Md Adil, Maximilian Schmidt, Julia Vogt, Thomas Diemant, Martin Oschatz, Birgit Esser
Sodium‐ion batteries using organic electrode materials are a promising alternative to state‐of‐the‐art lithium‐ion batteries. However, their practical viability is hindered by challenges such as a low specific capacity of the organic electrode materials, or their dissolution in the electrolyte. We herein present a double mitigation strategy to enhance the performance of pillar[5]quinone (P5Q) as positive electrode in sodium batteries. Using 5 M sodium bis(fluorosulfonyl)imide in succinonitrile as highly concentrated electrolyte, and encapsulating P5Q in CMK‐3 (Carbon Mesostructured by KAIST with hexagonally ordered rod‐like carbon domains) as templated ordered mesoporous carbon, we achieve a record cycling performance with improved cycling stability even at elevated temperature (40 °C). The P5Q@CMK‐3 composite electrode delivers 430 mAh g−1 specific discharge capacity at 0.2C rate with 90% retention over 200 cycles. This corresponds to an energy density of 831 Wh kg−1 (based on P5Q mass) and surpasses previous reports on pillarquinones. When operated at 40 °C, the P5Q@CMK‐3 composite electrodes deliver a specific discharge capacity of 438 mAh g−1 with 88% capacity retention over 500 cycles (0.02% per cycle). This study underscores the crucial role the electrolyte plays in advancing organic sodium batteries, offering a promising avenue for the future of sustainable energy technologies.
使用有机电极材料的钠离子电池有望替代最先进的锂离子电池。然而，有机电极材料的低比容量或在电解液中的溶解等难题阻碍了其实际可行性。我们在此提出一种双重缓解策略，以提高钠电池中作为正极的柱[5]醌（P5Q）的性能。我们使用琥珀腈中的 5 M 双（氟磺酰）亚胺钠作为高浓度电解液，并将 P5Q 包封在 CMK-3（由 KAIST 提供的具有六角有序棒状碳域的介质结构碳）作为模板有序介孔碳中，从而实现了创纪录的循环性能，即使在高温（40 °C）下也能提高循环稳定性。P5Q@CMK-3 复合电极在 0.2C 速率下的比放电容量为 430 mAh g-1，在 200 次循环中的保持率为 90%。这相当于 831 Wh kg-1 的能量密度（基于 P5Q 质量），超过了之前有关柱醌的报道。在 40 °C 下工作时，P5Q@CMK-3 复合电极的比放电容量为 438 mAh g-1，在 500 次循环中容量保持率为 88%（每次循环 0.02%）。这项研究强调了电解质在推动有机钠电池发展中的关键作用，为未来的可持续能源技术提供了一条前景广阔的途径。
{"title":"Mitigating Dissolution to Enhance the Performance of Pillar[5]quinone in Sodium Batteries","authors":"Md Adil, Maximilian Schmidt, Julia Vogt, Thomas Diemant, Martin Oschatz, Birgit Esser","doi":"10.1002/batt.202400312","DOIUrl":"https://doi.org/10.1002/batt.202400312","url":null,"abstract":"Sodium‐ion batteries using organic electrode materials are a promising alternative to state‐of‐the‐art lithium‐ion batteries. However, their practical viability is hindered by challenges such as a low specific capacity of the organic electrode materials, or their dissolution in the electrolyte. We herein present a double mitigation strategy to enhance the performance of pillar[5]quinone (P5Q) as positive electrode in sodium batteries. Using 5 M sodium bis(fluorosulfonyl)imide in succinonitrile as highly concentrated electrolyte, and encapsulating P5Q in CMK‐3 (Carbon Mesostructured by KAIST with hexagonally ordered rod‐like carbon domains) as templated ordered mesoporous carbon, we achieve a record cycling performance with improved cycling stability even at elevated temperature (40 °C). The P5Q@CMK‐3 composite electrode delivers 430 mAh g−1 specific discharge capacity at 0.2C rate with 90% retention over 200 cycles. This corresponds to an energy density of 831 Wh kg−1 (based on P5Q mass) and surpasses previous reports on pillarquinones. When operated at 40 °C, the P5Q@CMK‐3 composite electrodes deliver a specific discharge capacity of 438 mAh g−1 with 88% capacity retention over 500 cycles (0.02% per cycle). This study underscores the crucial role the electrolyte plays in advancing organic sodium batteries, offering a promising avenue for the future of sustainable energy technologies.","PeriodicalId":132,"journal":{"name":"Batteries & Supercaps","volume":null,"pages":null},"PeriodicalIF":5.7,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141526584","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Maciej Tobis, Mennatalla Elmanzalawy, Jaehoon Choi, Elżbieta Frąckowiak, Simon Fleischmann
