It is of great significance to develop clean and new energy sources with high-efficient energy storage technologies,due to the excessive use of fossil energy that has caused severe environmental damage.There is great ...It is of great significance to develop clean and new energy sources with high-efficient energy storage technologies,due to the excessive use of fossil energy that has caused severe environmental damage.There is great interest in exploring advanced rechargeable lithium batteries with desirable energy and power capabilities for applications in portable electronics,smart grids,and electric vehicles.In practice,high-capacity and low-cost electrode materials play an important role in sustaining the progresses in lithium-ion batteries.This review aims at giving an account of recent advances on the emerging high-capacity electrode materials and summarizing key barriers and corresponding strategies for the practical viability of these electrode materials.Effective approaches to enhance energy density of lithium-ion batteries are to increase the capacity of electrode materials and the output operation voltage.On account of major bottlenecks of the power lithium-ion battery,authors come up with the concept of integrated battery systems,which will be a promising future for high-energy lithium-ion batteries to improve energy density and alleviate anxiety of electric vehicles.展开更多
High-voltage lithium-ion batteries(HVLIBs) are considered as promising devices of energy storage for electric vehicle, hybrid electric vehicle, and other high-power equipment. HVLIBs require their own platform voltage...High-voltage lithium-ion batteries(HVLIBs) are considered as promising devices of energy storage for electric vehicle, hybrid electric vehicle, and other high-power equipment. HVLIBs require their own platform voltages to be higher than 4.5 V on charge. Lithium nickel manganese spinel LiNi_(0.5)Mn_(1.5)O_4(LNMO) cathode is the most promising candidate among the 5 V cathode materials for HVLIBs due to its flat plateau at 4.7 V. However, the degradation of cyclic performance is very serious when LNMO cathode operates over 4.2 V. In this review, we summarize some methods for enhancing the cycling stability of LNMO cathodes in lithium-ion batteries, including doping, cathode surface coating,electrolyte modifying, and other methods. We also discuss the advantages and disadvantages of different methods.展开更多
High-voltage high-nickel lithium layered oxide cathodes show great application prospects to meet the ever-increasing demand for further improvement of the energy density of rechargeable lithium-ion batteries(LIBs)main...High-voltage high-nickel lithium layered oxide cathodes show great application prospects to meet the ever-increasing demand for further improvement of the energy density of rechargeable lithium-ion batteries(LIBs)mainly due to their high output capacity.However,severe bulk structural degradation and undesired electrode-electrolyte interface reactions seriously endanger the cycle life and safety of the battery.Here,2 mol%Ti atom is used as modified material doping into LiNi_(0.8)Co_(0.2)Mn_(0.2O2)(NCM)to reform LiNi_(0.6)Co_(0.2)Mn_(0.18)Ti_(0.02)O_(2)(NCM-Ti)and address the long-standing inherent problem.At a high cut-off voltage of 4.5 V,NCM-Ti delivers a higher capacity retention ratio(91.8%vs.82.9%)after 150 cycles and a superior rate capacity(118 vs.105 mAh·g^(-1))at the high current density of 10 C than the pristine NCM.The designed high-voltage full battery with graphite as anode and NCM-Ti as cathode also exhibits high energy density(240 Wh·kg^(-1))and excellent electrochemical performance.The superior electrochemical behavior can be attributed to the improved stability of the bulk structure and the electrode-electrolyte interface owing to the strong Ti-O bond and no unpaired electrons.The in-situ X-ray diffraction analysis demonstrates that Ti-doping inhibits the undesired H2-H3 phase transition,minimizing the mechanical degradation.The ex-situ TEM and X-ray photoelectron spectroscopy reveal that Ti-doping suppresses the release of interfacial oxygen,reducing undesired interfacial reactions.This work provides a valuable strategic guideline for the application of high-voltage high-nickel cathodes in LIBs.展开更多
Solid electrolytes with desirable properties such as high ionic conductivity,wide electrochemical stable window,and suitable mechanical strength,and stable electrode-electrolyte interfaces on both cathode and anode si...Solid electrolytes with desirable properties such as high ionic conductivity,wide electrochemical stable window,and suitable mechanical strength,and stable electrode-electrolyte interfaces on both cathode and anode side are essential for high-voltage all-solid-state lithium batteries(ASSLBs)to achieve excellent cycle stability.In this work,a novel strategy of using LiF and LiNO_(3) as synergistic additives to boost the performance of PEO-PVDF/LLZTO-based composite solid electrolytes(CSEs)is developed,which also promotes the assembled high-voltage ASSLBs with dual-interfaces stability characteristic.Specifically,LiF as an inactive additive can increase the electrochemical stability of the CSE under high cut-off voltage,and improve the high-voltage compatibility between cathode and CSE,thus leading to a stable cathode/CSE interface.LiNO_(3) as an active additive can lead to an enhanced ionic conductivity of CSE due to the increased free-mobile Li+and ensure a stable CSE/Li interface by forming stable solid electrolyte interphase(SEI)on Li anode surface.Benefiting from the improved performance of CSE and stable dualinterfaces,the assembled NCM622/9[PEO_(15)-LiTFSI]-PVDF-15 LLZTO-2 LiF-3 LiNO_(3)/Li cell delivers a high rate capacity of 102.1 mAh g^(-1) at 1.0 C and a high capacity retention of 77.4%after 200 cycles at 0.5 C,which are much higher than those of the ASSLB assembled with additive-free CSE,with only 60.0 mAh g^(-1) and 52.0%,respectively.Furthermore,novel cycle test modes of resting for 5 h at different charge states after every 5 cycles are designed to investigate the high-voltage compatibility between cathode and CSE,and the results suggest that LiF additive can actually improve the high-voltage compatibility of cathode and CSE.All the obtained results confirm that the strategy of using synergistic additives in CSE is an effective way to achieve high-voltage ASSLBs with dual-interfaces stability.展开更多
Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the...Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.展开更多
High-voltage medium-nickel low-cobalt lithium layered oxide cathode materials are becoming a popular development route for high-energy lithium-ion batteries due to their relatively high capacity,low cost,and improved ...High-voltage medium-nickel low-cobalt lithium layered oxide cathode materials are becoming a popular development route for high-energy lithium-ion batteries due to their relatively high capacity,low cost,and improved safety.Unfortunately,capacity fading derived from surface lithium residue,electrode-electrolyte interfacial side reactions,and bulk structure degradation severely limits large-scale commercial utilization.In this work,an ultrathin and uniform NASICON-type Li_(3)V_(2)(PO_(4))_(3)(LVP)nanoscale functional coating is formed in situ by utilizing residual lithium to enhance the lithium storage performance of LiNi_(0.6)Co0.05Mn_(0.35)O_(2)(NCM)cathode.The GITT and ex-situ EIS and XPS demonstrate exceptional Li+diffusion and conductivity and attenuated interfacial side reactions,improving the electrode-electrolyte interface stability.The variable temperature in-situ XRD demonstrates delayed phase transition temperature to improve thermal stability.The battery in-situ XRD displays the singlephase H1-H2 reaction and weakened harmful H3 phase transition,minimizing the bulk mechanical degradation.These improvements are attributed to the removal of surface residual lithium and the formation of NASICON-type Li_(3)V_(2)(PO_(4))_(3)functional coatings with stable structure and high ionic and electronic conductivity.Consequently,the obtained NCM@LVP delivers a higher capacity retention rate(97.1%vs.79.6%)after 150 cycles and a superior rate capacity(87 mAh·g^(-1)vs.58 mAh·g^(-1))at a 5 C current density than the pristine NCM under a high cut-off voltage of 4.5 V.This work suggests a clever way to utilize residual lithium to form functional coatings in situ to improve the lithium storage performance of high-voltage medium-nickel low-cobalt cathode materials.展开更多
Fe-based sulfates are ideal cathode candidates for sodium-ion batteries(SIBs) owing to their high operating voltage and low cost but suffer from the nature of poor power performance. Herein, a hierarchical porous Na2F...Fe-based sulfates are ideal cathode candidates for sodium-ion batteries(SIBs) owing to their high operating voltage and low cost but suffer from the nature of poor power performance. Herein, a hierarchical porous Na2Fe(SO4)2@reduced graphene oxide/carbon dot(Na2Fe(SO4)2@rGO/C) with low carbon content(4.12 wt%) was synthesized via a facile homogeneous strategy benefiting for engineering application,which delivers excellent sodium storage performance(high voltage plateau of 3.75 V, 85 m Ah g-1 and330 Wh kg-1 at 0.05 C;5805 W kg-1 at 10 C) and high Na+diffusion coefficient(1.19 × 10-12 cm2 s-1).Moreover, the midpoint voltage of assembled full cell could reach 3.0 V. The electron transfer and reaction kinetics are effectively boosted since the nanoscale Na2Fe(SO4)2 is supported by a robust crosslinked carbon matrix with rGO sheets and carbon dots. The slight rGO sheets sufficiently enhance the electron transfer like a current collecter and restrain the aggregation, as well as ensure smooth ion channels. Meanwhile, the carbon dots in the whole space connect with Na2Fe(SO4)2 and help rGO to promote the conductivity of the electrode. Ex-situ X-ray powder diffraction and X-ray photoelectron spectrometry analysis confirm the high reversibility of this sodiation/desodiation process.展开更多
While argyrodite sulfides are getting more and more attention as highly promising solid-state electrolytes(SSEs)for solid batteries,they also suffer from the typical sulfide setbacks such as poor electrochemical compa...While argyrodite sulfides are getting more and more attention as highly promising solid-state electrolytes(SSEs)for solid batteries,they also suffer from the typical sulfide setbacks such as poor electrochemical compatibility with Li anode and high-voltage cathodes and serious sensitivity to humid air,which hinders their practical applications.Herein,we have devised an effective strategy to overcome these challenging shortcomings through modification of chalcogen chemistry under the guidance of theoretical modeling.The resultant Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)delivered excellent electrochemical compatibility with both pure Li anode and high-voltage LiCoO_(2)cathode,without compromising the superb ionic conductivity of the pristine sulfide.Furthermore,the current SSE also exhibited highly improved stability to oxygen and humidity,with further advantage being more insulating to electrons.The remarkably enhanced compatibility with electrodes is attributed to in situ formation of helpful electrolyte–electrode interphases.The formation of in situ anode–electrolyte interphase(AEI)enabled stable Li plating/stripping in the Li|Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)|Li symmetric cells at a high current density up to 1 mA cm^(-2)over 200 h and 2 mA cm^(-2)for another 100 h.The in situ amorphous nano-film cathode–electrolyte interphase(CEI)facilitated protection of the SSE from decomposition at elevated voltage.Consequently,the synergistic effect of AEI and CEI helped the LiCoO_(2)|Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)|Li full-battery cell to achieve markedly better cycling stability than that using the pristine Li_(6)PS_(5)Cl as SSE,at a high area loading of the active cathode material(4 mg cm^(-2))in type-2032 coin cells.This work is to add a desirable SSE in the argyrodite sulfide family,so that high-performance solid battery cells could be fabricated without the usual need of strict control of the ambient atmosphere.展开更多
