Lithium metal batteries(LMBs)have been regarded as one of the most promising alternatives in the post-lithium battery era due to their high energy density,which meets the needs of light-weight electronic devices and l...Lithium metal batteries(LMBs)have been regarded as one of the most promising alternatives in the post-lithium battery era due to their high energy density,which meets the needs of light-weight electronic devices and long-range electric vehicles.However,technical barriers such as dendrite growth and poor Li plating/stripping reversibility severely hinder the practical application of LMBs.However,lithium nitrate(LiNO_(3))is found to be able to stabilize the Li/electrolyte interface and has been used to address the above challenges.To date,considerable research efforts have been devoted toward understanding the roles of LiNO_(3) in regulating the surface properties of Li anodes and toward the development of many effective strategies.These research efforts are partially mentioned in some articles on LMBs and yet have not been reviewed systematically.To fill this gap,we discuss the recent advances in fundamental and technological research on LiNO_(3) and its derivatives for improving the performances of LMBs,particularly for Li-sulfur(S),Li-oxygen(O),and Li-Li-containing transition-metal oxide(LTMO)batteries,as well as LiNO_(3)-containing recipes for precursors in battery materials and interphase fabrication.This review pays attention to the effects of LiNO_(3) in lithium-based batteries,aiming to provide scientific guidance for the optimization of electrode/electrolyte interfaces and enrich the design of advanced LMBs.展开更多
Li-metal batteries(LMBs)regain research prominence owing to the ever-increasing high-energy requirements.Commercially available carbonate electrolytes exhibit unfavourable parasitic reactions with Limetal anode(LMA),l...Li-metal batteries(LMBs)regain research prominence owing to the ever-increasing high-energy requirements.Commercially available carbonate electrolytes exhibit unfavourable parasitic reactions with Limetal anode(LMA),leading to the formation of unstable solid electrolyte interphase(SEI)and the breed of Li dendrites/dead Li.Significantly,lithium nitrate(LiNO_(3)),an excellent film-forming additive,proves crucial to construct a robust Li_(3)N/Li_(2)O/Li_(x)NO_(y)-rich SEI after combining with ether-based electrolytes.Thus,the given challenge leads to natural ideas which suggest the incorporation of LiNO_(3) into commercial carbonate for practical LMBs.Regrettably,LiNO_(3) demonstrates limited solubility(~800 ppm)in commercial carbonate electrolytes.Thence,developing stable SEI and dendrite-free LMA with the incorporation of LiNO_(3) into carbonate electrolytes is an efficacious strategy to realize robust LMBs via a scalable and cost-effective route.Therefore,this review unravels the grievances between LMA,LiNO_(3)and carbonate electrolytes,and enables a comprehensive analysis of LMA stabilizing mechanism with LiNO_(3),dissolution principle of LiNO_(3) in carbonate electrolytes,and LiNO_(3) introduction strategies.This review converges attention on a point that the LiNO_(3)-introduction into commercial carbonate electrolytes is an imperious choice to realize practical LMBs with commercial 4 V layered cathode.展开更多
Lithium–sulfur(Li–S)batteries are promising candidates for next-generation energy storage systems,but practical use is limited by polysulfide(PS)shuttling and Li metal anode instability.Lithium nitrate(LiNO_(3))is w...Lithium–sulfur(Li–S)batteries are promising candidates for next-generation energy storage systems,but practical use is limited by polysulfide(PS)shuttling and Li metal anode instability.Lithium nitrate(LiNO_(3))is widely used to mitigate these issues;however,its interfacial effects across the anode,electrolyte,and cathode during operation are not fully understood.Here,operando optical microscopy with a custom side-by-side cell enables simultaneous monitoring of the Li anode,liquid electrolyte,and sulfur cathode in a single field of view under conditions with and without LiNO_(3).In