Understanding the failure mechanism towards developing high-voltage single-crystal Ni-rich Co-free cathodes

Benefited from its high process feasibility and controllable costs,binary-metal layered structured LiNi_(0.8)Mn_(0.2)O_(2)(NM)can effectively alleviate the cobalt supply crisis under the surge of global electric vehicles(EVs)sales,which is considered as the most promising nextgeneration cathode material for lithium-ion batteries(LIBs).However,the lack of deep understanding on the failure mechanism of NM has seriously hindered its application,especially under the harsh condition of high-voltage without sacrifices of reversible capacity.Herein,singlecrystal LiNi_(0.8)Mn_(0.2)O_(2) is selected and compared with traditional LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM),mainly focusing on the failure mechanism of Cofree cathode and illuminating the significant effect of Co element on the Li/Ni antisite defect and dynamic characteristic.Specifically,the presence of high Li/Ni antisite defect in NM cathode easily results in the extremely dramatic H2/H3 phase transition,which exacerbates the distortion of the lattice,mechanical strain changes and exhibits poor electrochemical performance,especially under the high cutoff voltage.Furthermore,the reaction kinetic of NM is impaired due to the absence of Co element,especially at the single-crystal architecture.Whereas,the negative influence of Li/Ni antisite defect is controllable at low current densities,owing to the attenuated polarization.Notably,Co-free NM can exhibit better safety performance than that of NCM cathode.These findings are beneficial for understanding the fundamental reaction mechanism of single-crystal Ni-rich Co-free cathode materials,providing new insights and great encouragements to design and develop the next generation of LIBs with low-cost and high-safety performances.

Alleviating the anisotropic microstructural change and boosting the lithium ions diffusion by grain orientation regulation for Ni-rich cathode materials

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.

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.

Boosting High-Voltage and Ultralong-Cycling Performance of Single-Crystal LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) Cathode Materials via Three-in-One Modification

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.

A flexible carbon nanotube@V_(2)O_(5) film as a high-capacity and durable cathode for zinc ion batteries

Aqueous zinc-ion batteries(ZIBs)are receiving a continuously increasing attention for mobile devices,especially for the flexible and wearable electronics,due to their non-toxicity,non-flammability,and low-cost features.Despite the significant progress in achieving higher capacities for electrode materials of ZIBs,to endow them with high flexibility and economic feasibility is,however,still a significant challenge remaining unsolved.Herein,we present a highly flexible composite film composed of carbon nanotube film and V_(2)O_(5)(CNTF@V_(2)O_(5))with high strength and high conductivity,which is prepared by simply impregnating a porous CNT film with an aqueous V_(2)O_(5)sol under vacuum.For this material,intimate incorporation between V_(2)O_(5)and CNTs has been achieved,successfully integrating the high zinc ion storage capability with high mechanical flexibility.As a result,this CNTF@V_(2)O_(5)film delivers a high capacity of 356.6 m Ah g^(-1)at 0.4 A g^(-1)and excellent cycling stability with 80.1%capacity retention after 500 cycles at 2.0 A g^(-1).The novel strategy and the outstanding battery performance presented in this work should shed light on the development of high-performance and flexible ZIBs.

Effective regeneration of high-performance anode material recycled from the whole electrodes in spent lithium-ion batteries via a simplified approach

Along with the extensive application of energy storage devices,the spent lithium-ion batteries(LIBs)are unquestionably classified into the secondary resources due to its high content of several valuable metals.However,current recycling methods have the main drawback to their tedious process,especially the purification and separation process.Herein,we propose a simplified process to recycle both cathode(LiCoO_(2))and anode(graphite)in the spent LIBs and regenerate newly high-performance anode material,CoO/CoFe2O4/expanded graphite(EG).This process not only has the advantages of succinct procedure and easy control of reaction conditions,but also effectively separates and recycles lithium from transition metals.The 98.43%of lithium is recovered from leachate when the solid product CoO/CoFe2O4/EG is synthesized as anode material for LIBs.And the product exhibits improved cyclic stability(890 mAh g^(-1) at 1 A g^(-1) after 700 cycles)and superior rate capability(208 mAh g^(-1) at 5 A g^(-1)).The merit of this delicate recycling design can be summarized as three aspects:the utilization of Fe impurity in waste LiCoO_(2),the transformation of waste graphite to EG,and the regeneration of anode material.This approach properly recycles the valuable components of spent LIBs,which introduces an insight into the future recycling.

