Pub Date : 2025-03-24DOI: 10.1016/j.ensm.2025.104203
Helong Jiang , Fangyi Chu , Xiangcun Li , Bo Zhao , Gaohong He
Herein, we propose a strategy involving Co atoms and Mo vacancies to precisely adjust the orbital orientation of sulfur atoms on MoS2 surface, accurately modulating their interaction with lithium and sulfur sites in polysulfide species for stronger interactions with short-chain polysulfides, thereby promoting efficient liquid-solid conversion. Through a combination of theoretical modeling and experimental validation, multiple electron-deficient sulfur sites are constructed to demonstrate the pz orbitals of unsaturated surface sulfur atoms couple strongly with the p orbitals of short-chain polysulfides, facilitating formation of selective S-S bonds via enhanced p-p interactions, thereby accelerating the transition kinetics from Li2S4 to Li2S2/Li2S. This selective coupling is driven by sulfur molecular orbital occupation, charge distribution, and lattice matching. Moreover, we construct an electrocatalytic membrane composed of vertically aligned MoS₂ nanosheets and carbon nanotube nanochannels to ensure efficient contact between reactants and catalysts, enabling continuous polysulfide conversion. Consequently, the cell shows ultralow capacity decay (0.022 % per cycle over 1000 cycles at 2 C). This study emphasizes manipulation of the 3p orbital orientation of sulfur atoms to form selective dual-coordination, and provides valuable insights for the rational design of advanced electrocatalysts at the atomic level.
{"title":"Constructing highly active sulfur atoms on MoS₂ surface via p-p orbital covalent coupling matching the liquid-solid transition in lithium-sulfur batteries","authors":"Helong Jiang , Fangyi Chu , Xiangcun Li , Bo Zhao , Gaohong He","doi":"10.1016/j.ensm.2025.104203","DOIUrl":"10.1016/j.ensm.2025.104203","url":null,"abstract":"<div><div>Herein, we propose a strategy involving Co atoms and Mo vacancies to precisely adjust the orbital orientation of sulfur atoms on MoS<sub>2</sub> surface, accurately modulating their interaction with lithium and sulfur sites in polysulfide species for stronger interactions with short-chain polysulfides, thereby promoting efficient liquid-solid conversion. Through a combination of theoretical modeling and experimental validation, multiple electron-deficient sulfur sites are constructed to demonstrate the <em>p</em><sub>z</sub> orbitals of unsaturated surface sulfur atoms couple strongly with the <em>p</em> orbitals of short-chain polysulfides, facilitating formation of selective S-S bonds via enhanced <em>p-p</em> interactions, thereby accelerating the transition kinetics from Li<sub>2</sub>S<sub>4</sub> to Li<sub>2</sub>S<sub>2</sub>/Li<sub>2</sub>S. This selective coupling is driven by sulfur molecular orbital occupation, charge distribution, and lattice matching. Moreover, we construct an electrocatalytic membrane composed of vertically aligned MoS₂ nanosheets and carbon nanotube nanochannels to ensure efficient contact between reactants and catalysts, enabling continuous polysulfide conversion. Consequently, the cell shows ultralow capacity decay (0.022 % per cycle over 1000 cycles at 2 C). This study emphasizes manipulation of the 3<em>p</em> orbital orientation of sulfur atoms to form selective dual-coordination, and provides valuable insights for the rational design of advanced electrocatalysts at the atomic level.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104203"},"PeriodicalIF":18.9,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677802","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 : 2025-03-24DOI: 10.1016/j.ensm.2025.104205
Zhongqian Lv , Bing Han , Zhen Liu , Shaobo Guo , Kai Dai , Fei Cao , Zhigao Hu , Genshui Wang
Dielectric capacitors are widely utilized in large-scale power systems, including applications in medical and military fields. However, their relatively low energy storage density limits further advancements in miniaturization and integration. Therefore, improving the energy storage density of dielectric capacitors is of paramount importance. In this work, novel lead-free Na0.70Sr0.15Nb0.75Ta0.25O3 (NSNT) ceramics were designed, which exhibit a unique combination of relaxor ferroelectric (FE) N phase and stabilized antiferroelectric (AFE) P phase, as confirmed through local structural analysis. The competing FE/AFE phase coexistence is attributed to the discrepancy in ion valence and radius. As a result, the NSNT ceramics demonstrate exceptional energy storage performance, featuring a recoverable energy density (Wrec) of 10.45 J/cm³ and an energy efficiency (η) of 83.0 % at 850 kV/cm, along with excellent stability. These outstanding energy storage properties not only confirm the promising application prospects of NN-based ceramics with competing FE/AFE phase coexistence, but also provide an innovative approach for advancing high-performance ceramic capacitors.