the absence of LiNO_(3),the Li surface undergoes rough stripping and fragmented,non-coalescent deposition,accompanied by PS-induced corrosion and accumulation of parasitic byproducts at the anode-electrolyte interface.Redness Intensity(RI),introduced to quantify electrolyte-phase PS dynamics,indicates sustained transport toward the anode and delayed conversion to elemental sulfur.By contrast,LiNO_(3)induces uniform Li stripping and the growth of aggregated,interconnected deposits,while mitigating PS crossover and promoting efficient sulfur crystallization at the cathode.Complementary SEM-EDS,UV–vis,XPS,TXM,and CT analyses corroborate these observations.By elucidating the multifunctional role of LiNO_(3),this study clarifies the interfacial dynamics that govern Li–S battery performance.展开更多
Lithium metal batteries(LMBs)are considered to be one of the most promising high-energy-density battery systems.However,their practical application in carbonate electrolytes is hampered by lithium dendrite growth,resu...Lithium metal batteries(LMBs)are considered to be one of the most promising high-energy-density battery systems.However,their practical application in carbonate electrolytes is hampered by lithium dendrite growth,resulting in short cycle life.Herein,an electrolyte regulation strategy is developed to improve the cyclability of LMBs in carbonate electrolytes by introducing LiNO3 using trimethyl phosphate with a slightly higher donor number compared to NO_(3)^(-)as a solubilizer.This not only allows the formaion of Li^(+)-coordinated NO3 but also achieves the regulation of electrolyte solvation structures,leading to the formation of robust and ion-conductive solid-electrolyte interphase films with inorganic-rich inner and organic-rich outer layers on the Li metal anodes.As a result,high Coulombic efficiency of 99.1%and stable plating/stripping cycling of Li metal anode in LilCu cells were realized.Furthermore,excellent performance was also demonstrated in Li||LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(NCM83)full cells and Cul/NCM83 anodefree cells using high mass-loading cathodes.This work provides a simple interphase engineering strategy through regulating the electrolyte solvation structures for high-energy-density LMBs.展开更多
An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium brom...An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium bromide(CTAB),a cationic surfactant,is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating.In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO_(3)^(−)/FSI−anions in the EDL region due to the positively charged CTA^(+).In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI,which helps improve the kinetics of Li^(+)transfer,lower the charge transfer activation energy,and homogenize Li deposition.As a result,the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm^(-2) with a capacity of 1 mAh cm^(-2).Moreover,Li||LiFePO_(4) and Li||LiCoO_(2) with a high cathode mass loading of>10 mg cm^(-2) can be stably cycled over 180 cycles.展开更多
It is challenging to balance the cyclability and rate capability of single crystal nickel-rich cathode materials(Ni>0.8).Multicomponent oxides by spray pyrolysis shows potential as highly-reactive precursors to syn...It is challenging to balance the cyclability and rate capability of single crystal nickel-rich cathode materials(Ni>0.8).Multicomponent oxides by spray pyrolysis shows potential as highly-reactive precursors to synthesize single crystal nickel-rich cathode at lower temperature,yet Ni^(2+)will severely inhibit particle growth when Ni content exceeds 0.9.Herein,lithium nitrate(LiNO_(3))with low melting point and strong oxidation is introduced as collaborate lithium salts for fabrication of well-dispersed submicron and micron single crystal LiNi_(0.9)Co_(0.055)Mn_(0.045)O_(2)(NCM90)cathode without extra unit operation.By changing amount of LiNO_(3),particle size regulation is realized and cation disorder can be diminished.The as-prepared material with optimal content of 4 wt%LiNO_(3)(NCM90-4 LN)displays the most appropriate particle size(1μm)with approximately stoichiometric structure,and presents better kinetics characterization of lithium-ion diffusion(15%higher than NCM90)and good electrochemical performance with specific discharge capacity of 220.6 and 173.8 mAh g^(-1) at 0.1 C and 10 C at room temperature,respectively.This work broadens the conventional research methodology of size regulation for single crystal Ni-rich cathode materials and is indispensable for the development of designing principal of nickel-rich cathode materials for lithium-ion batteries.展开更多