Molybdenum disulfide (MoS2)‐based electrode materials can exhibit a pseudocapacitive charge storage mechanism induced by nanosized dimension of the crystalline domains, which is why control over material structure via synthesis conditions is of significance. In this study, we investigate how the use of different sulfide precursors, specifically thiourea (TU), thioacetamide (TAA), and L‐cysteine (LC), during the hydrothermal synthesis of MoS2, affects its physicochemical, and consequently, electrochemical properties. The three materials obtained exhibit distinct morphologies, ranging from micron‐sized architectures (MoS2 TU), to nanosized flakes (MoS2 TAA and LC). While all three synthesized samples exhibit pseudocapacitive Li+ intercalation properties, the capacity retention of the latter two consisting of nanosized flakes is further improved at high cycling rates. The individual charge storage properties are analyzed by operando X‐ray diffraction, dilatometry, and 3D Bode analysis, revealing a correlation between the morphology, porosity, and the electrochemical intercalation behavior of the obtained electrode materials. The results demonstrate a facile strategy to control MoS2 structure and related functionality by choice of hydrothermal synthesis precursors.
{"title":"Controlling Structure and Morphology of MoS2 via Sulfur Precursor for Optimized Pseudocapacitive Lithium Intercalation Hosts","authors":"Maciej Tobis, Mennatalla Elmanzalawy, Jaehoon Choi, Elżbieta Frąckowiak, Simon Fleischmann","doi":"10.1002/batt.202400277","DOIUrl":"https://doi.org/10.1002/batt.202400277","url":null,"abstract":"Molybdenum disulfide (MoS2)‐based electrode materials can exhibit a pseudocapacitive charge storage mechanism induced by nanosized dimension of the crystalline domains, which is why control over material structure via synthesis conditions is of significance. In this study, we investigate how the use of different sulfide precursors, specifically thiourea (TU), thioacetamide (TAA), and L‐cysteine (LC), during the hydrothermal synthesis of MoS2, affects its physicochemical, and consequently, electrochemical properties. The three materials obtained exhibit distinct morphologies, ranging from micron‐sized architectures (MoS2 TU), to nanosized flakes (MoS2 TAA and LC). While all three synthesized samples exhibit pseudocapacitive Li+ intercalation properties, the capacity retention of the latter two consisting of nanosized flakes is further improved at high cycling rates. The individual charge storage properties are analyzed by operando X‐ray diffraction, dilatometry, and 3D Bode analysis, revealing a correlation between the morphology, porosity, and the electrochemical intercalation behavior of the obtained electrode materials. The results demonstrate a facile strategy to control MoS2 structure and related functionality by choice of hydrothermal synthesis precursors.","PeriodicalId":132,"journal":{"name":"Batteries & Supercaps","volume":null,"pages":null},"PeriodicalIF":5.7,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141526682","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The field of battery research has advanced significantly in the past 50 years. Despite the importance of electrolyte solutions for these devices, the battery community's perception of this essential component arguably aligns more with the 19th century reasoning than the 20th centuries advancements. This paper traces the historical evolution of electrolyte theories, emphasizing the consequences of an overly ion‐pairing‐centric view, and the benefits of a more nuanced analysis. A quantitative example is provided. It will be shown that an association constant of can be obtained from conductivity measurements of sodium acetate in water. However, studying the activity coefficients of this electrolyte reveals that this association constant would result in an unreasonable scenario where the free ions behave as uncharged particles at low concentrations. The aim is to promote a nuanced perspective on electrolyte solutions within the battery community, while also providing a collection of reputable references for the interested readers further studies.