{"title":"Achieving excellent energy storage properties in lead-free ceramics via competing FE/AFE phase coexistence","authors":"Zhongqian Lv , Bing Han , Zhen Liu , Shaobo Guo , Kai Dai , Fei Cao , Zhigao Hu , Genshui Wang","doi":"10.1016/j.ensm.2025.104205","DOIUrl":"10.1016/j.ensm.2025.104205","url":null,"abstract":"<div><div>Dielectric capacitors are widely utilized in large-scale power systems, including applications in medical and military fields. However, their relatively low energy storage density limits further advancements in miniaturization and integration. Therefore, improving the energy storage density of dielectric capacitors is of paramount importance. In this work, novel lead-free Na<sub>0.70</sub>Sr<sub>0.15</sub>Nb<sub>0.75</sub>Ta<sub>0.25</sub>O<sub>3</sub> (NSNT) ceramics were designed, which exhibit a unique combination of relaxor ferroelectric (FE) N phase and stabilized antiferroelectric (AFE) P phase, as confirmed through local structural analysis. The competing FE/AFE phase coexistence is attributed to the discrepancy in ion valence and radius. As a result, the NSNT ceramics demonstrate exceptional energy storage performance, featuring a recoverable energy density (<em>W</em><sub>rec</sub>) of 10.45 J/cm³ and an energy efficiency (<em>η</em>) of 83.0 % at 850 kV/cm, along with excellent stability. These outstanding energy storage properties not only confirm the promising application prospects of NN-based ceramics with competing FE/AFE phase coexistence, but also provide an innovative approach for advancing high-performance ceramic capacitors.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104205"},"PeriodicalIF":18.9,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695826","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 : 2025-03-23DOI: 10.1016/j.ensm.2025.104202
Kejie Jin , Liaoliao Li , Hao Tian , Mengxing Su , Yang Yang , Zhijun Wu , Shengnan He , Yanxia Liu , Chao Zheng , Jiantuo Gan , Wubin Du , Liaona She , Yaxiong Yang , Mingchang Zhang , Hongge Pan
Energy storage through additional anionic redox can deliver ultrahigh specific capacities of Lithium-rich manganese-based oxides cathode materials (LRMO). The commercial application of LRMO is hampered by several drawbacks, including structure degradation, continuous capacity and voltage decay, sluggish kinetics and severe irreversible oxygen release, stemming from generation of O2n− (0 ≤ n < 2) species during deep oxidation. Notably, relying solely on a single modification strategy only partially address the problems of LRMO materials. Herein, one-step phosphatizing-assisted interface engineering strategy was successfully implemented, simultaneously fabricating oxygen vacancies, spinel-like structure and an ionic conductor Li3PO4 capping layer on the surface. Among them, the formation of oxygen vacancies is accompanied by the production of a spinel phase buffer layer, which inhibits the generation of O–O dimers and oxygen loss, contributing to the stability and reversibility of anionic redox reactions. The lithium ions conductive protective layer of Li3PO4 accelerates Li+ diffusion rate while suppressing harmful interfacial side-reactions between the electrode and electrolyte. More importantly, the incorporation of P into the subsurface lattice regulates the local electron configuration and activates oxygen redox. As a result, the modification LRMO demonstrates an impressive reversible capacity of 312.9 mAh g−1, with excellent capacity retention of 91.87 % at 1 C and 82.43 % at 2 C after 500 cycles, respectively. The mult-ianionic redox mechanism provides an effective and straightforward method to stabilizing LRMO for next-generation high-energy lithium-ion batteries.
