Enhancing thermodynamic stability of single-crystal Ni-rich cathode material via a synergistic dual-substitution strategy

Nickel(Ni)-rich cathode materials have become promising candidates for the next-generation electrical vehicles due to their high specific capacity.However,the poor thermodynamic stability(including cyclic performance and safety performance or thermal stability)will restrain their wide commercial application.Herein,a single-crystal Ni-rich Li Ni_(0.83)Co_(0.12)Mn_(0.05)O_(2) cathode material is synthesized and modified by a dual-substitution strategy in which the high-valence doping element improves the structural stability by forming strong metal–oxygen binding forces,while the low-valence doping element eliminates high Li^(+)/Ni^(2+)mixing.As a result,this synergistic dual substitution can effectively suppress H2-H3 phase transition and generation of microcracks,thereby ultimately improving the thermodynamic stability of Ni-rich cathode material.Notably,the dual-doped Ni-rich cathode delivers an extremely high capacity retention of 81%after 250 cycles(vs.Li/Li+)in coin-type half cells and 87%after 1000 cycles(vs.graphite/Li^(+))in pouch-type full cells at a high temperature of 55℃.More impressively,the dual-doped sample exhibits excellent thermal stability,which demonstrates a higher thermal runaway temperature and a lower calorific value.The synergetic effects of this dual-substitution strategy pave a new pathway for addressing the critical challenges of Ni-rich cathode at high temperatures,which will significantly advance the high-energy-density and high-safety cathodes to the subsequent commercialization.

Corrigendum to“Anthraquinone derivatives supported by Ti_(3)C_(2)(MXene)as cathode materials for aluminum-organic batteries”[J.Energy Chem.74(2022)174–183]

The authors regret that the printed version of the above article contained an error reference.We hope to correct it here.[14]B.J.M.Christophe Legein,Franck Fayon,Angew.Chem.Int.Ed.,132(2020)19409–19415.

Influence of the position relationship between the cathode and magnetic separatrix on the discharge process of a Hall thruster

Previous studies have shown that there is an obvious coupling relationship between the installation location of the external cathode and the magnetic separatrix in the plume region of a Hall thruster.In this paper,the particle-in-cell simulation method is used to compare the thruster discharge process under the conditions of different position relationships between the cathode and the magnetic separatrix.By comparing the distribution of electron conduction,potential,plasma density and other microscopic parameters,we try to explain the formation mechanism of the discharge difference.The simulation results show that the cathode inside and outside the magnetic separatrix has a significant effect on the distribution of potential and plasma density.When the cathode is located on the outer side of the magnetic separatrix,the potential above the plume region is relatively low,and there is a strong potential gradient above the plume region.This potential gradient is more conducive to the radial diffusion of ions above the plume,which is the main reason for the strong divergence of the plume.The distribution of ion density is also consistent with the distribution of potential.When the cathode is located on the outer side of the magnetic separatrix,the radial diffusion of ions in the plume region is enhanced.Meanwhile,by comparing the results of electron conduction,it is found that the traiectories of electrons emitted from the cathode are significantly different between the inner and outer sides of the magnetic separatrix.This is mainly because the electrons are affected by the magnetic mirror effect of the magnetic tip,which makes it difficult for the electrons to move across the magnetic separatrix.This is the main reason for the difference in potential distribution.In this paper,the simulation results of macroscopic parameters under several conditions are also compared,and they are consistent with the experimental results.The cathode is located on the inner side of the magnetic separatrix,which can effectively reduce the plume divergence angle and improve the thrust.In this paper,the cathode moves from R=50 mm to R=35 mm along the radial direction,the thrust increases by 3.6 mN and the plume divergence angle decreases by 23.77%.Combined with the comparison of the ionization region and the peak ion density,it is found that the main reason for the change in thrust is the change in the radial diffusion of ions in the plume region.

Plasma potential measurements using an emissive probe made of oxide cathode

A novel emissive probe consisting of an oxide cathode coating is developed to achieve a low operating temperature and long service life.The properties of the novel emissive probe are investigated in detail,in comparison with a traditional tungsten emissive probe,including the operating temperature,the electron emission capability and the plasma potential measurement.Studies of the operating temperature and electron emission capability show that the tungsten emissive probe usually works at a temperature of 1800 K-2200 K while the oxide cathode emissive probe can function at about 1200 K-1400 K.In addition,plasma potential measurements using the oxide cathode emissive probe with different techniques have been accomplished in microwave electron cyclotron resonance plasmas with different discharge powers.It is found that a reliable plasma potential can be obtained using the improved inflection point method and the hot probe with zero emission limit method,while the floating point method is invalid for the oxide cathode emissive probe.