High-voltage lithium metal batteries(LMBs)have been considered promising next-generation highenergy-density batteries.However,commercial carbonate electrolytes can scarcely be employed in LMBs owing to their poor comp...High-voltage lithium metal batteries(LMBs)have been considered promising next-generation highenergy-density batteries.However,commercial carbonate electrolytes can scarcely be employed in LMBs owing to their poor compatibility with metallic lithium.N,N-dimethylacrylamide(DMAA)-a crosslinkable solubilizer with a high Gutmann donor number-is employed to facilitate the dissolution of insoluble lithium nitrate(LiNO3)in carbonate-based electrolytes and to form gel polymer electrolytes(GPEs)through in situ polymerization.The Lit solvation structure of the GPEs is regulated using LiNO3 and DMAA,which suppresses the decomposition of LiPFe and facilitates the formation of an inorganic-rich solid electrolyte interface.Consequently,the Coulombic efficiency(CE)of the LillCu cell assembled with a GPE increases to 98.5%at room temperature,and the high-voltage LillNCM622 cell achieves a capacity retention of 80.1%with a high CE of 99.5%after 400 cycles.The bifunctional polymer electrolytes are anticipated to pave the way for next-generation high-voltage LMBs.展开更多
With the increasing demand for high energy density energy storage device,Li metal has received intensive attention for its ultrahigh capacity and the lowest redox potential.LiNO_(3)is widely used as electrolyte additi...With the increasing demand for high energy density energy storage device,Li metal has received intensive attention for its ultrahigh capacity and the lowest redox potential.LiNO_(3)is widely used as electrolyte additive for ether electrolyte,which can improve the cycle performance of Li metal anode.Compared to ethers,carbonates are more suitable for Li metal batteries with high voltage cathode because they have a wider electrochemical window.However,LiNO_(3)performs poor solubility in carbonate electrolyte,restricting its application in high voltage Li battery.Herein,we presented a facile method to introduce abundant LiNO_(3)additive to carbonate electrolyte system by introducing LiNO_(3)-PAN es as the interlayer of the cell.LiNO_(3)-PAN es is in sufficient contact with the electrolyte so that it can continuously releases LiNO_(3)to assist the formation of Li_(2)N_(2)O_(2)-rich single nitrogenous component SEI layer on Li surface.With the help of LiNO_(3)-PAN es,Li metal anode shows excellent cycle stability even at a high current density of 4mA/cm^(2),so that the cycle performance of the full cells was significantly improved,whether in the anode-free Cu||LFP cell or the Li||NCM622 cell.展开更多
Lithium(Li)metal is one of the most promising anodes for next-generation energy storage systems.However,the Li dendrite formation and unstable solid-electrolyte interface(SEI)have hindered its further application.Lith...Lithium(Li)metal is one of the most promising anodes for next-generation energy storage systems.However,the Li dendrite formation and unstable solid-electrolyte interface(SEI)have hindered its further application.Lithium nitrate(LiNO3)is extensively used as an effective electrolyte additive in ether-based electrolytes to improve the stability of lithium metal.Nevertheless,it is rarely utilized in carbonate electrolytes due to its low solubility.Here,a novel gel polymer electrolyte(GPE)consisting of poly(vinylidene fluoride)(PVDF),poly(methyl methacrylate)(PMMA),poly(ethylene oxide)(PEO)with LiN03 additive is proposed to solve this issue.In this