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":"https://doi.org/10.1016/j.ensm.2025.104202","url":null,"abstract":"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 ≤ 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 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 g<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.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"34 1","pages":""},"PeriodicalIF":20.4,"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 : 2025-03-22DOI: 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":"https://doi.org/10.1016/j.ensm.2025.104201","url":null,"abstract":"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.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"3 1","pages":""},"PeriodicalIF":20.4,"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}
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 hours. 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":"https://doi.org/10.1016/j.ensm.2025.104196","url":null,"abstract":"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 hours. 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.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"8 1","pages":""},"PeriodicalIF":20.4,"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":"https://doi.org/10.1016/j.ensm.2025.104195","url":null,"abstract":"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.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"34 1","pages":""},"PeriodicalIF":20.4,"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":"","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":"https://doi.org/10.1016/j.ensm.2025.104194","url":null,"abstract":"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.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"95 1","pages":""},"PeriodicalIF":20.4,"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":"https://doi.org/10.1016/j.ensm.2025.104200","url":null,"abstract":"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.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"28 1","pages":""},"PeriodicalIF":20.4,"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":"https://doi.org/10.1016/j.ensm.2025.104197","url":null,"abstract":"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.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"27 1","pages":""},"PeriodicalIF":20.4,"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}
Ultra-high nickel layered cathodes suffer accelerated degradation through a mechanically and chemically coupled cycle, highlighting the need to concurrently enhance durability and stability, especially at high voltages to prolong service life. This work demonstrates that tungsten near-surface doping can induce spinel nanodots, effectively improving the mechanical-chemical synergy of LiNi0.9Co0.05Mn0.05O2. Micro-compression testing of individual cycled crystalline particles is employed to reveal the quantized compression strength and modulus of materials. The modified materials exhibit a better strength of 360.2 MPa and an increased modulus of 13.7 GPa, and even after cycling the materials can maintain high strength and modulus levels of 175.3 MPa and 5 GPa respectively. More importantly, in-situ XRD indicates that the improvement of mechanical integrity is achieved by suppressing the lattice distortion. Cross-sectional SEM, TEM and XPS demonstrate that the enhanced mechanical integrity can effectively inhibit particle cracking and improve the mechanical and chemical stability. As a result, this cathode with an arranged structure delivered 75.4 % capacity retention at 4.5 V after 300 cycles, representing a 16.3 % improvement. This surface nanodots approach provides new insights into interface engineering to ameliorate degradation at high voltage, offering a pathway toward high-energy cathodes with enhanced cycling endurance.
{"title":"Enhanced Mechanical Property Promote High Stability of Single-crystal Ni-rich Cathode at 4.5 V","authors":"Jianpeng Peng, Jiachao Yang, Shuaipeng Hao, Yunjiao Li, Shuaiwei Liu, Shijie Jiang, Shuhui Sun, Zhenjiang He","doi":"10.1016/j.ensm.2025.104199","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104199","url":null,"abstract":"Ultra-high nickel layered cathodes suffer accelerated degradation through a mechanically and chemically coupled cycle, highlighting the need to concurrently enhance durability and stability, especially at high voltages to prolong service life. This work demonstrates that tungsten near-surface doping can induce spinel nanodots, effectively improving the mechanical-chemical synergy of LiNi<sub>0.9</sub>Co<sub>0.05</sub>Mn<sub>0.05</sub>O<sub>2</sub>. Micro-compression testing of individual cycled crystalline particles is employed