Phase engineering of Ni-Mn binary layered oxide cathodes for sodiumion batteries

Nickel-manganese binary layered oxides with high working potential and low cost are potential candidates for sodium-ion batteries,but their electrochemical properties are highly related to compositional diversity.Diverse composite materials with various phase structures of P3,P2/P3,P2,P2/O3,and P2/P3/O3 were synthesized by manipulating the sodium content and calcination conditions,leading to the construction of a synthetic phase diagram for Na_(x)Ni_(0.25)Mn_(0.75)O_(2)(0.45≤x≤1.1).Then,we compared the electrochemical characteristics and structural evolution during the desodiation/sodiation process of P2,P2/P3,P2/03,and P2/P3/O3-Na_(x)Ni_(0.25)Mn_(0.75)O_(2).Among them,P2/P3-Na0.75Ni0.25Mn0.75O2exhibits the best rate capability of 90.9 mA h g^(-1)at 5 C,with an initial discharge capacity of 142.62 mA h g^(-1)at 0.1 C and a capacity retention rate of 78.25%after 100 cycles at 1 C in the voltage range of 2-4.3 V.The observed superior sodium storage performance of P2/P3 hybrids compared to other composite phases can be attributed to the enhanced Na^(+)transfer dynamic,reduction of the Jahn-teller effect,and improved reaction reversibility induced by the synergistic effect of P2 and P3 phases.The systematic research and exploration of phases in Na_(x)Ni_(0.25)Mn_(0.75)O_(2)provide new sights into high-performance nickel-manganese binary layered oxide for sodium-ion batteries.

Effect of crystal morphology of ultrahigh-nickel cathode materials on high temperature electrochemical stability of lithium ion batteries

Higher nickel content endows Ni-rich cathode materials LiNi_(x)Co_yMn_(1-x-y)O_(2)(x>0.6)with higher specific capacity and high energy density,which is regarded as the most promising cathode materials for Li-ion batteries.However,the deterioration of structural stability hinders its practical application,especially under harsh working conditions such as high-temperature cycling.Given these circumstances,it becomes particularly critical to clarify the impact of the crystal morphology on the structure and high-temperature performance as for the ultrahigh-nickel cathodes.Herein,we conducted a comprehensive comparison in terms of microstructure,high-temperature long-cycle phase evolution,and high-temperature electrochemical stability,revealing the differences and the working mechanisms among polycrystalline(PC),single-crystalline(SC)and Al doped SC ultrahigh-nickel materials.The results show that the PC sample suffers a severe irreversible phase transition along with the appearance of microcracks,resulting a serious decay of both average voltage and the energy density.While the Al doped SC sample exhibits superior cycling stability with intact layered structure.In-situ XRD and intraparticle structural evolution characterization reveal that Al doping can significantly alleviate the irreversible phase transition,thus inhibiting microcracks generation and enabling enhanced structure.Specifically,it exhibits excellent cycling performance in pouch-type full-cell with a high capacity retention of 91.8%after 500 cycles at 55℃.This work promotes the fundamental understanding on the correlation between the crystalline morphology and high-temperature electrochemical stability and provides a guide for optimization the Ni-rich cathode materials.

Reversible Mn^(2+)/Mn^(4+)double-electron redox in P3-type layer-structured sodium-ion cathode

The balance between cationic redox and oxygen redox in layer-structured cathode materials is an important issue for sodium batteries to obtain high energy density and considerable cycle stability.Oxygen redox can contribute extra capacity to increase energy density,but results in lattice instability and capacity fading caused by lattice oxygen gliding and oxygen release.In this work,reversible Mn^(2+)/Mn^(4+)redox is realized in a P3-Na_(0.65)Li_(0.2)Co_(0.05)Mn_(0.75)O_(2)cathode material with high specific capacity and structure stability via Co substitution.The contribution of oxygen redox is suppressed significantly by reversible Mn^(2+)/Mn^(4+)redox without sacrificing capacity,thus reducing lattice oxygen release and improving the structure stability.Synchrotron X-ray techniques reveal that P3 phase is well maintained in a wide voltage window of 1.5-4.5 V vs.Na^(+)/Na even at 10 C and after long-term cycling.It is disclosed that charge compensation from Co/Mn-ions contributes to the voltage region below 4.2 V and O-ions contribute to the whole voltage range.The synergistic contributions of Mn^(2+)/Mn^(4+),Co^(2+)/Co^(3+),and O^(2-)/(O_n)^(2-)redox in P3-Na_(0.65)Li_(0.2)Co_(0.05)Mn_(0.75)O_(2)lead to a high reversible capacity of 215.0 m A h g^(-1)at 0.1 C with considerable cycle stability.The strategy opens up new opportunities for the design of high capacity cathode materials for rechargeable batteries.