{"title":"Ion‐Pairing: A Bygone Treatment of Electrolyte Solutions?","authors":"Lars Olow Simon Colbin, Yunqi Shao, Reza Younesi","doi":"10.1002/batt.202400160","DOIUrl":"https://doi.org/10.1002/batt.202400160","url":null,"abstract":"The field of battery research has advanced significantly in the past 50 years. Despite the importance of electrolyte solutions for these devices, the battery community's perception of this essential component arguably aligns more with the 19<jats:sup>th</jats:sup> century reasoning than the 20<jats:sup>th</jats:sup> centuries advancements. This paper traces the historical evolution of electrolyte theories, emphasizing the consequences of an overly ion‐pairing‐centric view, and the benefits of a more nuanced analysis. A quantitative example is provided. It will be shown that an association constant of can be obtained from conductivity measurements of sodium acetate in water. However, studying the activity coefficients of this electrolyte reveals that this association constant would result in an unreasonable scenario where the free ions behave as uncharged particles at low concentrations. The aim is to promote a nuanced perspective on electrolyte solutions within the battery community, while also providing a collection of reputable references for the interested readers further studies.","PeriodicalId":132,"journal":{"name":"Batteries & Supercaps","volume":null,"pages":null},"PeriodicalIF":5.7,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141505905","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sodium‐ion batteries (SIBs) are promising in several aspects due to their many advantages over lithium‐ion batteries. Among SIB’s several outstanding attributes, its low cost, resource abundance, and potential safety make it suitable for large‐scale energy storage systems (ESS). Among the potential cathode materials, poly‐anionic cathode materials could be a better choice for their stability and safety in comparison to layered transition metal oxides and Prussian blue analogues (PBA). However, on the other hand, the conductivity as well as the available capacity of the polyanion compounds are still poor, which limits their applications; moreover, some polyanion cathode operate at low voltage, which reduces the energy density and raises the cost of the battery system. We here try to summarize the recent progress of polyanion compounds as cathode materials for SIB. These compounds are categorized based on the metal redox couple, including V‐, Cr‐, Mn‐, Fe‐, Co‐, and Ni‐polyanion compounds. Our attention is specifically drawn to properties such as reversible redox voltage, capacity, cycling stability, and sodium storage mechanisms. We also discuss the challenges and potential development strategies for the future.
{"title":"Enhancing Voltage Output in Polyanion‐Type Cathode Materials for Sodium Ion Batteries","authors":"Xiaodong Wu, Aifang Liu, Suwan Lu","doi":"10.1002/batt.202400290","DOIUrl":"https://doi.org/10.1002/batt.202400290","url":null,"abstract":"Sodium‐ion batteries (SIBs) are promising in several aspects due to their many advantages over lithium‐ion batteries. Among SIB’s several outstanding attributes, its low cost, resource abundance, and potential safety make it suitable for large‐scale energy storage systems (ESS). Among the potential cathode materials, poly‐anionic cathode materials could be a better choice for their stability and safety in comparison to layered transition metal oxides and Prussian blue analogues (PBA). However, on the other hand, the conductivity as well as the available capacity of the polyanion compounds are still poor, which limits their applications; moreover, some polyanion cathode operate at low voltage, which reduces the energy density and raises the cost of the battery system. We here try to summarize the recent progress of polyanion compounds as cathode materials for SIB. These compounds are categorized based on the metal redox couple, including V‐, Cr‐, Mn‐, Fe‐, Co‐, and Ni‐polyanion compounds. Our attention is specifically drawn to properties such as reversible redox voltage, capacity, cycling stability, and sodium storage mechanisms. We also discuss the challenges and potential development strategies for the future.","PeriodicalId":132,"journal":{"name":"Batteries & Supercaps","volume":null,"pages":null},"PeriodicalIF":5.7,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141505909","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tassadit Ouaneche, Lorenzo Stievano, Laure Monconduit, Claude Guéry, Moulay Tahar Sougrati, Nadir Recham