{"title":"Three birds with one stone: Reducing gases manipulate surface reconstruction of Li-rich Mn-based oxide cathodes for high-energy lithium-ion batteries","authors":"Kejie Jin , Liaoliao Li , Hao Tian , Mengxing Su , Yang Yang , Zhijun Wu , Shengnan He , Yanxia Liu , Chao Zheng , Jiantuo Gan , Wubin Du , Liaona She , Yaxiong Yang , Mingchang Zhang , Hongge Pan","doi":"10.1016/j.ensm.2025.104202","DOIUrl":"10.1016/j.ensm.2025.104202","url":null,"abstract":"<div><div>Energy storage through additional anionic redox can deliver ultrahigh specific capacities of Lithium-rich manganese-based oxides cathode materials (LRMO). The commercial application of LRMO is hampered by several drawbacks, including structure degradation, continuous capacity and voltage decay, sluggish kinetics and severe irreversible oxygen release, stemming from generation of O<sub>2</sub><sup>n−</sup> (0 ≤ <em>n</em> < 2) species during deep oxidation. Notably, relying solely on a single modification strategy only partially address the problems of LRMO materials. Herein, one-step phosphatizing-assisted interface engineering strategy was successfully implemented, simultaneously fabricating oxygen vacancies, spinel-like structure and an ionic conductor Li<sub>3</sub>PO<sub>4</sub> capping layer on the surface. Among them, the formation of oxygen vacancies is accompanied by the production of a spinel phase buffer layer, which inhibits the generation of O–O dimers and oxygen loss, contributing to the stability and reversibility of anionic redox reactions. The lithium ions conductive protective layer of Li<sub>3</sub>PO<sub>4</sub> accelerates Li<sup>+</sup> diffusion rate while suppressing harmful interfacial side-reactions between the electrode and electrolyte. More importantly, the incorporation of P into the subsurface lattice regulates the local electron configuration and activates oxygen redox. As a result, the modification LRMO demonstrates an impressive reversible capacity of 312.9 mAh <em>g</em><sup>−1</sup>, with excellent capacity retention of 91.87 % at 1 C and 82.43 % at 2 C after 500 cycles, respectively. The mult-ianionic redox mechanism provides an effective and straightforward method to stabilizing LRMO for next-generation high-energy lithium-ion batteries.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104202"},"PeriodicalIF":18.9,"publicationDate":"2025-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675287","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 : 2025-03-23DOI: 10.1016/j.ensm.2025.104204
Youyi Li , Yuhan Liu , Kun-Peng Wang , Zhenyu Xiao , Qi Zhang , Lei Wang , Volodymyr Turkevych
The performance of zinc ion batteries (ZIBs) is significantly constrained by dendrite growth and side reactions on the Zn anode. While epitaxial growth is an efficient strategy to stabilize the Zn anode by directing crystal alignment, the direct contact between the exposed crystal and electrolyte results in severe parasitic reactions. Here, we present a selective etching strategy on Zn anodes (denoted as ACE-Zn) that preferentially exposes the (101) plane, which features strong epitaxial growth characteristics to facilitate stably dense stacking of Zn atoms. Notably, the (101) plane also promotes the formation of a ZnS solid electrolyte interphase (SEI). This ZnS SEI exhibits high hydrophilicity and an ultrathin structure, contributing to exceptional ion transfer rate and isolating the Zn anode from water-related side reactions. As a result, ACE-Zn symmetric cells achieve an impressive cycle life of 4920 h at 0.5 mAh cm−2 and 0.5 mA cm−2, along with a high average Coulombic efficiency (CE) of 99.93 % over 3500 cycles. Furthermore, V-EG//ACE-Zn button-cells demonstrate prolonged cycle life of 7600 cycles at 10 A g−1. We believe this “one stone, two birds” strategy will provide new insights into texturing preferential planes and constructing SEI to stabilize Zn anodes.