to reveal the quantized compression strength and modulus of materials. The modified materials exhibit a better strength of 360.2 MPa and an increased modulus of 13.7 GPa, and even after cycling the materials can maintain high strength and modulus levels of 175.3 MPa and 5 GPa respectively. More importantly, in-situ XRD indicates that the improvement of mechanical integrity is achieved by suppressing the lattice distortion. Cross-sectional SEM, TEM and XPS demonstrate that the enhanced mechanical integrity can effectively inhibit particle cracking and improve the mechanical and chemical stability. As a result, this cathode with an arranged structure delivered 75.4 % capacity retention at 4.5 V after 300 cycles, representing a 16.3 % improvement. This surface nanodots approach provides new insights into interface engineering to ameliorate degradation at high voltage, offering a pathway toward high-energy cathodes with enhanced cycling endurance.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"33 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675242","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}
Solid-state sodium batteries present a high potential for future energy technology due to their high safety and energy density. However, sluggish Na+ transportation of solid-state electrolytes and serious Na dendrites hinder their further development. Herein, we propose a negatively charged-modified covalent organic framework (COF) with -SO3Na as a Na-ion quasi-solid-state electrolyte (QSSE-COF-SO3Na) for the first time to enhance the Na+ transportation. Density functional theory calculations and molecular dynamics simulations prove that the nano-scale ion channels of the COF-SO3Na and the interaction between the -SO3- and the anion PF6- effectively enhance the Na+ diffusion kinetics. The QSSE-COF-SO3Na exhibits a high ionic conductivity of 4.1 × 10-4 S cm-1 at room temperature and a high transference number of 0.89. Particularly, Na|QSSE-COF-SO3Na|Na symmetric cells show a stable Na plating/stripping process without Na dendrites over 1000 h and 800 h at 0.05 and 0.2 mA cm-2, respectively. Additionally, the QSSE-COF-SO3Na supports full cells, which respectively use NaTi2(PO4)3, Na3V2(PO4)3, and NaFePO4 as cathodes, to display good cycling stability and rate performance. This work highlights the novel strategy to develop the Na-ion quasi-solid-state devices.
{"title":"Ionic covalent organic frameworks-based electrolyte enables fast Na-ion diffusion towards quasi-solid-state sodium batteries","authors":"Tianxing Kang, Haoyuan Liu, Jian Cai, Xingyi Feng, Zhongqiu Tong, Hanbo Zou, Wei Yang, Junmin Nan, Shengzhou Chen","doi":"10.1016/j.ensm.2025.104192","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104192","url":null,"abstract":"Solid-state sodium batteries present a high potential for future energy technology due to their high safety and energy density. However, sluggish Na<sup>+</sup> transportation of solid-state electrolytes and serious Na dendrites hinder their further development. Herein, we propose a negatively charged-modified covalent organic framework (COF) with -SO<sub>3</sub>Na as a Na-ion quasi-solid-state electrolyte (QSSE-COF-SO<sub>3</sub>Na) for the first time to enhance the Na<sup>+</sup> transportation. Density functional theory calculations and molecular dynamics simulations prove that the nano-scale ion channels of the COF-SO<sub>3</sub>Na and the interaction between the -SO<sub>3</sub><sup>-</sup> and the anion PF<sub>6</sub><sup>-</sup> effectively enhance the Na<sup>+</sup> diffusion kinetics. The QSSE-COF-SO<sub>3</sub>Na exhibits a high ionic conductivity of 4.1 × 10<sup>-4</sup> S cm<sup>-1</sup> at room temperature and a high transference number of 0.89. Particularly, Na|QSSE-COF-SO<sub>3</sub>Na|Na symmetric cells show a stable Na plating/stripping process without Na dendrites over 1000 h and 800 h at 0.05 and 0.2 mA cm<sup>-2</sup>, respectively. Additionally, the QSSE-COF-SO<sub>3</sub>Na supports full cells, which respectively use NaTi<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, and NaFePO<sub>4</sub> as cathodes, to display good cycling stability and rate performance. This work highlights the novel strategy to develop the Na-ion quasi-solid-state devices.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"183 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666314","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 : 2025-03-20DOI: 10.1016/j.ensm.2025.104191
Xiaoping Yi, Yang Yang, Junjie Song, Luyu Gan, Bitong Wang, Guoliang Jiang, Kaishan Xiao, Xuening Song, Nan Wu, Liquan Chen, Hong Li