Sodium‐ion batteries continue to rise in the energy storage landscape, their increasing adoption being driven by factors such as cost‐effectiveness and sustainability. As a consequence, there is a growing emphasis on the development of new electrode materials. Among these, olivine phosphates emerge as a promising family of cathode materials. However, viable synthesis routes are still lacking. In this study, cathode materials of olivine NaMn1‐xFexPO4 (x=0.34 and 1) were prepared by directly sodiating Mn1‐xFexPO4 through a solid‐state process at 300 °C. X‐ray diffraction, Mössbauer spectroscopy and electrochemical measurements were employed to study their structural and electrochemical features. NaMn0.66Fe0.34PO4 exhibits two pseudo‐plateaus profile with an average potential of ~3.2 V vs. Na+/Na0 with a reversible capacity reaching 75 mAh/g at C/20 via a monophasic (de)intercalation mechanism. In parallel, the intermediate composition Na0.5Mn0.66Fe0.34PO4 could be prepared via the solid‐state reaction of NaMn0.66Fe0.34PO4 and Mn0.66Fe0.34PO4. Such a solvent‐free sodiation process not only provides a simplified preparation of NMFP, but also offers easy scalability compared to the more laborious electrochemical sodiation route, making it an interesting prospect for future industrialization. Finally, this research confirms that the olivine NMFP is indeed an attractive candidate as a cathode material for SIBs.
{"title":"Olivine NaMn0.66Fe0.34PO4 as a Cathode Material for Advanced Sodium Ion Batteries","authors":"Tassadit Ouaneche, Lorenzo Stievano, Laure Monconduit, Claude Guéry, Moulay Tahar Sougrati, Nadir Recham","doi":"10.1002/batt.202400214","DOIUrl":"https://doi.org/10.1002/batt.202400214","url":null,"abstract":"Sodium‐ion batteries continue to rise in the energy storage landscape, their increasing adoption being driven by factors such as cost‐effectiveness and sustainability. As a consequence, there is a growing emphasis on the development of new electrode materials. Among these, olivine phosphates emerge as a promising family of cathode materials. However, viable synthesis routes are still lacking. In this study, cathode materials of olivine NaMn<jats:sub>1‐x</jats:sub>Fe<jats:sub>x</jats:sub>PO<jats:sub>4</jats:sub> (x=0.34 and 1) were prepared by directly sodiating Mn<jats:sub>1‐x</jats:sub>Fe<jats:sub>x</jats:sub>PO<jats:sub>4</jats:sub> through a solid‐state process at 300 °C. X‐ray diffraction, Mössbauer spectroscopy and electrochemical measurements were employed to study their structural and electrochemical features. NaMn<jats:sub>0.66</jats:sub>Fe<jats:sub>0.34</jats:sub>PO<jats:sub>4</jats:sub> exhibits two pseudo‐plateaus profile with an average potential of ~3.2 V vs. Na<jats:sup>+</jats:sup>/Na<jats:sup>0</jats:sup> with a reversible capacity reaching 75 mAh/g at C/20 via a monophasic (de)intercalation mechanism. In parallel, the intermediate composition Na<jats:sub>0.5</jats:sub>Mn<jats:sub>0.66</jats:sub>Fe<jats:sub>0.34</jats:sub>PO<jats:sub>4</jats:sub> could be prepared via the solid‐state reaction of NaMn<jats:sub>0.66</jats:sub>Fe<jats:sub>0.34</jats:sub>PO<jats:sub>4</jats:sub> and Mn<jats:sub>0.66</jats:sub>Fe<jats:sub>0.34</jats:sub>PO<jats:sub>4</jats:sub>. Such a solvent‐free sodiation process not only provides a simplified preparation of NMFP, but also offers easy scalability compared to the more laborious electrochemical sodiation route, making it an interesting prospect for future industrialization. Finally, this research confirms that the olivine NMFP is indeed an attractive candidate as a cathode material for SIBs.","PeriodicalId":132,"journal":{"name":"Batteries & Supercaps","volume":null,"pages":null},"PeriodicalIF":5.7,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141526683","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qingchao Xia, Zhengnan Li, Dewei Liu, Nan Song, Nan Zhang, Shuyang Ma, Zeliang Wu, Weiyong Yuan
