Energy-storage systems and their production have attracted significant interest for practical applications.Batteries are the foundation of sustainable energy sources for electric vehicles(EVs),portable electronic devi...Energy-storage systems and their production have attracted significant interest for practical applications.Batteries are the foundation of sustainable energy sources for electric vehicles(EVs),portable electronic devices(PEDs),etc.In recent decades,Lithium-ion batteries(LIBs) have been extensively utilized in largescale energy storage devices owing to their long cycle life and high energy density.However,the high cost and limited availability of Li are the two main obstacles for LIBs.In this regard,sodium-ion batteries(SIBs) are attractive alternatives to LIBs for large-scale energy storage systems because of the abundance and low cost of sodium materials.Cathode is one of the most important components in the battery,which limits cost and performance of a battery.Among the classified cathode structures,layered structure materials have attracted attention because of their high ionic conductivity,fast diffusion rate,and high specific capacity.Here,we present a comprehensive review of the classification of layered structures and the preparation of layered materials.Furthermore,the review article discusses extensively about the issues of the layered materials,namely(1) electrochemical degradation,(2) irreversible structural changes,and(3) structural instability,and also it provides strategies to overcome the issues such as elemental phase composition,a small amount of elemental doping,structural design,and surface alteration for emerging SIBs.In addition,the article discusses about the recent research development on layered unary,binary,ternary,quaternary,quinary,and senary-based O3-and P2-type cathode materials for high-energy SIBs.This review article provides useful information for the development of high-energy layered sodium transition metal oxide P2 and O3-cathode materials for practical SIBs.展开更多
The high compacted density LiNi<sub>0.5-x</sub>Co<sub>0.2</sub>Mn<sub>0.3</sub>Mg<sub>x</sub>O<sub>2</sub> cathode material for lithium-ion batteries was syn...The high compacted density LiNi<sub>0.5-x</sub>Co<sub>0.2</sub>Mn<sub>0.3</sub>Mg<sub>x</sub>O<sub>2</sub> 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 Ni<sub>0.5</sub>Co<sub>0.2</sub>Mn<sub>0.3</sub> (OH)<sub>2</sub>, Li<sub>2</sub>CO<sub>3</sub> 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 LiNi<sub>0.4985</sub>Co<sub>0.2</sub>Mn<sub>0.3</sub> Mg<sub>0.0015</sub>O<sub>2</sub> 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/cm<sup>3</sup>. 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.展开更多
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 ...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.展开更多
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.
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 ba...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.展开更多
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 ...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.展开更多
Generally,layered Ni-rich cathode materials exhibit the morphology of polycrystalline secondary sphere composed of numerous primary particles.While the arrangement of primary particles plays a very important role in t...Generally,layered Ni-rich cathode materials exhibit the morphology of polycrystalline secondary sphere composed of numerous primary particles.While the arrangement of primary particles plays a very important role in the properties of Ni-rich cathodes.The disordered particle arrangement is harmful to the cyclic performance and structural stability,yet the fundamental understanding of disordered structure on the structural degradation behavior is unclarified.Herein,we have designed three kinds of LiNi_(0.83)Co_(0.06)Mn_(0.11)O_(2) cathode materials with different primary particle orientations by regulating the precursor coprecipitation process.Combining finite element simulation and in-situ characterization,the Li^(+)transport and structure evolution behaviors of different materials are unraveled.Specifically,the smooth Li^(+)diffusion minimizes the reaction heterogeneity,homogenizes the phase transition within grains,and mitigates the anisotropic microstructural change,thereby modulating the crack evolution behavior.Meanwhile,the optimized structure evolution ensures radial tight junctions of the primary particles,enabling enhanced Li^(+)diffusion during dynamic processes.Closed-loop bidirectional enhancement mechanism becomes critical for grain orientation regulation to stabilize the cyclic performance.This precursor engineering with particle orientation regulation provides the useful guidance for the structural design and feature enhancement of Ni-rich layered cathodes.展开更多
The self-charging concept has drawn considerable attention due to its excellent ability to achieve environmental energy harvesting,conversion and storage without an external power supply.However,most self-charging des...The self-charging concept has drawn considerable attention due to its excellent ability to achieve environmental energy harvesting,conversion and storage without an external power supply.However,most self-charging designs assembled by multiple energy harvesting,conversion and storage materials increase the energy transfer loss;the environmental energy supply is generally limited by climate and meteorological conditions,hindering the potential application of these selfpowered devices to be available at all times.Based on aerobic autoxidation of catechol,which is similar to the electrochemical oxidation of the catechol groups on the carbon materials under an electrical charge,we proposed an air-breathing chemical self-charge concept based on the aerobic autoxidation of catechol groups on oxygen-enriched carbon materials to ortho-quinone groups.Energy harvesting,conversion and storage functions could be integrated on a single carbon material to avoid the energy transfer loss among the different materials.Moreover,the assembled Cu/oxygen-enriched carbon battery confirmed the feasibility of the air-oxidation self-charging/electrical discharging mechanism for potential applications.This air-breathing chemical self-charge concept could facilitate the exploration of high-efficiency sustainable air self-charging devices.展开更多
