Pub Date : 2025-02-12DOI: 10.1016/j.ensm.2025.104119
Fei Yuan, Zhaojin Li, Qiujun Wang, Ranran Li, Huilan Sun, Di Zhang, Qujiang Sun, Bo Wang
Building abundant sp2 hybridized carbon and vacancies in hard carbon is highly approved in respect of boosting its low potential (below 1.0 V) charging capacity, but it remains a challenge based on current synthesis strategies. Herein, the hard carbon with high sp2 carbon and vacancy content is constructed by combining amidation reactions between esterified starch/N-containing fragments and temperature regulation. It is demonstrated that the introduced N-atoms can promote the formation of sp2 domains via replacing O-atoms, which tend to cause excessive cross-linking between precursor molecules. Besides, the N-atoms bonded to carbon-atoms are gradually removed as the pyrolysis proceeds, helping to emerge vacancies, while a higher carbonization temperature can induce partial vacancies to heal. As a result, the optimized electrode delivers an excellent low potential charging capacity (214.5 mAh g−1), based on “vacancy-adsorption/intercalation” mechanism, accounting for a high energy density (159.6 Wh kg−1). Benefiting from the beneficial effect of vacancies and sp2 domains on ion/electron migration, a superior rate capability is also gained (258.7 mAh g−1 at 2 A g−1). Moreover, rich vacancies synergize enlarged interlayer spacing to enable an ultra-long cycling stability over 4000 cycles (218.2 mAh g−1).
{"title":"sp2 configuration coupled vacancy rich carbon enables excellent low potential potassium storage","authors":"Fei Yuan, Zhaojin Li, Qiujun Wang, Ranran Li, Huilan Sun, Di Zhang, Qujiang Sun, Bo Wang","doi":"10.1016/j.ensm.2025.104119","DOIUrl":"10.1016/j.ensm.2025.104119","url":null,"abstract":"<div><div>Building abundant sp<sup>2</sup> hybridized carbon and vacancies in hard carbon is highly approved in respect of boosting its low potential (below 1.0 V) charging capacity, but it remains a challenge based on current synthesis strategies. Herein, the hard carbon with high sp<sup>2</sup> carbon and vacancy content is constructed by combining amidation reactions between esterified starch/N-containing fragments and temperature regulation. It is demonstrated that the introduced N-atoms can promote the formation of sp<sup>2</sup> domains via replacing O-atoms, which tend to cause excessive cross-linking between precursor molecules. Besides, the N-atoms bonded to carbon-atoms are gradually removed as the pyrolysis proceeds, helping to emerge vacancies, while a higher carbonization temperature can induce partial vacancies to heal. As a result, the optimized electrode delivers an excellent low potential charging capacity (214.5 mAh g<sup>−1</sup>), based on “vacancy-adsorption/intercalation” mechanism, accounting for a high energy density (159.6 Wh kg<sup>−1</sup>). Benefiting from the beneficial effect of vacancies and sp<sup>2</sup> domains on ion/electron migration, a superior rate capability is also gained (258.7 mAh g<sup>−1</sup> at 2 A g<sup>−1</sup>). Moreover, rich vacancies synergize enlarged interlayer spacing to enable an ultra-long cycling stability over 4000 cycles (218.2 mAh g<sup>−1</sup>).</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"76 ","pages":"Article 104119"},"PeriodicalIF":18.9,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-11DOI: 10.1016/j.ensm.2025.104122
Zhijian Qiu , Yongpeng Cui , Li Zhou , Bingyu Li , Xiuli Gao , Xuejin Li , Pengyun Liu , Zifeng Yan , Qingzhong Xue , Wei Xing
High concentration electrolytes attract significant attention in low temperature electrolyte systems due to their ability to effectively reduce the desolvation energy barrier of lithium ions. However, the actual low temperature electrochemical performance of LIBs using these high concentration electrolytes remains unsatisfactory. Researchers usually attribute this poor performance to increased viscosity, reduced wettability, and a sharp decline in conductivity at low temperatures. However, these traditional views alone are not enough to reveal the underlying nature of the poor electrochemical performance. Herein, we explore the microscopic mechanisms underlying the poor electrochemical behavior of high concentration electrolytes under low temperature conditions at the molecular level. Using in situ low temperature Raman spectroscopy, we reveal for the first time that the formation of large solvated ion clusters is the fundamental reason for the unsatisfactory electrochemical behavior of high concentration electrolytes at low temperatures. To address this, we propose the “pseudo-bilayer solvation sheath” strategy to suppress the formation of large ionized clusters, thereby enhancing lithium ion transport at low temperatures, especially during the desolvation process from the electrolyte to the electrode surface. As a result, the optimized electrolyte enables an NCM811//graphite full cell to achieve rapid charging within 30 min at -20 °C, with a high capacity retention rate of 55.4%.