New insights into the pre-lithiation kinetics of single-crystalline Ni-rich cathodes for long-life Li-ion batteries

Developing single-crystalline Ni-rich cathodes is an effective strategy to improve the safety and cycle life of Li-ion batteries(LIBs).However,the easy-to-loss of Li and O in high-temperature lithiation results in unsatisfactory ordered layered structure and stoichiometry.Herein,we demonstrate the synthesis of highly-ordered and fully-stoichiometric single-crystalline LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)cathodes by the regulation of pre-lithiation kinetics.The well-balanced pre-lithiation kinetics have been proved to greatly improve the proportion of layered phase in the intermediate by inhibiting the formation of metastable spinel phase,which promoted the rapid transformation of the intermediate into highly-ordered layered SC-NCM83 in the subsequent lithiation process.After coating a layer of Li_(2)O–B_(2)O_(3),the resultant cathodes deliver superior cycling stability with 90.9%capacity retention at 1C after 300 cycles in pouch-type full batteries.The enhancement mechanism has also been clarified.These findings exhibit fundamental insights into the pre-lithiation kinetics process for guiding the synthesis of high-quality singlecrystalline Ni-rich cathodes.

Cationic ordering transition in oxygen-redox layered oxide cathodes

Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na-ion cathodes.Here,we reveal the correlation between cationic ordering transition and OR degradation in ribbon-ordered P3-Na_(0.6)Li_(0.2)Mn_(0.8)O_(2) via in situ structural analysis.Comparing two different voltage windows,the OR capacity can be improved approximately twofold when suppressing the in-plane cationic ordering transition.We find that the intralayer cationic migration is promoted by electrochemical reduction from Mn^(4+)to Jahn–Teller Mn^(3+)and the concomitant NaO_(6) stacking transformation from triangular prisms to octahedra,resulting in the loss of ribbon ordering and electrochemical decay.First-principles calculations reveal that Mn^(4+)/Mn^(3+)charge ordering and alignment of the degenerate eg orbital induce lattice-level collective Jahn–Teller distortion,which favors intralayer Mn-ion migration and thereby accelerates OR degradation.These findings unravel the relationship between in-plane cationic ordering and OR reversibility and highlight the importance of superstructure protection for the rational design of reversible OR-active layered oxide cathodes.

Constructing a stable interface on Ni-rich LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) cathode via lactic acid-assisted engineering strategy

Ni-rich layered oxides are potential cathode materials for next-generation high energy density Li-ion batteries due to their high capacity and low cost.However,the inherently unstable surface properties,including high levels of residual Li compounds,dissolution of transition metal cations,and parasitic side reactions,have not been effectively addressed,leading to significant degradation in their electrochemical performance.In this study,we propose a simple and effective lactic acid-assisted interface engineering strategy to regulate the surface chemistry and properties of Ni-rich LiNi_(0.8)Co_(0.1)Mr_(0.1)O_(2) cathode.This novel surface treatment method successfully eliminates surface residual Li compounds,inhibits structural collapse,and mitigates cathode-electrolyte interface film growth.As a result,the lactic acidtreated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) achieved a remarkable capacity retention of 91.7% after 100 cycles at 0.5 C(25℃) and outstanding rate capability of 149.5 mA h g^(-1) at 10 C,significantly outperforming the pristine material.Furthermore,a pouch-type full cell incorporating the modified LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) cathode demonstrates impressive long-term cycle life,retaining 81.5% of its capacity after 500 cycles at 1 C.More importantly,the thermal stability of the modified cathode is also dramatically improved.This study offers a valuable surface modification strategy for enhancing the overall performance of Ni-rich cathode materials.