With the number of decommissioned electric vehicles increasing annually,a large amount of discarded power battery cathode material is in urgent need of treatment.However,common leaching methods for recovering metal sa...With the number of decommissioned electric vehicles increasing annually,a large amount of discarded power battery cathode material is in urgent need of treatment.However,common leaching methods for recovering metal salts are economically inefficient and polluting.Meanwhile,the recycled material obtained by lithium remediation alone has limited performance in cycling stability.Herein,a short method of solid-phase reduction is developed to recover spent LiFePO4 by simultaneously introducing Mg2+ions for hetero-atom doping.Issues of particle agglomeration,carbon layer breakage,lithium loss,and Fe3+defects in spent LiFePO4 are also addressed.Results show that Mg2+addition during regeneration can remarkably enhance the crystal structure stability and improve the Li+diffusion coefficient.The regenerated LiFePO4 exhibits significantly improved electrochemical performance with a specific discharge capacity of 143.2 mAh·g^(−1)at 0.2 C,and its capacity retention is extremely increased from 37.9%to 98.5%over 200 cycles at 1 C.Especially,its discharge capacity can reach 95.5 mAh·g^(−1)at 10 C,which is higher than that of spent LiFePO4(55.9 mAh·g^(−1)).All these results show that the proposed regeneration strategy of simultaneous carbon coating and Mg2+doping is suitable for the efficient treatment of spent LiFePO4.展开更多
Sulfur-containing polymer(SCP)is considered as an outstanding cathode material for lithium-sulfur batteries.However,undesirable soluble polysulfides may shuttle in electrolyte,concluding long-chain Li_(2)S_(n)(n>4)...Sulfur-containing polymer(SCP)is considered as an outstanding cathode material for lithium-sulfur batteries.However,undesirable soluble polysulfides may shuttle in electrolyte,concluding long-chain Li_(2)S_(n)(n>4)and short-chain Li2Sn(n≤4),as well as the sluggish conversion kinetics are yet to be solved to enhance the performance of lithium-sulfur batteries.Here Se-doped sulfurized polyaniline with adjusted sulfur-chain-S_(x)-(x≤6)contribute to ensure the absence of long-chain polysulfides,and the skeleton with quinoid imine can endow strongly adsorption towards short-chain polysulfides by the reversible transition between deprotonated/protonated imine(-NH^(+)=and-N=),which offer double insurance against suppressing“shuttle effect”.Furthermore,Se atoms are doped into sulfurized polysulfides to accelerate the redox conversion and take a frontier orbital theory-oriented view into catalytic mechanism.Se-doped sulfurized polyaniline as active materials for lithium-organosulfur batteries delivers good electrochemical performance,including high rate,reversible specific capacity(680 mA h g^(-1)at 0.1 A g^(-1)),and lower capacity decay rate only of 0.15%with near 100%coulomb efficiency during long-term cycle.This work provides a valuable guiding ideology and promising solution for the chemistry-oriented structure design and practical application for lithium-organosulfur batteries.展开更多
Defective layered Mn-based materials were synthesized by Li/Na ion exchange to improve their electrochemical activity and Coulombic efficiency.The annealing temperature of the Na precursors was important to control th...Defective layered Mn-based materials were synthesized by Li/Na ion exchange to improve their electrochemical activity and Coulombic efficiency.The annealing temperature of the Na precursors was important to control the P3-P2 phase transition,which directly affected the structure and electrochemical characteristics of the final products obtained by ion exchange.The O3-Li_(0.78)[Li_(0.25)Fe_(0.075)Mn_(0.675)]O_(δ) cathode made from a P3-type precursor calcined at 700℃ was analyzed using X-ray photoelectron spectrometry and electron paramagnetic resonance.The results showed that the presence of abundant trivalent manganese and defects resulted in a discharge capacity of 230 mAh/g with an initial Coulombic efficiency of about 109%.Afterward,galvanostatic intermittent titration was performed to examine the Li^(+) ion diffusion coefficients,which affected the reversible capacity.First principles calculations suggested that the charge redistribution induced by oxygen vacancies(OV_(s))greatly affected the local Mn coordination environment and enhanced the structural activity.Moreover,the Li-deficient cathode was a perfect match for the pre-lithiation anode,providing a novel approach to improve the initial Coulombic efficiency and activity of Mn-based materials in the commercial application.展开更多
Cathode materials,nickel doped Cr_(8)O_(21),were synthesized by a solid-state method.The effects of Ni doping on the electrochemical performances of Cr_(8)O_(21) were investigated.The experimental results show that th...Cathode materials,nickel doped Cr_(8)O_(21),were synthesized by a solid-state method.The effects of Ni doping on the electrochemical performances of Cr_(8)O_(21) were investigated.The experimental results show that the discharge capacities of the samples depend on the nickel contents,which increases firstly and then decreases with increasing Ni contents.Optimized Ni_(0.5)Cr_(7.5)O_(21)delivers a first capacity up to 392.6 m Ah·g^(-1)at 0.1C.In addition,Ni doped sample also demonstrates enhanced cycling stability and rate capability compared with that of the bare Cr_(8)O_(21).At 1 C,an initial discharge capacity of 348.7 m Ah·g^(-1)was achieved for Ni_(0.5)Cr_(7.5)O_(21),much higher than 271.4 m Ah·g^(-1)of the un-doped sample,with an increase of more than 28%.Electrochemical impedance spectroscopy results confirm that Ni doping reduces the growth of interface resistance and charge transfer resistance,which is conducive to the electrochemical kinetic behaviors during charge-discharge.展开更多
Rechargeable magnesium batteries(RMBs),as one of the most promising candidates for efficient energy storage devices with high energy,power density and high safety,have attracted increasing attention.However,searching ...Rechargeable magnesium batteries(RMBs),as one of the most promising candidates for efficient energy storage devices with high energy,power density and high safety,have attracted increasing attention.However,searching for suitable cathode materials with fast diffusion kinetics and exploring their magnesium storage mechanisms remains a great challenge.Cu S submicron spheres,made by a facile low-temperature synthesis strategy,were applied as the high-performance cathode for RMBs in this work,which can deliver a high specific capacity of 396mAh g^(-1)at 20 mA g^(-1) and a remarkable rate capacity of 250 m Ah g^(-1)at 1000 mA g^(-1).The excellent rate performance can be assigned to the nano needle-like particles on the surface of Cu S submicron spheres,which can facilitate the diffusion kinetics of Mg^(2+).Further storage mechanism investigations illustrate that the Cu S cathodes experience a two-step conversion reaction controlled by diffusion during the electrochemical reaction process.This work could make a contribution to the study of the enhancement of diffusion kinetics of Mg2+and the reaction mechanism of RMBs.展开更多