{"title":"Epitaxial growth of the (101) plane: High stability and dendrite-free Zn anode achieved by “one stone, two birds” strategy","authors":"Youyi Li , Yuhan Liu , Kun-Peng Wang , Zhenyu Xiao , Qi Zhang , Lei Wang , Volodymyr Turkevych","doi":"10.1016/j.ensm.2025.104204","DOIUrl":"10.1016/j.ensm.2025.104204","url":null,"abstract":"<div><div>The performance of zinc ion batteries (ZIBs) is significantly constrained by dendrite growth and side reactions on the Zn anode. While epitaxial growth is an efficient strategy to stabilize the Zn anode by directing crystal alignment, the direct contact between the exposed crystal and electrolyte results in severe parasitic reactions. Here, we present a selective etching strategy on Zn anodes (denoted as ACE-Zn) that preferentially exposes the (101) plane, which features strong epitaxial growth characteristics to facilitate stably dense stacking of Zn atoms. Notably, the (101) plane also promotes the formation of a ZnS solid electrolyte interphase (SEI). This ZnS SEI exhibits high hydrophilicity and an ultrathin structure, contributing to exceptional ion transfer rate and isolating the Zn anode from water-related side reactions. As a result, ACE-Zn symmetric cells achieve an impressive cycle life of 4920 h at 0.5 mAh cm<sup>−2</sup> and 0.5 mA cm<sup>−2</sup>, along with a high average Coulombic efficiency (CE) of 99.93 % over 3500 cycles. Furthermore, V-EG//ACE-Zn button-cells demonstrate prolonged cycle life of 7600 cycles at 10 A g<sup>−1</sup>. We believe this “one stone, two birds” strategy will provide new insights into texturing preferential planes and constructing SEI to stabilize Zn anodes.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104204"},"PeriodicalIF":18.9,"publicationDate":"2025-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677803","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 : 2025-03-22DOI: 10.1016/j.ensm.2025.104201
Hai Lei , Xinwei Cui , Jiexiang Li , Zihao Zeng , Chao Zhu , Xiaobo Ji , Wei Sun , Yue Yang , Peng Ge
Attracted by remarkable environmental/economic advantages, the direct regeneration of spent LiCoO2 (LCO) has been regarded as potential recycling method. However, limited by small-size and various designing-models, spent batteries are always industrially dismantled to obtain complex mixture, containing LCO, graphite, Cu-impurities, etc. Thus, exploring the synergetic effect of graphite removing and Cu-doping behaviors/threshold is crucial for the practical commercial production about spent mixture. Herein, spent mixtures are utilized to regenerate high-voltage LCO. Assisted by graphite self-heating and Li-vacancies, the doping-temperature and diffusion energy-barrier are lowering, facilitating Cu-atoms doping into bulk-phase. After optimizing Cu-content (0.7 wt.%), bulk-oriented doping at Li/Co sites is achieved with contrary gradient Cu-atoms distribution. Unique doping behaviors induce the evolution of morphology/lattice stability and the expanding of interlayer spacing. The as-optimized sample delivers a high capacity of 177.59 mAh g-1 at 0.2 C. Even at 5.0 C after 500 cycles, its capacity could reach up to 154.8 mAh g-1 with ∼82.4% retention. Supporting by electronic structure analysis, unique doping behaviors served as important roles in enhancing electronic conductivity and lowering O 2p band center. Given this, the work is expected to offer significant guidance of direct commercial regeneration, and shed light on the clear Cu-doping behaviors with threshold-value.
{"title":"Upcycling of spent LiCoO2/Graphite/Cu mixtures: Cu-doping with contrary gradient distribution towards high-rate and prolonged-cyclability","authors":"Hai Lei , Xinwei Cui , Jiexiang Li , Zihao Zeng , Chao Zhu , Xiaobo Ji , Wei Sun , Yue Yang , Peng Ge","doi":"10.1016/j.ensm.2025.104201","DOIUrl":"10.1016/j.ensm.2025.104201","url":null,"abstract":"<div><div>Attracted by remarkable environmental/economic advantages, the direct regeneration of spent LiCoO<sub>2</sub> (LCO) has been regarded as potential recycling method. However, limited by small-size and various designing-models, spent batteries are always industrially dismantled to obtain complex mixture, containing LCO, graphite, Cu-impurities, etc. Thus, exploring the synergetic effect of graphite removing and Cu-doping behaviors/threshold is crucial for the practical commercial production about spent mixture. Herein, spent mixtures are utilized to regenerate high-voltage LCO. Assisted by graphite self-heating and Li-vacancies, the doping-temperature and diffusion energy-barrier are lowering, facilitating Cu-atoms doping into bulk-phase. After optimizing Cu-content (0.7 wt.%), bulk-oriented doping at Li/Co sites is achieved with contrary gradient Cu-atoms distribution. Unique doping behaviors induce the evolution of morphology/lattice stability and the expanding of interlayer spacing. The as-optimized sample delivers a high capacity of 177.59 mAh g<sup>-1</sup> at 0.2 C. Even at 5.0 C after 500 cycles, its capacity could reach up to 154.8 mAh g<sup>-1</sup> with ∼82.4% retention. Supporting by electronic structure analysis, unique doping behaviors served as important roles in enhancing electronic conductivity and lowering O 2p band center. Given this, the work is expected to offer significant guidance of direct commercial regeneration, and shed light on the clear Cu-doping behaviors with threshold-value.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104201"},"PeriodicalIF":18.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675241","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 : 2025-03-22DOI: 10.1016/j.ensm.2025.104196