{"title":"Non-clusters pseudo-bilayer solvation sheaths for driving low temperature high power lithium ion batteries","authors":"Zhijian Qiu , Yongpeng Cui , Li Zhou , Bingyu Li , Xiuli Gao , Xuejin Li , Pengyun Liu , Zifeng Yan , Qingzhong Xue , Wei Xing","doi":"10.1016/j.ensm.2025.104122","DOIUrl":"10.1016/j.ensm.2025.104122","url":null,"abstract":"<div><div>High concentration electrolytes attract significant attention in low temperature electrolyte systems due to their ability to effectively reduce the desolvation energy barrier of lithium ions. However, the actual low temperature electrochemical performance of LIBs using these high concentration electrolytes remains unsatisfactory. Researchers usually attribute this poor performance to increased viscosity, reduced wettability, and a sharp decline in conductivity at low temperatures. However, these traditional views alone are not enough to reveal the underlying nature of the poor electrochemical performance. Herein, we explore the microscopic mechanisms underlying the poor electrochemical behavior of high concentration electrolytes under low temperature conditions at the molecular level. Using in situ low temperature Raman spectroscopy, we reveal for the first time that the formation of large solvated ion clusters is the fundamental reason for the unsatisfactory electrochemical behavior of high concentration electrolytes at low temperatures. To address this, we propose the “pseudo-bilayer solvation sheath” strategy to suppress the formation of large ionized clusters, thereby enhancing lithium ion transport at low temperatures, especially during the desolvation process from the electrolyte to the electrode surface. As a result, the optimized electrolyte enables an NCM811//graphite full cell to achieve rapid charging within 30 min at -20 °C, with a high capacity retention rate of 55.4%.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"76 ","pages":"Article 104122"},"PeriodicalIF":18.9,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393772","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-10DOI: 10.1016/j.ensm.2025.104111
Sara Drvarič Talian, Sergio Brutti, Maria Assunta Navarra, Jože Moškon, Miran Gaberscek
SB would like to thank the MOST – Sustainable Mobility Center and received funding from the European Union Next-GenerationEU (PIANO NAZIONALE DI RIPRESA E RESILIENZA (PNRR) – MISSIONE 4 COMPONENTE 2, INVESTIMENTO 1.4 – D.D. 1033 17/06/2022, CN00000023). This manuscript reflects only the authors’ views and opinions, neither the European Union nor the European Commission can be considered responsible for them.
