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
Solid-state polymer electrolytes(SPEs) capable of withstanding high voltage are considered to be key for next-generation energy storage devices with inherent safety as well as high energy density.This study involves t...Solid-state polymer electrolytes(SPEs) capable of withstanding high voltage are considered to be key for next-generation energy storage devices with inherent safety as well as high energy density.This study involves the rational design of solid-state-C≡N functionalized P(VEC_1-CEA_(0.3))/LiTFSI@CE SPEs and its synthesis by in-situ free radical polymerization of vinyl ethylene carbonate(VEC) and 2-cyanoethyl acrylate(CEA).In situ polymerization yields electrode/electrolyte interfaces with low interfacial resistance,forming a stable SEI layer enriched with LiF,Li_(3)N,and RCOOLi,ensuring stable Li plating/stripping for over 1400 h.The-C≡N moiety renders the αH on the adjacent αC positively charged,thereby endowing it with the capability to anchor TFSI^(-).Simultaneously,the incorporation of-C≡N moiety diminishes the electron-donating ability of the C=O,C-O-C,and-C≡N functional groups,facilitating not only the ion conductivity enhancement but also a more rapid Li^(+)migration proved by DFT theoretical calculations and Raman spectroscopy.At room temperature,t_(Li+) of 0.60 for P(VEC_1-CEA_(0.3))/LiTFSI@CE SPEs is achieved when the ionic conductivity σ_(Li+)is 2.63×10^(-4) S cm^(-1) and the electrochemical window is expanded to5.0 V.Both coin cells with high-areal-loading cathodes and the 6.5-mAh pouch cell,exhibit stable charge/discharge cycling.At 25℃,the 4.45-V Li|P(VEC_1-CEA_(0.3))/LiTFSI@CE|LiCoO_(2) battery performs stable cycling over 200 cycles at 0.2 C,with a capacity retention of 82.1%.展开更多
Cathode materials that possess high output voltage,as well as those that can be mass-produced using facile techniques,are crucial for the advancement of aqueous zinc-ion battery(ZIBs)applications,Herein,we present for...Cathode materials that possess high output voltage,as well as those that can be mass-produced using facile techniques,are crucial for the advancement of aqueous zinc-ion battery(ZIBs)applications,Herein,we present for the first time a new porous K_(0.5)VOPO_(4)·1.5H_(2)O polyanionic cathode(P-KIVP)with high output voltage(above 1.2 V)that can be manufactured at room temperature using straightforward coprecipitation and etching techniques.The P-KVP cathode experiences anisotropic crystal plane expansion via a sequential solid-solution intercalation and phase co nversion pathway throughout the Zn^(2+)storage process,as confirmed by in-situ synchrotron X-ray diffraction and ex-situ X-ray photoelectron spectroscopy.Similar to other layered vanadium-based polyanionic materials,the P-KVP cathode experiences a progressive decline in voltage during the cycle,which is demonstrated to be caused by the irreversible conversion into amorphous VO_(x).By introducing a new electrolyte containing Zn(OTF)_(2) to a mixed triethyl phosphate and water solution,it is possible to impede this irreversible conversion and obtain a high output voltage and longer cycle life by forming a P-rich cathode electrolyte interface layer.As a proof-of-concept,the flexible fiber-shaped ZIBs based on modified electrolyte woven into a fabric watch band can power an electronic watch,highlighting the application potential of P-KVP cathode.展开更多
With the increasing scale of energy storage,it is urgently demanding for further advancements on battery technologies in terms of energy density,cost,cycle life and safety.The development of lithium-ion batteries(LIBs...With the increasing scale of energy storage,it is urgently demanding for further advancements on battery technologies in terms of energy density,cost,cycle life and safety.The development of lithium-ion batteries(LIBs)not only relies on electrodes,but also the functional electrolyte systems to achieve controllable formation of solid electrolyte interphase and high ionic conductivity.In order to satisfy the needs of higher energy density,high-voltage(>4.3 V)cathodes such as Li-rich layered compounds,olivine LiNiPO_(4),spinel LiNi_(0.5)Mn_(1.5)O_(4) have been extensively studied.However,high-voltage cathodebased LIBs fade rapidly mainly owing to the anodic decomposition of electrolytes,gradually thickening of interfacial passivation layer and vast irreversible capacity loss,hence encountering huge obstacle toward practical applications.To tackle this roadblock,substantial progress has been made toward oxidation-resistant electrolytes to block its side reaction with high-voltage cathodes.In this review,we discuss degradation mechanisms of electrolytes at electrolyte/cathode interface and ideal requirements of electrolytes for high-voltage cathode,as well as summarize recent advances of oxidation-resistant electrolyte optimization mainly from solvents and additives.With these insights,it is anticipated that development of liquid electrolyte tolerable to high-voltage cathode will boost the large-scale practical applications of high-voltage cathode-based LIBs.展开更多