O3-type Na NiO_(2)-based cathode materials undergo irreversible phase transition and serious capacity decay at high voltage above 4.0 V in sodium-ion batteries. To address these challenges, effects of Fsubstitution on...O3-type Na NiO_(2)-based cathode materials undergo irreversible phase transition and serious capacity decay at high voltage above 4.0 V in sodium-ion batteries. To address these challenges, effects of Fsubstitution on the structure and electrochemical performance of Na Ni_(0.4)Mn_(0.25)Ti_(0.3)Co_(0.05)O_(2) are investigated in this article. The F-substitution leads to expanding of interlayer, which can enhance the mobility of Na+. NaNi_(0.4)Mn_(0.25)Ti_(0.3)Co_(0.05)O_(1.92)F_(0.08)(NMTC-F_(0.08)) with the optimal F-substitution degree exhibits much improved rate capability and cyclic stability. It delivers reversible capacities of 177 and 97 m Ah g^(-1) at 0.05 and 5 C within 2.0–4.4 V, respectively. Galvanostatic intermittent titration technique verifies faster kinetics of Na+diffusion in NMTC-F_(0.08). And in-situ XRD investigation reveals the phase evolution of NMTC-F_(0.08), indicating enhanced structural stability results from F-substitution. This study may shed light on the development of high performance cathode materials for sodium-ion storage at high voltage.展开更多
Poly(ethylene oxide)(PEO)-based solid polymer electrolyte(SPE)is considered as a promising solid-state electrolyte for all-solid-state lithium batteries(ASSLBs).Nevertheless,the poor interfacial stability with high-vo...Poly(ethylene oxide)(PEO)-based solid polymer electrolyte(SPE)is considered as a promising solid-state electrolyte for all-solid-state lithium batteries(ASSLBs).Nevertheless,the poor interfacial stability with high-voltage cathode materials(e.g.,LiCoO_(2))restricts its application in high energy density solid-state batteries.Herein,high-voltage stable Li_(3)AlF_(6) protective layer is coated on the surface of LiCoO_(2) particle to improve the performance and investigate the failure mechanism of PEO-based ASSLBs.The phase transition unveils that chemical redox reaction occurs between the highly reactive LiCoO_(2) surface and PEO-based SPE,resulting in structure collapse of LiCoO_(2),hence the poor cycle performance of PEO-based ASSLBs with LiCoO_(2) at charging voltage of 4.2 V vs Li/Li+.By sharp contrast,no obvious structure change can be found at the surface of Li_(3)AlF_(6)-coated LiCoO_(2),and the original layered phase was well retained.When the charging voltage reaches up to 4.5 V vs Li/Li+,the intensive electrochemical decomposition of PEO-based SPE occurs,leading to the constant increase of cell impedance and directly causing the poor performance.This work not only provides important supplement to the failure mechanism of PEO-based batter-ies with LiCoO_(2),but also presents a universal strategy to retain structure stability of cathode-electrolyte interface in high-voltage ASSLBs.展开更多
PEO-based all-solid-state electrolytes are extensively utilized and researched owing to their exceptional safety,low-mass-density,and cost-effectiveness.However,the low oxidation potential of PEO makes the interface p...PEO-based all-solid-state electrolytes are extensively utilized and researched owing to their exceptional safety,low-mass-density,and cost-effectiveness.However,the low oxidation potential of PEO makes the interface problem with the high-voltage cathode extremely severe.In this work,the impedance of PEO-based all-solid-state batteries with high-voltage cathode(NCM811)was studied at different potentials.The Nyquist plots displayed a gyrate arc at low-frequencies for NCM811/PEO interface.Based on the kinetic modeling,it was deduced that there is a decomposition reaction of PEO-matrix in addition to de-embedded reaction of NCM811,and the PEO intermediate product(dehydra-PEO)adsorbed on the electrode surface leading to low-frequency inductive arcs.Furthermore,the distribution of relaxation time shows the dehydra-PEO results in the kinetic tardiness of the charge transfer process in the temporal dimension.Hence,an artificial interface layer(CEI_(x))was modified on the surface of NCM811 to regulate the potential of cathode/electrolyte interface to prevent the high-voltage deterioration of PEO.NCM/CEI_(x)/PEO batteries exhibit capacity retentions of 96.0%,84.6%,and 76.8%after undergoing 100 cycles at cut-off voltages of 4.1,4.2,and 4.3 V,respectively.Therefore,here the failure mechanism of high-voltage PEO electrolyte is investigated by EIS and a proposed solving strategy is presented.展开更多
LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)with a spinel crystal structure presents a compelling avenue towards the development of economic cobalt-free and high voltage(~5 V)lithium-ion batteries.Nevertheless,the elevated operation...LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)with a spinel crystal structure presents a compelling avenue towards the development of economic cobalt-free and high voltage(~5 V)lithium-ion batteries.Nevertheless,the elevated operational voltage of LNMO gives rise to pronounced interfacial interactions between the distorted surface lattices characterized by Jahn-Teller(J-T)distortions and the electrolyte constituents.Herein,a localized crystallized coherent LaNiO_(3) and surface passivated Li_(3)PO_(4) layer is deposited on LNMO via a one-step calcination process.As evidenced by transmission electron microscopy(TEM),time-of-flight secondary ion mass spectrometry(ToF-SIMS)and density functional theory(DFT)calculation,the epitaxial growth of LaNiO_(3) along the LNMO lattice can effectively stabilize the structure and inhibit irreversible phase transitions,and the Li_(3)PO_(4) surface coating can prevent the chemical reaction between HF and transition metals without sacrificing the electrochemical activity.In addition,the ionic conductive Li_(3)PO_(4) and atomic wetting inter-layer enables fast charge transfer transport property.Consequently,the LNMO material enabled by the lattice bonding and surface passivating features,demonstrates high performance at high current densities and good capacity retention during long-term test.The rational design of interface coherent engineering and surface coating layers of the LNMO cathode material offers a new perspective for the practical application of high-voltage lithium-ion batteries.展开更多
