All-solid-state lithium batteries(ASSLBs),which use solid electrolytes instead of liquid ones,have become a hot research topic due to their high energy and power density,ability to solve battery safety issues,and capa...All-solid-state lithium batteries(ASSLBs),which use solid electrolytes instead of liquid ones,have become a hot research topic due to their high energy and power density,ability to solve battery safety issues,and capabilities to fulfill the increasing demand for energy storage in electric vehicles and smart grid applications.Garnet-type solid electrolytes have attracted considerable interest as they meet all the properties of an ideal solid electrolyte for ASSLBs.The garnet-type Li_(7)La_(3)Zr_(2)O_(12)(LLZO)has excellent environmental stability;experiments and computational analyses showed that this solid electrolyte has a high lithium(Li)ionic conductivity(10^(-4)-10^(-3) S·cm^(-1)),an electrochemical window as wide as 6 V,stability against Li metal anode,and compatibility with most of the cathode materials.In this review,we present the fundamentals of garnet-type solid electrolytes,preparation methods,air stability,some strategies for improving the conductivity based on experimental and computational results,interfacial issues,and finally applications and challenges for future developments of LLZO solid electrolytes for ASSLBs.展开更多
The key to realize long-life high energy density lithium batteries is to exploit functional electrolytes capable of stabilizing both high voltage cathode and lithium anode.The emergence of localized high-concentration...The key to realize long-life high energy density lithium batteries is to exploit functional electrolytes capable of stabilizing both high voltage cathode and lithium anode.The emergence of localized high-concentration electrolytes(LHCEs)shows great promise for ameliorating the above-mentioned interfacial issues.In this work,a lithium difluoro(oxalate)borate(LiDFOB)based nonflammable dual-anion LHCE is designed and prepared.Dissolving in the mixture of trimethyl phosphate(TMP)/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether(D_(2)),the continuously consumption of LiDFOB is suppressed by simply introducing lithium nitrate(LiNO_(3)).Meantime,as most of the TMP molecular are coordinated with Li^(+),the electrolyte does not show incompatibility issue between neither metal lithium nor graphite anode.Therefore,it demonstrates excellent capability in stabilizing the interface of Ni-rich cathode and regulating lithium deposition morphology.The Li||LiNi_(0.87)Co_(0.08)Mn_(0.05)O_(2)(NCM87)batteries exhibit high capacity retention of more than 90%after 200 cycles even under the high cutoff voltage of 4.5 V,1 C rate.This study offers a prospective method to develop safe electrolytes suitable for high voltage applications,thus providing higher energy densities.展开更多
Safety issues related to flammable electrolytes in lithium-ion batteries(LIBs) remain a major challenge for their extended applications.The use of non-flammable phosphate-based electrolytes has proved the validity in ...Safety issues related to flammable electrolytes in lithium-ion batteries(LIBs) remain a major challenge for their extended applications.The use of non-flammable phosphate-based electrolytes has proved the validity in inhibiting the combustion of LIBs.However,the strong interaction between Li^(+) and phosphate leads to a dominant solid electrolyte interphase(SEI) with limited electronic shielding,resulting in the poor Li^(+) intercalation at the graphite(Gr) anode when using high-phosphate-content electrolytes.To mitigate this issue and improve Li^(+) insertion,we propose an “In-N-Out” strategy to render phosphates “noncoordinative”.By employing a combination of strongly polar solvents for a “block effect” and weakly polar solvents for a “drag effect”,we reduce the Li^(+)–phosphate interaction.As a result,phosphates remain in the electrolyte phase(“In”),minimizing their impact on the incompatibility with the Gr electrode(“Out”).We have developed a non-flammable electrolyte with high triethyl phosphate(TEP) content(>60 wt.%),demonstrating the excellent ion conductivity(5.94 mS cm^(-1) at 30 ℃) and reversible Li^(+) intercalation at a standard concentration(~1 mol L^(-1)).This approach enables the manipulation of multiple electrolyte functions and holds the promise for the development of safe electrochemical energy storage systems using non-flammable electrolytes.展开更多