Tzu-Chi Chuang , Rupan Bera , Yi-Ting Wu , Shih-Yu Chen , I-Yu Tsao , Jeng-Kuei Chang , Ching-Yuan Su
Lithium metal batteries (LMBs) face significant challenges, including dendrite growth and degradation during cycling. Two effective strategies to address these issues involve utilizing a nano-structured current collector as a lithium host and forming an ideal solid-electrolyte interphase (SEI) as an artificial anode modifier. However, synthesizing an anode modifier that offers high cycling stability and efficient lithium diffusion/storage via a well-controlled deposition method remains challenging. This study presents a binder-free and novel gradient Janus interlayer(GJL) as anode modifier comprising gradient layered composite of fluorinated graphene (FECG) and intrinsic graphene (ECG), deposited through electrophoretic deposition (EPD). The gradient Janus structure provides separate ionic and electronic transport pathways. The top FECG layer with LiF-rich species enhances both electrolyte wettability and lithium ion transport for uniform Li plating, while the underlying ECG layer facilitates efficient electron transfer. Also, a thin CuF2-riched functional layer is designed to connecting the GJL to the copper substrate, ensures strong adhesion to the copper substrate without using any binder, enabling stable lithium deposition and improved structural integrity. The GJL as anode modifier demonstrates outstanding electrochemical performance, showing a low nucleation overpotential of 42.17 mV and stable polarization over 600 h. After 325 cycles, the Coulombic efficiency reached 97.2 %, indicating excellent stability. In full-cell testing, the specific capacity exceeded 120 mAh/g after 150 cycles, with 72 % capacity retention after 160 cycles. Overall, this innovative composite multilayer ASEI offers a promising solution to overcome the challenges of anode-free lithium metal batteries (AFLB), paving the way for safer and higher-energy-density battery technologies.
{"title":"Enabling efficient guiding of Li diffusion/plating toward high-performance lithium metal batteries by utilizing a gradient Janus interlayer","authors":"Tzu-Chi Chuang , Rupan Bera , Yi-Ting Wu , Shih-Yu Chen , I-Yu Tsao , Jeng-Kuei Chang , Ching-Yuan Su","doi":"10.1016/j.ensm.2025.104196","DOIUrl":"10.1016/j.ensm.2025.104196","url":null,"abstract":"<div><div>Lithium metal batteries (LMBs) face significant challenges, including dendrite growth and degradation during cycling. Two effective strategies to address these issues involve utilizing a nano-structured current collector as a lithium host and forming an ideal solid-electrolyte interphase (SEI) as an artificial anode modifier. However, synthesizing an anode modifier that offers high cycling stability and efficient lithium diffusion/storage via a well-controlled deposition method remains challenging. This study presents a binder-free and novel gradient Janus interlayer(GJL) as anode modifier comprising gradient layered composite of fluorinated graphene (FECG) and intrinsic graphene (ECG), deposited through electrophoretic deposition (EPD). The gradient Janus structure provides separate ionic and electronic transport pathways. The top FECG layer with LiF-rich species enhances both electrolyte wettability and lithium ion transport for uniform Li plating, while the underlying ECG layer facilitates efficient electron transfer. Also, a thin CuF<sub>2</sub>-riched functional layer is designed to connecting the GJL to the copper substrate, ensures strong adhesion to the copper substrate without using any binder, enabling stable lithium deposition and improved structural integrity. The GJL as anode modifier demonstrates outstanding electrochemical performance, showing a low nucleation overpotential of 42.17 mV and stable polarization over 600 h. After 325 cycles, the Coulombic efficiency reached 97.2 %, indicating excellent stability. In full-cell testing, the specific capacity exceeded 120 mAh/g after 150 cycles, with 72 % capacity retention after 160 cycles. Overall, this innovative composite multilayer ASEI offers a promising solution to overcome the challenges of anode-free lithium metal batteries (AFLB), paving the way for safer and higher-energy-density battery technologies.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104196"},"PeriodicalIF":18.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675284","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 : 2025-03-22DOI: 10.1016/j.ensm.2025.104195