Lithium-ion batteries play a crucial role in storing energy for renewable sources and electric vehicles,yet face challenges related to insufficient energy density.Elevating the working-voltage of cathodes is promising...Lithium-ion batteries play a crucial role in storing energy for renewable sources and electric vehicles,yet face challenges related to insufficient energy density.Elevating the working-voltage of cathodes is promising to boost the energy density of batteries by increasing both the output voltage and capacity of cathode,which however could compromise life cycle and safety.This review provides a comprehensive summary of essential factors governing pathways of cathode-induced thermal runaway,including electrolyte decomposition,phase transitions,and crosstalk-induced reactions.Electrode and electrolyte modifications aimed at mitigating parasitic reactions and preventing crosstalk were also discussed.The review concludes with insights into the future application of these strategies,providing a comprehensive perspective on the realization of high-energy and safe batteries.展开更多
Ethers are promising electrolyte solvents for secondary Li metal batteries because of their excellent reduction stability.However,their oxidation stability has been mostly relying on the high concentration approach,an...Ethers are promising electrolyte solvents for secondary Li metal batteries because of their excellent reduction stability.However,their oxidation stability has been mostly relying on the high concentration approach,and limited progress has been made on building effective interphase to protect the cathode from the corrosion of the electrolyte.In this work,we construct a semi-crystalline interfacial layer on the surface of Li(Ni_(0.8)Co_(0.1)Mn_(0.1))O_(2)cathode that can achieve improved electrochemical stability in the highly corrosive chemical environment formed by the decomposition of ether molecules.Different from traditional brittle crystalline interphases,the optimized semi-crystalline layer with low modulus and high ionic conductivity can effectively relieve electrode strain and maintain the integrity of the interface layer.Due to this design,the continuous oxidation decomposition of ether-based electrolytes could be significantly suppressed and the battery shows outstanding cycling stability(84%capacity retention after 300 cycles).This article provides a solution to address the oxidation instability issue of ether-based electrolytes.展开更多
The isolated inorganic particles within composite polymer electrolytes(CPEs) are not correlated to the Li^(+)transfer network,resulting in the polymer dominating the low ionic conductivity of CPEs.Therefore,we develop...The isolated inorganic particles within composite polymer electrolytes(CPEs) are not correlated to the Li^(+)transfer network,resulting in the polymer dominating the low ionic conductivity of CPEs.Therefore,we developed novel quasi-solid-state CPEs of a Ce-doped Na super ion conductors(NASICON)Na_(1.3+x)Al_(0.3)Ce_(x)Ti_(1.7-x)(PO_(4))_(3)(NCATP) chemically coupled poly(vinylidene fluoride-hexafluoropropylene)(PVDF-HFP)/Li-bis(trifluoromethanes-ulfonyl)imide(LiTFSI) matrix.A strong interaction between Ce^(3+)from NCATP and TFSI-anion from the polymer matrix contributes to the fast Li+transportation at the interface.The PVDF-HFP/NCATP CPEs exhibit an ionic conductivity of 2.16 × 0^(-3) S cm^(-1) and a Li^(+) transference number of 0.88.A symmetric Li/Li cell with NCATP-integrated CPEs at 0.1 mA cm^(-2) presents outstanding cycling stability over 2000 h at 25℃.The quasi-solid-state Li metal batteries of Li/CPEs/LiFePO_(4) at 2 C after 400 cycles and Li/CPEs/LiCoO_(2) at 0.2 C after 120 cycles deliver capacities of 100 and 152 mAh g^(-1) at 25℃,respectively.展开更多
Dual ion batteries(DIBs) exhibit broad application prospects in the field of electrical energy storage(EES)devices with excellent properties,such as high voltage,high energy density,and low cost.In the graphitebased D...Dual ion batteries(DIBs) exhibit broad application prospects in the field of electrical energy storage(EES)devices with excellent properties,such as high voltage,high energy density,and low cost.In the graphitebased DIBs,high voltage is needed to store enough anions with the formation of anion intercalation compound XCn(X=AlCl4-,PF6-,TFSI-,etc.).Hence,it is difficult for graphite-based DIBs to match proper anodes and electrolytes.Here,an Se/graphene composite is prepared via a convenient method,and assembled into a dual-ion full battery(DIFB) as anode with graphite cathode and 1 mol/L NaPF6 in EC:EMC(1:1,v:v).This DIFB has achieved a high discharge capacity of 75.9 mAh/g and high medium output voltage of 3.5 V at 0.1 A/g.Actually,the suitable anode materials,such as the present Se/graphene composite,are extremely important for the development and application of graphite-based DIBs.This study is enlightening for the design of future low-cost EES devices including graphite-based DIBs.展开更多
基金supported by National Natural Science Foundation of China(No.51902340)Chongqing Natural Science Foundation,and Chongqing Postdoctoral Science Foundation(No.2021000051).
文摘It is of great significance to develop clean and new energy sources with high-efficient energy storage technologies,due to the excessive use of fossil energy that has caused severe environmental damage.There is great interest in exploring advanced rechargeable lithium batteries with desirable energy and power capabilities for applications in portable electronics,smart grids,and electric vehicles.In practice,high-capacity and low-cost electrode materials play an important role in sustaining the progresses in lithium-ion batteries.This review aims at giving an account of recent advances on the emerging high-capacity electrode materials and summarizing key barriers and corresponding strategies for the practical viability of these electrode materials.Effective approaches to enhance energy density of lithium-ion batteries are to increase the capacity of electrode materials and the output operation voltage.On account of major bottlenecks of the power lithium-ion battery,authors come up with the concept of integrated battery systems,which will be a promising future for high-energy lithium-ion batteries to improve energy density and alleviate anxiety of electric vehicles.