As a promising solid electrolyte for thin-film lithium batteries,the amorphous Li_(0.33)La_(0.56)TiO_(3)(LLTO)thin film has gained great interest.However,enhancing ionic conductivity remains challenging in the field.H...As a promising solid electrolyte for thin-film lithium batteries,the amorphous Li_(0.33)La_(0.56)TiO_(3)(LLTO)thin film has gained great interest.However,enhancing ionic conductivity remains challenging in the field.Here,a systematical study was performed to improve the ionic conductivity of sputter-deposited LLTO thin films via the optimization of processing atmosphere and temperature.By combining the optimized oxygen partial pressure(30%),annealing temperature(300℃),and annealing atmosphere(air),an amorphous LLTO thin film with an ionic conductivity of 5.32910^(-5)·S·cm^(-1) at room temperature and activation energy of 0.26 eV was achieved.The results showed that,first,the oxygen partial pressure should be high enough to compensate for the oxygen loss,but low enough to avoid the abusive oxygen scattering effect on lithium precursors that results in a lithium-poor composition.The oxygen partial pressure needs to achieve a balance between lithium loss and oxygen defects to improve the ionic conductivity.Second,a proper annealing temperature reduces the oxygen defects of LLTO thin films while maintaining its amorphous state,which improves the ionic conductivity.Third,the highest ionic conductivity for the LLTO thin films that were annealed in air(a static space without a gas stream)occurs because of the decreased lithium loss and oxygen defects during annealing.These findings show that the lithium-ion concentration and oxygen defects affect the ionic conductivity for amorphous LLTO thin films,which provides insight into the optimization of LLTO thin-film solid electrolytes,and generates new opportunities for their application in thinfilm lithium batteries.展开更多
The Zintl compound Mg3Sb2 has been recently identified as promising thermoelectric material owing to its high thermoelectric performance and cost-effective,nontoxicity and environment friendly characteristics.However,...The Zintl compound Mg3Sb2 has been recently identified as promising thermoelectric material owing to its high thermoelectric performance and cost-effective,nontoxicity and environment friendly characteristics.However,the intrinsically p-type Mg3Sb2 shows low figure of merit（z T = 0.23 at 723 K） for its poor electrical conductivity.In this study,a series of Mg（3-x）LixSb2 bulk materials have been prepared by high-energy ball milling and spark plasma sintering（SPS） process.Electrical transport measurements on these materials revealed significant improvement on the power factor with respect to the undoped sample,which can be essentially attributed to the increased carrier concentration,leading to a maximum z T of0.59 at 723 K with the optimum doping level x = 0.01.Additionally,the engineering z T and energy conversion efficiency are calculated to be 0.235 and 4.89%,respectively.To our best knowledge,those are the highest values of all reported p-type Mg3Sb2-based compounds with single element doping.展开更多
Excess lithium in alumina is significantly bad for aluminum reduction.In this study,the concentration variation of lithium ion in sodium aluminate solution with addition of synthetic lithium aluminate was investigated...Excess lithium in alumina is significantly bad for aluminum reduction.In this study,the concentration variation of lithium ion in sodium aluminate solution with addition of synthetic lithium aluminate was investigated.Elevating temperature,increasing caustic soda concentration,reducing alumina concentration or raising molar ratioαk improved equilibrium concentration of lithium ion in sodium aluminate solution.Agitation speed had a minimal effect on lithium ion concentration.Over 0.65 g/L lithium ion equilibrium concentration was observed in digestion process,whereas 35 mg/L lithium ion concentration remained in solution after precipitation time of 9 h.Moreover,equilibrium concentration decreased sharply from digestion of boehmite or diaspore to seed precipitation,about 95%lithium was precipitated into red mud(bauxite residue)and aluminum hydroxide.This study provides a valuable perspective in removal or extraction of lithium from sodium aluminate solution in alumina refineries.展开更多
Li^(+) solvation structures have a decisive influence on the electrode/electrolyte interfacial properties and battery performances.Reduced salt concentration may result in an organic rich solid electrolyte interface(S...Li^(+) solvation structures have a decisive influence on the electrode/electrolyte interfacial properties and battery performances.Reduced salt concentration may result in an organic rich solid electrolyte interface(SEI)and catastrophic cycle stability,which makes low concentration electrolytes(LCEs)rather challenging.Solvents with low solvating power bring in new chances to LCEs due to the weak salt-solvent interactions.Herein,an LCE with only 0.25 mol L^(-1) salt is prepared with fluoroethylene carbonate(FEC)and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether(D_(2)).Molecular dynamics simulations and experiments prove that the low solvating power solvent FEC not only renders reduced desolvation energy to Li^(+) and improves the battery kinetics,but also promotes the formation of a LiF-rich SEI that hinders the electrolyte consumption.Li||Cu cell using the LCE shows a high coulombic efficiency of 99.20%,and LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)||Li cell also exhibits satisfying capacity retention of 89.93%in 200 cycles,which demonstrates the great potential of solvating power regulation in LCEs development.展开更多
