To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified ...To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming alternative.Among the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale applications.However,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their applications.This review provides a comprehensive overview of recent research advancements in OICSEs.Specifically,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically discussed.The lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic perspective.Besides,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of OICSEs.Finally,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.展开更多
The insurmountable charge transfer impedance at the Li metal/solid polymer electrolytes(SPEs)interface at room temperature as well as the ascending risk of short circuits at the operating temperature higher than the m...The insurmountable charge transfer impedance at the Li metal/solid polymer electrolytes(SPEs)interface at room temperature as well as the ascending risk of short circuits at the operating temperature higher than the melting point,dominantly limits their applications in solid-state batteries(SSBs).Although the inorganic filler such as CeO_(2)nanoparticle content of composite solid polymer electrolytes(CSPEs)can significantly reduce the enormous charge transfer impedance at the Li metal/SPEs interface,we found that the required content of CeO_(2)nanoparticles in SPEs varies for achieving a decent interfacial charge transfer impedance and the bulk ionic conductivity in CSPEs.In this regard,a sandwich-type composited solid polymer electrolyte with a 10%CeO_(2)CSPEs interlayer sandwiched between two 50%CeO_(2)CSPEs thin layers(sandwiched CSPEs)is constructed to simultaneously achieve low charge transfer impedance and superior ionic conductivity at 30℃.The sandwiched CSPEs allow for stable cycling of Li plating and stripping for 1000 h with 129 mV polarized voltage at 0.1 mA cm^(-2)and 30℃.In addition,the LiFePO_(4)/Sandwiched CSPEs/Li cell also exhibits exceptional cycle performance at 30℃and even elevated120℃without short circuits.Constructing multi-layered CSPEs with optimized contents of the inorganic fillers can be an efficient method for developing all solid-state PEO-based batteries with high performance at a wide range of temperatures.展开更多
Recent advances in utilizing ^(17)O isotopic labeling methods for solid-state nuclear magnetic resonance(NMR)investigations of metal oxides for lithium-ion batteries have yielded extensive insights into their structur...Recent advances in utilizing ^(17)O isotopic labeling methods for solid-state nuclear magnetic resonance(NMR)investigations of metal oxides for lithium-ion batteries have yielded extensive insights into their structural and dynamic details.Herein,we commence with a brief introduction to recent research on lithium-ion battery oxide materials studied using ^(17)O solid-state NMR spectroscopy.Then we delve into a review of ^(17)O isotopic labeling methods for tagging oxygen sites in both the bulk and surfaces of metal oxides.At last,the unresolved problems and the future research directions for advancing the ^(17)O labeling technique are discussed.展开更多
All-solid-state batteries(ASSBs)assembled with sulfide solid electrolytes(SSEs)and nickel(Ni)-rich oxide cathode materials are expected to achieve high energy density and safety,representing potential candidates for t...All-solid-state batteries(ASSBs)assembled with sulfide solid electrolytes(SSEs)and nickel(Ni)-rich oxide cathode materials are expected to achieve high energy density and safety,representing potential candidates for the next-generation energy storage systems.However,interfacial issues between SSEs and Nirich oxide cathode materials,attributed to space charge layer,interfacial side reactions,and mechanical contact failure,significantly restrict the performances of ASSBs.The interface degradation is closely related to the components of the composite cathode and the process of electrode fabrication.Focusing on the influencing factors of interface compatibility between SSEs and Ni-rich oxide cathode,this article systematically discusses how cathode active materials(CAMs),electrolytes,conductive additives,binders,and electrode fabrication impact the interface compatibility.In addition,the strategies for the compatibility modification are reviewed.Furthermore,the challenges and prospects of intensive research on the degradation and modification of the SSE/Ni-rich cathode material interface are discussed.This review is intended to inspire the development of high-energy-density and high-safety all-solid-state batteries.展开更多