基金supported by the foundation on the Creative Research Team Construction Promotion Project of Beijing Municipal Institutions and Science and Technology Foundation(ykj-2016-00161)partly supported by International Research Promotion Program(IRPR)of Osaka University
文摘High-voltage lithium-ion batteries(HVLIBs) are considered as promising devices of energy storage for electric vehicle, hybrid electric vehicle, and other high-power equipment. HVLIBs require their own platform voltages to be higher than 4.5 V on charge. Lithium nickel manganese spinel LiNi_(0.5)Mn_(1.5)O_4(LNMO) cathode is the most promising candidate among the 5 V cathode materials for HVLIBs due to its flat plateau at 4.7 V. However, the degradation of cyclic performance is very serious when LNMO cathode operates over 4.2 V. In this review, we summarize some methods for enhancing the cycling stability of LNMO cathodes in lithium-ion batteries, including doping, cathode surface coating,electrolyte modifying, and other methods. We also discuss the advantages and disadvantages of different methods.
基金This work is financially supported by the National Key R&D Program of China(No.2017YFE0198100)the National Natural Science Foundation of China(Nos.21975250 and 52072145)+4 种基金the Beijing Natural Science Foundation(No.2214061)the Scientific and Technological Developing Project of Jilin Province,China(No.YDZJ202101ZYTS185)the Capital Construction Fund Projects within the Budget of Jilin Province,China(No.2021C037-2)the Open Project Program of Key Laboratory of Preparation and Application of Environmental Friendly Materials(Jilin Normal University),Ministry of Education,China(No.2020005)the Open Program of State Key Laboratory of Metastable Materials Science and Technology(Yanshan University),China(No.202110).
文摘High-voltage high-nickel lithium layered oxide cathodes show great application prospects to meet the ever-increasing demand for further improvement of the energy density of rechargeable lithium-ion batteries(LIBs)mainly due to their high output capacity.However,severe bulk structural degradation and undesired electrode-electrolyte interface reactions seriously endanger the cycle life and safety of the battery.Here,2 mol%Ti atom is used as modified material doping into LiNi_(0.8)Co_(0.2)Mn_(0.2O2)(NCM)to reform LiNi_(0.6)Co_(0.2)Mn_(0.18)Ti_(0.02)O_(2)(NCM-Ti)and address the long-standing inherent problem.At a high cut-off voltage of 4.5 V,NCM-Ti delivers a higher capacity retention ratio(91.8%vs.82.9%)after 150 cycles and a superior rate capacity(118 vs.105 mAh·g^(-1))at the high current density of 10 C than the pristine NCM.The designed high-voltage full battery with graphite as anode and NCM-Ti as cathode also exhibits high energy density(240 Wh·kg^(-1))and excellent electrochemical performance.The superior electrochemical behavior can be attributed to the improved stability of the bulk structure and the electrode-electrolyte interface owing to the strong Ti-O bond and no unpaired electrons.The in-situ X-ray diffraction analysis demonstrates that Ti-doping inhibits the undesired H2-H3 phase transition,minimizing the mechanical degradation.The ex-situ TEM and X-ray photoelectron spectroscopy reveal that Ti-doping suppresses the release of interfacial oxygen,reducing undesired interfacial reactions.This work provides a valuable strategic guideline for the application of high-voltage high-nickel cathodes in LIBs.
基金supported by the National Natural Science Foundation of China(Grant No.21875071)the Guangzhou Scientific and Technological Planning Project(Grant No.201704030061)the Guangdong Key R&D Program of China(Grant No.2019B090908001)。
文摘Solid electrolytes with desirable properties such as high ionic conductivity,wide electrochemical stable window,and suitable mechanical strength,and stable electrode-electrolyte interfaces on both cathode and anode side are essential for high-voltage all-solid-state lithium batteries(ASSLBs)to achieve excellent cycle stability.In this work,a novel strategy of using LiF and LiNO_(3) as synergistic additives to boost the performance of PEO-PVDF/LLZTO-based composite solid electrolytes(CSEs)is developed,which also promotes the assembled high-voltage ASSLBs with dual-interfaces stability characteristic.Specifically,LiF as an inactive additive can increase the electrochemical stability of the CSE under high cut-off voltage,and improve the high-voltage compatibility between cathode and CSE,thus leading to a stable cathode/CSE interface.LiNO_(3) as an active additive can lead to an enhanced ionic conductivity of CSE due to the increased free-mobile Li+and ensure a stable CSE/Li interface by forming stable solid electrolyte interphase(SEI)on Li anode surface.Benefiting from the improved performance of CSE and stable dualinterfaces,the assembled NCM622/9[PEO_(15)-LiTFSI]-PVDF-15 LLZTO-2 LiF-3 LiNO_(3)/Li cell delivers a high rate capacity of 102.1 mAh g^(-1) at 1.0 C and a high capacity retention of 77.4%after 200 cycles at 0.5 C,which are much higher than those of the ASSLB assembled with additive-free CSE,with only 60.0 mAh g^(-1) and 52.0%,respectively.Furthermore,novel cycle test modes of resting for 5 h at different charge states after every 5 cycles are designed to investigate the high-voltage compatibility between cathode and CSE,and the results suggest that LiF additive can actually improve the high-voltage compatibility of cathode and CSE.All the obtained results confirm that the strategy of using synergistic additives in CSE is an effective way to achieve high-voltage ASSLBs with dual-interfaces stability.