GPE,polyether-based PEO serves as a matrix for dissolving LiNO3 which can be decomposed into a fast Li-ion conductor(Li3N)in conventional carbonate electrolytes to enhance the stability and Li^+conductivity of the SEI film.As a result,dendrite formation is effectively suppressed,and a significantly improved average Coulombic efficiency(CE)of 97.2%in Li-Cu cell is achieved.By using this novel GPE coupled with Li anode and LiNi0.5Mn0.3Co0.2O2(NMC532),excellent capacity retention of 94.1%and high average CE of over 99.2%are obtained after 200 cycles at 0.5 C.This work presents fresh insight into practical modification strategies on high-voltage Li metal batteries.展开更多
High-purity straight and discrete multiwalled boron nitride nanotubes （BNNTs） were grown via a boron oxide vapor reaction with ammonia using LiNO3 as a promoter. Only a trace amount of boron oxide was detected as an...High-purity straight and discrete multiwalled boron nitride nanotubes （BNNTs） were grown via a boron oxide vapor reaction with ammonia using LiNO3 as a promoter. Only a trace amount of boron oxide was detected as an impurity in the BNNTs by energy-dispersive X-ray （EDX） and Raman spectroscopies. Boron oxide vapor was generated from a mixture of B, FeO, and MgO powders heated to 1,150 ℃, and it was transported to the reaction zone by flowing ammonia. Lithium nitrate was applied to the upper side of a BN bar from a water solution. The bar was placed along a temperature gradient zone in a horizontal tubular furnace. BNNTs with average diameters of 30-50 nm were mostly observed in a temperature range of 1,280-1,320 ℃. At higher temperatures, curled polycrystalline BN fibers appeared. Above 1,320 ℃, the number of BNNTs drastically decreased, whereas the quantity and diameter of the fibers increased. The mechanism of BNNT and fiber growth is proposed and discussed.展开更多
基金supported by the Yunnan Fundamental Research Projects(Grant Nos.202401AU070163 and 202501AT070298)the Yunnan Engineering Research Center Innovation Ability Construction and Enhancement Projects(Grant No.2023-XMDJ-00617107)+5 种基金the University Service Key Industry Project of Yunnan Province(Grant No.FWCY-ZD2024005)the Expert Workstation Support Project of Yunnan Province(Grant No.202405AF140069)the Scientific Research Foundation of Kunming University of Science and Technology(Grant No.20220122)the Analysis and Test Foundation of Kunming University of Science and Technology(Grant No.2023T20220122)the Natural Science Foundation of Inner Mongolia Autonomous Region of China(Grant No.2025QN02057)the Ordos City Strategic Pioneering Science and Technology Special Program for New Energy(Grant No.DC2400003365).
文摘Lithium metal batteries(LMBs)have been regarded as one of the most promising alternatives in the post-lithium battery era due to their high energy density,which meets the needs of light-weight electronic devices and long-range electric vehicles.However,technical barriers such as dendrite growth and poor Li plating/stripping reversibility severely hinder the practical application of LMBs.However,lithium nitrate(LiNO_(3))is found to be able to stabilize the Li/electrolyte interface and has been used to address the above challenges.To date,considerable research efforts have been devoted toward understanding the roles of LiNO_(3) in regulating the surface properties of Li anodes and toward the development of many effective strategies.These research efforts are partially mentioned in some articles on LMBs and yet have not been reviewed systematically.To fill this gap,we discuss the recent advances in fundamental and technological research on LiNO_(3) and its derivatives for improving the performances of LMBs,particularly for Li-sulfur(S),Li-oxygen(O),and Li-Li-containing transition-metal oxide(LTMO)batteries,as well as LiNO_(3)-containing recipes for precursors in battery materials and interphase fabrication.This review pays attention to the effects of LiNO_(3) in lithium-based batteries,aiming to provide scientific guidance for the optimization of electrode/electrolyte interfaces and enrich the design of advanced LMBs.