Although high salt concentration electrolyte(HCE)can construct effective Li F-rich interphase film and solve the interphasial instability issue of graphite anode,its high cost,high viscosity and poor wettability with ...Although high salt concentration electrolyte(HCE)can construct effective Li F-rich interphase film and solve the interphasial instability issue of graphite anode,its high cost,high viscosity and poor wettability with electrode materials limit its large-scale application.Generally,localized high concentration electrolyte(LHCE)is obtained by introducing an electrochemically inert diluent into HCE to avoid the above-mentioned problems while maintaining the high interphasial stability of HCE with graphite anode.Unlike traditional inert diluents,1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluropropyl ether(TTE)with electrochemical activity is introduced into propylene carbonate(PC)-based HCE to obtain LHCE-2(1 M LiPF_(6),PC:DMC:TTE=1:1:6.1)herein.Experimental and theoretical simulation results show that TTE participates in the oxidation decomposition and film-forming reaction at the NCM622 cathode surface,conducting a cathode electrolyte interphase(CEI)rich in organic fluorides with excellent electron insulation ability,high structural stability and low interphasial impedance.Thanks to the outstanding interphasial properties induced by LHCE-2,the graphite||NMC622 pouch cell reaches a capacity retention of 80%after 500 cycles at 1 C under room temperature.While at sub-zero temperatures,the capacity released by the cell with LHCE-2 electrolyte is significantly higher than that of HCE and conventional EC-based electrolytes.Meanwhile,the LHCE-2 electrolyte inherits the advantages of TTE flame-resistant,thus improving the safety of the battery.展开更多
Lithium metal has a very outstanding theoretical capacity(3860 mAh/g)and is one of the most superior anode materials for high energy density batteries.However,the uncontrollable dendrite growth and the fo rmation of&q...Lithium metal has a very outstanding theoretical capacity(3860 mAh/g)and is one of the most superior anode materials for high energy density batteries.However,the uncontrollable dendrite growth and the fo rmation of"dead lithium"are the important hidden dangers of short cycle life and low safety.However,the uncontrollable dendrite growth and the fo rmation of dead lithium leads to short cycle life and hidden dange r,which hinder its practical application.Controlling the nucleation and growth process of lithium is an effective strategy to inhibit lithium dendrite.Herein,a simple in situ self-catalytic method is used to construct nitrogen doped carbon nanotube arrays on stainless steel mesh(N-CNT@SS)as a lithium composite anode.The N-doped CNTs provide a great number of N-functional groups,which enhance the lithiophilic of anode and provide a large number of uniform nucleation sites,hence it has excellent structural stability for cycles.The arrays provide neat lithium-ion transport channels to uniform lithiumion flux and inhibits dendrite generation,revealed by the COMSOL multi-physics concentration field simulation.The N-CNT@SS composite anode sustain stable at 98.9%over 300 cycles at 1 mA/cm2.NCNT@SS as the anode is coupled LiFePO_(4)(LFP)as the cathode construct a full battery,demonstrating excellent cycling stability with a capacity of 152.33 mAh/g and capacity retaining ratio of 95.4%after 100 cycles at 0.5 C.展开更多
Three-dimensional(3 D)frameworks have received much attention as an effective modification strategy for next-generation high-energy-density lithium metal batteries.However,the top-growth mode of lithium(Li)on the 3 D ...Three-dimensional(3 D)frameworks have received much attention as an effective modification strategy for next-generation high-energy-density lithium metal batteries.However,the top-growth mode of lithium(Li)on the 3 D framework remains a tough challenge.To achieve a uniform bottom-up Li growth,a scheme involving Ag concentration gradient in 3 D PVDF framework(C-Ag/PVDF)is proposed.Ag nanoparticles with a concentration gradient induce an interface activity gradient in the 3 D framework,and this gradient feature is still maintained during the cycle.As a result,the C-Ag/PVDF framework delivers a long lifespan over 1800 h at a current density of 1 mA cm^(-2) with a capacity of 1 mAh cm^(-2),and shows an ultra-long life(>1300 h)even at a high current density of 4 mA cm^(-2) with a capacity of 4 mAh cm^(-2).The advantage of concentration gradient provides further insights into the optimal design of the 3 D framework for stable Li metal anode.展开更多