The thermal stability window of current commercial carbonate-based electrolytes is no longer sufficient to meet the ever-increasing cathode working voltage requirements of high energy density lithium-ion batteries.It ...The thermal stability window of current commercial carbonate-based electrolytes is no longer sufficient to meet the ever-increasing cathode working voltage requirements of high energy density lithium-ion batteries.It is crucial to construct a robust cathode-electrolyte interphase(CEI)for high-voltage cathode electrodes to separate the electrolytes from the active cathode materials and thereby suppress the side reactions.Herein,this review presents a brief historic evolution of the mechanism of CEI formation and compositions,the state-of-art characterizations and modeling associated with CEI,and how to construct robust CEI from a practical electrolyte design perspective.The focus on electrolyte design is categorized into three parts:CEI-forming additives,anti-oxidation solvents,and lithium salts.Moreover,practical considerations for electrolyte design applications are proposed.This review will shed light on the future electrolyte design which enables aggressive high-voltage cathodes.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
Porous LiNiVO4 powder was synthesized via solution combustion synthesis method using lithium nitrate, nickel nitrate,ammonium metavanadate and citric acid as raw materials. Thermogravimetry (TG) and differential scann...Porous LiNiVO4 powder was synthesized via solution combustion synthesis method using lithium nitrate, nickel nitrate,ammonium metavanadate and citric acid as raw materials. Thermogravimetry (TG) and differential scanning calorimetry (DSC),X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy and transmission electron microscopy (TEM) were used toevaluate the structures and morphologies of samples. The results show that the calcination temperature has significant effect on thecrystallinity and morphologies. Pure LiNiVO4 flaky nanoparticles with a mean particle size around 20 nm can be readily prepared bycalcining the precursor in air at 500 °C for 2 h. As a cathode material for lithium-ion batteries, the porous LiNiVO4 powder exhibits agood structural reversibility.展开更多
LiNi_(0.5)Mn_(1.5)O_(4)was prepared under various conditions by one-step solid-state reaction in air and its properties were investigated by X-ray diffractormetry(XRD),scanning electron microscopy(SEM)and electrochemi...LiNi_(0.5)Mn_(1.5)O_(4)was prepared under various conditions by one-step solid-state reaction in air and its properties were investigated by X-ray diffractormetry(XRD),scanning electron microscopy(SEM)and electrochemical measurement.XRD patterns show that LiNi_(0.5)Mn_(1.5)O_(4)synthesized under various conditions has cubic spinel structure.SEM images exhibit that the particle size increases with increasing calcination temperature and time.Electro chemical test shows that the LiNi_(0.5)Mn_(1.5)O_(4)calcined at 700℃for 24 h delivers up to 143 mA·h/g,and the capacity retains 132 mA·h/g after 30 cycles.展开更多
Lithium cobalt phosphate (LiCoPO4, LCP), having a high operating potential (4.8 V vs. Li/Li+), a flat voltage profile and a good theoretical capacity (167 mAh/g), is considered a promising cathode material for improvi...Lithium cobalt phosphate (LiCoPO4, LCP), having a high operating potential (4.8 V vs. Li/Li+), a flat voltage profile and a good theoretical capacity (167 mAh/g), is considered a promising cathode material for improving the energy density of lithium-ion batteries (LIBs) [1] [2]. Here we report a category of method for synthesizing LCP, the solvothermal (ST) method with a binary solvent (deionized water: ethyl alcohol = 1:1), controlling the concentration of cobalt ion in 0.05 mol/L (ST-0.05) and 0.25mol/L (ST-0.25). The material phase was apparently identified via X-ray diffraction (XRD). Observed by scanning electron microscopy (SEM), the grain size of LCP powders synthesizing by solvothermal method with two kinds of the concentration of cobalt ion were 400 × 400 × 1000 nm cuboids (ST-0.05) and 150 × 150 × 250 nm hexagonal prisms containing nanoparticles (ST-0.25), respectively. Discharge capacities of LCP were 76.0 mAh/g (ST-0.05) and 94.5 mAh/g (ST-0.25), in the first cycle at 0.1 C, respectively.展开更多
Sulfide solid electrolytes(SEs)have attracted ever-increasing attention due to their superior roomtemperature ionic conductivity(~10^(-2) S cm^(-1)).Additionally,the integration of sulfide SEs and highvoltage cathodes...Sulfide solid electrolytes(SEs)have attracted ever-increasing attention due to their superior roomtemperature ionic conductivity(~10^(-2) S cm^(-1)).Additionally,the integration of sulfide SEs and highvoltage cathodes is promising to achieve higher energy density.However,the incompatible interfaces between sulfide SEs and high-voltage cathodes have been one of the key factors limiting their applications.Therefore,this review presents a critical summarization of the interfacial issues in all-solid-state lithium batteries based on sulfide SEs and high-voltage cathodes and proposes strategies to stabilize the electrolyte/cathode interfaces.Moreover,the future research direction of electrolyte/cathode interfaces and application prospects of powder technology in sulfide-based ASSLBs were also discussed.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
