Chemical bonding of perovskite LaFeO_(3) with Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2) to moderate anion redox for achieving high cycling stability

Oxygen anion redox reaction provides a high theoretical capacity for Li-rich manganese-based cathodes.However,irreversible surface oxygen release often results in further oxygen loss and exacerbates the decomposition of the electrolyte,which could reduce the capacity contribution from the anionic redox and produce more acidic substances to corrode the surface of the material.In this paper,the surface oxygen release is suppressed by moderating oxygen anion redox activity via constructing chemical bonds between M(M=Fe and La)in LaFeO_(3)and surface oxygen anions of Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2).The constructed interface layer stabilizes the surface lattice oxygen and retards the electrolyte from being attacked by the nucleophilic oxygen generated in the process of oxygen release,as evidenced by Differential Electrochemical Mass Spectrometry(DEMS)and X-ray Photoelectron Spectroscopy(XPS)detections.Moreover,in the charge and discharge process,the formed FeF_(3),located at the cathode electrolyte interfacial layer,is conducive to the stability of the cathode surface.The modified Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2)electrode with 3 wt%LaFeO_(13)exhibits a high specific capacity of 189.5 mA h g-at 1C(200 mA g^(-1))after 150 cycles with capacity retentions of 96.6%,and 112.6 mA h g^(-1)(84.7%)at 5C after 200 cycles higher than the pristine sample.This study provides a rational design chemical bonding method to suppress the oxygen release from the cathode surface and enhance cyclic stability.

卤化物固态电解质研究进展

全固态电池因其高能量密度和高安全性而成为具有发展前景的下一代储能技术。开发具有高室温离子电导率、优异化学/电化学稳定性、良好正/负极兼容性的固态电解质是实现全固态电池实用化的关键。卤化物固态电解质因其优异的电化学窗口、高正极稳定性、可接受的室温锂离子电导率等优势,受到了广泛的关注。本文通过对近年来卤化物电解质的相关研究进行总结,综述了该类电解质的组成、结构、离子传导路径及制备方法,并分析了金属卤化物电解质的电导率、稳定性特点,归纳了近年来该电解质在全固态电池中具有代表性的应用,并基于以上总结和分析,指出了卤化物固态电解质的研究难点及发展方向。

A facile finger-paint physical modification for bilateral electrode/electrolyte interface towards a stable aqueous Zn battery

Since the electrode/electrolyte interface(EEI)is the main redox center of electrochemical processes,proper manipulation of the EEI microenvironment is crucial to stabilize interfacial behaviors.Here,a finger-paint method is proposed to enable quick physical modification of glass-fiber separator without complicated chemical technology to modulate EEI of bilateral electrodes for aqueous zinc-ion batteries(ZIBs).An elaborate biochar derived from Aspergillus Niger is exploited as the modification agent of EEI,in which the multi-functional groups assist to accelerate Zn^(2+)desolvation and create a hydrophobic environment to homogenize the deposition behavior of Zn anode.Importantly,the finger-paint interface on separator can effectively protect cathodes from abnormal capacity fluctuation and/or rapid attenuation induced by H_(2)O molecular on the interface,which is demonstrated in modified MnO_(2),V_(2)O_(5),and KMn HCF-based cells.The as-proposed finger-paint method opens a new idea of bilateral interface engineering to facilitate the access to the practical application of the stable zinc electrochemistry.

Partial surface phase transformation of Li_(3)VO_(4) that enables superior rate performance and fast lithium-ion storage

Li_(3)VO_(4) is a promising electrode material for next-generation lithium-ion batteries(LIBs)due to its excellent specific capac-ity(592 mAh g^(−1)),suitable discharge voltage(0.5-1.0 V),and moderate volume change upon charge/discharge,while it still suffers from low electronic conductivity that usually gives a poor rate capability,low initial coulombic efficiency,and large polarization,imposing a challenge on its practical applications.In this work,a partial surface phase transformation of Li_(3)VO_(4) was initiated via a freeze-drying method followed by a heat treatment in inert gas.Using this method,Li_(3)VO_(4) was integrated with a conductive layer LiVO_(2) and carbon matrix.The synergistic effect among Li_(3)VO_(4),LiVO_(2) layer,and carbon matrix was systematically studied by optimizing the treatment conditions.When treated at 600°C in Ar,Li_(3)VO_(4)-based composite delivered outstanding electrochemical properties,as expressed by a specific capacity(689 mAh g^(−1) at 0.1 A g^(−1) after 100 cycles),rate performance(i.e.,448 mAh g^(−1) at 2 A g^(−1)),and longtime cycle stability(523 mAh g^(−1) after 200 cycles at 0.2 A g^(−1)),which are superior to those without LiVO_(2) conductive layer when treated at the same temperature in air.The findings reported in this work may offer novel hints of preparing more advanced anodes and promote the applications of vanadate materials such as Li_(3)VO_(4) for next-generation lithium-ion batteries.