Owing to the inherent advantages of low cost and high capacity,cobalt(Co)-free lithium(Li)-rich layered oxides have become one of the most promising cathodes for next-generation high-energy lithium-ion batteries.Howev...Owing to the inherent advantages of low cost and high capacity,cobalt(Co)-free lithium(Li)-rich layered oxides have become one of the most promising cathodes for next-generation high-energy lithium-ion batteries.However,these familial cathodes suffer from serious voltage decay due to many reasons,such as oxygen release and transition metal(TM)migration,which are closely related to nanoscale strain evolution.Here,by combining the synergistic effects of surface integration,bulk doping,and concentration gradient,we successfully construct a Co-free Li-rich layered cathode with a very small volumetric strain(1.05%)between 2.0 and 4.8 V,approaching the critical value of zero strain.Various characterizations indicate that the constructed zero-strain cathode can significantly suppress the TM migration,interfacial reactions,and structural degradation including cracks,lattice defects,phase evolution,and nanovoids,leading to improved voltage stability of Co-free Li-rich layered oxides during the prolonged cycles.This work provides a strategy to eliminate the lattice strain of Li-rich layered cathodes and facilitates the up-scaled application of the as-prepared cathode materials.展开更多
基金supported by the National Key R&D Program of China(Nos.2018YFB0905600 and 2017YFB0310400)the National Natural Science Foundation of China(No.51972246)+2 种基金Fundamental Research Funds for the Central Universities in China,State Key Laboratory of Advanced Electromagnetic Engineering and Technology(Huazhong University of Science and Technology)the"111"project(No.B13035)the Science and Technology Project of Global Energy Interconnection Research Institute Co.,Ltd.(No.SGGR0000WLJS1801080).
文摘All-solid-state lithium batteries(ASSLBs),which use solid electrolytes instead of liquid ones,have become a hot research topic due to their high energy and power density,ability to solve battery safety issues,and capabilities to fulfill the increasing demand for energy storage in electric vehicles and smart grid applications.Garnet-type solid electrolytes have attracted considerable interest as they meet all the properties of an ideal solid electrolyte for ASSLBs.The garnet-type Li_(7)La_(3)Zr_(2)O_(12)(LLZO)has excellent environmental stability;experiments and computational analyses showed that this solid electrolyte has a high lithium(Li)ionic conductivity(10^(-4)-10^(-3) S·cm^(-1)),an electrochemical window as wide as 6 V,stability against Li metal anode,and compatibility with most of the cathode materials.In this review,we present the fundamentals of garnet-type solid electrolytes,preparation methods,air stability,some strategies for improving the conductivity based on experimental and computational results,interfacial issues,and finally applications and challenges for future developments of LLZO solid electrolytes for ASSLBs.
基金financially supported by National Key Research and Development Program of China(No.2019YFA0705603)National Natural Science Foundation of China(No.22078341,No.21808228 and No.21776290)+1 种基金Science Fund for Creative Research Groups of the National Natural Science Foundation of China(No.21921005)S&T Program of Hebei(No.B2020103028).
文摘The key to realize long-life high energy density lithium batteries is to exploit functional electrolytes capable of stabilizing both high voltage cathode and lithium anode.The emergence of localized high-concentration electrolytes(LHCEs)shows great promise for ameliorating the above-mentioned interfacial issues.In this work,a lithium difluoro(oxalate)borate(LiDFOB)based nonflammable dual-anion LHCE is designed and prepared.Dissolving in the mixture of trimethyl phosphate(TMP)/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether(D_(2)),the continuously consumption of LiDFOB is suppressed by simply introducing lithium nitrate(LiNO_(3)).Meantime,as most of the TMP molecular are coordinated with Li^(+),the electrolyte does not show incompatibility issue between neither metal lithium nor graphite anode.Therefore,it demonstrates excellent capability in stabilizing the interface of Ni-rich cathode and regulating lithium deposition morphology.The Li||LiNi_(0.87)Co_(0.08)Mn_(0.05)O_(2)(NCM87)batteries exhibit high capacity retention of more than 90%after 200 cycles even under the high cutoff voltage of 4.5 V,1 C rate.This study offers a prospective method to develop safe electrolytes suitable for high voltage applications,thus providing higher energy densities.