Seonghun Lee , Ji Young Park , Hyungsub Yoon , Jiyoon Park , Joohyung Lee , Byungil Hwang , Vinod V.T. Padil , Jun Young Cheong , Tae Gwang Yun
Supercapacitor is one of most widely researched energy storage system because it stores more charge than capacitor and charges-discharges quicker than batteries. As surface reaction is prominent in the energy storage in supercapacitor, stable interface between electrode and electrolyte is a key to high performance. Although a formation of stable interface was achieved by surface modification of electrode and/or designing of novel materials/composites, they were limited by their complicated processing steps, costs, scalability, and eco-friendliness. In this work, we have firstly introduced a novel electrolyte additive composed of conjugated biopolymer of gum kondagogu/sodium alginate (KS), which is widely available and recyclable. At the KS concentration of 5 mg ml-1, the capacitance retention improved from 58 % to 93 % for 30,000 cycles at a current density of 4.0 mA cm-2, which was remarkable given the use of acidic H2SO4 electrolyte and carbon-based electrode. Postmortem analysis revealed the suitable concentration of KS necessary to ensure the interfacial protection as well as alleviation of side reactions by the introduction of KS, which can also be extended and scaled up in an industry scale.
{"title":"Long-lasting supercapacitor with stable electrode-electrolyte interface enabled by a biopolymer conjugate electrolyte additive","authors":"Seonghun Lee , Ji Young Park , Hyungsub Yoon , Jiyoon Park , Joohyung Lee , Byungil Hwang , Vinod V.T. Padil , Jun Young Cheong , Tae Gwang Yun","doi":"10.1016/j.ensm.2025.104195","DOIUrl":"10.1016/j.ensm.2025.104195","url":null,"abstract":"<div><div>Supercapacitor is one of most widely researched energy storage system because it stores more charge than capacitor and charges-discharges quicker than batteries. As surface reaction is prominent in the energy storage in supercapacitor, stable interface between electrode and electrolyte is a key to high performance. Although a formation of stable interface was achieved by surface modification of electrode and/or designing of novel materials/composites, they were limited by their complicated processing steps, costs, scalability, and eco-friendliness. In this work, we have firstly introduced a novel electrolyte additive composed of conjugated biopolymer of gum kondagogu/sodium alginate (KS), which is widely available and recyclable. At the KS concentration of 5 mg ml<sup>-1</sup>, the capacitance retention improved from 58 % to 93 % for 30,000 cycles at a current density of 4.0 mA cm<sup>-2</sup>, which was remarkable given the use of acidic H<sub>2</sub>SO<sub>4</sub> electrolyte and carbon-based electrode. Postmortem analysis revealed the suitable concentration of KS necessary to ensure the interfacial protection as well as alleviation of side reactions by the introduction of KS, which can also be extended and scaled up in an industry scale.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104195"},"PeriodicalIF":18.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675333","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-22DOI: 10.1016/j.ensm.2025.104194
Shenglin He, Shulin Gao, Sujuan Hu
The sluggish multi-electron transfer kinetics of oxygen reduction and evolution reactions (ORR and OER) on the air cathode significantly reduce the energy efficiency of rechargeable zinc-air batteries (RZABs). Light-assistance is an effective approach to enhance the cathode reaction rate. However, the critical scientific issue of how photogenerated electrons regulate the interfacial electronic structure and thereby influence the behavior of reaction intermediates remains unclear, posing a challenge to achieving high-performance light-assisted RZABs. This study employs delocalized electron-rich g-C3N4/NSs as a model material and applies in-situ electron paramagnetic resonance (EPR) and theoretical calculations to elucidate this issue. Under light assistance, delocalized electrons from g-C3N4/NSs alter the surface electron distribution and charge density, reducing O2 adsorption energy and the energy barriers of key intermediate steps, thereby markedly enhancing the adsorption and desorption behavior of O2 and key intermediates (OH*). As a result, the constructed light-assisted aqueous RZABs demonstrate a high energy density of 1020 mWh g-1 and exhibit excellent cycling stability at a current density of 5 mA cm-2 (cycle life of 1400 h, discharge voltage of 1.25 V, charge voltage of 2.0 V). Additionally, the developed light-assisted flexible RZABs (FRZABs) exhibit outstanding performance with excellent adaptability to extreme conditions.
