Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+d...Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+dynamics and rapid capacity decay.In this study,we propose a medium-entropy cathode by simultaneously introducing Fe,Mg,and Li dopants into a typical P2-type Na_(0.75)Ni_(0.25)Mn_(0.75)O_(2)cathode.The modified Na_(0.75)Ni_(0.2125)Mn_(0.6375)Fe_(0.05)Mg_(0.05)Li_(0.05)O_(2)cathode predominantly exhibits a main P2 phase(93.5%)with a minor O3 phase(6.5%).Through spectroscopy techniques and electrochemical investigations,we elucidate the redox mechanisms of Ni^(2+/3+/4+),Mn^(3+/4+),Fe^(3+/4+),and O_(2)-/O_(2)^(n-)during charging/discharging.The medium-entropy doping mitigates the detrimental P2-O_(2)phase transition at high-voltage,replacing it with a moderate and reversible structural evolution(P2-OP4),thereby enhancing structural stability.Consequently,the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g^(-1)at 10C,with a capacity retention of 99.0%after 200 cycles at 1C,82.5%after 500 cycles at 5C,and 76.7%after 600 cycles at 10C.Furthermore,it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature(55 and 0℃).This work offers solutions to critical challenges in sodium ion batteries cathode materials.展开更多
The cobalt-free Mn-based Li-rich layered oxide material has the advantages of low cost,high energy density,and good performance at low temperatures,and is the promising choice for energy storage batteries.However,the ...The cobalt-free Mn-based Li-rich layered oxide material has the advantages of low cost,high energy density,and good performance at low temperatures,and is the promising choice for energy storage batteries.However,the long-cycling stability of batteries needs to be improved.Herein,the Mn-based Li-rich cathode materials with small amounts of Li2 MnO3 crystal domains and gradient doping of Al and Ti elements from the surface to the bulk have been developed to improve the structure and interface stability.Then the batteries with a high energy density of 600 Wh kg^(-1),excellent capacity retention of 99.7%with low voltage decay of 0.03 mV cycle^(-1) after 800 cycles,and good rates performances can be achieved.Therefore,the structure and cycling stability of low voltage Mn-based Li-rich cathode materials can be significantly improved by the bulk structure design and interface regulation,and this work has paved the way for developing low-cost and high-energy Mn-based energy storage batteries with long lifetime.展开更多
03-type layered oxide serves as dominant components in sodium ion batteries;however,the unstable electronic structure between transition metal and oxygen inevitably induces framework instability and severe kinetic hin...03-type layered oxide serves as dominant components in sodium ion batteries;however,the unstable electronic structure between transition metal and oxygen inevitably induces framework instability and severe kinetic hindrance.In this study,a two-in-one approach to synergistically modulate the local electro nic and interfacial structure of NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)by Ce modification is proposed.We present an indepth study to reveal the strong-covalent Ce-O bonds,which make local charge around oxygen more negative,enhance O 2p-Mn 3d hybridization,and preserve the octahedral structural integrity.This modification tailors local electronic structure between the octahedral metal center and oxygen,thus enhancing reversibility of 03-P3-03 phase transition and expanding Na+octahedral-tetrahedral-octahedral transport channel.Additionally,the nanoscale perovskite layer induced by Ce element is in favor of minimizing interfacial side reaction as well as enhancing Na^(+)diffusivity.As a result,the designed 03-NaNi_(0.305)Fe_(0.33)Mn_(0.33)Ce_(0.025)O_(2)material delivers an exceptionally low volume variation,an ultrahigh rate capacity of 76.9 mA h g^(-1)at 10 C,and remarkable cycling life over 250 cycles with capacity retention of 80% at 5 C.展开更多
P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phas...P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.展开更多
The voltage decay of lithium-rich layered oxides(LLOs)is still one of the key challenges for their application in commercial battery although these materials possess the advantages of high specific capacity and low co...The voltage decay of lithium-rich layered oxides(LLOs)is still one of the key challenges for their application in commercial battery although these materials possess the advantages of high specific capacity and low cost.In this work,the relationship between voltage decay and tap density of LLOs has been focused.The voltage decay can be significantly suppressed with the increasing tap density as well as the homogenization of the primary or secondary particle size of agglomerated spherical LLOs.Experimental results have shown that an extreme small voltage decay of 0.98 m V cycle^(-1)can be obtained through adjusting the tap density of agglomerated spherical LLOs to 1.99 g cm^(-3),in which the size of primary and secondary particles are uniform.Our work offers a new insight towards the voltage decay and capacity fading of LLOs through precursor preparation process,promoting their application in the real battery in the future.展开更多
Undoubtedly,the enormous progress observed in recent years in the Ni-rich layered cathode materials has been crucial in terms of pushing boundaries of the Li-ion battery(LIB)technology.The achieved improvements in the...Undoubtedly,the enormous progress observed in recent years in the Ni-rich layered cathode materials has been crucial in terms of pushing boundaries of the Li-ion battery(LIB)technology.The achieved improvements in the energy density,cyclability,charging speed,reduced costs,as well as safety and stability,already contribute to the wider adoption of LIBs,which extends nowadays beyond mobile electronics,power tools,and electric vehicles,to the new range of applications,including grid storage solutions.With numerous published papers and broad reviews already available on the subject of Ni-rich oxides,this review focuses more on the most recent progress and new ideas presented in the literature references.The covered topics include doping and composition optimization,advanced coating,concentration gradient and single crystal materials,as well as innovations concerning new electrolytes and their modification,with the application of Ni-rich cathodes in solid-state batteries also discussed.Related cathode materials are briefly mentioned,with the high-entropy approach and zero-strain concept presented as well.A critical overview of the still unresolved issues is given,with perspectives on the further directions of studies and the expected gains provided.展开更多