Mg/Fe site-specific dual-doping to boost the performance of cobalt-free nickle-rich layered oxide cathode for high-energy lithium-ion batteries

Layer-type LiNi0.9Mn0.1O2is promising to be the primary cathode material for lithium-ion batteries(LIBs)due to its excellent electrochemical performance.Unfortunately,the cathode with high nickel content suffers from severely detrimental structural transformation that causes rapid capacity attenuation.Herein,site-specific dual-doping with Fe and Mg ions is proposed to enhance the structural stability of LiNi0.9Mn0.1O2.The Fe3+dopants are inserted into transition metal sites(3b)and can favorably provide additional redox potential to compensate for charge and enhance the reversibility of anionic redox.The Mg ions are doped into the Li sites(3a)and serve as O_(2)^(-)-Mg^(2+)-O_(2)^(-)pillar to reinforce the electrostatic cohesion between the two adjacent transition-metal layers,which further suppress the cracking and the generation of harmful phase transitions,ultimately improving the cyclability.The theoretical calculations,including Bader charge and crystal orbital Hamilton populations(COHP)analyses,confirm that the doped Fe and Mg can form stable bonds with oxygen and the electrostatic repulsion of O_(2)^(-)-O_(2)^(-)can be effectively suppressed,which effectively mitigates oxygen anion loss at the high delithiation state.This dual-site doping strategy offers new avenues for understanding and regulating the crystalline oxygen redox and demonstrates significant potential for designing high-performance cobalt-free nickel-rich cathodes.

Degradation analysis and doping modification optimization for high-voltage P-type layered cathode in sodium-ion batteries

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.

Structural and electrochemical stabilization enabling high-energy P3-type Cr-based layered oxide cathode for K-ion batteries

Layered-type transition metal(TM)oxides are considered as one of the most promising cathodes for K-ion batteries because of the large theoretical gravimetric capacity by low molar mass.However,they suffer from severe structural change by de/intercalation and diffusion of K^(+)ions with large ionic size,which results in not only much lower reversible capacity than the theoretical capacity but also poor power capability.Thus,it is important to enhance the structural stability of the layered-type TM oxides for outstanding electrochemical behaviors under the K-ion battery system.Herein,it is investigated that the substitution of the appropriate Ti^(4+)contents enables a highly enlarged reversible capacity of P3-type KxCrO_(2) using combined studies of first-principles calculation and various experiments.Whereas the pristine P3-type KxCrO_(2) just exhibits the reversible capacity of∼120 mAh g^(−1) in the voltage range of 1.5-4.0 V(vs.K^(+)/K),the∼0.61 mol K^(+)corresponding to∼150 mAh g^(−1) can be reversible de/intercalated at the structure of P3-type K0.71[Cr_(0.75)Ti_(0.25)]O_(2) under the same conditions.Furthermore,even at the high current density of 788 mA g^(−1),the specific capacity of P3-type K0.71[Cr_(0.75)Ti_(0.25)]O_(2) is∼120 mAh g^(−1),which is∼81 times larger than that of the pristine P3-type KxCrO_(2).It is believed that this research can provide an effective strategy to improve the electrochemical performances of the cathode materials suffered by severe structural change that occurred during charge/discharge under not only K-ion battery system but also other rechargeable battery systems.

A defective iron-based perovskite cathode for high-performance IT-SOFCs:Tailoring the oxygen vacancies using Nb/Ta co-doping

The sluggish kinetics of the electrochemical oxygen reduction reaction(ORR)in intermediatetemperature solid oxide fuel cells(IT-SOFCs)greatly limits the overall cell performance.In this study,an efficient and durable cathode material for IT-SOFCs is designed based on density functional theory(DFT)calculations by co-doping with Nb and Ta the B-site of the SrFeO_(3-δ)perovskite oxide.The DFT calculations suggest that Nb/Ta co-doping can regulate the energy band of the parent SrFeO_(3-δ)and help electron transfer.In symmetrical cells,such cathode with a SrFe_(0.8)Nb_(0.1)Ta_(0.1)O_(3-δ)(SFNT)detailed formula achieves a low cathode polarization resistance of 0.147Ωcm^(2) at 650℃.Electron spin resonance(ESR)and X-ray photoelectron spectroscopy(XPS)analysis confirm that the co-doping of Nb/Ta in SrFeO_(3-δ)B-site increases the balanced concentration of oxygen vacancies,enhancing the electrochemical performance when compared to 20 mol%Nb single-doped perovskite oxide.The cathode button cell with NiSDC|SDC|SFNT configuration achieves an outstanding peak power density of 1.3 W cm^(-2)at 650℃.Moreover,the button cell shows durability for 110 h under 0.65 V at 600℃ using wet H_(2) as fuel.