促进幼儿入学准备的园本活动体系

入学准备指学龄前儿童为了能够从即将开始的正规学校教育中受益所需要具备的各种关键特征或基础条件,主要涵盖身体素质适应、社会性适应和学习适应三个方面。构建促进幼儿入学准备的园本活动体系需要以促进幼儿身体素质发展为前提,以社会性适应为重点,帮助幼儿做好在早期读写和数概念学习等方面的准备。

Enhanced rate capability and mitigated capacity decay of ultrahigh-nickel cobalt-free LiNi_(0.9)Mn_(0.1)O_(2) cathode at high-voltage by selective tungsten substitution

Owing to the further requirement for electric vehicle market, it is appropriate to lower the cost and improve the energy density of lithium-ion batteries by adopting the Co-free and Ni-rich layered cathodes.However, their practical application is severely limited by structural instability and slow kinetics. Herein,ultrahigh-nickel cobalt-free LiNi_(0.9)Mn_(0.1)O_(2) cathode is elaborate designed via in-situ trace substitution of tungsten by a wet co-precipitation method following by high-temperature sintering. It is revealed that the in-situ doping strategy of high valence W^(6+) can effectively improve the structure stability by reducing irreversible phase transition and suppressing the formation of microcracks. Moreover, the transformed fine particles determined by W-doping can facilitate the kinetic characteristics by shortening Li^(+) diffusion paths. As expected, 0.3 mol% W-doped LiNi_(0.9)Mn_(0.1)O_(2) cathode exhibits a high specific capacity of 143.5 mAh/g after 200 cycles at high rate of 5 C in the wide potential range of 2.8-4.5 V, representing a potential next-generation cathode with low-cost, high energy-density and fast-charging capabilities.

Highly active and stable Cu_(9)S_(5)-MoS_(2)heterostructures nanocages enabled by dual-functional Cu electrocatalyst with enhanced potassium storage

The intrinsic poor electrical conductivity,severe dissolution of K x S y intermediates,and inferior conversion reaction reversibility extremely impede the practical application of the transition-metal chalcogenides(TMDs)anode for potassium-ion batteries(PIBs).Herein,a rationally designed Cu_(9)S_(5)/MoS_(2)/C heterostruc-ture hollow nanocage was synthesized with assistance from metal-organic frameworks(MOFs)precursor.During the K-storage process,the homogeneously distributed the sulfiphilic nature of Cu 0 reaction prod-uct could act as a dual-functional catalyst,not only facilitating the rapid charge transfer but also effec-tively anchoring(K x S y)polysulfides,thus boosting K-storage reactions reversibility during the conversion reaction process.When applied as an anode for PIBs,the as-prepared heterostructure exhibits excellent reversible capacity and long cycle lifespan(350.5 mAh g^(-1)at 0.1 A g^(-1)and 0.04%per cycle capacity de-cay at 1 A g^(-1)after 1000 cycles).Additionally,the potassium storage mechanism is distinctly revealed by in-situ characterizations.The nanoarchitecture designing strategy for the advanced electrode in this work could provide vital guidance for relevant energy storage materials.