Advancing high-voltage stability of layered sodium-ion oxides represents a pivotal avenue for their progress in energy storage applications.Despite this,a comprehensive understanding of the mechanisms underpinning the...Advancing high-voltage stability of layered sodium-ion oxides represents a pivotal avenue for their progress in energy storage applications.Despite this,a comprehensive understanding of the mechanisms underpinning their structural deterioration at elevated voltages remains insufficiently explored.In this study,we unveil a layer delamination phenomenon of Na_(0.67)Ni_(0.3)Mn_(0.7)O_(2)(NNM)within the 2.0-4.3 V voltage,attributed to considerable volumetric fluctuations along the c-axis and lattice oxygen reactions induced by the simultaneous Ni^(3+)/Ni^(4+)and anion redox reactions.By introducing Mg doping to diminished Ni-O antibonding,the anion oxidation-reduction reactions are effectively mitigated,and the structural integrity of the P2 phase remains firmly intact,safeguarding active sites and precluding the formation of novel interfaces.The Na_(0.67)Mg_(0.05)Ni_(0.25)Mn_(0.7)O_(2)(NMNM-5)exhibits a specific capacity of100.7 mA h g^(-1),signifying an 83%improvement compared to the NNM material within the voltage of2.0-4.3 V.This investigation underscores the intricate interplay between high-voltage stability and structural degradation mechanisms in layered sodium-ion oxides.展开更多
Benefited from its high process feasibility and controllable costs,binary-metal layered structured LiNi_(0.8)Mn_(0.2)O_(2)(NM)can effectively alleviate the cobalt supply crisis under the surge of global electric vehic...Benefited from its high process feasibility and controllable costs,binary-metal layered structured LiNi_(0.8)Mn_(0.2)O_(2)(NM)can effectively alleviate the cobalt supply crisis under the surge of global electric vehicles(EVs)sales,which is considered as the most promising nextgeneration cathode material for lithium-ion batteries(LIBs).However,the lack of deep understanding on the failure mechanism of NM has seriously hindered its application,especially under the harsh condition of high-voltage without sacrifices of reversible capacity.Herein,singlecrystal LiNi_(0.8)Mn_(0.2)O_(2) is selected and compared with traditional LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM),mainly focusing on the failure mechanism of Cofree cathode and illuminating the significant effect of Co element on the Li/Ni antisite defect and dynamic characteristic.Specifically,the presence of high Li/Ni antisite defect in NM cathode easily results in the extremely dramatic H2/H3 phase transition,which exacerbates the distortion of the lattice,mechanical strain changes and exhibits poor electrochemical performance,especially under the high cutoff voltage.Furthermore,the reaction kinetic of NM is impaired due to the absence of Co element,especially at the single-crystal architecture.Whereas,the negative influence of Li/Ni antisite defect is controllable at low current densities,owing to the attenuated polarization.Notably,Co-free NM can exhibit better safety performance than that of NCM cathode.These findings are beneficial for understanding the fundamental reaction mechanism of single-crystal Ni-rich Co-free cathode materials,providing new insights and great encouragements to design and develop the next generation of LIBs with low-cost and high-safety performances.展开更多
Lithium-ion batteries(LIBs)with the“double-high”characteristics of high energy density and high power density are in urgent demand for facilitating the development of advanced portable electronics.However,the lithiu...Lithium-ion batteries(LIBs)with the“double-high”characteristics of high energy density and high power density are in urgent demand for facilitating the development of advanced portable electronics.However,the lithium ion(Li+)-storage performance of the most commercialized lithium cobalt oxide(LiCoO_(2),LCO)cathodes is still far from satisfactory in terms of high-voltage and fast-charging capabilities for reaching the double-high target.Herein,we systematically summarize and discuss high-voltage and fast-charging LCO cathodes,covering in depth the key fundamental challenges,latest advancements in modification strategies,and future perspectives in this field.Comprehensive and elaborated discussions are first presented on key fundamental challenges related to structural degradation,interfacial instability,the inhomogeneity reactions,and sluggish interfacial kinetics.We provide an instructive summary of deep insights into promising modification strategies and underlying mechanisms,categorized into element doping(Li-site,cobalt-/oxygen-site,and multi-site doping)for improved Li+diffusivity and bulkstructure stability;surface coating(dielectrics,ionic/electronic conductors,and their combination)for surface stability and conductivity;nanosizing;combinations of these strategies;and other strategies(i.e.,optimization of the electrolyte,binder,tortuosity of electrodes,charging protocols,and prelithiation methods).Finally,forward-looking perspectives and promising directions are sketched out and insightfully elucidated,providing constructive suggestions and instructions for designing and realizing high-voltage and fast-charging LCO cathodes for next-generation double-high LIBs.展开更多