Rechargeable magnesium-ion batteries(MIBs) are favorable substitutes for conventional lithium-ion batteries(LIBs) because of abundant magnesium reserves, a high theoretical energy density, and great inherent safety. O...Rechargeable magnesium-ion batteries(MIBs) are favorable substitutes for conventional lithium-ion batteries(LIBs) because of abundant magnesium reserves, a high theoretical energy density, and great inherent safety. Organic electrode materials with excellent structural tunability,unique coordination reaction mechanisms, and environmental friendliness offer great potential to promote the electrochemical performance of MIBs. However, research on organic magnesium battery cathode materials is still preliminary with many significant challenges to be resolved including low electrical conductivity and unwanted but severe dissolution in useful electrolytes. Herein, we provide a detailed overview of reported organic cathode materials for MIBs. We begin with basic properties such as charge storage mechanisms(e.g., n-, p-, and bipolartype), moving to recent advances in various types of organic cathodes including carbonyl-, nitrogen-, and sulfur-based materials. To shed light on the diverse strategies targeting high-performance Mg-organic batteries, elaborate summaries of various approaches are presented.Generally, these strategies include molecular design, polymerization, mixing with carbon, nanosizing and electrolyte/separator optimization.This review provides insights on exploring high-performance organic cathodes in rechargeable MIBs.展开更多
Rechargeable aluminum batteries(RABs)are attractive cadidates for next-generation energy storage and conversion,due to the low cost and high safety of Al resources,and high capacity of metal Al based on the three-elec...Rechargeable aluminum batteries(RABs)are attractive cadidates for next-generation energy storage and conversion,due to the low cost and high safety of Al resources,and high capacity of metal Al based on the three-electrons reaction mechanism.However,the development of RABs is greatly limited,because of the lack of advanced cathode materials,and their complicated and unclear reaction mechanisms.Exploring the novel nanostructured transition metal and carbon composites is an effective route for obtaining ideal cathode materials.In this work,we synthesize porous CoSnO_(3)/C nanocubes with oxygen vacancies for utilizing as cathodes in RABs for the first time.The intrinsic structure stability of the mixed metal cations and carbon coating can improve the cycling performance of cathodes by regulating the internal strains of the electrodes during volume expansion.The nanocubes with porous structures contribute to fast mass transportation which improves the rate capability.In addition to this,abundant oxygen vacancies promote the adsorption affinity of cathodes,which improves storage capacity.As a result,the CoSnO_(3)/C cathodes display an excellent reversible capacity of 292.1 mAh g^(-1) at 0.1 A g^(-1),a good rate performance with 109 mAh g^(-1) that is maintained even at 1 A g^(-1) and the provided stable cycling behavior for 500 cycles.Besides,a mechanism of intercalation of Al^(3+)within CoSnO_(3)/C cathode is proposed for the electrochemical process.Overall,this work provides a step toward the development of advanced cathode materials for RABs by engineering novel nanostructured mixed transition-metal oxides with carbon composite and proposes novel insights into chemistry for RABs.展开更多
Multivalent-ion(such as Zn^(2+),Mg^(2+),Al^(3+))batteries are considered as a prospective alternative for large-scale energy storage.However,the main problem of cathode materials for multivalent-ion batteries is the s...Multivalent-ion(such as Zn^(2+),Mg^(2+),Al^(3+))batteries are considered as a prospective alternative for large-scale energy storage.However,the main problem of cathode materials for multivalent-ion batteries is the sluggish diffusion of multivalent ions.Many cathode materials will self-adjust under electrochemical conditions to achieve the optimal state for multivalent-ion storage.In this review,the significant role of electrochemical in situ structural reconstruction of cathode materials is suggested.The types,basic characteristics,and formation mechanisms of reconstructed phases have been systematically discussed and commented.The most important insight we pointed out is that the cathode materials with loose structures after in situ electrochemical activation are conducive to the reversible diffusion of multivalent ions.Moreover,several crucial issues of electrochemical activation and reconstruction were further analyzed and discussed.The challenges and future perspectives are presented in the final section.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
Potassium ion batteries(PIBs)are emerging as potential next-generation energy storage systems on account of their low cost and high theoretical energy density.Nevertheless,they also face challenges of low specific cap...Potassium ion batteries(PIBs)are emerging as potential next-generation energy storage systems on account of their low cost and high theoretical energy density.Nevertheless,they also face challenges of low specific capacity and suboptimal cycling stability.Herein,we synthesize a cocoon-like P3-type K_(0.5)Mn_(0.7)Ni_(0.3)O_(2)(KMNO)cathode material by a self-template method.The KMNO cocoons possess a hierarchical layered architecture composed of nanoparticle stacking,which can accelerate the transport kinetics of potassium ions,mitigate the stress caused by K^(+)intercalation and deintercalation,and improve structural stability.In addition,Ni can not only alleviate the Jahn-Teller distortion and suppress the phase transition to stabilize the structure,but also act as an electrochemically active element,providing the capacity of two electrons from Ni2+to Ni4+.Combining the advantages of structure and nickel substitution,the P3-type KMNO cocoons are used for electrochemical performance testing of PIB cathodes,delivering an excellent rate capability of 57.1 m A h g^(-1)at 500 m A g^(-1)and a remarkable cycling stability of 77.0%over 300 cycles at 100 m A g^(-1).Impressively,the KMNO cocoons//pitch-derived soft carbon assembled full battery exhibits superior electrochemical performance with a reversible capacity of 79.7 m A h g^(-1)at 50 m A g^(-1).Moreover,ex-situ XRD also further reveals a solid solution phase reaction with a volume change of only 1.46%.This work furnishes a suitable approach to fabricating highperformance layered oxide cathodes for PIBs with outstanding cycling stability and rate capability.展开更多