Sodium metal batteries(SMBs)are promising candidates for next-generation energy storage devices owing to their excellent safety performance and natural abunda nce of sodium.However,the insurmountable obstacles of dend...Sodium metal batteries(SMBs)are promising candidates for next-generation energy storage devices owing to their excellent safety performance and natural abunda nce of sodium.However,the insurmountable obstacles of dendrite formation and quick capacity decay are caused by an unstable and inhomogeneous solid electrolyte interphase that resulted from the immediate interactions between the Na metal anode and organic liquid electrolyte.Herein,a customised glass fibre separator coupled with chitosan(CS@GF)was developed to modulate the sodium ion(Na^(+))flux.The CS@GF separator facilitates the Na+homogeneous deposition on the anode side through redistribution at the chitosan polyactive sites and by inhibiting the decomposition of the electrolyte to robust solid electrolyte interphase(SEI)formation.Multiphysics simulations show that chitosan incorporated into SMBs through the separator can make the local electric field around the anode uniform,thus facilitating the transfer of cations.Na|Na symmetric cells utilising a CS@GF separator exhibited an outstanding cycle stability of over 600 h(0.5 mA cm^(-2)).Meanwhile,the Na|Na_(3)V_(5)(PO_(4))_(3)full cell exhibited excellent fast-charging performance(93.47%capacity retention after 1500 cycles at 5C).This study presents a promising strategy for inhibiting dendrite growth and realizes stable Na metal batteries,which significantly boosts the development of high-performance SMBs.展开更多
Achieving simultaneous fast-charging capabilities and low-temperature adaptability in graphite-based lithium-ion batteries(LIBs)with an acceptable cycle life remains challenging.Herein,an ether-based electrolyte with ...Achieving simultaneous fast-charging capabilities and low-temperature adaptability in graphite-based lithium-ion batteries(LIBs)with an acceptable cycle life remains challenging.Herein,an ether-based electrolyte with temperature-adaptive Li^(+)solvation structure is designed for graphite,and stable Li^(+)/solvent co-intercalation has been achieved at subzero.As revealed by in-situ variable temperature(-20℃)X-ray diffraction(XRD),the poor compatibility of graphite in ether-based electrolyte at 25℃is mainly due to the continuous electrolyte decomposition and the in-plane rearrangement below0.5 V.Former results in a significant irreversible capacity,while latter maintains graphite in a prolonged state of extreme expansion,ultimately leading to its exfoliation and failure.In contrast,low temperature triggers the rearra ngement of Li^(+)solvation structu re with stronger Li^(+)/solvent binding energy and sho rter Li^(+)-O bond length,which is conducive for reversible Li^(+)/solvent co-intercalation and reducing the time of graphite in an extreme expansion state.In addition,the co-intercalation of solvents minimizes the interaction between Li-ions and host graphite,endowing graphite with fast diffusion kinetics.As expected,the graphite anode delivers about 84%of the capacity at room temperature at-20℃.Moreover,within6 min,about 83%,73%,and 43%of the capacity could be charged at 25,-20,and-40℃,respectively.展开更多
Micrometer-sized silicon oxide(SiO)anodes encounter challenges in large-scale applications due to significant volume expansion during the alloy/de-alloy process.Herein,an innovative deep eutectic electrolyte derived f...Micrometer-sized silicon oxide(SiO)anodes encounter challenges in large-scale applications due to significant volume expansion during the alloy/de-alloy process.Herein,an innovative deep eutectic electrolyte derived from succinonitrile is introduced to enhance the cycling stability of SiO anodes.Density functional theory calculations validate a robust ion-dipole interaction between lithium ions(Li^(+))and succinonitrile(SN).The cosolvent fluoroethylene carbonate(FEC)optimizes the Li^(+)solvation structure in the SN-based electrolyte with its weakly solvating ability.Molecular dynamics simulations investigate the regulating mechanism of ion-dipole and cation-anion interaction.The unique Li^(+)solvation structure,enriched with FEC and TFSI^(-),facilitates the formation of an inorganic-organic composite solid electrolyte interphase on SiO anodes.Micro-CT further detects the inhibiting effect on the SiO volume expansion.As a result,the SiO|LiCoO_(2) full cells exhibit excellent electrochemical performance in deep eutectic-based electrolytes.This work presents an effective strategy for extending the cycle life of SiO anodes by designing a new SN-based deep eutectic electrolyte.展开更多