{"title":"Corrigendum to Impedance spectroscopy applied to lithium battery materials: Good practices in measurements and analyses Energy Storage Materials Volume 69, May 2024, 103413","authors":"Sara Drvarič Talian, Sergio Brutti, Maria Assunta Navarra, Jože Moškon, Miran Gaberscek","doi":"10.1016/j.ensm.2025.104111","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104111","url":null,"abstract":"SB would like to thank the MOST – Sustainable Mobility Center and received funding from the European Union Next-GenerationEU (PIANO NAZIONALE DI RIPRESA E RESILIENZA (PNRR) – MISSIONE 4 COMPONENTE 2, INVESTIMENTO 1.4 – D.D. 1033 17/06/2022, CN00000023). This manuscript reflects only the authors’ views and opinions, neither the European Union nor the European Commission can be considered responsible for them.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"144 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375528","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-10DOI: 10.1016/j.ensm.2025.104114
Zheng-Yao Li , Fanghua Ning , Xiaobai Ma , Kai Sun , Limei Sun , Hongliang Wang , Dongfeng Chen
In this study, manganese vacancy and Li-ion are introduced into Na2/3[Ni1/6Mn5/6]O2 to tailor the relationship between the structure and property. Neutron and X-ray diffraction confirm a structural transition from disordering to ordering in the transition-metal layers to form an in-plane honeycomb structure in the designed Na5/6[Ni1/6Li1/6□1/18Mn2/3]O2 (V-NNM, □ = Mn vacancy) material, which, for the first time, benefits from the Mn vacancies in transition-metal sites. Besides, neutron diffraction also uncovers that V-NNM adopts the P2 structure with the P63 space group, different from the P63/mmc space group by X-ray diffraction (XRD), and doped Li ions mainly enter the transition-metal sites in V-NNM. Electrochemical measurements demonstrate that V-NNM delivers a reversible specific capacity close to the theoretical value and long-term cycling stability (71.6% capacity retention after 1000 cycles). V-NNM also exhibits the excellent high-rate performance, such as the reversible capacities of 72.5%, 63.7%, 57.1% and 50.5% relative to the theoretical value at 10 C, 15 C, 20 C and 25 C, respectively, indicating the fast Na-storage. Theoretical calculations and molecular dynamics simulations further validate the structural disorder-to-order transformation, decreased band gap and enhanced Na+ diffusion kinetics in V-NNM, which are responsible for the electrochemical performance. In addition, in situ XRD experiments disclose a complete solid-solution reaction layered cathode accompanied by near zero-strain characteristic upon charging and discharging, ensuring the structural integrity and stability, as well as the resulting electrochemical performance. This work paves the way for comprehending and optimizing the structure-property relationship of layered materials for sodium-ion batteries.
{"title":"Manganese vacancy motivated structural disorder-to-order transformation to boost fast-charging and long-lasting sodium-ion battery P2-type layered cathode","authors":"Zheng-Yao Li , Fanghua Ning , Xiaobai Ma , Kai Sun , Limei Sun , Hongliang Wang , Dongfeng Chen","doi":"10.1016/j.ensm.2025.104114","DOIUrl":"10.1016/j.ensm.2025.104114","url":null,"abstract":"<div><div>In this study, manganese vacancy and Li-ion are introduced into Na<sub>2/3</sub>[Ni<sub>1/6</sub>Mn<sub>5/6</sub>]O<sub>2</sub> to tailor the relationship between the structure and property. Neutron and X-ray diffraction confirm a structural transition from disordering to ordering in the transition-metal layers to form an in-plane honeycomb structure in the designed Na<sub>5/6</sub>[Ni<sub>1/6</sub>Li<sub>1/6</sub>□<sub>1/18</sub>Mn<sub>2/3</sub>]O<sub>2</sub> (V-NNM, □ = Mn vacancy) material, which, for the first time, benefits from the Mn vacancies in transition-metal sites. Besides, neutron diffraction also uncovers that V-NNM adopts the P2 structure with the P6<sub>3</sub> space group, different from the P6<sub>3</sub>/mmc space group by X-ray diffraction (XRD), and doped Li ions mainly enter the transition-metal sites in V-NNM. Electrochemical measurements demonstrate that V-NNM delivers a reversible specific capacity close to the theoretical value and long-term cycling stability (71.6% capacity retention after 1000 cycles). V-NNM also exhibits the excellent high-rate performance, such as the reversible capacities of 72.5%, 63.7%, 57.1% and 50.5% relative to the theoretical value at 10 C, 15 C, 20 C and 25 C, respectively, indicating the fast Na-storage. Theoretical calculations and molecular dynamics simulations further validate the structural disorder-to-order transformation, decreased band gap and enhanced Na<sup>+</sup> diffusion kinetics in V-NNM, which are responsible for the electrochemical performance. In addition, in situ XRD experiments disclose a complete solid-solution reaction layered cathode accompanied by near zero-strain characteristic upon charging and discharging, ensuring the structural integrity and stability, as well as the resulting electrochemical performance. This work paves the way for comprehending and optimizing the structure-property relationship of layered materials for sodium-ion batteries.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"76 ","pages":"Article 104114"},"PeriodicalIF":18.9,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375529","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-10DOI: 10.1016/j.ensm.2025.104116