In this paper,overcharge behaviors and thermal runaway(TR)features of large format lithium-ion(Liion)cells with different cathode materials(LiFePO4(LFP),Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_(2)(NCM111),Li[Ni_(0.6)Co_(0.2)Mn_...In this paper,overcharge behaviors and thermal runaway(TR)features of large format lithium-ion(Liion)cells with different cathode materials(LiFePO4(LFP),Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_(2)(NCM111),Li[Ni_(0.6)Co_(0.2)Mn_(0.2)]O_(2)(NCM622)and Li[Ni_(0.8)Co_(0.1)Mn_(0.1)]O_(2)(NCM811))were investigated.The results showed that,under the same overcharge condition,the TR of LFP Li-ion cell occurred earlier compared with the NCM Li-ion cells,indicating its poor overcharge tolerance and high TR risk.However,when TR occurred,LFP Li-ion cell exhibited lower maximum temperature and mild TR response.All NCM Liion cells caught fire or exploded during TR,while the LFP Li-ion cell only released a large amount of smoke without fire.According to the overcharge behaviors and TR features,a safety assessment score system was proposed to evaluate the safety of the cells.In short,NCM Li-ion cells have better performance in energy density and overcharge tolerance(or low TR risk),while LFP Li-ion cell showed less severe response to overcharging(or less TR hazards).For NCM Li-ion cells,as the ratio of nickel in cathode material increases,the thermal stability of the cathode materials becomes poorer,and the TR hazards increase.Such a comparison study on large format Li-ion cells with different cathode materials can provide deeper insights into the overcharge behaviors and TR features,and provide guidance for engineers to reasonably choose battery materials in automotive applications.展开更多
With the rapid development of consumer electronics and electric vehicles(EV), a large number of spent lithium-ion batteries(LIBs) have been generated worldwide. Thus, effective recycling technologies to recapture a si...With the rapid development of consumer electronics and electric vehicles(EV), a large number of spent lithium-ion batteries(LIBs) have been generated worldwide. Thus, effective recycling technologies to recapture a significant amount of valuable metals contained in spent LIBs are highly desirable to prevent the environmental pollution and resource depletion. In this work, a novel recycling technology to regenerate a LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 cathode material from spent LIBs with different cathode chemistries has been developed. By dismantling, crushing,leaching and impurity removing, the LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2(selected as an example of LiNi_xCo_yMn_(1-x-y)O_2) powder can be directly prepared from the purified leaching solution via co-precipitation followed by solid-state synthesis. For comparison purposes, a fresh-synthesized sample with the same composition has also been prepared using the commercial raw materials via the same method. X-ray diffraction(XRD), scanning electron microscopy(SEM) and electrochemical measurements have been carried out to characterize these samples. The electrochemical test result suggests that the re-synthesized sample delivers cycle performance and low rate capability which are comparable to those of the freshsynthesized sample. This novel recycling technique can be of great value to the regeneration of a pure and marketable LiNi_xCo_yMn_(1-x-y)O_2 cathode material with low secondary pollution.展开更多
基金supported by a grant from the Subway Fine Dust Reduction Technology Development Project of the Ministry of Land Infrastructure and Transport,Republic of Korea(21QPPWB152306-03)the Basic Science Research Capacity Enhancement Project through a Korea Basic Science Institute(National Research Facilities and Equipment Center)grant funded by the Ministry of Education of the Republic of Korea(2019R1A6C1010016)。
文摘Energy-storage systems and their production have attracted significant interest for practical applications.Batteries are the foundation of sustainable energy sources for electric vehicles(EVs),portable electronic devices(PEDs),etc.In recent decades,Lithium-ion batteries(LIBs) have been extensively utilized in largescale energy storage devices owing to their long cycle life and high energy density.However,the high cost and limited availability of Li are the two main obstacles for LIBs.In this regard,sodium-ion batteries(SIBs) are attractive alternatives to LIBs for large-scale energy storage systems because of the abundance and low cost of sodium materials.Cathode is one of the most important components in the battery,which limits cost and performance of a battery.Among the classified cathode structures,layered structure materials have attracted attention because of their high ionic conductivity,fast diffusion rate,and high specific capacity.Here,we present a comprehensive review of the classification of layered structures and the preparation of layered materials.Furthermore,the review article discusses extensively about the issues of the layered materials,namely(1) electrochemical degradation,(2) irreversible structural changes,and(3) structural instability,and also it provides strategies to overcome the issues such as elemental phase composition,a small amount of elemental doping,structural design,and surface alteration for emerging SIBs.In addition,the article discusses about the recent research development on layered unary,binary,ternary,quaternary,quinary,and senary-based O3-and P2-type cathode materials for high-energy SIBs.This review article provides useful information for the development of high-energy layered sodium transition metal oxide P2 and O3-cathode materials for practical SIBs.