基金supported by the National Key Research and Development Program of China (2022YFB2404800)the National Natural Science Foundation of China (52022013,51974031 and U22A20438)。
文摘Safety issues related to flammable electrolytes in lithium-ion batteries(LIBs) remain a major challenge for their extended applications.The use of non-flammable phosphate-based electrolytes has proved the validity in inhibiting the combustion of LIBs.However,the strong interaction between Li^(+) and phosphate leads to a dominant solid electrolyte interphase(SEI) with limited electronic shielding,resulting in the poor Li^(+) intercalation at the graphite(Gr) anode when using high-phosphate-content electrolytes.To mitigate this issue and improve Li^(+) insertion,we propose an “In-N-Out” strategy to render phosphates “noncoordinative”.By employing a combination of strongly polar solvents for a “block effect” and weakly polar solvents for a “drag effect”,we reduce the Li^(+)–phosphate interaction.As a result,phosphates remain in the electrolyte phase(“In”),minimizing their impact on the incompatibility with the Gr electrode(“Out”).We have developed a non-flammable electrolyte with high triethyl phosphate(TEP) content(>60 wt.%),demonstrating the excellent ion conductivity(5.94 mS cm^(-1) at 30 ℃) and reversible Li^(+) intercalation at a standard concentration(~1 mol L^(-1)).This approach enables the manipulation of multiple electrolyte functions and holds the promise for the development of safe electrochemical energy storage systems using non-flammable electrolytes.
基金This study was financially supported by the National Natural Science Funds of China(No.21905040)the Startup Funds from the University of Electronic Science and Technology of China,the National Key Research and Development Program of China(Nos.2017YFB0702802 and 2018YFB0905400)Shanghai Venus Project(No.18QB1402600).
文摘As a promising solid electrolyte for thin-film lithium batteries,the amorphous Li_(0.33)La_(0.56)TiO_(3)(LLTO)thin film has gained great interest.However,enhancing ionic conductivity remains challenging in the field.Here,a systematical study was performed to improve the ionic conductivity of sputter-deposited LLTO thin films via the optimization of processing atmosphere and temperature.By combining the optimized oxygen partial pressure(30%),annealing temperature(300℃),and annealing atmosphere(air),an amorphous LLTO thin film with an ionic conductivity of 5.32910^(-5)·S·cm^(-1) at room temperature and activation energy of 0.26 eV was achieved.The results showed that,first,the oxygen partial pressure should be high enough to compensate for the oxygen loss,but low enough to avoid the abusive oxygen scattering effect on lithium precursors that results in a lithium-poor composition.The oxygen partial pressure needs to achieve a balance between lithium loss and oxygen defects to improve the ionic conductivity.Second,a proper annealing temperature reduces the oxygen defects of LLTO thin films while maintaining its amorphous state,which improves the ionic conductivity.Third,the highest ionic conductivity for the LLTO thin films that were annealed in air(a static space without a gas stream)occurs because of the decreased lithium loss and oxygen defects during annealing.These findings show that the lithium-ion concentration and oxygen defects affect the ionic conductivity for amorphous LLTO thin films,which provides insight into the optimization of LLTO thin-film solid electrolytes,and generates new opportunities for their application in thinfilm lithium batteries.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.U1601213 and 51572287)the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(Grant No.QYZDB-SSW-SLH013)
文摘The Zintl compound Mg3Sb2 has been recently identified as promising thermoelectric material owing to its high thermoelectric performance and cost-effective,nontoxicity and environment friendly characteristics.However,the intrinsically p-type Mg3Sb2 shows low figure of merit（z T = 0.23 at 723 K） for its poor electrical conductivity.In this study,a series of Mg（3-x）LixSb2 bulk materials have been prepared by high-energy ball milling and spark plasma sintering（SPS） process.Electrical transport measurements on these materials revealed significant improvement on the power factor with respect to the undoped sample,which can be essentially attributed to the increased carrier concentration,leading to a maximum z T of0.59 at 723 K with the optimum doping level x = 0.01.Additionally,the engineering z T and energy conversion efficiency are calculated to be 0.235 and 4.89%,respectively.To our best knowledge,those are the highest values of all reported p-type Mg3Sb2-based compounds with single element doping.