P2-type Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2)is considered as a potential cathode material for sodium-ion batteries due to the merits of high voltage,low cost,and air stability.However,the unsatisfied cycling stability and...P2-type Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2)is considered as a potential cathode material for sodium-ion batteries due to the merits of high voltage,low cost,and air stability.However,the unsatisfied cycling stability and rate performance caused by the destructive phase transition and side reactions hinder its practical application.Herein,we present a feasible dual strategy of Mg^(2+)doping integrated with ZrO_(2)surface modification for P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2),which can well address the issues of phase transition and side reactions benefitting from the enhanced structural and interfacial stabilities.Specifically,it exhibits a decent cycling stability with a capacity retention of 81.5%at 1 C and promising rate performance with a discharge capacity of 76.6 mA h g^(−1)at 5 C.The in situ X-ray diffraction measurement confirms that the damaged P2-O2 phase transition is suppressed with better reversibility in high-voltage region,whereas the side reactions are inhibited due to the protective ZrO_(2)surfacemodification.Commendably,the full cell achieves an outstanding operating voltage of 3.57 V and a fabulous energy density of 238.91 W h kg^(−1)at 36.73 W kg^(−1),demonstrating great practicability.This work is expected to provide a new insight for designing stable high-voltage cathode materials and high energy density full cells for sodium ion batteries.展开更多
The Co-free Li Ni_(0.5)Mn_(1.5)O_(4)(LNMO)is a promising cathode for lithium-ion batteries owing to its high operating voltage and low costs.However,the synthesis of LNMO is generally time and energy consuming,and its...The Co-free Li Ni_(0.5)Mn_(1.5)O_(4)(LNMO)is a promising cathode for lithium-ion batteries owing to its high operating voltage and low costs.However,the synthesis of LNMO is generally time and energy consuming,and its practical application is hindered by the lack of a compatible electrolyte.Herein,a spray pyrolysis-based energy-saving synthesis method as well as a diluted low concentration electrolyte(0.5 M LiPF_(6) in a mixture of fluoroethylene carbonate/dimethyl carbonate/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(FEC:DMC:TTE,1:4:5 by volume))are proposed to address these challenges.Owing to the unique features of the precursor prepared by spray pyrolysis,well-crystallized LNMO single-crystal can be obtained within 1 h calcination at 900℃.Besides,the fluorinated interphases derived from the diluted low concentration electrolyte not only mitigate the Mn dissolution and Al corrosion at the cathode side,but also suppresses dendritic Li deposition at the anode side,thus enabling stable cycling of both LNMO and Li metal anode.Thus,30μm Li|LNMO(1.75 m A h cm^(-2))cells achieve a high capacity retention(90.9%)after 168 cycles in the diluted low concentration electrolyte.展开更多
LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) is extensively researched as one of the most widely used commercially materials for Li-ion batteries at present.However,the poor high-voltage performance(≥4.3 V)with low reversible cap...LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) is extensively researched as one of the most widely used commercially materials for Li-ion batteries at present.However,the poor high-voltage performance(≥4.3 V)with low reversible capacity limits its replacement for LiCoO_(2) in high-end digital field.Herein,three-in-one modification,Na-doping and Al_(2)O_(3)@Li_(3)BO_(3) dual-coating simultaneously,is explored for single-crystalline LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(N-NCM@AB),which exhibits excellent high-voltage performance.N-NCM@AB displays a discharge-specific capacity of 201.8 mAh g^(−1) at 0.2 C with a high upper voltage of 4.6 V and maintains 158.9 mAh g^(−1) discharge capacity at 1 C over 200 cycles with the corresponding capacity retention of 87.8%.Remarkably,the N-NCM@AB||graphite pouch-type full cell retains 81.2% of its initial capacity with high working voltage of 4.4 V over 1600 cycles.More importantly,the fundamental understandings of three-in-one modification on surface morphology,crystal structure,and phase transformation of N-NCM@AB are clearly revealed.The Na+doped into the Li–O slab can enhance the bond energy,stabilize the crystal structure,and facilitate Li+transport.Additionally,the interior surface layer of Li^(+)-ions conductor Li_(3)BO_(3) relieves the charge transfer resistance with surface coating,whereas the outer surface Al_(2)O_(3) coating layer is beneficial for reducing the active materials loss and alleviating the electrode/electrolyte parasite reaction.This three-in-one strategy provides a reference for the further research on the performance attenuation mechanism of NCM,paving a new avenue to boost the high-voltage performance of NCM cathode in Li-ion batteries.展开更多
Li-ion batteries(LIBs)have gained wide recognition as effective energy storage devices and power supply sources due to their exceptional volumetric energy density,mass energy density and cycling performance.The cathod...Li-ion batteries(LIBs)have gained wide recognition as effective energy storage devices and power supply sources due to their exceptional volumetric energy density,mass energy density and cycling performance.The cathode materials,a key component of LIBs,play a crucial role in determining the electrochemical performance of these batteries.Therefore,there is an increasing demand to explore and investigate suitable high-energy electrode materials that can provide greater capacity and output voltage for the next generation of LIBs.This paper aims to provide a comprehensive overview of the latest researches on five typical high-voltage cathode materials.Specifically,this review will focus on the detailed analysis of their crystalline structures,reaction mechanisms during cycling,current research status and strategies aimed at improving or enhancing their overall electrochemical performance.Overall,the insights presented in this review will help researchers design and develop high-energy cathode materials with improved performance for the next generation of LIBs.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