文摘The high compacted density LiNi<sub>0.5-x</sub>Co<sub>0.2</sub>Mn<sub>0.3</sub>Mg<sub>x</sub>O<sub>2</sub> 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 Ni<sub>0.5</sub>Co<sub>0.2</sub>Mn<sub>0.3</sub> (OH)<sub>2</sub>, Li<sub>2</sub>CO<sub>3</sub> 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 LiNi<sub>0.4985</sub>Co<sub>0.2</sub>Mn<sub>0.3</sub> Mg<sub>0.0015</sub>O<sub>2</sub> 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/cm<sup>3</sup>. 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.
基金financially supported by the Natural Science Foundation of Jiangsu Province,China (BK20210887)the Jiangsu Provincial Double Innovation Program,China (JSSCB20210984)+1 种基金the Natural Science Fund for Colleges and Universities of Jiangsu Province,China (21KJB450003)the Jiangsu University of Science and Technology Doctoral Research Start-up Fund,China (120200012)。
文摘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.
文摘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.
基金supported by the Natural Science Foundation of Jiangsu Province (BK20210887)the Jiangsu Provincial Double Innovation Program (JSSCB20210984)+1 种基金the Natural Science Fund for Colleges and Universities of Jiangsu Province (21KJB450003)the Jiangsu University of Science and Technology Doctoral Research Start-up Fund (120200012)。
文摘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.
基金This work was supported by the Fundamental Research Funds for the Central Universities(DUT20LAB123 and DUT20LAB307)the Natural Science Foundation of Jiangsu Province(BK20191167).
文摘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.
基金supported by National Natural Science Foundation of China (52070194,52073309)Natural Science Foundation of Hunan Province (2022JJ20069)。
文摘Generally,layered Ni-rich cathode materials exhibit the morphology of polycrystalline secondary sphere composed of numerous primary particles.While the arrangement of primary particles plays a very important role in the properties of Ni-rich cathodes.The disordered particle arrangement is harmful to the cyclic performance and structural stability,yet the fundamental understanding of disordered structure on the structural degradation behavior is unclarified.Herein,we have designed three kinds of LiNi_(0.83)Co_(0.06)Mn_(0.11)O_(2) cathode materials with different primary particle orientations by regulating the precursor coprecipitation process.Combining finite element simulation and in-situ characterization,the Li^(+)transport and structure evolution behaviors of different materials are unraveled.Specifically,the smooth Li^(+)diffusion minimizes the reaction heterogeneity,homogenizes the phase transition within grains,and mitigates the anisotropic microstructural change,thereby modulating the crack evolution behavior.Meanwhile,the optimized structure evolution ensures radial tight junctions of the primary particles,enabling enhanced Li^(+)diffusion during dynamic processes.Closed-loop bidirectional enhancement mechanism becomes critical for grain orientation regulation to stabilize the cyclic performance.This precursor engineering with particle orientation regulation provides the useful guidance for the structural design and feature enhancement of Ni-rich layered cathodes.
基金financially supported by the National Natural Science Foundation of China(51503178,52202048,52027801)National Key R&D Program of China(2017YFA0206301)+1 种基金China-Germany Collaboration Project(M-0199)Natural Science Foundation of Hebei Province(B2021203012,E2022203082)。
文摘The self-charging concept has drawn considerable attention due to its excellent ability to achieve environmental energy harvesting,conversion and storage without an external power supply.However,most self-charging designs assembled by multiple energy harvesting,conversion and storage materials increase the energy transfer loss;the environmental energy supply is generally limited by climate and meteorological conditions,hindering the potential application of these selfpowered devices to be available at all times.Based on aerobic autoxidation of catechol,which is similar to the electrochemical oxidation of the catechol groups on the carbon materials under an electrical charge,we proposed an air-breathing chemical self-charge concept based on the aerobic autoxidation of catechol groups on oxygen-enriched carbon materials to ortho-quinone groups.Energy harvesting,conversion and storage functions could be integrated on a single carbon material to avoid the energy transfer loss among the different materials.Moreover,the assembled Cu/oxygen-enriched carbon battery confirmed the feasibility of the air-oxidation self-charging/electrical discharging mechanism for potential applications.This air-breathing chemical self-charge concept could facilitate the exploration of high-efficiency sustainable air self-charging devices.