In this paper, the superhydrophobic polyurethane sponge(SS-PU) was facilely fabricated by etching with Jones reagent to bind the nanoparticles of Ni-Co double layered oxides(LDOs) on the surface, and following modific...In this paper, the superhydrophobic polyurethane sponge(SS-PU) was facilely fabricated by etching with Jones reagent to bind the nanoparticles of Ni-Co double layered oxides(LDOs) on the surface, and following modification with n-dodecyl mercaptan(DDT). This method provides a new strategy to fabricate superhydrophobic PU sponge with a water contact angle of 157° for absorbing oil with low cost and in large scale. It exhibits the strong absorption capacity and highly selective characteristic for various kinds of oils which can be recycled by simple squeezing. Besides, the as-prepared sponge can deal with the floating and underwater oils, indicating its application value in handling oil spills and domestic oily wastewater. The good self-cleaning ability shows the potential to clear the pollutants due to the ultralow adhesion to water. Especially, the most important point is that the superhydrophobic sponge can continuously and effectively separate the oil/water mixture against the condition of turbulent disturbance by using our designed device system, which exhibit its good superhydrophobicity, strong stability.Furthermore, the SS-PU still maintained stable absorption performance after 150 cycle tests without losing capacity obviously, showing excellent durability in long-term operation and significant potential as an efficient absorbent in large-scale dispose of oily water.展开更多
Lithium-rich layered oxides(LLOs)are promising candidate cathode materials for safe and inexpensive high-energy-density Li-ion batteries.However,oxygen dimers are formed from the cathode material through oxygen redox ...Lithium-rich layered oxides(LLOs)are promising candidate cathode materials for safe and inexpensive high-energy-density Li-ion batteries.However,oxygen dimers are formed from the cathode material through oxygen redox activity,which can result in morphological changes and structural transitions that cause performance deterioration and safety concerns.Herein,a flake-like LLO is prepared and aberration-corrected scanning transmission electron microscopy(STEM),in situ high-temperature X-ray diffraction(HT-XRD),and soft X-ray absorption spectrum(sXAS)are used to explore its crystal facet degradation behavior in terms of both thermal and electrochemical processes.Void-induced degradation behavior of LLO in different facet reveals significant anisotropy at high voltage.Particle degradation originates from side facets,such as the(010)facet,while the close(003)facet is stable.These results are further understood through ab initio molecular dynamics calculations,which show that oxygen atoms are lost from the{010}facets.Therefore,the facet degradation process is that oxygen molecular formed in the interlayer and accumulated in the ab plane during heating,which result in crevice-voids in the ab plane facets.The study reveals important aspects of the mechanism responsible for oxygen-anionic activity-based degradation of LLO cathode materials used in lithium-ion batteries.In particular,this study provides insight that enables precise and efficient measures to be taken to improve the thermal and electrochemical stability of an LLO.展开更多
Sodium-ion batteries are very promising in large-scale energy storage.The exploration of Na layered oxides as cathode materials for Na ion batteries usually consumes much resource,while the performances of Na layered ...Sodium-ion batteries are very promising in large-scale energy storage.The exploration of Na layered oxides as cathode materials for Na ion batteries usually consumes much resource,while the performances of Na layered oxides are dominated by their crystal structures.Therefore,it is highly desired to predict the stacking mode of the target oxides in advance:whether O3-type with higher ordered structure and stability,or P2-type with more Na content.For this purpose density functional theory computations do not work.Very recently,Hu's group and international collaborators have proposed a cationic potential to provide a very timely,effective,and accurate criterion to predict the stacking mode of Na layered oxides(Science,370(2020)708-711).Under the guidance of the cationic potential phase map,Na layered oxides could be rationally designed.Here we would like to highlight the progress that novel Na layered oxides could be obtained with the combination of large specific capacity,high power density and good cycling stability.展开更多
Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the i...Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the involvement of oxygen redox.Herein,a Co-free Li-rich layered oxide Li_(1.286)Ni_(0.071)Mn_(0.643)O_(2)has been prepared by a co-precipitation method to systematically investigate the undefined effects of the oxygen defects.A significant O_(2)release and the propagation of oxygen vacancies were detected by operando differential electrochemical mass spectroscopy(DEMS)and electron energy loss spectroscopy(EELS),respectively.Scanning transmission electron microscopy-high angle annular dark field(STEMHAADF)reveals the oxygen vacancies fusing to nanovoids and monitors a stepwise electrochemical activation process of the large Li_(2)MnO_(3)domain upon cycling.Combined with the quantitative analysis conducted by the energy dispersive spectrometer(EDS),existed nano-scale oxygen defects actually expose more surface to the electrolyte for facilitating the electrochemical activation and subsequently increasing available capacity.Overall,this work persuasively elucidates the function of oxygen defects on oxygen redox in Co-free Li-rich layered oxides.展开更多
Anionic redox reaction(ARR) in layered manganese-based oxide cathodes has been considered as an effective strategy to improve the energy density of sodium-ion batteries.Mn-vacancy layered oxides deliver a high ARR-rel...Anionic redox reaction(ARR) in layered manganese-based oxide cathodes has been considered as an effective strategy to improve the energy density of sodium-ion batteries.Mn-vacancy layered oxides deliver a high ARR-related capacity with small voltage hysteresis,however,they are limited by rapid capacity degradation and poor rate capability,which arise from inferior structure changes due to repeated redox of lattice oxygen.Herein,redox-inactive Ti^(4+)is introduced to substitute partial Mn^(4+)to form Na_(2) Ti_(0.5)Mn_(2.5)O_7(Na_(4/7)[□_(1/7)Ti_(1/7)Mn_(5/7)]O_(2),□ for Mn vacancies),which can effectively restrain unfavorable interlayer gliding of Na2 Mn307 at high charge voltages,as reflected by an ultralow-strain volume variation of 0.11%.There is no irreversible O_(2) evolution observed in Na_(2) Ti_(0.5)Mn_(2.5)O_7 upon charging,which stabilizes the lattice oxygen and ensures the overall structural stability.It exhibits increased capacity retention of 79.1% after 60 cycles in Na_(2) Ti_(0.5)Mn_(2.5)O_7(17.1% in Na_(2) Mn_(3) O_7) and good rate capability(92.1 mAh g^(-1) at 0.5 A g^(-1)).This investigation provides new insights into designing high-performance cathode materials with reversible ARR and structural stability for SIBs.展开更多