Residual alkali-evoked cross-linked polymer layer for anti-air-sensitivity LiNi_(0.89)Co_(0.06)Mn_(0.05)O_(2)cathode

High-energy density lithium-ion batteries(LIBs)with layered high-nickel oxide cathodes(LiNi_(x)Co_(y)Mn_(1-x-y)O_(2),x≥0.8)show great promise in consumer electronics and vehicular applications.However,LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)faces challenges related to capacity decay caused by residual alkalis owing to high sensitivity to air.To address this issue,we propose a hazardous substances upcycling method that fundamentally mitigates alkali content and concurrently induces the emergence of an anti-air-sensitive layer on the cathode surface.Through the neutralization of polyacrylic acid(PAA)with residual alkalis and then coupling it with 3-aminopropyl triethoxysilane(KH550),a stable and ion-conductive cross-linked polymer layer is in situ integrated into the LiNi_(0.89)Co_(0.06)Mn_(0.05)O_(2)(NCM)cathode.Our characterization and measurements demonstrate its effectiveness.The NCM material exhibits impressive cycling performance,retaining 88.4%of its capacity after 200 cycles at 5 C and achieving an extraordinary specific capacity of 170.0 mA h g^(-1) at 10 C.Importantly,this layer on the NCM efficiently suppresses unfavorable phase transitions,severe electrolyte degradation,and CO_(2)gas evolution,while maintaining commendable resistance to air exposure.This surface modification strategy shows widespread potential for creating air-stable LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)cathodes,thereby advancing high-performance LIBs.

Manipulating Na occupation and constructing protective film of P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2) as long-term cycle stability cathode for sodium-ion batteries

P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2)(NNMO)is promising cathode material for sodium-ion batteries(SIBs)due to its high specific capacity and fast Na+diffusion rate.Nonetheless,the irreversible P2-O_(2)phase transformation,Na+/vacancy ordering,and transition metal(TM)dissolution seriously damage its cycling stability and restrict its commercialization process.Herein,Na occupation manipulation and interface stabilization are proposed to strengthen the phase structure of NNMO by synergistic Zn/Ti co-doping and introducing lithium difluorophosp(LiPO_(2)F_(2))film-forming electrolyte additive.The Zn/Ti co-doping regulates the occupancy ratio of Nae/Nafat Na sites and disorganizes the Na+/vacancy ordering,resulting in a faster Na+diffusion kinetics and reversible P2-Z phase transition for P2-Na_(0.67)Ni_(0.28)Zn_(0.05)Mn_(0.62)Ti_(0.05)O_(2)(NNZMTO).Meanwhile,the LiPO_(2)F_(2)additive can form homogeneous and ultrathin cathode-electrolyte interphase(CEI)on NNZMTO surface,which can stabilize the NNZMTO-electrolyte interface to prevent TM dissolution,surface structure transformation,and micro-crack generation.Combination studies of in situ and ex situ characterizations and theoretical calculations were used to elucidate the storage mechanism of NNZMTO with Li PO_(2)F_(2)additive.As a result,the NNZMTO displays outstanding capacity retention of 94.44%after 500 cycles at 1C with 0.3 wt%Li PO_(2)F_(2),excellent rate performance of 92.5 mA h g^(-1)at 8C with 0.1 wt%Li PO_(2)F_(2),and remarkable full cell capability.This work highlights the important role of manipulating Na occupation and constructing protective film in the design of layered materials,which provides a promising direction for developing high-performance cathodes for SIBs.

Research on Preparation and Electrochemical Performance of the High Compacted Density Ni-Co-Mn Ternary Cathode Materials

The high compacted density LiNi0.5-xCo0.2Mn0.3MgxO2 cathode material for lithium-ion batteries was synthesized by high temperature solid-state method, taking the Mg element as a doping element and the spherical Ni0.5Co0.2Mn0.3 (OH)2, Li2CO3 as raw materials. The effects of calcination temperature on the structure and properties of the products were investigated. The structure and morphology of cathode materials powder were analyzed by X-ray diffraction spectroscopy (XRD) and scanning electronmicroscopy (SEM). The electrochemical properties of the cathode materials were studied by charge-discharge test and cyclic properties test. The results show that LiNi0.4985Co0.2Mn0.3 Mg0.0015O2 cathode material prepared at calcination temperature 930°C has a good layered structure, and the compacted density of the electrode sheet is above 3.68 g/cm3. The discharge capacity retention rate is more than 97.5% after 100 cycles at a charge-discharge rate of 1C, displaying a good cyclic performance.