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
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National Natural Science Foundation of China (22078228)。
文摘Solid-state polymer electrolytes(SPEs) capable of withstanding high voltage are considered to be key for next-generation energy storage devices with inherent safety as well as high energy density.This study involves the rational design of solid-state-C≡N functionalized P(VEC_1-CEA_(0.3))/LiTFSI@CE SPEs and its synthesis by in-situ free radical polymerization of vinyl ethylene carbonate(VEC) and 2-cyanoethyl acrylate(CEA).In situ polymerization yields electrode/electrolyte interfaces with low interfacial resistance,forming a stable SEI layer enriched with LiF,Li_(3)N,and RCOOLi,ensuring stable Li plating/stripping for over 1400 h.The-C≡N moiety renders the αH on the adjacent αC positively charged,thereby endowing it with the capability to anchor TFSI^(-).Simultaneously,the incorporation of-C≡N moiety diminishes the electron-donating ability of the C=O,C-O-C,and-C≡N functional groups,facilitating not only the ion conductivity enhancement but also a more rapid Li^(+)migration proved by DFT theoretical calculations and Raman spectroscopy.At room temperature,t_(Li+) of 0.60 for P(VEC_1-CEA_(0.3))/LiTFSI@CE SPEs is achieved when the ionic conductivity σ_(Li+)is 2.63×10^(-4) S cm^(-1) and the electrochemical window is expanded to5.0 V.Both coin cells with high-areal-loading cathodes and the 6.5-mAh pouch cell,exhibit stable charge/discharge cycling.At 25℃,the 4.45-V Li|P(VEC_1-CEA_(0.3))/LiTFSI@CE|LiCoO_(2) battery performs stable cycling over 200 cycles at 0.2 C,with a capacity retention of 82.1%.
基金financially supported by National Natural Science Foundation of China(No.52102270)the Natural Science Foundation of Shandong Province of China(ZR2021QE002)+1 种基金the support from the Institute startup grant from Qingdao Universitythe Shandong Center for Engineered Nonwovens(SCEN)。
文摘Cathode materials that possess high output voltage,as well as those that can be mass-produced using facile techniques,are crucial for the advancement of aqueous zinc-ion battery(ZIBs)applications,Herein,we present for the first time a new porous K_(0.5)VOPO_(4)·1.5H_(2)O polyanionic cathode(P-KIVP)with high output voltage(above 1.2 V)that can be manufactured at room temperature using straightforward coprecipitation and etching techniques.The P-KVP cathode experiences anisotropic crystal plane expansion via a sequential solid-solution intercalation and phase co nversion pathway throughout the Zn^(2+)storage process,as confirmed by in-situ synchrotron X-ray diffraction and ex-situ X-ray photoelectron spectroscopy.Similar to other layered vanadium-based polyanionic materials,the P-KVP cathode experiences a progressive decline in voltage during the cycle,which is demonstrated to be caused by the irreversible conversion into amorphous VO_(x).By introducing a new electrolyte containing Zn(OTF)_(2) to a mixed triethyl phosphate and water solution,it is possible to impede this irreversible conversion and obtain a high output voltage and longer cycle life by forming a P-rich cathode electrolyte interface layer.As a proof-of-concept,the flexible fiber-shaped ZIBs based on modified electrolyte woven into a fabric watch band can power an electronic watch,highlighting the application potential of P-KVP cathode.
基金supported by the National Natural Science Foundation of China(No.22071133)the China Postdoctoral Science Foundation(No.2021M691763)+1 种基金the Tsinghua-Foshan Innovation Special Fund(TFISF),China(No.2020THFS0130)the Fund of the Tsinghua University-China Petrochemical Corporation Joint Institute for Green Chemical Engineering(No.421120).
文摘With the increasing scale of energy storage,it is urgently demanding for further advancements on battery technologies in terms of energy density,cost,cycle life and safety.The development of lithium-ion batteries(LIBs)not only relies on electrodes,but also the functional electrolyte systems to achieve controllable formation of solid electrolyte interphase and high ionic conductivity.In order to satisfy the needs of higher energy density,high-voltage(>4.3 V)cathodes such as Li-rich layered compounds,olivine LiNiPO_(4),spinel LiNi_(0.5)Mn_(1.5)O_(4) have been extensively studied.However,high-voltage cathodebased LIBs fade rapidly mainly owing to the anodic decomposition of electrolytes,gradually thickening of interfacial passivation layer and vast irreversible capacity loss,hence encountering huge obstacle toward practical applications.To tackle this roadblock,substantial progress has been made toward oxidation-resistant electrolytes to block its side reaction with high-voltage cathodes.In this review,we discuss degradation mechanisms of electrolytes at electrolyte/cathode interface and ideal requirements of electrolytes for high-voltage cathode,as well as summarize recent advances of oxidation-resistant electrolyte optimization mainly from solvents and additives.With these insights,it is anticipated that development of liquid electrolyte tolerable to high-voltage cathode will boost the large-scale practical applications of high-voltage cathode-based LIBs.