Lithium-ion batteries(LIBs)have greatly facilitated our daily lives since 1990s[1,2].To meet the ever-increasing demand on energy density,Li metal is seen as the ultimate anode because of its ultra-high specific capac...Lithium-ion batteries(LIBs)have greatly facilitated our daily lives since 1990s[1,2].To meet the ever-increasing demand on energy density,Li metal is seen as the ultimate anode because of its ultra-high specific capacity(3860 m Ah/g)and the lowest electrochemical potential(-3.04 V vs.the standard hydrogen electrode)[3–6].However,issues of Li metal anode,such as Li dendrite formation and large volume change during plating/stripping。展开更多
It is challenging for aqueous Zn-ion batteries(ZIBs)to achieve comparable low-temperature(low-T)performance due to the easy-frozen electrolyte and severe Zn dendrites.Herein,an aqueous electrolyte with a low freezing ...It is challenging for aqueous Zn-ion batteries(ZIBs)to achieve comparable low-temperature(low-T)performance due to the easy-frozen electrolyte and severe Zn dendrites.Herein,an aqueous electrolyte with a low freezing point and high ionic conductivity is proposed.Combined with molecular dynamics simulation and multi-scale interface analysis(time of flight secondary ion mass spectrometry threedimensional mapping and in-situ electrochemical impedance spectroscopy method),the temperature independence of the V_(2)O_(5)cathode and Zn anode is observed to be opposite.Surprisingly,dominated by the solvent structure of the designed electrolyte at low temperatures,vanadium dissolution/shuttle is significantly inhibited,and the zinc dendrites caused by this electrochemical crosstalk are greatly relieved,thus showing an abnormal temperature inversion effect.Through the disclosure and improvement of the above phenomena,the designed Zn||V_(2)O_(5)full cell delivers superior low-T performance,maintaining almost 99%capacity retention after 9500 cycles(working more than 2500 h)at-20°C.This work proposes a kind of electrolyte suitable for low-T ZIBs and reveals the inverse temperature dependence of the Zn anode,which might offer a novel perspective for the investigation of low-T aqueous battery systems.展开更多
Single crystallization has proven to be effective in enhancing the capacity and stability of Ni-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(SNCM)cathode materials,particularly at high cut-off voltages.Nevertheless,the synthesi...Single crystallization has proven to be effective in enhancing the capacity and stability of Ni-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(SNCM)cathode materials,particularly at high cut-off voltages.Nevertheless,the synthesis of high-quality single-crystal particles remains challenging because of severe particle agglomeration and irregular morphologies.Moreover,the limited kinetics of solid-phase Li^(+)diffusion pose a significant concern because of the extended diffusion path in large single-crystal particles.To address these challenges,we developed a Tb-doped single-crystal LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(SNCM-Tb)cathode material using a straightforward mixed molten salt sintering process.The Tb-doped Ni-rich single crystals presented a quasi-spherical morphology,which is markedly different from those reported in previous studies.Tb^(4+)oping significantly enhanced the dynamic transport of Li^(+)ions in the layered oxide phase by reducing the Ni valence state and creating Li vacancies.A SNCM-Tb material with 1 at%Tb doping shows a Li^(+)diffusion coefficient up to more than 9 times higher than pristine SNCM in the non-diluted state.In situ X-ray diffraction analysis demonstrated a significantly facilitated H1-H2-H3 phase transition in the SNCM-Tb materials,thereby enhancing their rate capacity and structural stability.SNCM-Tb exhibited a reversible capacity of 186.9 mA h g^(-1)at 5 C,retaining 94.6%capacity after 100 cycles at 0.5 C under a 4,5 V cut-off.Our study elucidates the Tb^(4+)doping mechanisms and proposes a scalable method for enhancing the performance of single-crystal Ni-rich NCM materials.展开更多