Liping Zhang , Leiqiang Qin , Yeying Li , Leixi Du , Manting Song , Yue Wang , Jingkun Xu , Baoyang Lu , Johanna Rosen , Jianxia Jiang
Optimizing electrolytes is essential for improving the electrochemical stability window (ESW) and energy storage capacity of aqueous energy storage devices. High-concentration electrolytes improve performance but face solubility, conductivity, and stability issues. Here, a strong chaotropic anion, ClO4−, is introduced into 1 M ZnSO4 to expand the ESW and boost performance in dilute electrolytes. Theoretical simulation and experimental results provide that perchlorate not only significantly enhances ionic conductivity, leading to faster ion diffusion, but also weakens hydrogen bonds formation, reduces free water at the electrode surface, and promote the desolvation of hydrated zinc ions. Collectively, these factors lead to an improvement in the ESW and enhance overall device performance. Therefore, in the mixed electrolyte of 0.005 M Zn(ClO4)2 and 1 M ZnSO4, the Zn//Mo2ScC2Tz aqueous zinc-ion hybrid supercapacitor (ZHSC) achieves a voltage window expansion from 1.0 to 1.3 V, delivering a high specific capacitance of 692.3 F g−1 at 0.2 A g−1. Furthermore, an asymmetric supercapacitor with the same electrolyte operates at 1.8 V, delivering an energy density of 98.1 Wh kg−1 at 180 W kg−1 and maintaining 17 Wh kg−1 at 9000 W kg−1. Notably, this electrolyte design strategy is universally applicable for enhancing Zn-ion storage performance of MXene-based materials.
{"title":"Dilute electrolyte with chaotropic anion addition for enhanced Zn-Ion storage performance in MXenes","authors":"Liping Zhang , Leiqiang Qin , Yeying Li , Leixi Du , Manting Song , Yue Wang , Jingkun Xu , Baoyang Lu , Johanna Rosen , Jianxia Jiang","doi":"10.1016/j.ensm.2025.104116","DOIUrl":"10.1016/j.ensm.2025.104116","url":null,"abstract":"<div><div>Optimizing electrolytes is essential for improving the electrochemical stability window (ESW) and energy storage capacity of aqueous energy storage devices. High-concentration electrolytes improve performance but face solubility, conductivity, and stability issues. Here, a strong chaotropic anion, ClO<sub>4</sub><sup>−</sup>, is introduced into 1 M ZnSO<sub>4</sub> to expand the ESW and boost performance in dilute electrolytes. Theoretical simulation and experimental results provide that perchlorate not only significantly enhances ionic conductivity, leading to faster ion diffusion, but also weakens hydrogen bonds formation, reduces free water at the electrode surface, and promote the desolvation of hydrated zinc ions. Collectively, these factors lead to an improvement in the ESW and enhance overall device performance. Therefore, in the mixed electrolyte of 0.005 M Zn(ClO<sub>4</sub>)<sub>2</sub> and 1 M ZnSO<sub>4</sub>, the Zn//Mo<sub>2</sub>ScC<sub>2</sub>T<sub>z</sub> aqueous zinc-ion hybrid supercapacitor (ZHSC) achieves a voltage window expansion from 1.0 to 1.3 V, delivering a high specific capacitance of 692.3 F g<sup>−1</sup> at 0.2 A g<sup>−1</sup>. Furthermore, an asymmetric supercapacitor with the same electrolyte operates at 1.8 V, delivering an energy density of 98.1 Wh kg<sup>−1</sup> at 180 W kg<sup>−1</sup> and maintaining 17 Wh kg<sup>−1</sup> at 9000 W kg<sup>−1</sup>. Notably, this electrolyte design strategy is universally applicable for enhancing Zn-ion storage performance of MXene-based materials.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"76 ","pages":"Article 104116"},"PeriodicalIF":18.9,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-10DOI: 10.1016/j.ensm.2025.104115
Katrina Mazloomian , Thomas R. Dore , Mark Buckwell , Liam Bird , Paul R. Shearing , Thomas S. Miller
While supercapacitors are widely considered to be safer than current lithium-ion battery technologies, their reputation for safety, stability, and long cycling lifetimes is primarily based on their testing under highly favourable electrochemical and environmental conditions. However, the impact of extreme conditions on even the most common Electrochemical Double Layer Capacitors (EDLCs) remains unclear, limiting the understanding of their potential failure mechanisms and the risks they could present to individuals and systems into which they are increasingly being integrated. In this study, we investigate the effects of thermal abuse conditions, induced by overheating and overcharging, on a typical commercial EDLC. Our findings reveal that while EDLC cell failures are less extreme than the well-documented failures of Li-ion batteries, they still pose significant risks to the integrity of the cell itself and the direct environment. This is most evident from the fact that between the overheating and overcharging tests, more than half of all the cells tested in this study failed catastrophically, leading to an explosive event. The high cell temperatures induced by these abusive tests led to electrolyte vaporisation and cell gassing that was not effectively mitigated by cell vent designs. This study therefore challenges the perception of intrinsic supercapacitor safety and provides a foundation onto which safer system designs can be built.