{"title":"Light-assisted delocalized electron-driven g-C3N4/NSs-based cathode catalysts for high-performance rechargeable zinc-air batteries","authors":"Shenglin He, Shulin Gao, Sujuan Hu","doi":"10.1016/j.ensm.2025.104194","DOIUrl":"10.1016/j.ensm.2025.104194","url":null,"abstract":"<div><div>The sluggish multi-electron transfer kinetics of oxygen reduction and evolution reactions (ORR and OER) on the air cathode significantly reduce the energy efficiency of rechargeable zinc-air batteries (RZABs). Light-assistance is an effective approach to enhance the cathode reaction rate. However, the critical scientific issue of how photogenerated electrons regulate the interfacial electronic structure and thereby influence the behavior of reaction intermediates remains unclear, posing a challenge to achieving high-performance light-assisted RZABs. This study employs delocalized electron-rich g-C<sub>3</sub>N<sub>4</sub>/NSs as a model material and applies <em>in-situ</em> electron paramagnetic resonance (EPR) and theoretical calculations to elucidate this issue. Under light assistance, delocalized electrons from g-C<sub>3</sub>N<sub>4</sub>/NSs alter the surface electron distribution and charge density, reducing O<sub>2</sub> adsorption energy and the energy barriers of key intermediate steps, thereby markedly enhancing the adsorption and desorption behavior of O<sub>2</sub> and key intermediates (OH*). As a result, the constructed light-assisted aqueous RZABs demonstrate a high energy density of 1020 mWh g<sup>-1</sup> and exhibit excellent cycling stability at a current density of 5 mA cm<sup>-2</sup> (cycle life of 1400 h, discharge voltage of 1.25 V, charge voltage of 2.0 V). Additionally, the developed light-assisted flexible RZABs (FRZABs) exhibit outstanding performance with excellent adaptability to extreme conditions.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104194"},"PeriodicalIF":18.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675280","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 : 2025-03-22DOI: 10.1016/j.ensm.2025.104200
Xuri Wang , Bo Zhao , Xiangcun Li , Xinhong Qi , Yan Dai , Tiantian Li , Gaohong He , Fangyi Chu , Xiaobin Jiang
Nonuniform Li-ion gradient and electric fields in conventional host lead to uncontrollable Li top-growth behavior and Li dendrite, impeding the practical application of lithium metal anodes (LMAs). Herein, we design a 3D hierarchical flexible membrane host with gradient lithiophilic properties (GFC@PVDF) to regulate bottom-up growth of the spherical Li within host, by optimizing the electric field and Li-ion flux. The membrane networks with CNT as cores and β-PVDF as linking shells enabling fast electron transfer and low Li-ion migration energy barriers. Gradient Fe2O3 particles in the membrane by layer-by-layer bottom-up attenuating could induce Li-ion dredging and pumps towards the bottom for bottom-up deposition regime, reducing ion concentration gradient via lithiophilic gradient properties. Meanwhile, the Fe2O3 is converted into hybrid electron/ion conductor Fe/Li2O during cycling, which acts as charge decoupling and fast transport path that enhances the bottom transport of Li-ions. Consequently, stable symmetric cells over 500 cycles with Li spherical uniform deposition are obtained under an ultrahigh current density of 50 mA cm-2. The full cell paired with LiFePO4 cathode exhibits remarkable cycling stability at a low N/P ratio of 1.7. This study provides new insights into dendrite-free Li metal anodes, paving the way for high-energy, fast-charging LMAs.