基金the financial supports from the KeyArea Research and Development Program of Guangdong Province (2020B090919001)the National Natural Science Foundation of China (22078144)the Guangdong Natural Science Foundation for Basic and Applied Basic Research (2021A1515010138 and 2023A1515010686)。
文摘Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.
基金the National Key R&D Program of China(No.2017YFE0198100)the National Natural Science Foundation of China(No.21975250)+1 种基金the Key R&D Program of Jilin Province(No.20220201132GX),the Key R&D Program of Hubei Province(No.2022BAA084)the Capital Construction Fund Projects within the Budget of Jilin Province(2021C037-2).
文摘High-voltage medium-nickel low-cobalt lithium layered oxide cathode materials are becoming a popular development route for high-energy lithium-ion batteries due to their relatively high capacity,low cost,and improved safety.Unfortunately,capacity fading derived from surface lithium residue,electrode-electrolyte interfacial side reactions,and bulk structure degradation severely limits large-scale commercial utilization.In this work,an ultrathin and uniform NASICON-type Li_(3)V_(2)(PO_(4))_(3)(LVP)nanoscale functional coating is formed in situ by utilizing residual lithium to enhance the lithium storage performance of LiNi_(0.6)Co0.05Mn_(0.35)O_(2)(NCM)cathode.The GITT and ex-situ EIS and XPS demonstrate exceptional Li+diffusion and conductivity and attenuated interfacial side reactions,improving the electrode-electrolyte interface stability.The variable temperature in-situ XRD demonstrates delayed phase transition temperature to improve thermal stability.The battery in-situ XRD displays the singlephase H1-H2 reaction and weakened harmful H3 phase transition,minimizing the bulk mechanical degradation.These improvements are attributed to the removal of surface residual lithium and the formation of NASICON-type Li_(3)V_(2)(PO_(4))_(3)functional coatings with stable structure and high ionic and electronic conductivity.Consequently,the obtained NCM@LVP delivers a higher capacity retention rate(97.1%vs.79.6%)after 150 cycles and a superior rate capacity(87 mAh·g^(-1)vs.58 mAh·g^(-1))at a 5 C current density than the pristine NCM under a high cut-off voltage of 4.5 V.This work suggests a clever way to utilize residual lithium to form functional coatings in situ to improve the lithium storage performance of high-voltage medium-nickel low-cobalt cathode materials.
基金the National Natural Science Foundation of China(Nos.21771164,U1804129 and 21671205)Postdoctoral Research Grant in Henan Province(001702055)+1 种基金Center of Advanced Analysis&Gene Sequencing of Zhengzhou Universitythe Zhongyuan Youth Talent support program in Henan province。
文摘Fe-based sulfates are ideal cathode candidates for sodium-ion batteries(SIBs) owing to their high operating voltage and low cost but suffer from the nature of poor power performance. Herein, a hierarchical porous Na2Fe(SO4)2@reduced graphene oxide/carbon dot(Na2Fe(SO4)2@rGO/C) with low carbon content(4.12 wt%) was synthesized via a facile homogeneous strategy benefiting for engineering application,which delivers excellent sodium storage performance(high voltage plateau of 3.75 V, 85 m Ah g-1 and330 Wh kg-1 at 0.05 C;5805 W kg-1 at 10 C) and high Na+diffusion coefficient(1.19 × 10-12 cm2 s-1).Moreover, the midpoint voltage of assembled full cell could reach 3.0 V. The electron transfer and reaction kinetics are effectively boosted since the nanoscale Na2Fe(SO4)2 is supported by a robust crosslinked carbon matrix with rGO sheets and carbon dots. The slight rGO sheets sufficiently enhance the electron transfer like a current collecter and restrain the aggregation, as well as ensure smooth ion channels. Meanwhile, the carbon dots in the whole space connect with Na2Fe(SO4)2 and help rGO to promote the conductivity of the electrode. Ex-situ X-ray powder diffraction and X-ray photoelectron spectrometry analysis confirm the high reversibility of this sodiation/desodiation process.
基金supported in part by the Zhengzhou Materials Genome Institutethe National Natural Science Foundation of China(No.52171082,51001091,51571182,111174256,91233101,51602094,11274100)the Program for Science&Technology Innovation Talents in the Universities of Henan Province(18HASTIT009)。
文摘While argyrodite sulfides are getting more and more attention as highly promising solid-state electrolytes(SSEs)for solid batteries,they also suffer from the typical sulfide setbacks such as poor electrochemical compatibility with Li anode and high-voltage cathodes and serious sensitivity to humid air,which hinders their practical applications.Herein,we have devised an effective strategy to overcome these challenging shortcomings through modification of chalcogen chemistry under the guidance of theoretical modeling.The resultant Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)delivered excellent electrochemical compatibility with both pure Li anode and high-voltage LiCoO_(2)cathode,without compromising the superb ionic conductivity of the pristine sulfide.Furthermore,the current SSE also exhibited highly improved stability to oxygen and humidity,with further advantage being more insulating to electrons.The remarkably enhanced compatibility with electrodes is attributed to in situ formation of helpful electrolyte–electrode interphases.The formation of in situ anode–electrolyte interphase(AEI)enabled stable Li plating/stripping in the Li|Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)|Li symmetric cells at a high current density up to 1 mA cm^(-2)over 200 h and 2 mA cm^(-2)for another 100 h.The in situ amorphous nano-film cathode–electrolyte interphase(CEI)facilitated protection of the SSE from decomposition at elevated voltage.Consequently,the synergistic effect of AEI and CEI helped the LiCoO_(2)|Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)|Li full-battery cell to achieve markedly better cycling stability than that using the pristine Li_(6)PS_(5)Cl as SSE,at a high area loading of the active cathode material(4 mg cm^(-2))in type-2032 coin cells.This work is to add a desirable SSE in the argyrodite sulfide family,so that high-performance solid battery cells could be fabricated without the usual need of strict control of the ambient atmosphere.