Phase-engineering modulation of Mn-based oxide cathode for constructing super-stable sodium storage

The Mn-based oxide cathode with enriched crystal phase structure and component diversity can provide the excellent chemistry structure for Na-ion batteries.Nevertheless,the broad application prospect is obstructed by the sluggish Na^(+)kinetics and the phase transitions upon cycling.Herein,we establish the thermodynamically stable phase diagram of various Mn-based oxide composites precisely controlled by sodium content tailoring strategy coupling with co-doping and solid-state reaction.The chemical environment of the P2/P'3 and P2/P3 biphasic composites indicate that the charge compensation mechanism stems from the cooperative contribution of anions and cations.Benefiting from the no phase transition to scavenge the structure strain,P2/P'3 electrode can deliver long cycling stability(capacity retention of 73.8%after 1000 cycles at 10 C)and outstanding rate properties(the discharge capacity of 84.08 mA h g^(-1)at 20 C)than P2/P3 electrode.Furthermore,the DFT calculation demonstrates that the introducing novel P'3 phase can significantly regulate the Na^(+)reaction dynamics and modify the local electron configuration of Mn.The effective phase engineering can provide a reference for designing other high-performance electrode materials for Na-ion batteries.

High‑Entropy Layered Oxide Cathode Enabling High‑Rate for Solid‑State Sodium‑Ion Batteries

Na-ion O3-type layered oxides are prospective cathodes for Na-ion batteries due to high energy density and low-cost.Nevertheless,such cathodes usually suffer from phase transitions,sluggish kinetics and air instability,making it difficult to achieve high performance solid-state sodium-ion batteries.Herein,the high-entropy design and Li doping strategy alleviate lattice stress and enhance ionic conductivity,achieving high-rate performance,air stability and electrochemically thermal stability for Na_(0.95)Li_(0.06)Ni_(0.25)Cu_(0.05)Fe_(0.15)Mn_(0.49)O_(2).This cathode delivers a high reversible capacity(141 mAh g^(−1)at 0.2C),excellent rate capability(111 mAh g^(−1)at 8C,85 mAh g^(−1)even at 20C),and long-term stability(over 85%capacity retention after 1000 cycles),which is attributed to a rapid and reversible O3–P3 phase transition in regions of low voltage and suppresses phase transition.Moreover,the compound remains unchanged over seven days and keeps thermal stability until 279℃.Remarkably,the polymer solid-state sodium battery assembled by this cathode provides a capacity of 92 mAh g^(−1)at 5C and keeps retention of 96%after 400 cycles.This strategy inspires more rational designs and could be applied to a series of O3 cathodes to improve the performance of solid-state Na-ion batteries.

Suppress oxygen evolution of lithium-rich manganese-based cathode materials via an integrated strategy

Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous lithiation strategy combining the advantages of yttrium doping and LiYO_(2) surface coating is proposed.Yttrium doping effectively suppresses the oxygen evolution during the delithiation process by increasing the energy barrier of oxygen evolution reaction through strong Y–O bond energy.LiYO_(2) nanocoating has the function of structural constraint and protection,that protecting the lattice oxygen exposed to the surface,thus avoiding irreversible oxidation.As an Li^(+) conductor,LiYO_(2) nano-coating can provide a fast Li^(+) transfer channel,which enables the sample to have excellent rate performance.The synergistic effect of Y doping and nano-LiYO_(2) coating integration suppresses the oxygen release from the surface,accelerates the diffusion of Li^(+)from electrolyte to electrode and decreases the interfacial side reactions,enabling the lithium ion batteries to obtain good electrochemical performance.The lithium-ion full cell employing the Y-1 sample(cathode)and commercial graphite(anode)exhibit an excellent specific energy density of 442.9 Wh kg^(-1) at a current density of 0.1C,with very stable safety performance,which can be used in a wide temperature range(60 to-15℃)stable operation.This result illustrates a new integration strategy for advanced cathode materials to achieve high specific energy density.