基金supported by the Science and Technology Innovation Program of Hunan Province(No.2020SK2007)the Natural Science Foundation of Hunan Province(No.2019JJ50814)+2 种基金the Fundamental Research Funds for the Central Universities of Central South University(No.1053320211765)the Science and Technology Planning Project of Guangdong Province of China(No.2017B030314046)Guangdong Academy of Sciences for Innovation Capacity Building(No.2016GDASRC0201).
文摘With the number of decommissioned electric vehicles increasing annually,a large amount of discarded power battery cathode material is in urgent need of treatment.However,common leaching methods for recovering metal salts are economically inefficient and polluting.Meanwhile,the recycled material obtained by lithium remediation alone has limited performance in cycling stability.Herein,a short method of solid-phase reduction is developed to recover spent LiFePO4 by simultaneously introducing Mg2+ions for hetero-atom doping.Issues of particle agglomeration,carbon layer breakage,lithium loss,and Fe3+defects in spent LiFePO4 are also addressed.Results show that Mg2+addition during regeneration can remarkably enhance the crystal structure stability and improve the Li+diffusion coefficient.The regenerated LiFePO4 exhibits significantly improved electrochemical performance with a specific discharge capacity of 143.2 mAh·g^(−1)at 0.2 C,and its capacity retention is extremely increased from 37.9%to 98.5%over 200 cycles at 1 C.Especially,its discharge capacity can reach 95.5 mAh·g^(−1)at 10 C,which is higher than that of spent LiFePO4(55.9 mAh·g^(−1)).All these results show that the proposed regeneration strategy of simultaneous carbon coating and Mg2+doping is suitable for the efficient treatment of spent LiFePO4.
基金partly supported by the National Natural Science Foundation of China(51763014 and 52073133)the Key Talent Project Foundation of Gansu Province+3 种基金Joint fund between Shenyang National Laboratory for Materials Science and State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals(18LHPY002)the Incubation Program of Excellent Doctoral Dissertation-Lanzhou University of Technologyexcellent doctoral Program of Gansu Province(22JR5RA240)the Program for Hongliu Distinguished Young Scholars in Lanzhou University of Technology。
文摘Sulfur-containing polymer(SCP)is considered as an outstanding cathode material for lithium-sulfur batteries.However,undesirable soluble polysulfides may shuttle in electrolyte,concluding long-chain Li_(2)S_(n)(n>4)and short-chain Li2Sn(n≤4),as well as the sluggish conversion kinetics are yet to be solved to enhance the performance of lithium-sulfur batteries.Here Se-doped sulfurized polyaniline with adjusted sulfur-chain-S_(x)-(x≤6)contribute to ensure the absence of long-chain polysulfides,and the skeleton with quinoid imine can endow strongly adsorption towards short-chain polysulfides by the reversible transition between deprotonated/protonated imine(-NH^(+)=and-N=),which offer double insurance against suppressing“shuttle effect”.Furthermore,Se atoms are doped into sulfurized polysulfides to accelerate the redox conversion and take a frontier orbital theory-oriented view into catalytic mechanism.Se-doped sulfurized polyaniline as active materials for lithium-organosulfur batteries delivers good electrochemical performance,including high rate,reversible specific capacity(680 mA h g^(-1)at 0.1 A g^(-1)),and lower capacity decay rate only of 0.15%with near 100%coulomb efficiency during long-term cycle.This work provides a valuable guiding ideology and promising solution for the chemistry-oriented structure design and practical application for lithium-organosulfur batteries.
基金The Beijing Municipal Education Commission(KZ201910005003)supported this work。
文摘Defective layered Mn-based materials were synthesized by Li/Na ion exchange to improve their electrochemical activity and Coulombic efficiency.The annealing temperature of the Na precursors was important to control the P3-P2 phase transition,which directly affected the structure and electrochemical characteristics of the final products obtained by ion exchange.The O3-Li_(0.78)[Li_(0.25)Fe_(0.075)Mn_(0.675)]O_(δ) cathode made from a P3-type precursor calcined at 700℃ was analyzed using X-ray photoelectron spectrometry and electron paramagnetic resonance.The results showed that the presence of abundant trivalent manganese and defects resulted in a discharge capacity of 230 mAh/g with an initial Coulombic efficiency of about 109%.Afterward,galvanostatic intermittent titration was performed to examine the Li^(+) ion diffusion coefficients,which affected the reversible capacity.First principles calculations suggested that the charge redistribution induced by oxygen vacancies(OV_(s))greatly affected the local Mn coordination environment and enhanced the structural activity.Moreover,the Li-deficient cathode was a perfect match for the pre-lithiation anode,providing a novel approach to improve the initial Coulombic efficiency and activity of Mn-based materials in the commercial application.