基金financial support from the Foundation for Innovative Research Groups of the National Natural Science Foundation of China (No. NSFC51621001)the Guangdong Special Support Program (2017TQ04N224)+1 种基金the Guangdong Natural Science Funds for Distinguished Young Scholar (Grant No. 2017B030306004)the Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme。
文摘O3-type Na NiO_(2)-based cathode materials undergo irreversible phase transition and serious capacity decay at high voltage above 4.0 V in sodium-ion batteries. To address these challenges, effects of Fsubstitution on the structure and electrochemical performance of Na Ni_(0.4)Mn_(0.25)Ti_(0.3)Co_(0.05)O_(2) are investigated in this article. The F-substitution leads to expanding of interlayer, which can enhance the mobility of Na+. NaNi_(0.4)Mn_(0.25)Ti_(0.3)Co_(0.05)O_(1.92)F_(0.08)(NMTC-F_(0.08)) with the optimal F-substitution degree exhibits much improved rate capability and cyclic stability. It delivers reversible capacities of 177 and 97 m Ah g^(-1) at 0.05 and 5 C within 2.0–4.4 V, respectively. Galvanostatic intermittent titration technique verifies faster kinetics of Na+diffusion in NMTC-F_(0.08). And in-situ XRD investigation reveals the phase evolution of NMTC-F_(0.08), indicating enhanced structural stability results from F-substitution. This study may shed light on the development of high performance cathode materials for sodium-ion storage at high voltage.
基金We acknowledge financial support from The Shenzhen Science and Technology Research Grant(No.JCYJ20200109140416788)Soft Science Research Project of Guangdong Province(No.2017B030301013)The National Natural Science Foundation of China(No.52102200).
文摘Poly(ethylene oxide)(PEO)-based solid polymer electrolyte(SPE)is considered as a promising solid-state electrolyte for all-solid-state lithium batteries(ASSLBs).Nevertheless,the poor interfacial stability with high-voltage cathode materials(e.g.,LiCoO_(2))restricts its application in high energy density solid-state batteries.Herein,high-voltage stable Li_(3)AlF_(6) protective layer is coated on the surface of LiCoO_(2) particle to improve the performance and investigate the failure mechanism of PEO-based ASSLBs.The phase transition unveils that chemical redox reaction occurs between the highly reactive LiCoO_(2) surface and PEO-based SPE,resulting in structure collapse of LiCoO_(2),hence the poor cycle performance of PEO-based ASSLBs with LiCoO_(2) at charging voltage of 4.2 V vs Li/Li+.By sharp contrast,no obvious structure change can be found at the surface of Li_(3)AlF_(6)-coated LiCoO_(2),and the original layered phase was well retained.When the charging voltage reaches up to 4.5 V vs Li/Li+,the intensive electrochemical decomposition of PEO-based SPE occurs,leading to the constant increase of cell impedance and directly causing the poor performance.This work not only provides important supplement to the failure mechanism of PEO-based batter-ies with LiCoO_(2),but also presents a universal strategy to retain structure stability of cathode-electrolyte interface in high-voltage ASSLBs.
基金financially supported by the National Natural Science Foundation of China (Nos. 51972023, 11210304)
文摘PEO-based all-solid-state electrolytes are extensively utilized and researched owing to their exceptional safety,low-mass-density,and cost-effectiveness.However,the low oxidation potential of PEO makes the interface problem with the high-voltage cathode extremely severe.In this work,the impedance of PEO-based all-solid-state batteries with high-voltage cathode(NCM811)was studied at different potentials.The Nyquist plots displayed a gyrate arc at low-frequencies for NCM811/PEO interface.Based on the kinetic modeling,it was deduced that there is a decomposition reaction of PEO-matrix in addition to de-embedded reaction of NCM811,and the PEO intermediate product(dehydra-PEO)adsorbed on the electrode surface leading to low-frequency inductive arcs.Furthermore,the distribution of relaxation time shows the dehydra-PEO results in the kinetic tardiness of the charge transfer process in the temporal dimension.Hence,an artificial interface layer(CEI_(x))was modified on the surface of NCM811 to regulate the potential of cathode/electrolyte interface to prevent the high-voltage deterioration of PEO.NCM/CEI_(x)/PEO batteries exhibit capacity retentions of 96.0%,84.6%,and 76.8%after undergoing 100 cycles at cut-off voltages of 4.1,4.2,and 4.3 V,respectively.Therefore,here the failure mechanism of high-voltage PEO electrolyte is investigated by EIS and a proposed solving strategy is presented.
基金supported by the National Natural Science Foundation of China(Nos.22209075,12004145)the Key Science and Technology Plan Project of Ji’an City(No.20211-015311)the Natural Science Foundation of Jiangsu Province(No.BK20200800).