{"title":"Supercapacitor safety: Temperature driven instability and failure of electrochemical double layer capacitors","authors":"Katrina Mazloomian , Thomas R. Dore , Mark Buckwell , Liam Bird , Paul R. Shearing , Thomas S. Miller","doi":"10.1016/j.ensm.2025.104115","DOIUrl":"10.1016/j.ensm.2025.104115","url":null,"abstract":"<div><div>While supercapacitors are widely considered to be safer than current lithium-ion battery technologies, their reputation for safety, stability, and long cycling lifetimes is primarily based on their testing under highly favourable electrochemical and environmental conditions. However, the impact of extreme conditions on even the most common Electrochemical Double Layer Capacitors (EDLCs) remains unclear, limiting the understanding of their potential failure mechanisms and the risks they could present to individuals and systems into which they are increasingly being integrated. In this study, we investigate the effects of thermal abuse conditions, induced by overheating and overcharging, on a typical commercial EDLC. Our findings reveal that while EDLC cell failures are less extreme than the well-documented failures of Li-ion batteries, they still pose significant risks to the integrity of the cell itself and the direct environment. This is most evident from the fact that between the overheating and overcharging tests, more than half of all the cells tested in this study failed catastrophically, leading to an explosive event. The high cell temperatures induced by these abusive tests led to electrolyte vaporisation and cell gassing that was not effectively mitigated by cell vent designs. This study therefore challenges the perception of intrinsic supercapacitor safety and provides a foundation onto which safer system designs can be built.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"76 ","pages":"Article 104115"},"PeriodicalIF":18.9,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375527","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}
The energy conversion and utilization of lithium sulfur batteries are inextricably linked to the adsorption-catalysis-conversion processes of polysulfide intermediates at the cathode side. Herein, we report novel carbon nanofibers (CNFs) bridged spatial reinforced multifunctional catalysts (Ni-CNFs-MnS) to accelerate the cascade adsorption-catalysis-conversion processes of carbon/sulfur cathodes prepared via vesicle reactors. The composite catalysts grow quasi-vertically on the carbon hosts, with CNFs acting as the bridges to connect top-end Ni nanoparticles (NPs) and bottom-end MnS NPs to achieve synergistic cascade desolvation-adsorption-catalysis-conversion for lithium polysulfides. In situ Raman and theoretical calculation results reveal that the top-end Ni NPs can effectively enhance the desolvation/adsorption and catalytic conversion of long-chain polysulfides, while the bottom-end MnS NPs could preferentially adsorb and catalytically convert short-chain polysulfides. Meanwhile, CNFs serve as conductive bridges to offer rapid electron/ion transfer paths for polysulfide conversion, and simultaneously provide spatial confinement to suppress the shuttle effect of polysulfides. Accordingly, our cascade configuration combines multifunctional catalytic sites and carbon bridges with different spatial dimension to obtain fast adsorption-catalysis-conversion processes for polysulfides, endowing the carbon/sulfur cathodes with enhanced high-rate capacity and superior cycling stability. This work provides valuable insights into the design of high-efficiency spatially bridged cascade catalysts for multistage conversion reactions of sulfur.