The poor performance of metal/water batteries caused by self‐corrosion of anodes and low catalytic activity of cathodes has been a long‐standing challenge, greatly limiting their practical applications, in particular the underwater unmanned vehicle (UUV) application. We have fabricated an Al/seawater battery using simulated seawater with an appropriate pH and added with polyacrylic acid (PAA) as the electrolyte. This electrolyte simultaneously greatly retards self‐corrosion of the Al anode by in situ forming a PAA‐Al3+ complex film on it and increases the electrocatalytic activity toward the hydrogen evolution reaction by improving the electronic structure of Pt. When utilizing the multielement‐doped Al sheet as the anode and nickel foam supported loading‐amount‐optimized Pt/C catalyst as the cathode and adopting the developed new electrolyte, the obtained Al/H2O battery exhibits an energy density of 2271 Wh kg‐1, which is the highest among those of all the reported batteries, and a power density of 20.87 mW cm‐2, which outperforms all the reported metal/H2O batteries. This work not only develops a new type of high‐performance Al/H2O batteries for practical applications such as UUVs, but provides scientific insight into the design of superior electrolytes, which could be further extended for improving the performances of various metal batteries.
{"title":"Highly Effective Electrolytes toward High‐Performance Aluminum/Seawater Batteries","authors":"Qingchao Xia, Zhengnan Li, Dewei Liu, Nan Song, Nan Zhang, Shuyang Ma, Zeliang Wu, Weiyong Yuan","doi":"10.1002/batt.202400307","DOIUrl":"https://doi.org/10.1002/batt.202400307","url":null,"abstract":"The poor performance of metal/water batteries caused by self‐corrosion of anodes and low catalytic activity of cathodes has been a long‐standing challenge, greatly limiting their practical applications, in particular the underwater unmanned vehicle (UUV) application. We have fabricated an Al/seawater battery using simulated seawater with an appropriate pH and added with polyacrylic acid (PAA) as the electrolyte. This electrolyte simultaneously greatly retards self‐corrosion of the Al anode by in situ forming a PAA‐Al3+ complex film on it and increases the electrocatalytic activity toward the hydrogen evolution reaction by improving the electronic structure of Pt. When utilizing the multielement‐doped Al sheet as the anode and nickel foam supported loading‐amount‐optimized Pt/C catalyst as the cathode and adopting the developed new electrolyte, the obtained Al/H2O battery exhibits an energy density of 2271 Wh kg‐1, which is the highest among those of all the reported batteries, and a power density of 20.87 mW cm‐2, which outperforms all the reported metal/H2O batteries. This work not only develops a new type of high‐performance Al/H2O batteries for practical applications such as UUVs, but provides scientific insight into the design of superior electrolytes, which could be further extended for improving the performances of various metal batteries.","PeriodicalId":132,"journal":{"name":"Batteries & Supercaps","volume":null,"pages":null},"PeriodicalIF":5.7,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141526684","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
David Fuchs, Harry Hoster, Christoph Müller, Mandy Schaffeld, Falko Mahlendorf
We present a detailed analysis of the behavior of a new zinc‐air flow cell. This system offers several unique insights into the zinc electrochemistry. Due to the constant slurry flow, concentration gradients are completely destroyed every few seconds and therefore negligible and it is possible to take samples from the anode without interrupting the discharge process. To clarify the underlying processes, the potential of the zinc electrode, the zincate concentration (by titration) and the zinc‐particles (by SEM) were analyzed. These measurements offer the unique opportunity to distinguish between thermodynamic and kinetic contributions to the cell voltage. We found, that in this system zinc passivation, is caused by a critical zincate concentration and the steep increase of the cell potential is a kinetic effect, caused by partial passivation. The key factor for passivation, which limits the capacity to 82 mAh gzinc‑1 or 41 mAh gslurry‑1, is the nucleation of ZnO before the critical zincate concentration is reached. This allows capacities of up to 420 mAh gzinc‑1 or 210 mAh gslurry‑1. These results are therefore not only essential for a further increase of the practical capacity of the system but also offer unique insights in the zinc electrochemistry.