Kinetic Control of Hexagonal Mg（OH）2 Nanoflakes for Catalytic Application of Preferential CO Oxidation

Controlling the growth of nanocrystals is one of the most challenged issues in current catalytic field, which helps to further understand the size and morphology related behaviors for catalytic applications. In this work, we investigated the plane growth kinetics of Mg（OH）2 for catalytic application in preferential CO oxidation. Nanoflakes were synthesized through hydrothermal method. The morphology and structure of nanoflakes were characterized by TEM, SEM, and XRD. By varying the reaction temperature and time, Mg（OH）2 nanoflakes un- derwent an anisotropic growth. Benefited from the Ostwald ripening process, the thickness of nanoflake corre- sponding to the （110） plane of Mg（OH）2 was tuned from 7.6 nm to 24.0 nm, while the diameter of （001） plane in- creased from 18.2 nm to 30.2 nm. The grain growth kinetics for the thickness was well described in terms of an equation, D5= 7.65＋ 6.9 × 10^8exp（-28.14/RT）. After depositing Pt nanoparticles onto these Mg（OH）2 nanoflakes, an excellent catalytic performance was achieved for preferential CO oxidation in H2-rich streams with a wide temper- ature window from 140 ℃ to 240 ℃ for complete CO conversion due to the interaction between Pt and hydroxyl groups. The findings reported here would be helpful in discovering novel catalysts for application of proton ex- change membrane fuel cells.

A Biomimetic Tooth Replicate That Is Hard,Damage-Tolerant,and Self-Healable

Hard materials typically lack the mechanism of energy dissipation and cannot self-heal.Nature addresses this challenge by creating multiscale interfaces between high-contrast materials,namely minerals and biopolymers.Inspired by the enamel-dentin junction in nature,an enamel-like crown consisting ofβFeOOH nanocolumns is interdigitated with a flexible self-healing layer.The iron oxide top layer has exceptionally high modulus and hardness,which is more resistant to cyclic deformation than the bottom layer.The latter however provides an additional pathway for viscous and plastic energy dissipation and enables self-healing by allowing upward polymer diffusion to seal the damage.Picture-frame crack patterns were observed under large loading conditions using microindentation,which localizes the damage at the indentation site.The bending properties can be optimized by varying the thickness of the bottom layer,and the crack induced by bending can be effectively captured at the interface without any delamination.The biomimetic tooth replicate is highly adhesive to a ceramic surface and shows an obvious inhibition effect against Streptococcus mutans,a significant contributor to tooth decay.Combined with ultralow thermal diffusivity,this has great potential as dental material.Learning from nature,our work thus provides a powerful pathway to broadening the scope of synthetic materials for dental replicates.

Synergistic Co-doping effect of CNTs and PVP in Na_(4)MnCr(PO_(4))3 cathode as a strategy for improving the electrochemical performance of SIBs

In order to solve the contradiction between the rapidly growing energy demand and the excessive exploitation of fossil fuels,it is urgent to research and develops more environmentally friendly and efficient energy storage technologies.Therefore,the development of high-performance cathode materials to enhance the energy density of SIB is currently one of the most important topics of scientific research.Advanced high-voltage and low-cost cathode material for SIBs,a composite of carbon-coated Na_(4)MnCr(PO_(4))_(3)(NASICON-type),polyvinylpyrrolidone(PVP),and modified carbon nanotubes(CNTs)is prepared by sol-gel and freeze-drying method.Due to the high conductivity of CNTs,the conductivity of the composite is significantly improved,and its initial capacity is increased to 114 mAh/g at 0.5 C and 96 mAh/g at 5 C(Mn^(2+)/Mn^(4+)conversion for voltage windows 1.4-4.3 V).Moreover,the multi-electrons transfer of Cr^(3+)/Cr^(4+) and Mn^(2+)/Mn^(4+) can provide a high capacity of 165 mAh/g at 0.1 C and 102 mAh/g at 5 C in the high voltage window of 1.4-4.6 V.Furthermore,PVP can effectively inhibit the Jahn-Teller effect caused by Mn ion,making the composite have more excellent high-rate performance and stability.In addition,GITT,EIS and CV curves were drawn to better reveal the excellent kinetic properties of Na_(4)MnCr(PO_(4))_(3)@C@PVP@CNT cathode,and the mechanism of its performance improvement is deeply studied and discussed.Accordingly,the co-doping of CNTs and PVP is a simple way to high conductivity and fast charging of cathode materials for SIBs.

Manipulation and observation of atomic-scale superlattices in perovskite manganate

Superlattices in crystals,particularly in perovskite oxides with strong correlation effects,can create new states of matter and produce peculiar physicochemical phenomena.However,the newfangled perovskite superlattices depend on physical deposition with unit-cell precision.It has been challenging to explore a new suitable chemical method to tailor perovskite superlattices.Herein,we present a new bottomup strategy to precisely prepare atomic-scale oxide superlattices of(LaMnO_(3))_(1)-(La_(1-x-y)Ca_(x)K_(y)MnO_(3))_(2)in a monodispersed perovskite La_(0.66)Ca_(0.29)K_(0.05)MnO_(3)(LCKMO).The special atomic-scale perovskite superlattices are demonstrated using SAED,HAADF-STEM,XRD,and atomic-resolution elemental mapping.Our experiments reveal that the perovskite superlattices can be fabricated under extreme hydrothermal conditions utilizing ultra-high concentrations of KOH.An approximate molten salt system in the hydrothermal process can induce the disproportionation reaction of MnO_(2)solids,which is vital to the growth of ordered perovskite superlattices.This work not only clarifies the hydrothermal growth process of perovskite oxides in extreme conditions,but also proposes a novel engineering route toward perovskite superlattices.