{"title":"Inducing spherical lithium deposition via simultaneously optimized electric field and ionic flux for fast-charging lithium metal batteries","authors":"Xuri Wang , Bo Zhao , Xiangcun Li , Xinhong Qi , Yan Dai , Tiantian Li , Gaohong He , Fangyi Chu , Xiaobin Jiang","doi":"10.1016/j.ensm.2025.104200","DOIUrl":"10.1016/j.ensm.2025.104200","url":null,"abstract":"<div><div>Nonuniform Li-ion gradient and electric fields in conventional host lead to uncontrollable Li top-growth behavior and Li dendrite, impeding the practical application of lithium metal anodes (LMAs). Herein, we design a 3D hierarchical flexible membrane host with gradient lithiophilic properties (GFC@PVDF) to regulate bottom-up growth of the spherical Li within host, by optimizing the electric field and Li-ion flux. The membrane networks with CNT as cores and β-PVDF as linking shells enabling fast electron transfer and low Li-ion migration energy barriers. Gradient Fe<sub>2</sub>O<sub>3</sub> particles in the membrane by layer-by-layer bottom-up attenuating could induce Li-ion dredging and pumps towards the bottom for bottom-up deposition regime, reducing ion concentration gradient via lithiophilic gradient properties. Meanwhile, the Fe<sub>2</sub>O<sub>3</sub> is converted into hybrid electron/ion conductor Fe/Li<sub>2</sub>O during cycling, which acts as charge decoupling and fast transport path that enhances the bottom transport of Li-ions. Consequently, stable symmetric cells over 500 cycles with Li spherical uniform deposition are obtained under an ultrahigh current density of 50 mA cm<sup>-2</sup>. The full cell paired with LiFePO<sub>4</sub> cathode exhibits remarkable cycling stability at a low N/P ratio of 1.7. This study provides new insights into dendrite-free Li metal anodes, paving the way for high-energy, fast-charging LMAs.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104200"},"PeriodicalIF":18.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675330","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}
Sodium-ion batteries (SIBs) have emerged as promising alternatives to lithium-ion batteries due to the advantages of low cost, abundant resources, and superior low-temperature performance. However, research on the thermal runaway (TR) behavior of large-format prismatic SIBs remains limited. To address this research gap, this work investigates the TR behavior of 185 Ah SIBs at different states of charges (SOCs). In contrast to prior research, the primary contribution of this work is the investigation of heat generation, gas production, and mechanical changes in SIBs during TR. Two significant conclusions are obtained: 1) The proportion of H2 increases significantly with SOC, reaching as high as 42% at 100% SOC, with an explosion range of 6.5%∼69.0%, suggesting substantial combustion and explosion hazards associated with SIBs; 2) SIBs release a large amount of heat during TR, resulting in the ejection of internal hot particles as sparks. However, the intense gas production behavior during TR process effectively dissipates heat from SIBs while isolating the combustible gases from the sparks and oxygen, leading to a self-extinguishing phenomenon. This study highlights the influence of SOC on TR and gas production behavior in SIBs, providing critical insights for the advancement of electrochemical energy storage systems.
{"title":"Thermal runaway and gas venting behaviors of large-format prismatic sodium-ion battery","authors":"Zhiyuan Li, Yin Yu, Junjie Wang, Chengdong Wang, Xiaofang He, Zhixiang Cheng, Huang Li, Wenxin Mei, Qingsong Wang","doi":"10.1016/j.ensm.2025.104197","DOIUrl":"10.1016/j.ensm.2025.104197","url":null,"abstract":"<div><div>Sodium-ion batteries (SIBs) have emerged as promising alternatives to lithium-ion batteries due to the advantages of low cost, abundant resources, and superior low-temperature performance. However, research on the thermal runaway (TR) behavior of large-format prismatic SIBs remains limited. To address this research gap, this work investigates the TR behavior of 185 Ah SIBs at different states of charges (SOCs). In contrast to prior research, the primary contribution of this work is the investigation of heat generation, gas production, and mechanical changes in SIBs during TR. Two significant conclusions are obtained: 1) The proportion of H<sub>2</sub> increases significantly with SOC, reaching as high as 42% at 100% SOC, with an explosion range of 6.5%∼69.0%, suggesting substantial combustion and explosion hazards associated with SIBs; 2) SIBs release a large amount of heat during TR, resulting in the ejection of internal hot particles as sparks. However, the intense gas production behavior during TR process effectively dissipates heat from SIBs while isolating the combustible gases from the sparks and oxygen, leading to a self-extinguishing phenomenon. This study highlights the influence of SOC on TR and gas production behavior in SIBs, providing critical insights for the advancement of electrochemical energy storage systems.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"77 ","pages":"Article 104197"},"PeriodicalIF":18.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675281","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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