基金Open access funding provided by Shanghai Jiao Tong University
文摘The thermal stability window of current commercial carbonate-based electrolytes is no longer sufficient to meet the ever-increasing cathode working voltage requirements of high energy density lithium-ion batteries.It is crucial to construct a robust cathode-electrolyte interphase(CEI)for high-voltage cathode electrodes to separate the electrolytes from the active cathode materials and thereby suppress the side reactions.Herein,this review presents a brief historic evolution of the mechanism of CEI formation and compositions,the state-of-art characterizations and modeling associated with CEI,and how to construct robust CEI from a practical electrolyte design perspective.The focus on electrolyte design is categorized into three parts:CEI-forming additives,anti-oxidation solvents,and lithium salts.Moreover,practical considerations for electrolyte design applications are proposed.This review will shed light on the future electrolyte design which enables aggressive high-voltage cathodes.
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.
文摘Porous LiNiVO4 powder was synthesized via solution combustion synthesis method using lithium nitrate, nickel nitrate,ammonium metavanadate and citric acid as raw materials. Thermogravimetry (TG) and differential scanning calorimetry (DSC),X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy and transmission electron microscopy (TEM) were used toevaluate the structures and morphologies of samples. The results show that the calcination temperature has significant effect on thecrystallinity and morphologies. Pure LiNiVO4 flaky nanoparticles with a mean particle size around 20 nm can be readily prepared bycalcining the precursor in air at 500 °C for 2 h. As a cathode material for lithium-ion batteries, the porous LiNiVO4 powder exhibits agood structural reversibility.
基金Project(76600)supported by Postdoctoral Science Foundation of Central South University
文摘LiNi_(0.5)Mn_(1.5)O_(4)was prepared under various conditions by one-step solid-state reaction in air and its properties were investigated by X-ray diffractormetry(XRD),scanning electron microscopy(SEM)and electrochemical measurement.XRD patterns show that LiNi_(0.5)Mn_(1.5)O_(4)synthesized under various conditions has cubic spinel structure.SEM images exhibit that the particle size increases with increasing calcination temperature and time.Electro chemical test shows that the LiNi_(0.5)Mn_(1.5)O_(4)calcined at 700℃for 24 h delivers up to 143 mA·h/g,and the capacity retains 132 mA·h/g after 30 cycles.
文摘Lithium cobalt phosphate (LiCoPO4, LCP), having a high operating potential (4.8 V vs. Li/Li+), a flat voltage profile and a good theoretical capacity (167 mAh/g), is considered a promising cathode material for improving the energy density of lithium-ion batteries (LIBs) [1] [2]. Here we report a category of method for synthesizing LCP, the solvothermal (ST) method with a binary solvent (deionized water: ethyl alcohol = 1:1), controlling the concentration of cobalt ion in 0.05 mol/L (ST-0.05) and 0.25mol/L (ST-0.25). The material phase was apparently identified via X-ray diffraction (XRD). Observed by scanning electron microscopy (SEM), the grain size of LCP powders synthesizing by solvothermal method with two kinds of the concentration of cobalt ion were 400 × 400 × 1000 nm cuboids (ST-0.05) and 150 × 150 × 250 nm hexagonal prisms containing nanoparticles (ST-0.25), respectively. Discharge capacities of LCP were 76.0 mAh/g (ST-0.05) and 94.5 mAh/g (ST-0.25), in the first cycle at 0.1 C, respectively.
基金supported by the Beijing Natural Science Foundation(grant No.L223009)the National Natural Science Foundation of China(grant No.22075029)+1 种基金the National Key Research and Development Program of China(grant No.2021YFB2500300)the Key Research and Development(R&D)Projects of Shanxi Province(grant No.2021020660301013).
文摘Sulfide solid electrolytes(SEs)have attracted ever-increasing attention due to their superior roomtemperature ionic conductivity(~10^(-2) S cm^(-1)).Additionally,the integration of sulfide SEs and highvoltage cathodes is promising to achieve higher energy density.However,the incompatible interfaces between sulfide SEs and high-voltage cathodes have been one of the key factors limiting their applications.Therefore,this review presents a critical summarization of the interfacial issues in all-solid-state lithium batteries based on sulfide SEs and high-voltage cathodes and proposes strategies to stabilize the electrolyte/cathode interfaces.Moreover,the future research direction of electrolyte/cathode interfaces and application prospects of powder technology in sulfide-based ASSLBs were also discussed.