Lithium-rich layered oxides(LrLOs) deliver extremely high specific capacities and are considered to be promising candidates for electric vehicle and smart grid applications. However, the application of LrLOs needs fur...Lithium-rich layered oxides(LrLOs) deliver extremely high specific capacities and are considered to be promising candidates for electric vehicle and smart grid applications. However, the application of LrLOs needs further understanding of the structural complexity and dynamic evolution of monoclinic and rhombohedral phases, in order to overcome the issues including voltage decay, poor rate capability, initial irreversible capacity loss and etc. The development of aberration correction for the transmission electron microscope and concurrent progress in electron spectroscopy, have fueled rapid progress in the understanding of the mechanism of such issues. New techniques based on the transmission electron microscope are first surveyed, and the applications of these techniques for the study of the structure, migration of transition metal, and the activation of oxygen of LrLOs are then explored in detail, with a particular focus on the mechanism of voltage decay.展开更多
P2-type layered oxides are highly promising cathode candidates for sodium-ion batteries(SIBs)owing to their substantial theoretical capacity.Nevertheless,structural degradation caused by transition metal dissolution a...P2-type layered oxides are highly promising cathode candidates for sodium-ion batteries(SIBs)owing to their substantial theoretical capacity.Nevertheless,structural degradation caused by transition metal dissolution and irreversible phase transitions at high voltage severely compromises cycling stability.To address this limitation,we propose a Li/Ti co-doping strategy to design a Na_(0.67)Li_(0.06)Ni_(0.27)Mn_(0.5)7Ti_(0.1)O_(2)(NLMT) cathode for SIBs.In-situ X-ray diffraction(XRD) confirms that this deliberate strategy eliminates the adverse phase transition at high voltage and sustains the unitary P2phase throughout cycling.In addition,strengthened transition metal-oxygen(TM-O) bonding via electronic modulation suppresses transition metal dissolution and reinforces the layered oxide framework,contributing to exceptional electrochemical performance.Consequently,the NLMT cathode exhibits an outstanding capacity of 92.8 mA h gLi+(-1) within 2.5-4.3 V at 5 C(865 mA g Li^(+)(-1)),with 87 % capacity retention over 200 cycles.Configured into a full cell,which achieves a competitive capacity of 107.7 mA h g^(-1) at0.1 C and retains 86.4 % capacity over 100 cycles at 0.5 C.This study validates co-doping as a potent strategy for significantly improving the long-term cyclability of layered oxide cathodes in SIBs.展开更多
Nickel-rich layered oxides(LiNixCoyMnzO2,NCM)are among the most promising cathode materials for high-energy lithium-ion batteries,offering high specific capacity and output voltage at a relatively low cost.However,ind...Nickel-rich layered oxides(LiNixCoyMnzO2,NCM)are among the most promising cathode materials for high-energy lithium-ion batteries,offering high specific capacity and output voltage at a relatively low cost.However,industrialscale co-precipitation presents significant challenges,particularly in maintaining particle sphericity,ensuring a stable concentration gradient,and preserving production yield when transitioning from lab-scale compositions.This study addresses a critical issue in the large-scale synthesis of nickel-rich NCM(x=0.8381):nickel leaching,which compromises particle uniformity and battery performance.To mitigate this,we optimize the reaction process and develop an artificial intelligence-driven defect prediction system that enhances precursor stability.Our domain adaptation based machine learning model,which accounts for equipment wear and environmental variations,achieves a defect detection accuracy of 97.8%based on machine data and process conditions.By implementing this approach,we successfully scale up NCM precursor production to over 2 tons,achieving 83%capacity retention after 500 cycles at a 1C rate.In addition,the proposed approach demonstrates the formation of a concentration gradient in the composition and a high sphericity of 0.951(±0.0796).This work provides new insights into the stable mass production of NCM precursors,ensuring both high yield and performance reliability.展开更多
With the rapid development of the economy,increasing demand for energy storage and electric vehicles require electrode materials for batteries with high energy density,safety,and cyclability,especially for lithium-ion...With the rapid development of the economy,increasing demand for energy storage and electric vehicles require electrode materials for batteries with high energy density,safety,and cyclability,especially for lithium-ion(Li-ion)battery cathodes.However,the understanding of their degradation mechanism remains insufficient due to the complex battery system,the transient nature of the de/lithiation processes,and the lack of advanced characterization techniques.Among these challenges,the mechanism of the Li-rich layered cathode family with high operating voltage and cationic-anionic hybrid charge compensation is particularly difficult to study.For the Li-rich family,their electrochemical mechanisms,for example,oxygen redox reaction and structural evolution,were almost impossible to completely clarify in terms of conventional characterization techniques until the development of various in situ techniques.It is obvious that advanced in situ techniques have accelerated the pace of scientific truth exploration.In this review,these intricate mechanisms revealed by various in situ techniques are summarized to clarify the failure mechanism of Li-rich layered cathodes,and an outlook on the application of these advanced techniques within different battery systems is provided.This review highlights how in situ devices can clearly reveal complex mechanisms and further provides the consultation on characterization techniques for mechanism exploration in various research fields.展开更多
The development of sustainable energy storage solutions has driven research toward alternatives to lithiumion batteries.Sodium-ion battery(SIB)was considered a promising candidate due to their cost-effectiveness and s...The development of sustainable energy storage solutions has driven research toward alternatives to lithiumion batteries.Sodium-ion battery(SIB)was considered a promising candidate due to their cost-effectiveness and sodium abundance.To introduce defects and enhance the electrochemical performance of O_(3)-phase sodium-ion layered oxide materials,high-temperature shock(HTS)was employed.However,given the characteristics of HTS,especially the rapid heating rate and short sintering time,suitable precursor systems need to be explored.We systematically compared three precursor systems:traditional metal oxides(HTS-O),decomposable salts(HTS-D),and a novel pre-reacted precursor system(HTS-S).The pre-reacted precursor,developed by leveraging the ethanol solubility of C_(4)H_(14)MnO_(8) and modified ball milling conditions,enabled rapid O_(3) phase formation and resulted in impurity-free O_(3)-NaCu_(0.2)Fe_(0.3)Mn _(0.5)O_(2).This material demonstrated superior electrochemical performance,achieving a discharge capacity of 144.05 mAh g^(−1) within 2.0-4.1 V,along with enhanced rate capabilities.Our findings underscore the critical role of precursor selection and modification in HTS synthesis,contributing to the advancement of high-performance sodium-ion battery materials.展开更多