Nucleophile oxidation reaction(NOR), represented by ethanol oxidation reaction(EOR), is a promising pathway to replace oxygen evolution reaction(OER). EOR can effectively reduce the driving voltage of hydrogen product...Nucleophile oxidation reaction(NOR), represented by ethanol oxidation reaction(EOR), is a promising pathway to replace oxygen evolution reaction(OER). EOR can effectively reduce the driving voltage of hydrogen production in direct water splitting. In this work, large current and high efficiency of EOR on a Ni, Fe layered double hydroxide(NiFe-LDH) catalyst were simultaneously achieved by a facile fluorination strategy. F in NiFe-LDH can reduce the activation energy of the dehydrogenation reaction, thus promoting the deprotonation process of NiFe-LDH to achieve a lower EOR onset potential. It also weakens the absorption of OH-and nucleophile electrooxidation products on the surface of NiFe-LDH at a higher potential, achieving a high current density and EOR selectivity, according to density functional theory calculations. Based on our experiment results, the optimized fluorinated NiFe-LDH catalyst achieves a low potential of 1.386 V to deliver a 10 mA cm^(-2)EOR. Moreover, the Faraday efficiency is greater than 95%, with a current density ranging from 10 to 250 mA cm^(-2). This work provides a promising pathway for an efficient and cost-effective NOR catalyst design for economic hydrogen production.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.22075064,52302234,52272241)Zhejiang Provincial Natural Science Foundation of China under Grant No.LR24E020001+2 种基金Natural Science of Heilongjiang Province(No.LH2023B009)China Postdoctoral Science Foundation(2022M710950)Heilongjiang Postdoctoral Fund(LBH-Z21131),National Key Laboratory Projects(No.SYSKT20230056).
文摘To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming alternative.Among the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale applications.However,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their applications.This review provides a comprehensive overview of recent research advancements in OICSEs.Specifically,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically discussed.The lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic perspective.Besides,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of OICSEs.Finally,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.
基金supported by the National Key R&D Program of China(2021YFB2400400)the National Natural Science Foundation of China(Grant No.22379120,22179085)+5 种基金the Key Research and Development Plan of Shanxi Province(China,Grant No.2018ZDXM-GY-135,2021JLM-36)the National Natural Science Foundation of China(Grant No.22108218)the“Young Talent Support Plan”of Xi’an Jiaotong University(71211201010723)the Qinchuangyuan Innovative Talent Project(QCYRCXM-2022-137)the“Young Talent Support Plan”of Xi’an Jiaotong University(HG6J003)the“1000-Plan program”of Shaanxi Province。
文摘The insurmountable charge transfer impedance at the Li metal/solid polymer electrolytes(SPEs)interface at room temperature as well as the ascending risk of short circuits at the operating temperature higher than the melting point,dominantly limits their applications in solid-state batteries(SSBs).Although the inorganic filler such as CeO_(2)nanoparticle content of composite solid polymer electrolytes(CSPEs)can significantly reduce the enormous charge transfer impedance at the Li metal/SPEs interface,we found that the required content of CeO_(2)nanoparticles in SPEs varies for achieving a decent interfacial charge transfer impedance and the bulk ionic conductivity in CSPEs.In this regard,a sandwich-type composited solid polymer electrolyte with a 10%CeO_(2)CSPEs interlayer sandwiched between two 50%CeO_(2)CSPEs thin layers(sandwiched CSPEs)is constructed to simultaneously achieve low charge transfer impedance and superior ionic conductivity at 30℃.The sandwiched CSPEs allow for stable cycling of Li plating and stripping for 1000 h with 129 mV polarized voltage at 0.1 mA cm^(-2)and 30℃.In addition,the LiFePO_(4)/Sandwiched CSPEs/Li cell also exhibits exceptional cycle performance at 30℃and even elevated120℃without short circuits.Constructing multi-layered CSPEs with optimized contents of the inorganic fillers can be an efficient method for developing all solid-state PEO-based batteries with high performance at a wide range of temperatures.