我们对新型锌-空气流动池的行为进行了详细分析。该系统为锌的电化学提供了一些独特的见解。由于浆液持续流动，浓度梯度每隔几秒钟就会被完全破坏，因此可以忽略不计，而且可以在不中断放电过程的情况下从阳极取样。为了弄清基本过程，我们对锌电极的电位、锌酸盐浓度（通过滴定法）和锌颗粒（通过扫描电镜）进行了分析。这些测量结果为区分电池电压的热力学贡献和动力学贡献提供了独特的机会。我们发现，在该系统中，锌钝化是由临界锌酸盐浓度引起的，而电池电位的急剧上升则是由部分钝化引起的动力学效应。将容量限制在 82 mAh gzinc-1 或 41 mAh gslurry-1 的钝化关键因素是在达到临界锌酸盐浓度之前氧化锌的成核。这使得电池容量可高达 420 mAh gzinc-1 或 210 mAh gslurry-1。因此，这些结果不仅对进一步提高系统的实际容量至关重要，而且还为锌电化学提供了独特的见解。
{"title":"New Insights Into Zinc Passivation Through In‐Operando Measured Zincate Concentrations","authors":"David Fuchs, Harry Hoster, Christoph Müller, Mandy Schaffeld, Falko Mahlendorf","doi":"10.1002/batt.202400298","DOIUrl":"https://doi.org/10.1002/batt.202400298","url":null,"abstract":"We present a detailed analysis of the behavior of a new zinc‐air flow cell. This system offers several unique insights into the zinc electrochemistry. Due to the constant slurry flow, concentration gradients are completely destroyed every few seconds and therefore negligible and it is possible to take samples from the anode without interrupting the discharge process. To clarify the underlying processes, the potential of the zinc electrode, the zincate concentration (by titration) and the zinc‐particles (by SEM) were analyzed. These measurements offer the unique opportunity to distinguish between thermodynamic and kinetic contributions to the cell voltage. We found, that in this system zinc passivation, is caused by a critical zincate concentration and the steep increase of the cell potential is a kinetic effect, caused by partial passivation. The key factor for passivation, which limits the capacity to 82 mAh gzinc‑1 or 41 mAh gslurry‑1, is the nucleation of ZnO before the critical zincate concentration is reached. This allows capacities of up to 420 mAh gzinc‑1 or 210 mAh gslurry‑1. These results are therefore not only essential for a further increase of the practical capacity of the system but also offer unique insights in the zinc electrochemistry.","PeriodicalId":132,"journal":{"name":"Batteries & Supercaps","volume":null,"pages":null},"PeriodicalIF":5.7,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141505906","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Robin Moschner, Heather Cavers, Peter Michalowski, Arno Kwade
Sulfur‐polyacrylonitrile (SPAN) is a sulfur‐based active material for next‐generation lithium‐sulfur battery cathodes. Due to the covalent bonding between sulfur chains and the polymeric backbone, the shuttle effect degrading classical sulfur‐based cathodes can be suppressed while also achieving a high active material content in the cathode. In this paper, we investigate the processability of an industrially scalable SPAN active material with 38 wt.‐% of sulfur in a water‐based and scalable process route. The potential of the SPAN material for industrial adoption and the impact of the process route on the cell performance are discussed. We show that when processed correctly, the SPAN material delivers exceptional cycling stability and good C‐rate performance with ether‐based electrolytes. However, the performance of the SPAN cathode is influenced by the mixing characteristic. Using higher mixing intensities during the slurry preparation leads to deterioration of the electrochemical performance. This can be attributed to a decreasing carbon black percolation with increasing tip speed in combination with the kinetic limitation of sulfur cathodes during Li2S2 and Li2S oxidation.