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the financial support from the National Natural Science Foundation of China(52202338)。
文摘Advancing high-voltage stability of layered sodium-ion oxides represents a pivotal avenue for their progress in energy storage applications.Despite this,a comprehensive understanding of the mechanisms underpinning their structural deterioration at elevated voltages remains insufficiently explored.In this study,we unveil a layer delamination phenomenon of Na_(0.67)Ni_(0.3)Mn_(0.7)O_(2)(NNM)within the 2.0-4.3 V voltage,attributed to considerable volumetric fluctuations along the c-axis and lattice oxygen reactions induced by the simultaneous Ni^(3+)/Ni^(4+)and anion redox reactions.By introducing Mg doping to diminished Ni-O antibonding,the anion oxidation-reduction reactions are effectively mitigated,and the structural integrity of the P2 phase remains firmly intact,safeguarding active sites and precluding the formation of novel interfaces.The Na_(0.67)Mg_(0.05)Ni_(0.25)Mn_(0.7)O_(2)(NMNM-5)exhibits a specific capacity of100.7 mA h g^(-1),signifying an 83%improvement compared to the NNM material within the voltage of2.0-4.3 V.This investigation underscores the intricate interplay between high-voltage stability and structural degradation mechanisms in layered sodium-ion oxides.
基金the National Natural Science Foundation of China(52070194,52073309,51902347,51908555)Natural Science Foundation of Hunan Province(2022JJ20069,2020JJ5741).
文摘Benefited from its high process feasibility and controllable costs,binary-metal layered structured LiNi_(0.8)Mn_(0.2)O_(2)(NM)can effectively alleviate the cobalt supply crisis under the surge of global electric vehicles(EVs)sales,which is considered as the most promising nextgeneration cathode material for lithium-ion batteries(LIBs).However,the lack of deep understanding on the failure mechanism of NM has seriously hindered its application,especially under the harsh condition of high-voltage without sacrifices of reversible capacity.Herein,singlecrystal LiNi_(0.8)Mn_(0.2)O_(2) is selected and compared with traditional LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM),mainly focusing on the failure mechanism of Cofree cathode and illuminating the significant effect of Co element on the Li/Ni antisite defect and dynamic characteristic.Specifically,the presence of high Li/Ni antisite defect in NM cathode easily results in the extremely dramatic H2/H3 phase transition,which exacerbates the distortion of the lattice,mechanical strain changes and exhibits poor electrochemical performance,especially under the high cutoff voltage.Furthermore,the reaction kinetic of NM is impaired due to the absence of Co element,especially at the single-crystal architecture.Whereas,the negative influence of Li/Ni antisite defect is controllable at low current densities,owing to the attenuated polarization.Notably,Co-free NM can exhibit better safety performance than that of NCM cathode.These findings are beneficial for understanding the fundamental reaction mechanism of single-crystal Ni-rich Co-free cathode materials,providing new insights and great encouragements to design and develop the next generation of LIBs with low-cost and high-safety performances.
基金supported by the National Key Research and Development Program of China(2022YFA1504100)the National Natural Science Foundation of China(22125903,51872283,and 22005298)+4 种基金Dalian Innovation Support Plan for High Level Talents(2019RT09)Dalian National Laboratory For Clean Energy(DNL),Chinese Academy of Sciences(CAS),DNL Cooperation Fund,CAS(DNL202016 and DNL202019)Dalian Institute of Chemical Physics(DICP I2020032)Exploratory Research Project of Yanchang Petroleum International Limited and DICP(yc-hw-2022ky-01)the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy(YLU-DNL Fund 2021002 and 2021009).
文摘Lithium-ion batteries(LIBs)with the“double-high”characteristics of high energy density and high power density are in urgent demand for facilitating the development of advanced portable electronics.However,the lithium ion(Li+)-storage performance of the most commercialized lithium cobalt oxide(LiCoO_(2),LCO)cathodes is still far from satisfactory in terms of high-voltage and fast-charging capabilities for reaching the double-high target.Herein,we systematically summarize and discuss high-voltage and fast-charging LCO cathodes,covering in depth the key fundamental challenges,latest advancements in modification strategies,and future perspectives in this field.Comprehensive and elaborated discussions are first presented on key fundamental challenges related to structural degradation,interfacial instability,the inhomogeneity reactions,and sluggish interfacial kinetics.We provide an instructive summary of deep insights into promising modification strategies and underlying mechanisms,categorized into element doping(Li-site,cobalt-/oxygen-site,and multi-site doping)for improved Li+diffusivity and bulkstructure stability;surface coating(dielectrics,ionic/electronic conductors,and their combination)for surface stability and conductivity;nanosizing;combinations of these strategies;and other strategies(i.e.,optimization of the electrolyte,binder,tortuosity of electrodes,charging protocols,and prelithiation methods).Finally,forward-looking perspectives and promising directions are sketched out and insightfully elucidated,providing constructive suggestions and instructions for designing and realizing high-voltage and fast-charging LCO cathodes for next-generation double-high LIBs.