基金supported by National Key R&D Program of China(2021YFA1502803)the National Natural Science Foundation of China(NSFC)(21972066,91745202)+3 种基金NSFC-Royal Society Joint Program(21661130149)L.P.thanks the Royal Society and Newton Fund for a Royal Society-Newton Advanced Fellowshipsupported by the Research Funds for the Frontiers Science Centre for Critical Earth Material Cycling,Nanjing Universitya Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘Recent advances in utilizing ^(17)O isotopic labeling methods for solid-state nuclear magnetic resonance(NMR)investigations of metal oxides for lithium-ion batteries have yielded extensive insights into their structural and dynamic details.Herein,we commence with a brief introduction to recent research on lithium-ion battery oxide materials studied using ^(17)O solid-state NMR spectroscopy.Then we delve into a review of ^(17)O isotopic labeling methods for tagging oxygen sites in both the bulk and surfaces of metal oxides.At last,the unresolved problems and the future research directions for advancing the ^(17)O labeling technique are discussed.
基金financially supported by the National Natural Science Foundation of China(52072036,52272187)the China Petroleum&Chemical Corporation(SINOPEC)project(223128).
文摘All-solid-state batteries(ASSBs)assembled with sulfide solid electrolytes(SSEs)and nickel(Ni)-rich oxide cathode materials are expected to achieve high energy density and safety,representing potential candidates for the next-generation energy storage systems.However,interfacial issues between SSEs and Nirich oxide cathode materials,attributed to space charge layer,interfacial side reactions,and mechanical contact failure,significantly restrict the performances of ASSBs.The interface degradation is closely related to the components of the composite cathode and the process of electrode fabrication.Focusing on the influencing factors of interface compatibility between SSEs and Ni-rich oxide cathode,this article systematically discusses how cathode active materials(CAMs),electrolytes,conductive additives,binders,and electrode fabrication impact the interface compatibility.In addition,the strategies for the compatibility modification are reviewed.Furthermore,the challenges and prospects of intensive research on the degradation and modification of the SSE/Ni-rich cathode material interface are discussed.This review is intended to inspire the development of high-energy-density and high-safety all-solid-state batteries.
基金funded by the Key Research and Development Program of Shandong Province(2023CXPT069)Opening Funds of the State Key Laboratory of Building Safety and Built Environment(BSBE2022-EET-06)Innovation Project of Guangwei Group Academician Workstation(GWYS-2022-04)。
文摘Sodium metal batteries(SMBs)are promising candidates for next-generation energy storage devices owing to their excellent safety performance and natural abunda nce of sodium.However,the insurmountable obstacles of dendrite formation and quick capacity decay are caused by an unstable and inhomogeneous solid electrolyte interphase that resulted from the immediate interactions between the Na metal anode and organic liquid electrolyte.Herein,a customised glass fibre separator coupled with chitosan(CS@GF)was developed to modulate the sodium ion(Na^(+))flux.The CS@GF separator facilitates the Na+homogeneous deposition on the anode side through redistribution at the chitosan polyactive sites and by inhibiting the decomposition of the electrolyte to robust solid electrolyte interphase(SEI)formation.Multiphysics simulations show that chitosan incorporated into SMBs through the separator can make the local electric field around the anode uniform,thus facilitating the transfer of cations.Na|Na symmetric cells utilising a CS@GF separator exhibited an outstanding cycle stability of over 600 h(0.5 mA cm^(-2)).Meanwhile,the Na|Na_(3)V_(5)(PO_(4))_(3)full cell exhibited excellent fast-charging performance(93.47%capacity retention after 1500 cycles at 5C).This study presents a promising strategy for inhibiting dendrite growth and realizes stable Na metal batteries,which significantly boosts the development of high-performance SMBs.
基金financially supported by the National Natural Science Foundation of China(52372191)the Natural Science Foundation of Fujian Province(2023J05047)+1 种基金the Natural Science Foundation of Xiamen,China(3502Z202372036)the support of the High-Performance Computing Center(HPCC)at Harbin Institute of Technology on first-principles calculations.