基金Project(2015BAB04B01)supported by the National Key Technology R&D Program of ChinaProject(FA2017029)supported by Science and Technology Program of Chongzuo,ChinaProject(CSUZC201811)supported by the Open-End Fund for the Valuable and Precision Instruments of Central South University,China
文摘Excess lithium in alumina is significantly bad for aluminum reduction.In this study,the concentration variation of lithium ion in sodium aluminate solution with addition of synthetic lithium aluminate was investigated.Elevating temperature,increasing caustic soda concentration,reducing alumina concentration or raising molar ratioαk improved equilibrium concentration of lithium ion in sodium aluminate solution.Agitation speed had a minimal effect on lithium ion concentration.Over 0.65 g/L lithium ion equilibrium concentration was observed in digestion process,whereas 35 mg/L lithium ion concentration remained in solution after precipitation time of 9 h.Moreover,equilibrium concentration decreased sharply from digestion of boehmite or diaspore to seed precipitation,about 95%lithium was precipitated into red mud(bauxite residue)and aluminum hydroxide.This study provides a valuable perspective in removal or extraction of lithium from sodium aluminate solution in alumina refineries.
基金supported by the National Key Research and Development Program of China(2019YFA0705603)the National Natural Science Foundation of China(22078341)+1 种基金the Natural Science Foundation of Hebei Province(B2020103028)financial support from York University。
文摘Li^(+) solvation structures have a decisive influence on the electrode/electrolyte interfacial properties and battery performances.Reduced salt concentration may result in an organic rich solid electrolyte interface(SEI)and catastrophic cycle stability,which makes low concentration electrolytes(LCEs)rather challenging.Solvents with low solvating power bring in new chances to LCEs due to the weak salt-solvent interactions.Herein,an LCE with only 0.25 mol L^(-1) salt is prepared with fluoroethylene carbonate(FEC)and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether(D_(2)).Molecular dynamics simulations and experiments prove that the low solvating power solvent FEC not only renders reduced desolvation energy to Li^(+) and improves the battery kinetics,but also promotes the formation of a LiF-rich SEI that hinders the electrolyte consumption.Li||Cu cell using the LCE shows a high coulombic efficiency of 99.20%,and LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)||Li cell also exhibits satisfying capacity retention of 89.93%in 200 cycles,which demonstrates the great potential of solvating power regulation in LCEs development.
基金supported by the National Natural Science Foundation of China (No.21972049)the Guangdong-Hong KongMacao Greater Bay Area Exchange Programs of SCNU (2022)。
文摘Although high salt concentration electrolyte(HCE)can construct effective Li F-rich interphase film and solve the interphasial instability issue of graphite anode,its high cost,high viscosity and poor wettability with electrode materials limit its large-scale application.Generally,localized high concentration electrolyte(LHCE)is obtained by introducing an electrochemically inert diluent into HCE to avoid the above-mentioned problems while maintaining the high interphasial stability of HCE with graphite anode.Unlike traditional inert diluents,1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluropropyl ether(TTE)with electrochemical activity is introduced into propylene carbonate(PC)-based HCE to obtain LHCE-2(1 M LiPF_(6),PC:DMC:TTE=1:1:6.1)herein.Experimental and theoretical simulation results show that TTE participates in the oxidation decomposition and film-forming reaction at the NCM622 cathode surface,conducting a cathode electrolyte interphase(CEI)rich in organic fluorides with excellent electron insulation ability,high structural stability and low interphasial impedance.Thanks to the outstanding interphasial properties induced by LHCE-2,the graphite||NMC622 pouch cell reaches a capacity retention of 80%after 500 cycles at 1 C under room temperature.While at sub-zero temperatures,the capacity released by the cell with LHCE-2 electrolyte is significantly higher than that of HCE and conventional EC-based electrolytes.Meanwhile,the LHCE-2 electrolyte inherits the advantages of TTE flame-resistant,thus improving the safety of the battery.