基金National Natural Science Foundation of China(No.51790490)。
文摘Cathode materials,nickel doped Cr_(8)O_(21),were synthesized by a solid-state method.The effects of Ni doping on the electrochemical performances of Cr_(8)O_(21) were investigated.The experimental results show that the discharge capacities of the samples depend on the nickel contents,which increases firstly and then decreases with increasing Ni contents.Optimized Ni_(0.5)Cr_(7.5)O_(21)delivers a first capacity up to 392.6 m Ah·g^(-1)at 0.1C.In addition,Ni doped sample also demonstrates enhanced cycling stability and rate capability compared with that of the bare Cr_(8)O_(21).At 1 C,an initial discharge capacity of 348.7 m Ah·g^(-1)was achieved for Ni_(0.5)Cr_(7.5)O_(21),much higher than 271.4 m Ah·g^(-1)of the un-doped sample,with an increase of more than 28%.Electrochemical impedance spectroscopy results confirm that Ni doping reduces the growth of interface resistance and charge transfer resistance,which is conducive to the electrochemical kinetic behaviors during charge-discharge.
基金the support from the Fundamental Research Funds for the Central Universities of Chongqing University(No.2020CDCGCL005)。
文摘Rechargeable magnesium batteries(RMBs),as one of the most promising candidates for efficient energy storage devices with high energy,power density and high safety,have attracted increasing attention.However,searching for suitable cathode materials with fast diffusion kinetics and exploring their magnesium storage mechanisms remains a great challenge.Cu S submicron spheres,made by a facile low-temperature synthesis strategy,were applied as the high-performance cathode for RMBs in this work,which can deliver a high specific capacity of 396mAh g^(-1)at 20 mA g^(-1) and a remarkable rate capacity of 250 m Ah g^(-1)at 1000 mA g^(-1).The excellent rate performance can be assigned to the nano needle-like particles on the surface of Cu S submicron spheres,which can facilitate the diffusion kinetics of Mg^(2+).Further storage mechanism investigations illustrate that the Cu S cathodes experience a two-step conversion reaction controlled by diffusion during the electrochemical reaction process.This work could make a contribution to the study of the enhancement of diffusion kinetics of Mg2+and the reaction mechanism of RMBs.
基金the support from the National Key Research & Development Program (2022YFB3803700) of ChinaNational Natural Science Foundation (No.52171186)the support from the Center of Hydrogen Science,Shanghai Jiao Tong University。
文摘Rechargeable magnesium-ion batteries(MIBs) are favorable substitutes for conventional lithium-ion batteries(LIBs) because of abundant magnesium reserves, a high theoretical energy density, and great inherent safety. Organic electrode materials with excellent structural tunability,unique coordination reaction mechanisms, and environmental friendliness offer great potential to promote the electrochemical performance of MIBs. However, research on organic magnesium battery cathode materials is still preliminary with many significant challenges to be resolved including low electrical conductivity and unwanted but severe dissolution in useful electrolytes. Herein, we provide a detailed overview of reported organic cathode materials for MIBs. We begin with basic properties such as charge storage mechanisms(e.g., n-, p-, and bipolartype), moving to recent advances in various types of organic cathodes including carbonyl-, nitrogen-, and sulfur-based materials. To shed light on the diverse strategies targeting high-performance Mg-organic batteries, elaborate summaries of various approaches are presented.Generally, these strategies include molecular design, polymerization, mixing with carbon, nanosizing and electrolyte/separator optimization.This review provides insights on exploring high-performance organic cathodes in rechargeable MIBs.
基金supported by the National Natural Science Foundation of China (Grant No.22075028).
文摘Rechargeable aluminum batteries(RABs)are attractive cadidates for next-generation energy storage and conversion,due to the low cost and high safety of Al resources,and high capacity of metal Al based on the three-electrons reaction mechanism.However,the development of RABs is greatly limited,because of the lack of advanced cathode materials,and their complicated and unclear reaction mechanisms.Exploring the novel nanostructured transition metal and carbon composites is an effective route for obtaining ideal cathode materials.In this work,we synthesize porous CoSnO_(3)/C nanocubes with oxygen vacancies for utilizing as cathodes in RABs for the first time.The intrinsic structure stability of the mixed metal cations and carbon coating can improve the cycling performance of cathodes by regulating the internal strains of the electrodes during volume expansion.The nanocubes with porous structures contribute to fast mass transportation which improves the rate capability.In addition to this,abundant oxygen vacancies promote the adsorption affinity of cathodes,which improves storage capacity.As a result,the CoSnO_(3)/C cathodes display an excellent reversible capacity of 292.1 mAh g^(-1) at 0.1 A g^(-1),a good rate performance with 109 mAh g^(-1) that is maintained even at 1 A g^(-1) and the provided stable cycling behavior for 500 cycles.Besides,a mechanism of intercalation of Al^(3+)within CoSnO_(3)/C cathode is proposed for the electrochemical process.Overall,this work provides a step toward the development of advanced cathode materials for RABs by engineering novel nanostructured mixed transition-metal oxides with carbon composite and proposes novel insights into chemistry for RABs.
基金This work was supported by the National Natural Science Foundation of China (Grant no.51774330,52072411,51932011)the Natural Science Foundation of Hunan Province (Grant no.2021JJ20060)The science and technology innovation Program of Hunan Province (Grant no.2021RC3001).