文摘LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)with a spinel crystal structure presents a compelling avenue towards the development of economic cobalt-free and high voltage(~5 V)lithium-ion batteries.Nevertheless,the elevated operational voltage of LNMO gives rise to pronounced interfacial interactions between the distorted surface lattices characterized by Jahn-Teller(J-T)distortions and the electrolyte constituents.Herein,a localized crystallized coherent LaNiO_(3) and surface passivated Li_(3)PO_(4) layer is deposited on LNMO via a one-step calcination process.As evidenced by transmission electron microscopy(TEM),time-of-flight secondary ion mass spectrometry(ToF-SIMS)and density functional theory(DFT)calculation,the epitaxial growth of LaNiO_(3) along the LNMO lattice can effectively stabilize the structure and inhibit irreversible phase transitions,and the Li_(3)PO_(4) surface coating can prevent the chemical reaction between HF and transition metals without sacrificing the electrochemical activity.In addition,the ionic conductive Li_(3)PO_(4) and atomic wetting inter-layer enables fast charge transfer transport property.Consequently,the LNMO material enabled by the lattice bonding and surface passivating features,demonstrates high performance at high current densities and good capacity retention during long-term test.The rational design of interface coherent engineering and surface coating layers of the LNMO cathode material offers a new perspective for the practical application of high-voltage lithium-ion batteries.
基金supported by Research Grants Council of the Hong Kong Special Administrative Region under grant(Nos.R5019-22 and C1002-21G).
文摘Lithium-ion batteries play a crucial role in storing energy for renewable sources and electric vehicles,yet face challenges related to insufficient energy density.Elevating the working-voltage of cathodes is promising to boost the energy density of batteries by increasing both the output voltage and capacity of cathode,which however could compromise life cycle and safety.This review provides a comprehensive summary of essential factors governing pathways of cathode-induced thermal runaway,including electrolyte decomposition,phase transitions,and crosstalk-induced reactions.Electrode and electrolyte modifications aimed at mitigating parasitic reactions and preventing crosstalk were also discussed.The review concludes with insights into the future application of these strategies,providing a comprehensive perspective on the realization of high-energy and safe batteries.
基金National Natural Science Foundation of China(22005163,U1932205)Natural Science Foundation of Shandong Province(ZR2020MA084)+1 种基金Key R&D Program of Shandong Province(2021CXGC010401)Taishan Scholars Program(ts201712035)。
基金supported by the National Natural Science Foundation of China(22179124,21905265)the Fundamental Research Funds for the Central Universities(WK3430000007)。
文摘Ethers are promising electrolyte solvents for secondary Li metal batteries because of their excellent reduction stability.However,their oxidation stability has been mostly relying on the high concentration approach,and limited progress has been made on building effective interphase to protect the cathode from the corrosion of the electrolyte.In this work,we construct a semi-crystalline interfacial layer on the surface of Li(Ni_(0.8)Co_(0.1)Mn_(0.1))O_(2)cathode that can achieve improved electrochemical stability in the highly corrosive chemical environment formed by the decomposition of ether molecules.Different from traditional brittle crystalline interphases,the optimized semi-crystalline layer with low modulus and high ionic conductivity can effectively relieve electrode strain and maintain the integrity of the interface layer.Due to this design,the continuous oxidation decomposition of ether-based electrolytes could be significantly suppressed and the battery shows outstanding cycling stability(84%capacity retention after 300 cycles).This article provides a solution to address the oxidation instability issue of ether-based electrolytes.
基金the National Key Research and Development Program of China (No. 2020YFC1909604)the Shenzhen Key Projects of Technological Research (JSGG2020092514 5800001)。
文摘The isolated inorganic particles within composite polymer electrolytes(CPEs) are not correlated to the Li^(+)transfer network,resulting in the polymer dominating the low ionic conductivity of CPEs.Therefore,we developed novel quasi-solid-state CPEs of a Ce-doped Na super ion conductors(NASICON)Na_(1.3+x)Al_(0.3)Ce_(x)Ti_(1.7-x)(PO_(4))_(3)(NCATP) chemically coupled poly(vinylidene fluoride-hexafluoropropylene)(PVDF-HFP)/Li-bis(trifluoromethanes-ulfonyl)imide(LiTFSI) matrix.A strong interaction between Ce^(3+)from NCATP and TFSI-anion from the polymer matrix contributes to the fast Li+transportation at the interface.The PVDF-HFP/NCATP CPEs exhibit an ionic conductivity of 2.16 × 0^(-3) S cm^(-1) and a Li^(+) transference number of 0.88.A symmetric Li/Li cell with NCATP-integrated CPEs at 0.1 mA cm^(-2) presents outstanding cycling stability over 2000 h at 25℃.The quasi-solid-state Li metal batteries of Li/CPEs/LiFePO_(4) at 2 C after 400 cycles and Li/CPEs/LiCoO_(2) at 0.2 C after 120 cycles deliver capacities of 100 and 152 mAh g^(-1) at 25℃,respectively.
基金financial support by the National Natural Science Foundation of China(No.91963118)Fundamental Research Funds for the Central Universities(No.2412019ZD010)。
文摘Dual ion batteries(DIBs) exhibit broad application prospects in the field of electrical energy storage(EES)devices with excellent properties,such as high voltage,high energy density,and low cost.In the graphitebased DIBs,high voltage is needed to store enough anions with the formation of anion intercalation compound XCn(X=AlCl4-,PF6-,TFSI-,etc.).Hence,it is difficult for graphite-based DIBs to match proper anodes and electrolytes.Here,an Se/graphene composite is prepared via a convenient method,and assembled into a dual-ion full battery(DIFB) as anode with graphite cathode and 1 mol/L NaPF6 in EC:EMC(1:1,v:v).This DIFB has achieved a high discharge capacity of 75.9 mAh/g and high medium output voltage of 3.5 V at 0.1 A/g.Actually,the suitable anode materials,such as the present Se/graphene composite,are extremely important for the development and application of graphite-based DIBs.This study is enlightening for the design of future low-cost EES devices including graphite-based DIBs.