The burgeoning growth in electric vehicles and portable energy storage systems necessitates advances in the energy density and cost-effectiveness of lithium-ion batteries(LIBs),areas where lithium-rich manganese-based...The burgeoning growth in electric vehicles and portable energy storage systems necessitates advances in the energy density and cost-effectiveness of lithium-ion batteries(LIBs),areas where lithium-rich manganese-based oxide(LLO)materials naturally stand out.Despite their inherent advantages,these materials encounter significant practical hurdles,including low initial Coulombic efficiency(ICE),diminished cycle/rate performance,and voltage fading during cycling,hindering their widespread adoption.In response,we introduce an ionic-electronic dual-conductive(IEDC)surface control strategy that integrates an electronically conductive graphene framework with an ionically conductive heteroepitaxial spinel Li_(4)Mn_(5)O_(12)layer.Prolonged electrochemical and structural analyses demonstrate that this IEDC heterostructure effectively minimizes polarization,mitigates structural distortion,and enhances electronic/ionic diffusion.Density functional theory calculations highlight an extensive Li^(+)percolation network and lower Li^(+)migration energies at the layered-spinel interface.The designed LLO cathode with IEDC interface engineering(LMOSG)exhibits improved ICE(82.9%at 0.1 C),elevated initial discharge capacity(296.7 mAh g^(-1)at 0.1 C),exceptional rate capability(176.5 mAh g^(-1)at 5 C),and outstanding cycle stability(73.7%retention at 5 C after 500 cycles).These findings and the novel dual-conductive surface architecture design offer promising directions for advancing highperformance electrode materials.展开更多
In order to achieve better Na storage performance, most layered oxide positive electrode materials contain toxic and expensive transition metals Ni and/or Co, which are also widely used for lithium-ion batteries. Here...In order to achieve better Na storage performance, most layered oxide positive electrode materials contain toxic and expensive transition metals Ni and/or Co, which are also widely used for lithium-ion batteries. Here we report a new quaternary layered oxide consisting of Cu, Fe, Mn, and Ti transition metals with O3-type oxygen stacking as a positive electrode for room-temperature sodium-ion batteries. The material can be simply prepared by a high-temperature solidstate reaction route and delivers a reversible capacity of 94 m Ah/g with an average storage voltage of 3.2 V. This paves the way for cheaper and non-toxic batteries with high Na storage performance.展开更多
Lithium rich layered oxides(LLOs)are attractive cathode materials for Li-ion batteries owing to their high capacity(>250 mA h g^(-1))and suitable voltage(∼3.6 V).However,they suffer from serious voltage and capaci...Lithium rich layered oxides(LLOs)are attractive cathode materials for Li-ion batteries owing to their high capacity(>250 mA h g^(-1))and suitable voltage(∼3.6 V).However,they suffer from serious voltage and capacity fading,which is focused in this review.First,an overview of crystal structure,band structure and electrochemical performances of LLOs is provided.After that,current understanding on oxygen loss,capacity fading and voltage fading is summarized.Finally,five strategies to mitigate capacity and voltage fading are reviewed.It is believed that these understandings can help solve the fading problems of LLOs.展开更多
Lithium-rich layered oxides(LLOs)have been extensively studied as cathode materials for lithium-ion batteries(LIBs)by researchers all over the world in the past decades due to their high specific capacities and high c...Lithium-rich layered oxides(LLOs)have been extensively studied as cathode materials for lithium-ion batteries(LIBs)by researchers all over the world in the past decades due to their high specific capacities and high charge-discharge voltages.However,as cathode materials LLOs have disadvantages of significant voltage and capacity decays during the charge-discharge cycling.It was shown in the past that fine-tuning of structures and compositions was critical to the performances of this kind of materials.In this report,LLOs with target composition of Li1.17Mn0.50Ni0.24Co0.09O2 were prepared by carbonate co-precipitation method with different pH values.X-ray powder diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscope(TEM),and electrochemical impedance spectroscopies(EIS)were used to investigate the structures and morphologies of the materials and to understand the improvements of their electrochemical performances.With the pH values increased from 7.5 to 8.5,the Li/Ni ratios in the compositions decreased from 5.17 to 4.64,and the initial Coulombic efficiency,cycling stability and average discharge voltages were gained impressively.Especially,the material synthesized at pH=8.5 delivered a reversible discharge capacity of 263 mAhg−1 during the first cycle,with 79.0%initial Coulombic efficiency,at the rate of 0.1 C and a superior capacity retention of 94%after 100 cycles at the rate of 1 C.Furthermore,this material exhibited an initial average discharge voltage of 3.65 V,with a voltage decay of only 0.09 V after 50 charge-discharge cycles.The improved electrochemical performances by varying the pH values in the synthesis process can be explained by the mitigation of layered-to-spinel phase transformation and the reduction of solid-electrolyte interface(SEI)resistance.We hope this work can shed some light on the alleviation of voltage and capacity decay issues of the LLOs cathode materials.展开更多
基金supported by the National Natural Science Foundation of China(No.21805018)by Sichuan Science and Technology Program(Nos.2022ZHCG0018,2023NSFSC0117 and 2023ZHCG0060)Yibin Science and Technology Program(No.2022JB005)and China Postdoctoral Science Foundation(No.2022M722704).
文摘Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+dynamics and rapid capacity decay.In this study,we propose a medium-entropy cathode by simultaneously introducing Fe,Mg,and Li dopants into a typical P2-type Na_(0.75)Ni_(0.25)Mn_(0.75)O_(2)cathode.The modified Na_(0.75)Ni_(0.2125)Mn_(0.6375)Fe_(0.05)Mg_(0.05)Li_(0.05)O_(2)cathode predominantly exhibits a main P2 phase(93.5%)with a minor O3 phase(6.5%).Through spectroscopy techniques and electrochemical investigations,we elucidate the redox mechanisms of Ni^(2+/3+/4+),Mn^(3+/4+),Fe^(3+/4+),and O_(2)-/O_(2)^(n-)during charging/discharging.The medium-entropy doping mitigates the detrimental P2-O_(2)phase transition at high-voltage,replacing it with a moderate and reversible structural evolution(P2-OP4),thereby enhancing structural stability.Consequently,the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g^(-1)at 10C,with a capacity retention of 99.0%after 200 cycles at 1C,82.5%after 500 cycles at 5C,and 76.7%after 600 cycles at 10C.Furthermore,it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature(55 and 0℃).This work offers solutions to critical challenges in sodium ion batteries cathode materials.