基金supported by the National Natural Science Foundation of China(No.21646012)the State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology(No.2019DX13)+2 种基金China Postdoctoral Science Foundation(Nos.2016M600253,2017T100246)the Post-doctoralFoundation of Heilongjiang Province(No.LBH-Z16060)the Fundamental Research Funds for the Central Universities(No.HIT.NSRIF.201836)。
文摘Lithium metal has a very outstanding theoretical capacity(3860 mAh/g)and is one of the most superior anode materials for high energy density batteries.However,the uncontrollable dendrite growth and the fo rmation of"dead lithium"are the important hidden dangers of short cycle life and low safety.However,the uncontrollable dendrite growth and the fo rmation of dead lithium leads to short cycle life and hidden dange r,which hinder its practical application.Controlling the nucleation and growth process of lithium is an effective strategy to inhibit lithium dendrite.Herein,a simple in situ self-catalytic method is used to construct nitrogen doped carbon nanotube arrays on stainless steel mesh(N-CNT@SS)as a lithium composite anode.The N-doped CNTs provide a great number of N-functional groups,which enhance the lithiophilic of anode and provide a large number of uniform nucleation sites,hence it has excellent structural stability for cycles.The arrays provide neat lithium-ion transport channels to uniform lithiumion flux and inhibits dendrite generation,revealed by the COMSOL multi-physics concentration field simulation.The N-CNT@SS composite anode sustain stable at 98.9%over 300 cycles at 1 mA/cm2.NCNT@SS as the anode is coupled LiFePO_(4)(LFP)as the cathode construct a full battery,demonstrating excellent cycling stability with a capacity of 152.33 mAh/g and capacity retaining ratio of 95.4%after 100 cycles at 0.5 C.
基金supported by the Fundamental Research Funds for the Central Universities,China(ZYGX2019Z008)the National Natural Science Foundation of China(52072061)the Open Fund of the Key Laboratory for Renewable Energy,Chinese Academy of Sciences,Beijing Key Laboratory for New Energy Materials and Devices。
文摘Three-dimensional(3 D)frameworks have received much attention as an effective modification strategy for next-generation high-energy-density lithium metal batteries.However,the top-growth mode of lithium(Li)on the 3 D framework remains a tough challenge.To achieve a uniform bottom-up Li growth,a scheme involving Ag concentration gradient in 3 D PVDF framework(C-Ag/PVDF)is proposed.Ag nanoparticles with a concentration gradient induce an interface activity gradient in the 3 D framework,and this gradient feature is still maintained during the cycle.As a result,the C-Ag/PVDF framework delivers a long lifespan over 1800 h at a current density of 1 mA cm^(-2) with a capacity of 1 mAh cm^(-2),and shows an ultra-long life(>1300 h)even at a high current density of 4 mA cm^(-2) with a capacity of 4 mAh cm^(-2).The advantage of concentration gradient provides further insights into the optimal design of the 3 D framework for stable Li metal anode.
基金the funding supports of National Natural Science Foundation of China(Project 52004070,51874104)Key Technology and Supporting Platform of Genetic Engineering of Materials under States Key Project of Research and Development Plan of China(Project 2016YFB0700600)。
文摘Owing to the inherent advantages of low cost and high capacity,cobalt(Co)-free lithium(Li)-rich layered oxides have become one of the most promising cathodes for next-generation high-energy lithium-ion batteries.However,these familial cathodes suffer from serious voltage decay due to many reasons,such as oxygen release and transition metal(TM)migration,which are closely related to nanoscale strain evolution.Here,by combining the synergistic effects of surface integration,bulk doping,and concentration gradient,we successfully construct a Co-free Li-rich layered cathode with a very small volumetric strain(1.05%)between 2.0 and 4.8 V,approaching the critical value of zero strain.Various characterizations indicate that the constructed zero-strain cathode can significantly suppress the TM migration,interfacial reactions,and structural degradation including cracks,lattice defects,phase evolution,and nanovoids,leading to improved voltage stability of Co-free Li-rich layered oxides during the prolonged cycles.This work provides a strategy to eliminate the lattice strain of Li-rich layered cathodes and facilitates the up-scaled application of the as-prepared cathode materials.