{"title":"Spatial reinforced cascade catalysts towards optimization of Polysulfide conversion kinetics in Lithium Sulfur batteries","authors":"Yanbin Chen, Tianqi Yang, Chao Chen, Zibo Zhang, Tong Ban, Xinyi Gu, Ketong Chen, Yaning Liu, Jiayuan Xiang, Yuhong Zhang, Fangfang Tu, Yongfeng Yuan, Fengxiang Chen, Yang Xia, Xinhui Xia, Shenghui Shen, Ningzhong Bao, Wenkui Zhang","doi":"10.1016/j.ensm.2025.104061","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104061","url":null,"abstract":"The energy conversion and utilization of lithium sulfur batteries are inextricably linked to the adsorption-catalysis-conversion processes of polysulfide intermediates at the cathode side. Herein, we report novel carbon nanofibers (CNFs) bridged spatial reinforced multifunctional catalysts (Ni-CNFs-MnS) to accelerate the cascade adsorption-catalysis-conversion processes of carbon/sulfur cathodes prepared via vesicle reactors. The composite catalysts grow quasi-vertically on the carbon hosts, with CNFs acting as the bridges to connect top-end Ni nanoparticles (NPs) and bottom-end MnS NPs to achieve synergistic cascade desolvation-adsorption-catalysis-conversion for lithium polysulfides. In situ Raman and theoretical calculation results reveal that the top-end Ni NPs can effectively enhance the desolvation/adsorption and catalytic conversion of long-chain polysulfides, while the bottom-end MnS NPs could preferentially adsorb and catalytically convert short-chain polysulfides. Meanwhile, CNFs serve as conductive bridges to offer rapid electron/ion transfer paths for polysulfide conversion, and simultaneously provide spatial confinement to suppress the shuttle effect of polysulfides. Accordingly, our cascade configuration combines multifunctional catalytic sites and carbon bridges with different spatial dimension to obtain fast adsorption-catalysis-conversion processes for polysulfides, endowing the carbon/sulfur cathodes with enhanced high-rate capacity and superior cycling stability. This work provides valuable insights into the design of high-efficiency spatially bridged cascade catalysts for multistage conversion reactions of sulfur.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"1 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371642","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-09DOI: 10.1016/j.ensm.2025.104113
Hui Chen , Le Zhou , Yanchun Sun , Tianyu Zhang , Haiyan Wang , Hao Huang , Jiqiang Ning , Yong Hu
Aqueous zinc-iodine (Zn-I2) batteries are considered a promising contender for grid energy storage, but their practical application is hindered by such problems as the grievous polyiodide shuttle, parasitic corrosion and Zn dendrite growth. Herein, an immune cell-inspired biomass hydrogel interfacial layer composed of carboxymethyl chitosan/sodium alginate (CCS/SA) is constructed on the Zn anode by an in-situ gelation strategy, which exhibits the enhanced cycling stability of Zn-I2 batteries. The multifunctional CCS/SA hydrogel interface with a unique ion-selective responsive sieving mechanism acts as a pre-interception layer to block polyiodide ions but favors Zn2+ ion transfer and nucleation behavior. Furthermore, the hydrogen bond networks of water are perturbed with the CCS/SA layer, thereby restraining the activity of water molecules and alleviating the detrimental Zn corrosion. As a result, the Zn-I2 battery with a CCS/SA-Zn anode achieves an ultra-long cycle life of 60,000 cycles at 5 A g−1, superior to bare Zn-based cells and the state-of-the-art batteries ever reported. This work demonstrates the important role of the bio-inspired multifunctional biomass hydrogel interface developed for zinc-ion batteries and provides in-depth insight into the engineering strategy to promote the actual application of Zn-I2 batteries.