基金supported by the National Key R&D Program of China(No.2022YFB2404400)the National Natural Science Foundation of China(Nos.U23A20577,52372168,92263206 and 21975006)+1 种基金the“The Youth Beijing Scholars program”(No.PXM2021_014204_000023)the Beijing Natural Science Foundation(Nos.2222001 and KM202110005009).
文摘The cobalt-free Mn-based Li-rich layered oxide material has the advantages of low cost,high energy density,and good performance at low temperatures,and is the promising choice for energy storage batteries.However,the long-cycling stability of batteries needs to be improved.Herein,the Mn-based Li-rich cathode materials with small amounts of Li2 MnO3 crystal domains and gradient doping of Al and Ti elements from the surface to the bulk have been developed to improve the structure and interface stability.Then the batteries with a high energy density of 600 Wh kg^(-1),excellent capacity retention of 99.7%with low voltage decay of 0.03 mV cycle^(-1) after 800 cycles,and good rates performances can be achieved.Therefore,the structure and cycling stability of low voltage Mn-based Li-rich cathode materials can be significantly improved by the bulk structure design and interface regulation,and this work has paved the way for developing low-cost and high-energy Mn-based energy storage batteries with long lifetime.
基金supported by the Science and technology plan project of Yulin(2023-CXY-193)the Project funded by Shaanxi Postdoctoral Science Foundation(2023BSHEDZZ274)+2 种基金the Shaanxi Province(2023-ZDLGY-24,2023-JC-QN-0588,Z20210201)the Science and technology plan project of Beilin(GX2319)the Science and technology plan project of Ankang(AK2023-GY-08)。
文摘03-type layered oxide serves as dominant components in sodium ion batteries;however,the unstable electronic structure between transition metal and oxygen inevitably induces framework instability and severe kinetic hindrance.In this study,a two-in-one approach to synergistically modulate the local electro nic and interfacial structure of NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)by Ce modification is proposed.We present an indepth study to reveal the strong-covalent Ce-O bonds,which make local charge around oxygen more negative,enhance O 2p-Mn 3d hybridization,and preserve the octahedral structural integrity.This modification tailors local electronic structure between the octahedral metal center and oxygen,thus enhancing reversibility of 03-P3-03 phase transition and expanding Na+octahedral-tetrahedral-octahedral transport channel.Additionally,the nanoscale perovskite layer induced by Ce element is in favor of minimizing interfacial side reaction as well as enhancing Na^(+)diffusivity.As a result,the designed 03-NaNi_(0.305)Fe_(0.33)Mn_(0.33)Ce_(0.025)O_(2)material delivers an exceptionally low volume variation,an ultrahigh rate capacity of 76.9 mA h g^(-1)at 10 C,and remarkable cycling life over 250 cycles with capacity retention of 80% at 5 C.
基金supported by the National Natural Science Foundation of China (22169002)the Chongzuo Key Research and Development Program of China (20220603)the Counterpart Aid Project for Discipline Construction from Guangxi University(2023M02)
文摘P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.
基金financially supported by the Beijing Natural Science Foundation(JQ19003)National Key R&D Program of China(grant no.2018YFB0104300)+4 种基金National Natural Science Foundation of China(grant no 51622202,21603009,and 21875007)Beijing Natural Science Foundation(B)(KZ201910005002)Beijing Natural Science Foundation(L182009)Project of Youth Talent Plan of Beijing Municipal Education Commission(CIT&TCD201804013)High-grade discipline construction of Beijing(PXM2019-014204-500031)。
文摘The voltage decay of lithium-rich layered oxides(LLOs)is still one of the key challenges for their application in commercial battery although these materials possess the advantages of high specific capacity and low cost.In this work,the relationship between voltage decay and tap density of LLOs has been focused.The voltage decay can be significantly suppressed with the increasing tap density as well as the homogenization of the primary or secondary particle size of agglomerated spherical LLOs.Experimental results have shown that an extreme small voltage decay of 0.98 m V cycle^(-1)can be obtained through adjusting the tap density of agglomerated spherical LLOs to 1.99 g cm^(-3),in which the size of primary and secondary particles are uniform.Our work offers a new insight towards the voltage decay and capacity fading of LLOs through precursor preparation process,promoting their application in the real battery in the future.
基金supported by the program“Excellence Initiative-Research University”for the AGH University of Krakow(IDUB AGH,No.501.696.7996,Action 4,ID 6354)partially supported by the AGH University of Krakow under No.16.16.210.476.
文摘Undoubtedly,the enormous progress observed in recent years in the Ni-rich layered cathode materials has been crucial in terms of pushing boundaries of the Li-ion battery(LIB)technology.The achieved improvements in the energy density,cyclability,charging speed,reduced costs,as well as safety and stability,already contribute to the wider adoption of LIBs,which extends nowadays beyond mobile electronics,power tools,and electric vehicles,to the new range of applications,including grid storage solutions.With numerous published papers and broad reviews already available on the subject of Ni-rich oxides,this review focuses more on the most recent progress and new ideas presented in the literature references.The covered topics include doping and composition optimization,advanced coating,concentration gradient and single crystal materials,as well as innovations concerning new electrolytes and their modification,with the application of Ni-rich cathodes in solid-state batteries also discussed.Related cathode materials are briefly mentioned,with the high-entropy approach and zero-strain concept presented as well.A critical overview of the still unresolved issues is given,with perspectives on the further directions of studies and the expected gains provided.