基金National Natural Science Foundation of China,Grant/Award Number:51772284Recruitment Program of Global ExpertsFundamental Research Funds for the Central Universities,Grant/Award Number:WK2060190081。
文摘P2-type Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2)is considered as a potential cathode material for sodium-ion batteries due to the merits of high voltage,low cost,and air stability.However,the unsatisfied cycling stability and rate performance caused by the destructive phase transition and side reactions hinder its practical application.Herein,we present a feasible dual strategy of Mg^(2+)doping integrated with ZrO_(2)surface modification for P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2),which can well address the issues of phase transition and side reactions benefitting from the enhanced structural and interfacial stabilities.Specifically,it exhibits a decent cycling stability with a capacity retention of 81.5%at 1 C and promising rate performance with a discharge capacity of 76.6 mA h g^(−1)at 5 C.The in situ X-ray diffraction measurement confirms that the damaged P2-O2 phase transition is suppressed with better reversibility in high-voltage region,whereas the side reactions are inhibited due to the protective ZrO_(2)surfacemodification.Commendably,the full cell achieves an outstanding operating voltage of 3.57 V and a fabulous energy density of 238.91 W h kg^(−1)at 36.73 W kg^(−1),demonstrating great practicability.This work is expected to provide a new insight for designing stable high-voltage cathode materials and high energy density full cells for sodium ion batteries.
基金supported by the Fund of University of South China (No.201RGC013 and N0.200XQD052)。
文摘The Co-free Li Ni_(0.5)Mn_(1.5)O_(4)(LNMO)is a promising cathode for lithium-ion batteries owing to its high operating voltage and low costs.However,the synthesis of LNMO is generally time and energy consuming,and its practical application is hindered by the lack of a compatible electrolyte.Herein,a spray pyrolysis-based energy-saving synthesis method as well as a diluted low concentration electrolyte(0.5 M LiPF_(6) in a mixture of fluoroethylene carbonate/dimethyl carbonate/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(FEC:DMC:TTE,1:4:5 by volume))are proposed to address these challenges.Owing to the unique features of the precursor prepared by spray pyrolysis,well-crystallized LNMO single-crystal can be obtained within 1 h calcination at 900℃.Besides,the fluorinated interphases derived from the diluted low concentration electrolyte not only mitigate the Mn dissolution and Al corrosion at the cathode side,but also suppresses dendritic Li deposition at the anode side,thus enabling stable cycling of both LNMO and Li metal anode.Thus,30μm Li|LNMO(1.75 m A h cm^(-2))cells achieve a high capacity retention(90.9%)after 168 cycles in the diluted low concentration electrolyte.
基金We gratefully acknowledge the financial support from the National Natural Science Foundation of China(52070194,51902347,51908555,and 51822812)Natural Science Foundation of Hunan Province(2020JJ5741)the Graduate Innovation Project of Central South University(2020zzts093).
文摘LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) is extensively researched as one of the most widely used commercially materials for Li-ion batteries at present.However,the poor high-voltage performance(≥4.3 V)with low reversible capacity limits its replacement for LiCoO_(2) in high-end digital field.Herein,three-in-one modification,Na-doping and Al_(2)O_(3)@Li_(3)BO_(3) dual-coating simultaneously,is explored for single-crystalline LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(N-NCM@AB),which exhibits excellent high-voltage performance.N-NCM@AB displays a discharge-specific capacity of 201.8 mAh g^(−1) at 0.2 C with a high upper voltage of 4.6 V and maintains 158.9 mAh g^(−1) discharge capacity at 1 C over 200 cycles with the corresponding capacity retention of 87.8%.Remarkably,the N-NCM@AB||graphite pouch-type full cell retains 81.2% of its initial capacity with high working voltage of 4.4 V over 1600 cycles.More importantly,the fundamental understandings of three-in-one modification on surface morphology,crystal structure,and phase transformation of N-NCM@AB are clearly revealed.The Na+doped into the Li–O slab can enhance the bond energy,stabilize the crystal structure,and facilitate Li+transport.Additionally,the interior surface layer of Li^(+)-ions conductor Li_(3)BO_(3) relieves the charge transfer resistance with surface coating,whereas the outer surface Al_(2)O_(3) coating layer is beneficial for reducing the active materials loss and alleviating the electrode/electrolyte parasite reaction.This three-in-one strategy provides a reference for the further research on the performance attenuation mechanism of NCM,paving a new avenue to boost the high-voltage performance of NCM cathode in Li-ion batteries.
文摘Li-ion batteries(LIBs)have gained wide recognition as effective energy storage devices and power supply sources due to their exceptional volumetric energy density,mass energy density and cycling performance.The cathode materials,a key component of LIBs,play a crucial role in determining the electrochemical performance of these batteries.Therefore,there is an increasing demand to explore and investigate suitable high-energy electrode materials that can provide greater capacity and output voltage for the next generation of LIBs.This paper aims to provide a comprehensive overview of the latest researches on five typical high-voltage cathode materials.Specifically,this review will focus on the detailed analysis of their crystalline structures,reaction mechanisms during cycling,current research status and strategies aimed at improving or enhancing their overall electrochemical performance.Overall,the insights presented in this review will help researchers design and develop high-energy cathode materials with improved performance for the next generation of LIBs.
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.