文摘Achieving simultaneous fast-charging capabilities and low-temperature adaptability in graphite-based lithium-ion batteries(LIBs)with an acceptable cycle life remains challenging.Herein,an ether-based electrolyte with temperature-adaptive Li^(+)solvation structure is designed for graphite,and stable Li^(+)/solvent co-intercalation has been achieved at subzero.As revealed by in-situ variable temperature(-20℃)X-ray diffraction(XRD),the poor compatibility of graphite in ether-based electrolyte at 25℃is mainly due to the continuous electrolyte decomposition and the in-plane rearrangement below0.5 V.Former results in a significant irreversible capacity,while latter maintains graphite in a prolonged state of extreme expansion,ultimately leading to its exfoliation and failure.In contrast,low temperature triggers the rearra ngement of Li^(+)solvation structu re with stronger Li^(+)/solvent binding energy and sho rter Li^(+)-O bond length,which is conducive for reversible Li^(+)/solvent co-intercalation and reducing the time of graphite in an extreme expansion state.In addition,the co-intercalation of solvents minimizes the interaction between Li-ions and host graphite,endowing graphite with fast diffusion kinetics.As expected,the graphite anode delivers about 84%of the capacity at room temperature at-20℃.Moreover,within6 min,about 83%,73%,and 43%of the capacity could be charged at 25,-20,and-40℃,respectively.
基金supported by the National Natural Science Foundation of China(22279026)the National Key Research and Development Program of China(2022YFE0138900)+2 种基金the Young Elite Scientist sponsorship program by CAST(no.20200148)the Natural Science Funds of Heilongjiang Province(YQ2021B003)the Fundamental Research Funds for the Central Universities(grant no.HIT.OCEF.2022017).
文摘Micrometer-sized silicon oxide(SiO)anodes encounter challenges in large-scale applications due to significant volume expansion during the alloy/de-alloy process.Herein,an innovative deep eutectic electrolyte derived from succinonitrile is introduced to enhance the cycling stability of SiO anodes.Density functional theory calculations validate a robust ion-dipole interaction between lithium ions(Li^(+))and succinonitrile(SN).The cosolvent fluoroethylene carbonate(FEC)optimizes the Li^(+)solvation structure in the SN-based electrolyte with its weakly solvating ability.Molecular dynamics simulations investigate the regulating mechanism of ion-dipole and cation-anion interaction.The unique Li^(+)solvation structure,enriched with FEC and TFSI^(-),facilitates the formation of an inorganic-organic composite solid electrolyte interphase on SiO anodes.Micro-CT further detects the inhibiting effect on the SiO volume expansion.As a result,the SiO|LiCoO_(2) full cells exhibit excellent electrochemical performance in deep eutectic-based electrolytes.This work presents an effective strategy for extending the cycle life of SiO anodes by designing a new SN-based deep eutectic electrolyte.
基金financial support by the National Natural Science Foundation of China(No.51802224)“Shanghai Rising-Star Program”(19QA1409300)Shanghai Aerospace Science and Technology Innovation Fundation(SISP2018)。
文摘Lithium-ion batteries(LIBs)have greatly facilitated our daily lives since 1990s[1,2].To meet the ever-increasing demand on energy density,Li metal is seen as the ultimate anode because of its ultra-high specific capacity(3860 m Ah/g)and the lowest electrochemical potential(-3.04 V vs.the standard hydrogen electrode)[3–6].However,issues of Li metal anode,such as Li dendrite formation and large volume change during plating/stripping。
基金financially supported by the National Natural Science Foundation of China(52372191)the Natural Science Foundation of Xiamen,China(3502Z202372036)+1 种基金the China Postdoctoral Science Foundation(2022TQ0282)the support of the High-Performance Computing Center(HPCC)at Harbin Institute of Technology on first-principles calculations。
文摘It is challenging for aqueous Zn-ion batteries(ZIBs)to achieve comparable low-temperature(low-T)performance due to the easy-frozen electrolyte and severe Zn dendrites.Herein,an aqueous electrolyte with a low freezing point and high ionic conductivity is proposed.Combined with molecular dynamics simulation and multi-scale interface analysis(time of flight secondary ion mass spectrometry threedimensional mapping and in-situ electrochemical impedance spectroscopy method),the temperature independence of the V_(2)O_(5)cathode and Zn anode is observed to be opposite.Surprisingly,dominated by the solvent structure of the designed electrolyte at low temperatures,vanadium dissolution/shuttle is significantly inhibited,and the zinc dendrites caused by this electrochemical crosstalk are greatly relieved,thus showing an abnormal temperature inversion effect.Through the disclosure and improvement of the above phenomena,the designed Zn||V_(2)O_(5)full cell delivers superior low-T performance,maintaining almost 99%capacity retention after 9500 cycles(working more than 2500 h)at-20°C.This work proposes a kind of electrolyte suitable for low-T ZIBs and reveals the inverse temperature dependence of the Zn anode,which might offer a novel perspective for the investigation of low-T aqueous battery systems.