基金the financial support from National Key Research & Development Program of China (2017B0602702)。
文摘In this paper, the superhydrophobic polyurethane sponge(SS-PU) was facilely fabricated by etching with Jones reagent to bind the nanoparticles of Ni-Co double layered oxides(LDOs) on the surface, and following modification with n-dodecyl mercaptan(DDT). This method provides a new strategy to fabricate superhydrophobic PU sponge with a water contact angle of 157° for absorbing oil with low cost and in large scale. It exhibits the strong absorption capacity and highly selective characteristic for various kinds of oils which can be recycled by simple squeezing. Besides, the as-prepared sponge can deal with the floating and underwater oils, indicating its application value in handling oil spills and domestic oily wastewater. The good self-cleaning ability shows the potential to clear the pollutants due to the ultralow adhesion to water. Especially, the most important point is that the superhydrophobic sponge can continuously and effectively separate the oil/water mixture against the condition of turbulent disturbance by using our designed device system, which exhibit its good superhydrophobicity, strong stability.Furthermore, the SS-PU still maintained stable absorption performance after 150 cycle tests without losing capacity obviously, showing excellent durability in long-term operation and significant potential as an efficient absorbent in large-scale dispose of oily water.
基金supported by the Guangdong Provincial Science and Technology Commission,Guangdong Key Areas R&D Program(2020B0909030004)the Beijing Natural Science Foundation Committee,Haidian Original Innovation Joint Fund Project(L182023)Youth Fund Project of GRINM(Grant No.12620203129011).
文摘Lithium-rich layered oxides(LLOs)are promising candidate cathode materials for safe and inexpensive high-energy-density Li-ion batteries.However,oxygen dimers are formed from the cathode material through oxygen redox activity,which can result in morphological changes and structural transitions that cause performance deterioration and safety concerns.Herein,a flake-like LLO is prepared and aberration-corrected scanning transmission electron microscopy(STEM),in situ high-temperature X-ray diffraction(HT-XRD),and soft X-ray absorption spectrum(sXAS)are used to explore its crystal facet degradation behavior in terms of both thermal and electrochemical processes.Void-induced degradation behavior of LLO in different facet reveals significant anisotropy at high voltage.Particle degradation originates from side facets,such as the(010)facet,while the close(003)facet is stable.These results are further understood through ab initio molecular dynamics calculations,which show that oxygen atoms are lost from the{010}facets.Therefore,the facet degradation process is that oxygen molecular formed in the interlayer and accumulated in the ab plane during heating,which result in crevice-voids in the ab plane facets.The study reveals important aspects of the mechanism responsible for oxygen-anionic activity-based degradation of LLO cathode materials used in lithium-ion batteries.In particular,this study provides insight that enables precise and efficient measures to be taken to improve the thermal and electrochemical stability of an LLO.
基金supported by the Fundamental Research Funds for the Central Universities(FRF-TP-18-091A1)。
文摘Sodium-ion batteries are very promising in large-scale energy storage.The exploration of Na layered oxides as cathode materials for Na ion batteries usually consumes much resource,while the performances of Na layered oxides are dominated by their crystal structures.Therefore,it is highly desired to predict the stacking mode of the target oxides in advance:whether O3-type with higher ordered structure and stability,or P2-type with more Na content.For this purpose density functional theory computations do not work.Very recently,Hu's group and international collaborators have proposed a cationic potential to provide a very timely,effective,and accurate criterion to predict the stacking mode of Na layered oxides(Science,370(2020)708-711).Under the guidance of the cationic potential phase map,Na layered oxides could be rationally designed.Here we would like to highlight the progress that novel Na layered oxides could be obtained with the combination of large specific capacity,high power density and good cycling stability.
基金supported by the National Natural Science Foundation of China(52272253)the"Lingyan"Research and Development Plan of Zhejiang Province(2022C01071)+2 种基金the S&T Innovation 2025 Major Special Programme of Ningbo(2018B10081)the Natural Science Foundation of Ningbo(202003N4030)the Youth Innovation Promotion Association of Chinese Academy of Sciences(2022299)。
文摘Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the involvement of oxygen redox.Herein,a Co-free Li-rich layered oxide Li_(1.286)Ni_(0.071)Mn_(0.643)O_(2)has been prepared by a co-precipitation method to systematically investigate the undefined effects of the oxygen defects.A significant O_(2)release and the propagation of oxygen vacancies were detected by operando differential electrochemical mass spectroscopy(DEMS)and electron energy loss spectroscopy(EELS),respectively.Scanning transmission electron microscopy-high angle annular dark field(STEMHAADF)reveals the oxygen vacancies fusing to nanovoids and monitors a stepwise electrochemical activation process of the large Li_(2)MnO_(3)domain upon cycling.Combined with the quantitative analysis conducted by the energy dispersive spectrometer(EDS),existed nano-scale oxygen defects actually expose more surface to the electrolyte for facilitating the electrochemical activation and subsequently increasing available capacity.Overall,this work persuasively elucidates the function of oxygen defects on oxygen redox in Co-free Li-rich layered oxides.
基金Financial supports from the National Natural Science Foundation of China (21822506 and 51761165025)the Tianjin Natural Science Foundation (19JCJQJC62400)the 111 project of B12015。
文摘Anionic redox reaction(ARR) in layered manganese-based oxide cathodes has been considered as an effective strategy to improve the energy density of sodium-ion batteries.Mn-vacancy layered oxides deliver a high ARR-related capacity with small voltage hysteresis,however,they are limited by rapid capacity degradation and poor rate capability,which arise from inferior structure changes due to repeated redox of lattice oxygen.Herein,redox-inactive Ti^(4+)is introduced to substitute partial Mn^(4+)to form Na_(2) Ti_(0.5)Mn_(2.5)O_7(Na_(4/7)[□_(1/7)Ti_(1/7)Mn_(5/7)]O_(2),□ for Mn vacancies),which can effectively restrain unfavorable interlayer gliding of Na2 Mn307 at high charge voltages,as reflected by an ultralow-strain volume variation of 0.11%.There is no irreversible O_(2) evolution observed in Na_(2) Ti_(0.5)Mn_(2.5)O_7 upon charging,which stabilizes the lattice oxygen and ensures the overall structural stability.It exhibits increased capacity retention of 79.1% after 60 cycles in Na_(2) Ti_(0.5)Mn_(2.5)O_7(17.1% in Na_(2) Mn_(3) O_7) and good rate capability(92.1 mAh g^(-1) at 0.5 A g^(-1)).This investigation provides new insights into designing high-performance cathode materials with reversible ARR and structural stability for SIBs.