基金the support by the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2019R01006)the National Natural Science Foundation of China(NSFC:12205252)+3 种基金A Project Supported by Scientific Research Fund of Zhejiang Provincial Education Department(Y202250795)the Research Funds of Institute of Zhejiang University-Quzhou,the Basic Public Welfare Research Special Project of Zhejiang Province(LZY22B040001)the Science and Technology Project of Quzhou Research Institute,Zhejiang University(IZQ2021KJ2032)the Independent Scientific Research Project of Quzhou Research Institute,Zhejiang University(IZQ2021RCZX007)。
文摘Li-metal batteries(LMBs)regain research prominence owing to the ever-increasing high-energy requirements.Commercially available carbonate electrolytes exhibit unfavourable parasitic reactions with Limetal anode(LMA),leading to the formation of unstable solid electrolyte interphase(SEI)and the breed of Li dendrites/dead Li.Significantly,lithium nitrate(LiNO_(3)),an excellent film-forming additive,proves crucial to construct a robust Li_(3)N/Li_(2)O/Li_(x)NO_(y)-rich SEI after combining with ether-based electrolytes.Thus,the given challenge leads to natural ideas which suggest the incorporation of LiNO_(3) into commercial carbonate for practical LMBs.Regrettably,LiNO_(3) demonstrates limited solubility(~800 ppm)in commercial carbonate electrolytes.Thence,developing stable SEI and dendrite-free LMA with the incorporation of LiNO_(3) into carbonate electrolytes is an efficacious strategy to realize robust LMBs via a scalable and cost-effective route.Therefore,this review unravels the grievances between LMA,LiNO_(3)and carbonate electrolytes,and enables a comprehensive analysis of LMA stabilizing mechanism with LiNO_(3),dissolution principle of LiNO_(3) in carbonate electrolytes,and LiNO_(3) introduction strategies.This review converges attention on a point that the LiNO_(3)-introduction into commercial carbonate electrolytes is an imperious choice to realize practical LMBs with commercial 4 V layered cathode.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(RS-2024-00455177)the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(RS-2025-00518953)+1 种基金the National Research Council of Science&Technology(NST)grant by the Korea government(MSIT)(No.GTL24012-000)This study was also supported by LG Energy Solution.Jong-Seong Bae acknowledges the support by the Ministry of Science and ICT in Korea via KBSI(Grant No.C524100).
文摘Lithium–sulfur(Li–S)batteries are promising candidates for next-generation energy storage systems,but practical use is limited by polysulfide(PS)shuttling and Li metal anode instability.Lithium nitrate(LiNO_(3))is widely used to mitigate these issues;however,its interfacial effects across the anode,electrolyte,and cathode during operation are not fully understood.Here,operando optical microscopy with a custom side-by-side cell enables simultaneous monitoring of the Li anode,liquid electrolyte,and sulfur cathode in a single field of view under conditions with and without LiNO_(3).In the absence of LiNO_(3),the Li surface undergoes rough stripping and fragmented,non-coalescent deposition,accompanied by PS-induced corrosion and accumulation of parasitic byproducts at the anode-electrolyte interface.Redness Intensity(RI),introduced to quantify electrolyte-phase PS dynamics,indicates sustained transport toward the anode and delayed conversion to elemental sulfur.By contrast,LiNO_(3)induces uniform Li stripping and the growth of aggregated,interconnected deposits,while mitigating PS crossover and promoting efficient sulfur crystallization at the cathode.Complementary SEM-EDS,UV–vis,XPS,TXM,and CT analyses corroborate these observations.By elucidating the multifunctional role of LiNO_(3),this study clarifies the interfacial dynamics that govern Li–S battery performance.
基金supported by the National Key Research and Development Program of China(No.2019YFE0118800).
文摘Lithium metal batteries(LMBs)are considered to be one of the most promising high-energy-density battery systems.However,their practical application in carbonate electrolytes is hampered by lithium dendrite growth,resulting in short cycle life.Herein,an electrolyte regulation strategy is developed to improve the cyclability of LMBs in carbonate electrolytes by introducing LiNO3 using trimethyl phosphate with a slightly higher donor number compared to NO_(3)^(-)as a solubilizer.This not only allows the formaion of Li^(+)-coordinated NO3 but also achieves the regulation of electrolyte solvation structures,leading to the formation of robust and ion-conductive solid-electrolyte interphase films with inorganic-rich inner and organic-rich outer layers on the Li metal anodes.As a result,high Coulombic efficiency of 99.1%and stable plating/stripping cycling of Li metal anode in LilCu cells were realized.Furthermore,excellent performance was also demonstrated in Li||LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(NCM83)full cells and Cul/NCM83 anodefree cells using high mass-loading cathodes.This work provides a simple interphase engineering strategy through regulating the electrolyte solvation structures for high-energy-density LMBs.