基金financial support from the horizontal project“Research and Application of All-Solid-State Lithium-Ion Battery Technology” (MH20220255)from Zibo Torch Energy Co.,Ltdthe Heilongjiang Touyan Innovation Team Program (HITTY20190033)+1 种基金Zibo Torch Energy Co.,Ltd.China State Shipbuilding Corporation,Limited for their financial support。
文摘Single crystallization has proven to be effective in enhancing the capacity and stability of Ni-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(SNCM)cathode materials,particularly at high cut-off voltages.Nevertheless,the synthesis of high-quality single-crystal particles remains challenging because of severe particle agglomeration and irregular morphologies.Moreover,the limited kinetics of solid-phase Li^(+)diffusion pose a significant concern because of the extended diffusion path in large single-crystal particles.To address these challenges,we developed a Tb-doped single-crystal LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(SNCM-Tb)cathode material using a straightforward mixed molten salt sintering process.The Tb-doped Ni-rich single crystals presented a quasi-spherical morphology,which is markedly different from those reported in previous studies.Tb^(4+)oping significantly enhanced the dynamic transport of Li^(+)ions in the layered oxide phase by reducing the Ni valence state and creating Li vacancies.A SNCM-Tb material with 1 at%Tb doping shows a Li^(+)diffusion coefficient up to more than 9 times higher than pristine SNCM in the non-diluted state.In situ X-ray diffraction analysis demonstrated a significantly facilitated H1-H2-H3 phase transition in the SNCM-Tb materials,thereby enhancing their rate capacity and structural stability.SNCM-Tb exhibited a reversible capacity of 186.9 mA h g^(-1)at 5 C,retaining 94.6%capacity after 100 cycles at 0.5 C under a 4,5 V cut-off.Our study elucidates the Tb^(4+)doping mechanisms and proposes a scalable method for enhancing the performance of single-crystal Ni-rich NCM materials.
基金the financial support from the National Natural Science Foundation of China (22197121)Knowledge Innovation Program of Wuhan-Basic Research (2022010801010202)Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology (FC202201)。
文摘Nucleophile oxidation reaction(NOR), represented by ethanol oxidation reaction(EOR), is a promising pathway to replace oxygen evolution reaction(OER). EOR can effectively reduce the driving voltage of hydrogen production in direct water splitting. In this work, large current and high efficiency of EOR on a Ni, Fe layered double hydroxide(NiFe-LDH) catalyst were simultaneously achieved by a facile fluorination strategy. F in NiFe-LDH can reduce the activation energy of the dehydrogenation reaction, thus promoting the deprotonation process of NiFe-LDH to achieve a lower EOR onset potential. It also weakens the absorption of OH-and nucleophile electrooxidation products on the surface of NiFe-LDH at a higher potential, achieving a high current density and EOR selectivity, according to density functional theory calculations. Based on our experiment results, the optimized fluorinated NiFe-LDH catalyst achieves a low potential of 1.386 V to deliver a 10 mA cm^(-2)EOR. Moreover, the Faraday efficiency is greater than 95%, with a current density ranging from 10 to 250 mA cm^(-2). This work provides a promising pathway for an efficient and cost-effective NOR catalyst design for economic hydrogen production.