基金finically supported by the National Key Research and Development Program of China (Grant No. 2016YFB0100100)Strategic Priority Research Program of Chinese Academy of Sciences (CAS, Grant No. XDA09010101)Ningbo Key Science and Technology Projects "Industrial Application Development of Graphene" (Grant No. 2014S10008)
文摘Lithium-rich layered oxides(LrLOs) deliver extremely high specific capacities and are considered to be promising candidates for electric vehicle and smart grid applications. However, the application of LrLOs needs further understanding of the structural complexity and dynamic evolution of monoclinic and rhombohedral phases, in order to overcome the issues including voltage decay, poor rate capability, initial irreversible capacity loss and etc. The development of aberration correction for the transmission electron microscope and concurrent progress in electron spectroscopy, have fueled rapid progress in the understanding of the mechanism of such issues. New techniques based on the transmission electron microscope are first surveyed, and the applications of these techniques for the study of the structure, migration of transition metal, and the activation of oxygen of LrLOs are then explored in detail, with a particular focus on the mechanism of voltage decay.
基金supported by the National Science Foundation of China (Grant No.22179094)the Science and Technology Program of Cangzhou (Grant No.222103001)the research funding of Cangzhou Institute of Tiangong University (Grant No.TGCYY-Z0202)。
文摘P2-type layered oxides are highly promising cathode candidates for sodium-ion batteries(SIBs)owing to their substantial theoretical capacity.Nevertheless,structural degradation caused by transition metal dissolution and irreversible phase transitions at high voltage severely compromises cycling stability.To address this limitation,we propose a Li/Ti co-doping strategy to design a Na_(0.67)Li_(0.06)Ni_(0.27)Mn_(0.5)7Ti_(0.1)O_(2)(NLMT) cathode for SIBs.In-situ X-ray diffraction(XRD) confirms that this deliberate strategy eliminates the adverse phase transition at high voltage and sustains the unitary P2phase throughout cycling.In addition,strengthened transition metal-oxygen(TM-O) bonding via electronic modulation suppresses transition metal dissolution and reinforces the layered oxide framework,contributing to exceptional electrochemical performance.Consequently,the NLMT cathode exhibits an outstanding capacity of 92.8 mA h gLi+(-1) within 2.5-4.3 V at 5 C(865 mA g Li^(+)(-1)),with 87 % capacity retention over 200 cycles.Configured into a full cell,which achieves a competitive capacity of 107.7 mA h g^(-1) at0.1 C and retains 86.4 % capacity over 100 cycles at 0.5 C.This study validates co-doping as a potent strategy for significantly improving the long-term cyclability of layered oxide cathodes in SIBs.
基金Ministry of SMEs and Startups,Grant/Award Number:S3248116National Research Foundation of Korea,Grant/Award Numbers:RS-2023-00211636,RS-2024-00416891Ministry of Science and ICT,South Korea,Grant/Award Number:RS-2020-II201336。
文摘Nickel-rich layered oxides(LiNixCoyMnzO2,NCM)are among the most promising cathode materials for high-energy lithium-ion batteries,offering high specific capacity and output voltage at a relatively low cost.However,industrialscale co-precipitation presents significant challenges,particularly in maintaining particle sphericity,ensuring a stable concentration gradient,and preserving production yield when transitioning from lab-scale compositions.This study addresses a critical issue in the large-scale synthesis of nickel-rich NCM(x=0.8381):nickel leaching,which compromises particle uniformity and battery performance.To mitigate this,we optimize the reaction process and develop an artificial intelligence-driven defect prediction system that enhances precursor stability.Our domain adaptation based machine learning model,which accounts for equipment wear and environmental variations,achieves a defect detection accuracy of 97.8%based on machine data and process conditions.By implementing this approach,we successfully scale up NCM precursor production to over 2 tons,achieving 83%capacity retention after 500 cycles at a 1C rate.In addition,the proposed approach demonstrates the formation of a concentration gradient in the composition and a high sphericity of 0.951(±0.0796).This work provides new insights into the stable mass production of NCM precursors,ensuring both high yield and performance reliability.
基金financially supported by the National Natural Science Foundation of China(Grants 52371217 and 52104304)the Applied Basic Research Fund of Guangdong Province(Grant 2024B1515020071)the Science and Technology Innovation Plan Project of Hunan Province(Grant 2024RC3217).
文摘With the rapid development of the economy,increasing demand for energy storage and electric vehicles require electrode materials for batteries with high energy density,safety,and cyclability,especially for lithium-ion(Li-ion)battery cathodes.However,the understanding of their degradation mechanism remains insufficient due to the complex battery system,the transient nature of the de/lithiation processes,and the lack of advanced characterization techniques.Among these challenges,the mechanism of the Li-rich layered cathode family with high operating voltage and cationic-anionic hybrid charge compensation is particularly difficult to study.For the Li-rich family,their electrochemical mechanisms,for example,oxygen redox reaction and structural evolution,were almost impossible to completely clarify in terms of conventional characterization techniques until the development of various in situ techniques.It is obvious that advanced in situ techniques have accelerated the pace of scientific truth exploration.In this review,these intricate mechanisms revealed by various in situ techniques are summarized to clarify the failure mechanism of Li-rich layered cathodes,and an outlook on the application of these advanced techniques within different battery systems is provided.This review highlights how in situ devices can clearly reveal complex mechanisms and further provides the consultation on characterization techniques for mechanism exploration in various research fields.