基金financial support from Singapore Ministry of Education under its AcRF Tier 2 Grant No MOE-T2EP10123-0001Singapore National Research Foundation Investigatorship under Grant No NRF-NRFI08-2022-0009Academic Excellence Foundation of BUAA for PhD Students(applicant:Hongfei Xu).
文摘An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium bromide(CTAB),a cationic surfactant,is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating.In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO_(3)^(−)/FSI−anions in the EDL region due to the positively charged CTA^(+).In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI,which helps improve the kinetics of Li^(+)transfer,lower the charge transfer activation energy,and homogenize Li deposition.As a result,the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm^(-2) with a capacity of 1 mAh cm^(-2).Moreover,Li||LiFePO_(4) and Li||LiCoO_(2) with a high cathode mass loading of>10 mg cm^(-2) can be stably cycled over 180 cycles.
基金financially supported by the National Natural Science of China (Grant Nos. 51834008, 51874360)the National Key Research and Development Program of China (Grant No. 2018YFC1902205)。
文摘It is challenging to balance the cyclability and rate capability of single crystal nickel-rich cathode materials(Ni>0.8).Multicomponent oxides by spray pyrolysis shows potential as highly-reactive precursors to synthesize single crystal nickel-rich cathode at lower temperature,yet Ni^(2+)will severely inhibit particle growth when Ni content exceeds 0.9.Herein,lithium nitrate(LiNO_(3))with low melting point and strong oxidation is introduced as collaborate lithium salts for fabrication of well-dispersed submicron and micron single crystal LiNi_(0.9)Co_(0.055)Mn_(0.045)O_(2)(NCM90)cathode without extra unit operation.By changing amount of LiNO_(3),particle size regulation is realized and cation disorder can be diminished.The as-prepared material with optimal content of 4 wt%LiNO_(3)(NCM90-4 LN)displays the most appropriate particle size(1μm)with approximately stoichiometric structure,and presents better kinetics characterization of lithium-ion diffusion(15%higher than NCM90)and good electrochemical performance with specific discharge capacity of 220.6 and 173.8 mAh g^(-1) at 0.1 C and 10 C at room temperature,respectively.This work broadens the conventional research methodology of size regulation for single crystal Ni-rich cathode materials and is indispensable for the development of designing principal of nickel-rich cathode materials for lithium-ion batteries.
基金supported by the National Natural Science Foundation of China(51971250)China Postdoctoral Science Foundation(2023M733933)+1 种基金the Natural Science Foundation of Hunan Province(2023J40759)the State Key Laboratory of Powder Metallurgy at Central South University.
文摘High-voltage lithium metal batteries(LMBs)have been considered promising next-generation highenergy-density batteries.However,commercial carbonate electrolytes can scarcely be employed in LMBs owing to their poor compatibility with metallic lithium.N,N-dimethylacrylamide(DMAA)-a crosslinkable solubilizer with a high Gutmann donor number-is employed to facilitate the dissolution of insoluble lithium nitrate(LiNO3)in carbonate-based electrolytes and to form gel polymer electrolytes(GPEs)through in situ polymerization.The Lit solvation structure of the GPEs is regulated using LiNO3 and DMAA,which suppresses the decomposition of LiPFe and facilitates the formation of an inorganic-rich solid electrolyte interface.Consequently,the Coulombic efficiency(CE)of the LillCu cell assembled with a GPE increases to 98.5%at room temperature,and the high-voltage LillNCM622 cell achieves a capacity retention of 80.1%with a high CE of 99.5%after 400 cycles.The bifunctional polymer electrolytes are anticipated to pave the way for next-generation high-voltage LMBs.
