 1 M dual-salt electrolyte, the cathode failure and Al corrosion are suppressed in the 4.5 V-NCM622||Li batteries, because a uniform interfacial layer and weaker Li<sup>+</sup>-solvent interactions are built to inhibit the parasitic reactions. As a result, the capacity retention reaches 94.68% after 200 cycles and the 10 C-rate capacity is about 160 mA h g<sup>-1</sup> in the 1 M T + D dual-salt electrolyte. Unlike the commonly used electrolyte, the FEC additive increases the de-solvation barrier and disturbs the cycle stability in (T + D) dual-salt systems. Density functional theory (DFT) calculation and nuclear magnetic resonance (NMR) spectra reveal that the additive FEC changes the solvent-solvent and solvent-anion interactions in the presence of T + D, which weakens the electrolyte-cathode compatibility. This work indicates that regulating the solvation structure and interfacial chemistry from solvent-solvent/anion interactions is promising for designing high-performance LIBs by using dual‐salt electrolytes.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"73 ","pages":"Article 103816"},"PeriodicalIF":18.9,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142360398","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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