基金supported by the National Natural Science Foundation of China(92372107,52304338,and 52171219)。
文摘The development of sustainable energy storage solutions has driven research toward alternatives to lithiumion batteries.Sodium-ion battery(SIB)was considered a promising candidate due to their cost-effectiveness and sodium abundance.To introduce defects and enhance the electrochemical performance of O_(3)-phase sodium-ion layered oxide materials,high-temperature shock(HTS)was employed.However,given the characteristics of HTS,especially the rapid heating rate and short sintering time,suitable precursor systems need to be explored.We systematically compared three precursor systems:traditional metal oxides(HTS-O),decomposable salts(HTS-D),and a novel pre-reacted precursor system(HTS-S).The pre-reacted precursor,developed by leveraging the ethanol solubility of C_(4)H_(14)MnO_(8) and modified ball milling conditions,enabled rapid O_(3) phase formation and resulted in impurity-free O_(3)-NaCu_(0.2)Fe_(0.3)Mn _(0.5)O_(2).This material demonstrated superior electrochemical performance,achieving a discharge capacity of 144.05 mAh g^(−1) within 2.0-4.1 V,along with enhanced rate capabilities.Our findings underscore the critical role of precursor selection and modification in HTS synthesis,contributing to the advancement of high-performance sodium-ion battery materials.
基金National Natural Science Foundation of China,Grant/Award Numbers:22179008,21875022Yibin“Jie Bang Gua Shuai”,Grant/Award Number:2022JB004+2 种基金Beijing Nova Program,Grant/Award Number:20230484241Postdoctoral Fellowship Program of CPSF,Grant/Award Number:GZB20230931Special Support of Chongqing Postdoctoral Research Project,Grant/Award Number:2023CQBSHTB2041。
文摘The burgeoning growth in electric vehicles and portable energy storage systems necessitates advances in the energy density and cost-effectiveness of lithium-ion batteries(LIBs),areas where lithium-rich manganese-based oxide(LLO)materials naturally stand out.Despite their inherent advantages,these materials encounter significant practical hurdles,including low initial Coulombic efficiency(ICE),diminished cycle/rate performance,and voltage fading during cycling,hindering their widespread adoption.In response,we introduce an ionic-electronic dual-conductive(IEDC)surface control strategy that integrates an electronically conductive graphene framework with an ionically conductive heteroepitaxial spinel Li_(4)Mn_(5)O_(12)layer.Prolonged electrochemical and structural analyses demonstrate that this IEDC heterostructure effectively minimizes polarization,mitigates structural distortion,and enhances electronic/ionic diffusion.Density functional theory calculations highlight an extensive Li^(+)percolation network and lower Li^(+)migration energies at the layered-spinel interface.The designed LLO cathode with IEDC interface engineering(LMOSG)exhibits improved ICE(82.9%at 0.1 C),elevated initial discharge capacity(296.7 mAh g^(-1)at 0.1 C),exceptional rate capability(176.5 mAh g^(-1)at 5 C),and outstanding cycle stability(73.7%retention at 5 C after 500 cycles).These findings and the novel dual-conductive surface architecture design offer promising directions for advancing highperformance electrode materials.
基金supported by the National Natural Science Foundation of China(Grant Nos.51222210 and 11234013)the One Hundred Talent Project of the Chinese Academy of Sciences
文摘In order to achieve better Na storage performance, most layered oxide positive electrode materials contain toxic and expensive transition metals Ni and/or Co, which are also widely used for lithium-ion batteries. Here we report a new quaternary layered oxide consisting of Cu, Fe, Mn, and Ti transition metals with O3-type oxygen stacking as a positive electrode for room-temperature sodium-ion batteries. The material can be simply prepared by a high-temperature solidstate reaction route and delivers a reversible capacity of 94 m Ah/g with an average storage voltage of 3.2 V. This paves the way for cheaper and non-toxic batteries with high Na storage performance.
基金supported by China-Japanese Research Cooperative Program founded by the Ministry of Science and Technology of the People’s Republic of China(2017YFE0127600)the National Natural Science Foundation of China(No.21978153,51774191).
文摘Lithium rich layered oxides(LLOs)are attractive cathode materials for Li-ion batteries owing to their high capacity(>250 mA h g^(-1))and suitable voltage(∼3.6 V).However,they suffer from serious voltage and capacity fading,which is focused in this review.First,an overview of crystal structure,band structure and electrochemical performances of LLOs is provided.After that,current understanding on oxygen loss,capacity fading and voltage fading is summarized.Finally,five strategies to mitigate capacity and voltage fading are reviewed.It is believed that these understandings can help solve the fading problems of LLOs.
基金the National Natural Science Foundation of China(No.21271145)the National Science Foundation of Hubei Province(No.2015CFB537)+1 种基金the Science and Technology Innovation Committee of Shenzhen Municipality(No.JCYJ20170306171321438)the financial support for this investigation.
文摘Lithium-rich layered oxides(LLOs)have been extensively studied as cathode materials for lithium-ion batteries(LIBs)by researchers all over the world in the past decades due to their high specific capacities and high charge-discharge voltages.However,as cathode materials LLOs have disadvantages of significant voltage and capacity decays during the charge-discharge cycling.It was shown in the past that fine-tuning of structures and compositions was critical to the performances of this kind of materials.In this report,LLOs with target composition of Li1.17Mn0.50Ni0.24Co0.09O2 were prepared by carbonate co-precipitation method with different pH values.X-ray powder diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscope(TEM),and electrochemical impedance spectroscopies(EIS)were used to investigate the structures and morphologies of the materials and to understand the improvements of their electrochemical performances.With the pH values increased from 7.5 to 8.5,the Li/Ni ratios in the compositions decreased from 5.17 to 4.64,and the initial Coulombic efficiency,cycling stability and average discharge voltages were gained impressively.Especially,the material synthesized at pH=8.5 delivered a reversible discharge capacity of 263 mAhg−1 during the first cycle,with 79.0%initial Coulombic efficiency,at the rate of 0.1 C and a superior capacity retention of 94%after 100 cycles at the rate of 1 C.Furthermore,this material exhibited an initial average discharge voltage of 3.65 V,with a voltage decay of only 0.09 V after 50 charge-discharge cycles.The improved electrochemical performances by varying the pH values in the synthesis process can be explained by the mitigation of layered-to-spinel phase transformation and the reduction of solid-electrolyte interface(SEI)resistance.We hope this work can shed some light on the alleviation of voltage and capacity decay issues of the LLOs cathode materials.