{"title":"Investigation Of An Industrially Scalable Production Of Sulfur‐polyacrylonitrile Based Cathodes","authors":"Robin Moschner, Heather Cavers, Peter Michalowski, Arno Kwade","doi":"10.1002/batt.202400154","DOIUrl":"https://doi.org/10.1002/batt.202400154","url":null,"abstract":"Sulfur‐polyacrylonitrile (SPAN) is a sulfur‐based active material for next‐generation lithium‐sulfur battery cathodes. Due to the covalent bonding between sulfur chains and the polymeric backbone, the shuttle effect degrading classical sulfur‐based cathodes can be suppressed while also achieving a high active material content in the cathode. In this paper, we investigate the processability of an industrially scalable SPAN active material with 38 wt.‐% of sulfur in a water‐based and scalable process route. The potential of the SPAN material for industrial adoption and the impact of the process route on the cell performance are discussed. We show that when processed correctly, the SPAN material delivers exceptional cycling stability and good C‐rate performance with ether‐based electrolytes. However, the performance of the SPAN cathode is influenced by the mixing characteristic. Using higher mixing intensities during the slurry preparation leads to deterioration of the electrochemical performance. This can be attributed to a decreasing carbon black percolation with increasing tip speed in combination with the kinetic limitation of sulfur cathodes during Li2S2 and Li2S oxidation.","PeriodicalId":132,"journal":{"name":"Batteries & Supercaps","volume":null,"pages":null},"PeriodicalIF":5.7,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141505907","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The Li‐rich antifluorite‐type oxides Li5FeO4, Li5.5Fe0.5Co0.5O4 and Li6CoO4 have been investigated as positive electrode materials for Li‐ion batteries in a combined operando XANES and XRD experiment. All materials show a similar two‐step behaviour upon initial charge (termed Stage I and Stage II), and reversibility of subsequent cycling depends upon whether the initial charge cycle is terminated following Stage I or allowed to proceed through Stage II. By tracking the energetic evolution of the XANES pre‐edge feature present in both Fe and Co K‐edge spectra, as well as the evolution of X‐ray diffractograms during charge and discharge, we correlate the changes in chemical coordination and oxidation states in both species and the structural changes to the electrochemical potential profile, and infer the role of anionic redox processes.
通过 XANES 和 XRD 联合操作实验，研究了作为锂离子电池正极材料的富锂反萤石型氧化物 Li5FeO4、Li5.5Fe0.5Co0.5O4 和 Li6CoO4。所有材料在初始充电时都表现出类似的两步行为（称为阶段 I 和阶段 II），后续循环的可逆性取决于初始充电循环是在阶段 I 后终止还是在阶段 II 后继续进行。通过跟踪铁和钴 K 边光谱中出现的 XANES 前沿特征的能量演变，以及充放电过程中 X 射线衍射图的演变，我们将两种材料中化学配位和氧化态的变化以及结构变化与电化学势曲线联系起来，并推断出阴离子氧化还原过程的作用。
{"title":"Elucidation of the reaction mechanisms in antifluorite‐type Li5+xFe1‐xCoxO4 positive electrodes for Li‐ion batteries","authors":"Rasmus Vester Thøgersen, Halvor Høen Hval, Helmer Fjellvåg","doi":"10.1002/batt.202400348","DOIUrl":"https://doi.org/10.1002/batt.202400348","url":null,"abstract":"The Li‐rich antifluorite‐type oxides Li5FeO4, Li5.5Fe0.5Co0.5O4 and Li6CoO4 have been investigated as positive electrode materials for Li‐ion batteries in a combined operando XANES and XRD experiment. All materials show a similar two‐step behaviour upon initial charge (termed Stage I and Stage II), and reversibility of subsequent cycling depends upon whether the initial charge cycle is terminated following Stage I or allowed to proceed through Stage II. By tracking the energetic evolution of the XANES pre‐edge feature present in both Fe and Co K‐edge spectra, as well as the evolution of X‐ray diffractograms during charge and discharge, we correlate the changes in chemical coordination and oxidation states in both species and the structural changes to the electrochemical potential profile, and infer the role of anionic redox processes.","PeriodicalId":132,"journal":{"name":"Batteries & Supercaps","volume":null,"pages":null},"PeriodicalIF":5.7,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141526686","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sebastian Kirchhoff, Paul Härtel, Susanne Dörfler, Thomas Abendroth, Holger Althues, Stefan Kaskel
Lithium‐sulfur batteries (LSBs) are discussed as the most promising post‐lithium‐ion battery technology due to the high theoretical energy density and the cost‐efficient, environmental‐friendly active material sulfur. Unfortunately, LSBs still suffer from several limitations such as cycle life and rate capability. To overcome these issues, the development of adapted electrolytes is one promising path. Consequently, in this study, we focus on the influence of the lithium salt on the performance of LSBs. In a fixed solvent system without employing LiNO3, five different lithium salts are compared. The electrolyte properties as well as the influence of polysulfides are determined and discussed in relation with the battery performance. Interestingly, although the different salts lead to different electrolyte properties, only a minor influence of the salt is observed at low C‐rates. By performing a rate capability test, however, a strong influence of the lithium salt is detected at high C‐rates, with LiFSI outperforming the other salts. This correlates well with ionic conductivity and a suppressed influence of polysulfides in case of LiFSI. To verify the results, multi‐layered pouch cells were tested under lean electrolyte conditions. The study emphasizes the significance of the lithium salt and provides guidance for electrolyte design under lean electrolyte conditions.