基金supported by the National Key R&D Program of China(No.2022YFB2402600)National Natural Science Foundation of China(No.22279166)+1 种基金Basic and Applied Basic Research Foundation of Guangdong Province-Regional joint fund project(No.2022B1515120019)the Fundamental Research Funds for the Central Universities,Sun Yat-Sen University(Nos.22qntd0101 and 22dfx01).
文摘With the increasing demand for high energy density energy storage device,Li metal has received intensive attention for its ultrahigh capacity and the lowest redox potential.LiNO_(3)is widely used as electrolyte additive for ether electrolyte,which can improve the cycle performance of Li metal anode.Compared to ethers,carbonates are more suitable for Li metal batteries with high voltage cathode because they have a wider electrochemical window.However,LiNO_(3)performs poor solubility in carbonate electrolyte,restricting its application in high voltage Li battery.Herein,we presented a facile method to introduce abundant LiNO_(3)additive to carbonate electrolyte system by introducing LiNO_(3)-PAN es as the interlayer of the cell.LiNO_(3)-PAN es is in sufficient contact with the electrolyte so that it can continuously releases LiNO_(3)to assist the formation of Li_(2)N_(2)O_(2)-rich single nitrogenous component SEI layer on Li surface.With the help of LiNO_(3)-PAN es,Li metal anode shows excellent cycle stability even at a high current density of 4mA/cm^(2),so that the cycle performance of the full cells was significantly improved,whether in the anode-free Cu||LFP cell or the Li||NCM622 cell.
基金This work was financially supported by National Key R&D Program of China(No.2016 YFB0700600)Soft Science Research Project of Guangdong Province(No.2017B030301013)and Shenzhen Science and Technology Research Grant(No.ZDSYS201707281026184).
文摘Lithium(Li)metal is one of the most promising anodes for next-generation energy storage systems.However,the Li dendrite formation and unstable solid-electrolyte interface(SEI)have hindered its further application.Lithium nitrate(LiNO3)is extensively used as an effective electrolyte additive in ether-based electrolytes to improve the stability of lithium metal.Nevertheless,it is rarely utilized in carbonate electrolytes due to its low solubility.Here,a novel gel polymer electrolyte(GPE)consisting of poly(vinylidene fluoride)(PVDF),poly(methyl methacrylate)(PMMA),poly(ethylene oxide)(PEO)with LiN03 additive is proposed to solve this issue.In this GPE,polyether-based PEO serves as a matrix for dissolving LiNO3 which can be decomposed into a fast Li-ion conductor(Li3N)in conventional carbonate electrolytes to enhance the stability and Li^+conductivity of the SEI film.As a result,dendrite formation is effectively suppressed,and a significantly improved average Coulombic efficiency(CE)of 97.2%in Li-Cu cell is achieved.By using this novel GPE coupled with Li anode and LiNi0.5Mn0.3Co0.2O2(NMC532),excellent capacity retention of 94.1%and high average CE of over 99.2%are obtained after 200 cycles at 0.5 C.This work presents fresh insight into practical modification strategies on high-voltage Li metal batteries.
文摘High-purity straight and discrete multiwalled boron nitride nanotubes （BNNTs） were grown via a boron oxide vapor reaction with ammonia using LiNO3 as a promoter. Only a trace amount of boron oxide was detected as an impurity in the BNNTs by energy-dispersive X-ray （EDX） and Raman spectroscopies. Boron oxide vapor was generated from a mixture of B, FeO, and MgO powders heated to 1,150 ℃, and it was transported to the reaction zone by flowing ammonia. Lithium nitrate was applied to the upper side of a BN bar from a water solution. The bar was placed along a temperature gradient zone in a horizontal tubular furnace. BNNTs with average diameters of 30-50 nm were mostly observed in a temperature range of 1,280-1,320 ℃. At higher temperatures, curled polycrystalline BN fibers appeared. Above 1,320 ℃, the number of BNNTs drastically decreased, whereas the quantity and diameter of the fibers increased. The mechanism of BNNT and fiber growth is proposed and discussed.