人口老龄化背景下日本健康产业发展现状、政策及启示

在介绍人口老龄化背景下日本健康产业发展现状的基础上,总结分析日本政府为推动健康产业发展制定的产业政策要点与特征,旨在为全面推进我国健康产业快速发展提供有益借鉴。

Ammonia leaching mechanism and kinetics of LiCoO_(2) material from spent lithium-ion batteries

In this paper,the ammonia leaching process and high-energy ball milling method were adapted to recover spent LiCoO_(2) material.The ammonia reduction leaching mechanism of LiCoO_(2) material in the ammonia-sodium sulfite-ammonium chloride system was elucidated.Compared with untreated LiCoO_(2) material,the leaching equilibrium time of LiCoO_(2) after ball-milled for 5 h was reduced from 48 h to 4 h,and the leaching efficiency of lithium and cobalt was improved from 69.86%and 70.80%to 89.86%and98.22%,respectively.Importantly,the apparent activation energy and leaching kinetic equation of the reaction was calculated by the shrinking core reaction model,indicating that the reaction was controlled by the chemical reaction.

High-density/efficient surface active sites on modified separators to boost Li-S batteries via atomic Co^(3+)-Se termination

Various and critical electrocatalytic processes are involved during the redox reactions in the Li-S batteries,which extremely depend on the surface structure and chemical state.Recently,single-atom concept unlocks a route to maximize the use of surface-active atoms,however,further increasing the density of active site is still strictly limited by the inherent structure that single-atoms are only highly-dispersed on substrate.Herein,we provide a viewpoint that an elaborate facet design with singlecrystalline structure engineering can harvest high-density surface active sites,which can significantly boost the electrocatalyst performance for excellent Li-S batteries.Specifically,the single-crystal CoSe_(2)(scCS)exhibits three-types of terminated(011)facet,efficiently obtaining the surface with a high-rich Co^(3+)–Se bond termination,in contrast with lots of surface grain boundaries and dangling bonds in polycrystalline CoSe_(2).Surprisingly,the surface active sites concentration can reach more than 69%.As anticipated,it can provide high-density and high-efficient active sites,enormously suppressing the shuttle effect and improving the reaction kinetics via accelerating the conversion and deposition of polysulfides and Li2S.This surface lattice strategy with element terminated mode is a promising approach for designing electrocatalyst effect-based energy system,not merely for Li-S batteries.

Quasi-two-dimensional bismuth oxychalcogenide nanoflakes as novel anode for potassium-ion batteries

Potassium-ion batteries(PlBs)are considered as the promising alternative of lithium-ion batteries,due to their abundance natural resources,high cost-effectiveness,and similar working principle.With the development of PIBs,due to the larger ionic radius of potassium compared to that of lithium,the urgent demand of suitable anode materials with steady structure and fast carrier diffusion is of primary importance.

Van der Waals heterostructure engineering by 2D space-confinement for advanced potassium-ion storage

Molybdenum disulfide (MoS_(2)) has received enormous attentions in the electrochemical energy storage due to its unique two-dimensional layered structure and relatively high reversible capacity. However, the application of MoS_(2) in potassium-ion batteries (PIBs) is restricted by poor rate capability and cyclability, which are associated with the sluggish reaction kinetics and the huge volume expansion during K+ intercalation. Herein, we propose a two-dimensional (2D) space confined strategy to construct van der Waals heterostructure for superior PIB anode, in which the MoS_(2) nanosheets can be well dispersed on reduced graphene oxide nanosheets by leveraging the confinement effect within the graphene layers and amorphous carbon. The strong synergistic effects in 2D van der Waals heterostructure can extremely promote the electron transportation and ions diffusion during K+ insertion/extraction. More significantly, the 2D space-confinement effect and van der Waals force inhibit polysulfide conversion product dissolution into the electrolyte, which significantly strengthens the structural durability during the long-term cycling process. As anticipated, the as-synthesized the “face-to-face” C/MoS_(2)/G anode delivers remarkable K-storage performance, especially for high reversible capacity (362.5 mAh·g^(-1) at 0.1 A·g^(-1)), excellent rate capability (195.4 mAh·g^(-1) at 10 Ag^(-1)) and superior ultrahigh-rate long-cycling stability (126.4 mAh·g^(-1) after 4000 cycles at high rate of 5 A·g^(-1)). This work presents a promise strategy of structure designing and composition optimization for 2D layered materials in advanced energy storage application.