{"title":"Bio-inspired biomass hydrogel interface with ion-selective responsive sieving mechanism for corrosion-resistant and dendrite-free zinc-iodine batteries","authors":"Hui Chen , Le Zhou , Yanchun Sun , Tianyu Zhang , Haiyan Wang , Hao Huang , Jiqiang Ning , Yong Hu","doi":"10.1016/j.ensm.2025.104113","DOIUrl":"10.1016/j.ensm.2025.104113","url":null,"abstract":"<div><div>Aqueous zinc-iodine (Zn-I<sub>2</sub>) batteries are considered a promising contender for grid energy storage, but their practical application is hindered by such problems as the grievous polyiodide shuttle, parasitic corrosion and Zn dendrite growth. Herein, an immune cell-inspired biomass hydrogel interfacial layer composed of carboxymethyl chitosan/sodium alginate (CCS/SA) is constructed on the Zn anode by an in-situ gelation strategy, which exhibits the enhanced cycling stability of Zn-I<sub>2</sub> batteries. The multifunctional CCS/SA hydrogel interface with a unique ion-selective responsive sieving mechanism acts as a pre-interception layer to block polyiodide ions but favors Zn<sup>2+</sup> ion transfer and nucleation behavior. Furthermore, the hydrogen bond networks of water are perturbed with the CCS/SA layer, thereby restraining the activity of water molecules and alleviating the detrimental Zn corrosion. As a result, the Zn-I<sub>2</sub> battery with a CCS/SA-Zn anode achieves an ultra-long cycle life of 60,000 cycles at 5 A g<sup>−1</sup>, superior to bare Zn-based cells and the state-of-the-art batteries ever reported. This work demonstrates the important role of the bio-inspired multifunctional biomass hydrogel interface developed for zinc-ion batteries and provides in-depth insight into the engineering strategy to promote the actual application of Zn-I<sub>2</sub> batteries.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"76 ","pages":"Article 104113"},"PeriodicalIF":18.9,"publicationDate":"2025-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375530","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-08DOI: 10.1016/j.ensm.2025.104104
Xiaoyu Gao , Guojie Chen , Wenqing Yao , Yongbiao Mu , Lipeng Hu , Tao Zeng , Wenguang Zhao , Zhongyuan Huang , Maolin Yang , Yuguang Pu , Wenhai Ji , Zhenhong Tan , Ping Miao , Nian Zhang , Litao Yu , Lin Zeng , Rui Wang , Yinguo Xiao
Cobalt-free Li- and Mn-rich layered (LMR) cathode materials have the merits of being low-cost and environmentally compatible. However, their practical discharge capacities are much lower than the theoretical ones because the lack of cobalt reduces the anion redox activity. Furthermore, the issues related to anionic redox reactions, such as irreversible oxygen loss and phase transitions, hinder their commercialization. In this study, we present a novel method that involves premixing active materials and conductive agents followed by post-processing using spark plasma sintering (SPS). This rapid treatment (10 min) significantly enhances the discharge capacity of Co-free LMR materials. Specifically, the treated materials can achieve 319.4 mAh g⁻¹ at 0.1C, approximately 90 mAh g⁻¹ higher than the untreated LMR. Noticeably, the SPS-treated LMR exhibits excellent capacity retention of 71.8% after 800 cycles at 5C. Multi-angle characterizations demonstrate that SPS treatment induces a reconstructed surface with cationic disordering increasing from the bulk to the surface. This interlayer cationic disordering effectively enhances oxygen redox activity and the reconstructed rock-salt surface protects the interior layered structure. This study develops a new approach to activating the oxygen activity and enhancing the capacity in cathode materials through an innovative SPS technology.