文摘Multivalent-ion(such as Zn^(2+),Mg^(2+),Al^(3+))batteries are considered as a prospective alternative for large-scale energy storage.However,the main problem of cathode materials for multivalent-ion batteries is the sluggish diffusion of multivalent ions.Many cathode materials will self-adjust under electrochemical conditions to achieve the optimal state for multivalent-ion storage.In this review,the significant role of electrochemical in situ structural reconstruction of cathode materials is suggested.The types,basic characteristics,and formation mechanisms of reconstructed phases have been systematically discussed and commented.The most important insight we pointed out is that the cathode materials with loose structures after in situ electrochemical activation are conducive to the reversible diffusion of multivalent ions.Moreover,several crucial issues of electrochemical activation and reconstruction were further analyzed and discussed.The challenges and future perspectives are presented in the final section.
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.
基金supported by the National Natural Science Foundation of China(22179063)。
文摘Potassium ion batteries(PIBs)are emerging as potential next-generation energy storage systems on account of their low cost and high theoretical energy density.Nevertheless,they also face challenges of low specific capacity and suboptimal cycling stability.Herein,we synthesize a cocoon-like P3-type K_(0.5)Mn_(0.7)Ni_(0.3)O_(2)(KMNO)cathode material by a self-template method.The KMNO cocoons possess a hierarchical layered architecture composed of nanoparticle stacking,which can accelerate the transport kinetics of potassium ions,mitigate the stress caused by K^(+)intercalation and deintercalation,and improve structural stability.In addition,Ni can not only alleviate the Jahn-Teller distortion and suppress the phase transition to stabilize the structure,but also act as an electrochemically active element,providing the capacity of two electrons from Ni2+to Ni4+.Combining the advantages of structure and nickel substitution,the P3-type KMNO cocoons are used for electrochemical performance testing of PIB cathodes,delivering an excellent rate capability of 57.1 m A h g^(-1)at 500 m A g^(-1)and a remarkable cycling stability of 77.0%over 300 cycles at 100 m A g^(-1).Impressively,the KMNO cocoons//pitch-derived soft carbon assembled full battery exhibits superior electrochemical performance with a reversible capacity of 79.7 m A h g^(-1)at 50 m A g^(-1).Moreover,ex-situ XRD also further reveals a solid solution phase reaction with a volume change of only 1.46%.This work furnishes a suitable approach to fabricating highperformance layered oxide cathodes for PIBs with outstanding cycling stability and rate capability.
基金supported by the National Natural Science Foundation of China(Nos.U1564206,U1764258)the National Key R&D Program of China(No.2018YFB0105700)+1 种基金the support from China Scholarship Council(No.201806030115)supported by the Department of Energy(DOE),Office of Electricity(OE)at Oak Ridge National Laboratory managed by UL-Battelle LLC under contract DE-AC05-00OR22725。
文摘In this paper,overcharge behaviors and thermal runaway(TR)features of large format lithium-ion(Liion)cells with different cathode materials(LiFePO4(LFP),Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_(2)(NCM111),Li[Ni_(0.6)Co_(0.2)Mn_(0.2)]O_(2)(NCM622)and Li[Ni_(0.8)Co_(0.1)Mn_(0.1)]O_(2)(NCM811))were investigated.The results showed that,under the same overcharge condition,the TR of LFP Li-ion cell occurred earlier compared with the NCM Li-ion cells,indicating its poor overcharge tolerance and high TR risk.However,when TR occurred,LFP Li-ion cell exhibited lower maximum temperature and mild TR response.All NCM Liion cells caught fire or exploded during TR,while the LFP Li-ion cell only released a large amount of smoke without fire.According to the overcharge behaviors and TR features,a safety assessment score system was proposed to evaluate the safety of the cells.In short,NCM Li-ion cells have better performance in energy density and overcharge tolerance(or low TR risk),while LFP Li-ion cell showed less severe response to overcharging(or less TR hazards).For NCM Li-ion cells,as the ratio of nickel in cathode material increases,the thermal stability of the cathode materials becomes poorer,and the TR hazards increase.Such a comparison study on large format Li-ion cells with different cathode materials can provide deeper insights into the overcharge behaviors and TR features,and provide guidance for engineers to reasonably choose battery materials in automotive applications.
基金supported by the National Natural Science Foundation of China(No.51274075)the National Environmental Technology Special Project(No.201009028)Guangdong Province-department University-industry Collaboration Project(Grant No.2012B091100315)
文摘With the rapid development of consumer electronics and electric vehicles(EV), a large number of spent lithium-ion batteries(LIBs) have been generated worldwide. Thus, effective recycling technologies to recapture a significant amount of valuable metals contained in spent LIBs are highly desirable to prevent the environmental pollution and resource depletion. In this work, a novel recycling technology to regenerate a LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 cathode material from spent LIBs with different cathode chemistries has been developed. By dismantling, crushing,leaching and impurity removing, the LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2(selected as an example of LiNi_xCo_yMn_(1-x-y)O_2) powder can be directly prepared from the purified leaching solution via co-precipitation followed by solid-state synthesis. For comparison purposes, a fresh-synthesized sample with the same composition has also been prepared using the commercial raw materials via the same method. X-ray diffraction(XRD), scanning electron microscopy(SEM) and electrochemical measurements have been carried out to characterize these samples. The electrochemical test result suggests that the re-synthesized sample delivers cycle performance and low rate capability which are comparable to those of the freshsynthesized sample. This novel recycling technique can be of great value to the regeneration of a pure and marketable LiNi_xCo_yMn_(1-x-y)O_2 cathode material with low secondary pollution.