All-solid-state lithium batteries hold tremendous potential for next-generation batteries due to their exceptional theoretical energy density and intrinsic safety advantages. The forthcoming solid-state batteries employing solid electrolytes are widely expected to adopt a separator-free design strategy. However, porous separators, distinguished by their mechanical robustness, economic viability, and manufacturing scalability, present a feasible solution to address the industrialization challenges faced by solid electrolytes. Herein, a multifunctional polyethylene separator (denoted as S7540) was rationally designed through systematic optimization of structural parameters and anisotropic characteristics. Notably, the developed S7540 separator achieves an optimal balance between ultra-high porosity and broad pore size spectrum while maintaining superior mechanical integrity, enabling seamless compatibility across both liquid and solid state battery production lines. When implemented in Li/LiCoO2 configurations, the S7540 separator shows long-term cycling stability under high rate (10C) and high areal capacity (∼ 6.2 mAh cm−2), significantly outperforming the traditional commercial separator. Additionally, the S7540 architecture boosts mechanical properties of polymer-oxide solid electrolytes by approximately 50 times, demonstrating excellent tensile strength (42.1 MPa) and great cyclability (>6000 h) in Li/Li symmetric cells. All-solid-state Li/LiFePO4 cells exhibit outstanding capacity retention rates of 90.7% and 81.3% after 500 and 700 cycles at 0.5C, respectively. Importantly, the solvent-free S7540-based electrolyte demonstrates exceptional thermal stability with negligible mass loss (< 0.3%) during prolonged 120°C exposure (6h) and minimal decomposition below 250°C. This work emphasizes the crucial relationship between separator structure optimization and battery performance metrics, while establishing a cost-effective and scalable manufacturing pathway for practical solid electrolyte implementation across various battery systems.
{"title":"Strategically tailored polyethylene separator parameters enable cost-effective, facile, and scalable development of ultra-stable liquid and all-solid-state lithium batteries","authors":"Xiaoping Yi, Yang Yang, Junjie Song, Luyu Gan, Bitong Wang, Guoliang Jiang, Kaishan Xiao, Xuening Song, Nan Wu, Liquan Chen, Hong Li","doi":"10.1016/j.ensm.2025.104191","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104191","url":null,"abstract":"All-solid-state lithium batteries hold tremendous potential for next-generation batteries due to their exceptional theoretical energy density and intrinsic safety advantages. The forthcoming solid-state batteries employing solid electrolytes are widely expected to adopt a separator-free design strategy. However, porous separators, distinguished by their mechanical robustness, economic viability, and manufacturing scalability, present a feasible solution to address the industrialization challenges faced by solid electrolytes. Herein, a multifunctional polyethylene separator (denoted as S7540) was rationally designed through systematic optimization of structural parameters and anisotropic characteristics. Notably, the developed S7540 separator achieves an optimal balance between ultra-high porosity and broad pore size spectrum while maintaining superior mechanical integrity, enabling seamless compatibility across both liquid and solid state battery production lines. When implemented in Li/LiCoO<sub>2</sub> configurations, the S7540 separator shows long-term cycling stability under high rate (10C) and high areal capacity (∼ 6.2 mAh cm<sup>−2</sup>), significantly outperforming the traditional commercial separator. Additionally, the S7540 architecture boosts mechanical properties of polymer-oxide solid electrolytes by approximately 50 times, demonstrating excellent tensile strength (42.1 MPa) and great cyclability (>6000 h) in Li/Li symmetric cells. All-solid-state Li/LiFePO<sub>4</sub> cells exhibit outstanding capacity retention rates of 90.7% and 81.3% after 500 and 700 cycles at 0.5C, respectively. Importantly, the solvent-free S7540-based electrolyte demonstrates exceptional thermal stability with negligible mass loss (< 0.3%) during prolonged 120°C exposure (6h) and minimal decomposition below 250°C. This work emphasizes the crucial relationship between separator structure optimization and battery performance metrics, while establishing a cost-effective and scalable manufacturing pathway for practical solid electrolyte implementation across various battery systems.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"20 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660513","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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