{"title":"Unlocking the ultra-high capacity and cost-effectiveness of cobalt-free lithium-rich cathode materials","authors":"Xiaoyu Gao , Guojie Chen , Wenqing Yao , Yongbiao Mu , Lipeng Hu , Tao Zeng , Wenguang Zhao , Zhongyuan Huang , Maolin Yang , Yuguang Pu , Wenhai Ji , Zhenhong Tan , Ping Miao , Nian Zhang , Litao Yu , Lin Zeng , Rui Wang , Yinguo Xiao","doi":"10.1016/j.ensm.2025.104104","DOIUrl":"10.1016/j.ensm.2025.104104","url":null,"abstract":"<div><div>Cobalt-free Li- and Mn-rich layered (LMR) cathode materials have the merits of being low-cost and environmentally compatible. However, their practical discharge capacities are much lower than the theoretical ones because the lack of cobalt reduces the anion redox activity. Furthermore, the issues related to anionic redox reactions, such as irreversible oxygen loss and phase transitions, hinder their commercialization. In this study, we present a novel method that involves premixing active materials and conductive agents followed by post-processing using spark plasma sintering (SPS). This rapid treatment (10 min) significantly enhances the discharge capacity of Co-free LMR materials. Specifically, the treated materials can achieve 319.4 mAh g⁻¹ at 0.1C, approximately 90 mAh g⁻¹ higher than the untreated LMR. Noticeably, the SPS-treated LMR exhibits excellent capacity retention of 71.8% after 800 cycles at 5C. Multi-angle characterizations demonstrate that SPS treatment induces a reconstructed surface with cationic disordering increasing from the bulk to the surface. This interlayer cationic disordering effectively enhances oxygen redox activity and the reconstructed rock-salt surface protects the interior layered structure. This study develops a new approach to activating the oxygen activity and enhancing the capacity in cathode materials through an innovative SPS technology.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"76 ","pages":"Article 104104"},"PeriodicalIF":18.9,"publicationDate":"2025-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371531","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-08DOI: 10.1016/j.ensm.2025.104112
Xueyi Lu , Weixin Chen , Jianfang Yang , Xuemin Wu , Yan Wang , Oliver G. Schmidt , Lifeng Liu , Daiming Tang , Xia Lu
Electrochemistry of heterostructures plays a fundamental role in developing high-performance energy storage and conversion devices. However, current superlattice heterostructures based on assembling 2D materials are limited to a small number of alternating units with weak interfacial interaction and ambiguous function mechanism. Herein, the high-order -Sn/TiO2/Sn/TiO2- (S/TO) superlattice heterojunctions with built-in electric fields (BIEFs) are designed for sodium storage using a strain release method. The results show that the accommodated BIEFs and the spatial confinement effect in this periodic nanostructured electrode co-contribute to the outstanding electrochemical performance. The nanosizing and pulverization of Sn are effectively space-limited in between the TiO2 slabs and the notorious catalytic reaction between electrolyte and TiO2 surface region is sophisticatedly mitigated by the electron accumulation in the TiO2 component, synergistically accelerating sodium storage and transfer kinetics of S/TO superlattice electrodes. The covalent Sn-O-Ti interactions further enhance the robustness to sustain repeated (de)sodiation processes. These findings provide a rewarding avenue towards the development of high-performance electrodes by heterostructural electrochemistry.
{"title":"Sodium storage of -Sn/TiO2/Sn/TiO2- Superlattice heterojunctions","authors":"Xueyi Lu , Weixin Chen , Jianfang Yang , Xuemin Wu , Yan Wang , Oliver G. Schmidt , Lifeng Liu , Daiming Tang , Xia Lu","doi":"10.1016/j.ensm.2025.104112","DOIUrl":"10.1016/j.ensm.2025.104112","url":null,"abstract":"<div><div>Electrochemistry of heterostructures plays a fundamental role in developing high-performance energy storage and conversion devices. However, current superlattice heterostructures based on assembling 2D materials are limited to a small number of alternating units with weak interfacial interaction and ambiguous function mechanism. Herein, the high-order -Sn/TiO<sub>2</sub>/Sn/TiO<sub>2</sub>- (S/TO) superlattice heterojunctions with built-in electric fields (BIEFs) are designed for sodium storage using a strain release method. The results show that the accommodated BIEFs and the spatial confinement effect in this periodic nanostructured electrode co-contribute to the outstanding electrochemical performance. The nanosizing and pulverization of Sn are effectively space-limited in between the TiO<sub>2</sub> slabs and the notorious catalytic reaction between electrolyte and TiO<sub>2</sub> surface region is sophisticatedly mitigated by the electron accumulation in the TiO<sub>2</sub> component, synergistically accelerating sodium storage and transfer kinetics of S/TO superlattice electrodes. The covalent Sn-O-Ti interactions further enhance the robustness to sustain repeated (de)sodiation processes. These findings provide a rewarding avenue towards the development of high-performance electrodes by heterostructural electrochemistry.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"76 ","pages":"Article 104112"},"PeriodicalIF":18.9,"publicationDate":"2025-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371641","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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