锂硫电池（LSB）具有理论能量密度高、成本效益高、活性材料硫环保等优点，被认为是最有前途的后锂离子电池技术。遗憾的是，LSB 仍然受到一些限制，如循环寿命和速率能力。为了克服这些问题，开发适合的电解质是一条大有可为的途径。因此，在本研究中，我们重点研究了锂盐对 LSB 性能的影响。在不使用 LiNO3 的固定溶剂体系中，我们比较了五种不同的锂盐。研究确定了电解质特性以及多硫化物的影响，并结合电池性能进行了讨论。有趣的是，虽然不同的盐会导致不同的电解质特性，但在低 C 速率时，盐的影响很小。然而，通过进行速率能力测试，可以发现锂盐在高 C 速率下有很大的影响，其中 LiFSI 的性能优于其他盐类。这与离子导电性和多硫化物对 LiFSI 影响的抑制作用密切相关。为了验证结果，在贫电解质条件下对多层袋式电池进行了测试。这项研究强调了锂盐的重要性，并为贫电解质条件下的电解质设计提供了指导。
{"title":"Lithium‐Sulfur‐Batteries Under Lean Electrolyte Conditions: Improving Rate Capability By The Choice Of The Lithium Salt In Dimethoxyethane‐Hydrofluoroether‐based Electrolyte","authors":"Sebastian Kirchhoff, Paul Härtel, Susanne Dörfler, Thomas Abendroth, Holger Althues, Stefan Kaskel","doi":"10.1002/batt.202400155","DOIUrl":"https://doi.org/10.1002/batt.202400155","url":null,"abstract":"Lithium‐sulfur batteries (LSBs) are discussed as the most promising post‐lithium‐ion battery technology due to the high theoretical energy density and the cost‐efficient, environmental‐friendly active material sulfur. Unfortunately, LSBs still suffer from several limitations such as cycle life and rate capability. To overcome these issues, the development of adapted electrolytes is one promising path. Consequently, in this study, we focus on the influence of the lithium salt on the performance of LSBs. In a fixed solvent system without employing LiNO3, five different lithium salts are compared. The electrolyte properties as well as the influence of polysulfides are determined and discussed in relation with the battery performance. Interestingly, although the different salts lead to different electrolyte properties, only a minor influence of the salt is observed at low C‐rates. By performing a rate capability test, however, a strong influence of the lithium salt is detected at high C‐rates, with LiFSI outperforming the other salts. This correlates well with ionic conductivity and a suppressed influence of polysulfides in case of LiFSI. To verify the results, multi‐layered pouch cells were tested under lean electrolyte conditions. The study emphasizes the significance of the lithium salt and provides guidance for electrolyte design under lean electrolyte conditions.","PeriodicalId":132,"journal":{"name":"Batteries & Supercaps","volume":null,"pages":null},"PeriodicalIF":5.7,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141526687","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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