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

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Tungsten 2019年第4期1卷 276-286页

作者： Xiaoqing liu liping li guangshe li State Key Laboratory of Inorganic Synthesis and Preparative Chemistry College of ChemistryJilin UniversityChangchun 130012China

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 *** 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 *** this method,li_(3)VO_(4) was integrated with a conductive layer liVO_(2) and carbon *** synergistic effect among li_(3)VO_(4),liVO_(2) layer,and carbon matrix was systematically studied by optimizing the treatment *** 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 *** 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.

关键词： li_(3)VO_(4) liVO_(2) Rate performance Electronic conductivity li^(+)diffusion

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

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Chinese Journal of Chemistry 2017年第6期35卷 903-910页

作者： Huixia li liping li Shaoqing Chen Yuelan Zhang guangshe li State Key Laboratory of Inorganic Synthesis and Preparative Chemistry College of Chemistry Jilin University Changchun 130012 China Key Laboratory of Design and Assembly of Functional Nanostructures Fujian Institute of Research on the Structure of Matter Fuzhou Fujian 350002 China

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.

关键词： kinetics CO-PROX size-dependent nanoflakes

Tuning Shell Thickness of MnO/C Core-shell Nanowires for Optimum Performance of lithium-ion Batteries

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Chemical Research in Chinese Universities 2017年第6期33卷 924-928页

作者： ZHANG Dan li guangshe FAN Jianming li Baoyun li liping State Key Laboratory of Inorganic Synthesis and Preparative Chemistry College of Chemistry Jilin University Changehun 130012 P. R. China Key Laboratory of Design and Assembly of Functional Nanostructures Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences Fuzhou 350002 R R. China

MnO/C core-shell nanowires with varying carbon shell thickness were synthesized via calcining resorci- nol-formaldehyde resin（RF） with different amounts of hydrothermally synthesized MnO2 nanowires. The relationship between the carbon shell thickness and the anode performance of the MnO/C materials was discussed. With a suitable carbon shell thickness（6.8 nm）, the MnO/C core-shell nanowires exhibit better cycling and rate performance than those with a smaller or larger thickness. The TEM results show that after 50 cycles, the core-shell structure with this thickness can be retained, which leads to superior performance. This contribution provides a significant guiding model for optimizing the electrochemical performance of MnO/C core-shell materials by controlling the thickness of carbon shells.

关键词： Anode MnO Conductivity Capacity

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

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Journal of Energy Chemistry 2023年第4期79卷 330-339页

作者： Xin Zhang Chaochao Fu Dong Luo Xiaoqing liu Qiao Wang Baoyun li guangshe li liping li State Key Laboratory of Inorganic Synthesis and Preparative Chemistry College of ChemistryJilin UniversityChangchun 130012JilinChina Hebei Technology Innovation Center for lightweight of New Energy Vehicle Power System School of Quality and Technical SupervisionHebei UniversityBaoding 071002HebeiChina Guangzhou Key Laboratory of Clean Transportation Energy Chemistry School of Chemical Engineering and Light IndustryGuangdong University of TechnologyGuangzhou 510006GuangdongChina

Oxygen anion redox reaction provides a high theoretical capacity for li-rich manganese-based ***,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 *** 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)***,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 *** 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 *** study provides a rational design chemical bonding method to suppress the oxygen release from the cathode surface and enhance cyclic stability.

关键词： lithium battery li_(1.2)Mn_(0.6)Ni_(0.2)O_(2) Oxygen release Interface chemical bond Electrolyte decomposition

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

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Journal of Energy Chemistry 2023年第6期81卷 101-109,I0004页

作者： Hang Yang Duo Chen Yicheng Tan Hao Xu li li Yiming Zhang Chenglin Miao guangshe li Wei Han College of Physics the State Key Laboratory of Inorganic Synthesis and Preparative ChemistryInternational Center of Future ScienceJilin UniversityChangchun 130012JilinChina Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies College of Materials Science and TechnologyNanjing University of Aeronautics and AstronauticsNanjing 210016JiangsuChina State Key Laboratory of Inorganic Synthesis and Preparative Chemistry College of ChemistryJilin UniversityChangchun 130012JilinChina

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 ***,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 ***,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 *** 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.

关键词： Aqueous Zinc battery Electrode/electrolyte interface Interface modification MnO_(2) V_(2)O_(5) KMnHCF

Manipulation and observation of atomic-scale superlattices in perovskite manganate

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Chinese Chemical Letters 2023年第12期34卷 481-485页

作者： Xiyang Wang Keke Huang Xiaofeng Wu Long Yuan liping li guangshe li Shouhua Feng State Key Laboratory of Inorganic Synthesis and Preparative Chemistry College of ChemistryJilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materialsjilin UniversityChangchun 130012China

Superlattices in crystals,particularly in perovskite oxides with strong correlation effects,can create new states of matter and produce peculiar physicochemical ***,the newfangled perovskite superlattices depend on physical deposition with unit-cell *** has been challenging to explore a new suitable chemical method to tailor perovskite ***,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 *** experiments reveal that the perovskite superlattices can be fabricated under extreme hydrothermal conditions utilizing ultra-high concentrations of *** 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 *** work not only clarifies the hydrothermal growth process of perovskite oxides in extreme conditions,but also proposes a novel engineering route toward perovskite superlattices.

关键词： Perovskite oxides Hydrothermal Ordered superstructure Perovskite superlattice Disproportionation reaction

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

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Chinese Chemical Letters 2024年第2期35卷 539-543页

作者： Ruoyu Chen Denys S.Butenko Shilin li Xinyu Zhang guangshe li Igor V.Zatovsky Wei Han College of Physics State Key Laboratory of Inorganic Synthesis and Preparative ChemistryInternational Center of Future ScienceJilin UniversityChangchun 130012China Academy for Advanced Interdisciplinary Studies Southern University of Science and TechnologyShenzhen 518055China State Key Laboratory of Inorganic Synthesis and Preparative Chemistry College of ChemistryJilin UniversityChangchun 130012China F.D.Ovcharenko Institute of Biocolloidal Chemistry NAS UkraineKyiv 03142Ukraine

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 ***,the development of high-performance cathode materials to enhance the energy density of SIB is currently one of the most important topics of scientific *** 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 *** 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 ***,PVP can effectively inhibit the Jahn-Teller effect caused by Mn ion,making the composite have more excellent high-rate performance and *** 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 ***,the co-doping of CNTs and PVP is a simple way to high conductivity and fast charging of cathode materials for SIBs.

关键词： Sodium-ion batteries Na_(4)MnCr(PO_(4))_(3) Carbon nanotubes Polyvinylpyrrolidone Synergistic effect

Understanding the defect chemistry of oxide nanoparticles for creating new functionalities:A critical review

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Science China Chemistry 2011年第6期54卷 876-886页

作者： li guangshe,li liPing & ZHENG Jing State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China 1. State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences Fuzhou 350002 China

This work presents a critical review on the studies of defect chemistry of oxide nanoparticles for creating new functionalities pertinent to energy applications including dilute-magnetic semiconductors,giant-dielectrics,or white light *** is placed on the relationships between the internal structure and defective surfaces of oxide nanoparticles and their synergy in tailoring the materials *** review is arranged in a sequence:(1) structural fundamentals of bulk oxides,using TiO2 as a model simple oxide to highlight the importance of polymorphs in tuning the electronic structures;(2) structural features of simple oxide nanoparticles distinct from the bulk,which show that nanoparticles can be considered as a special solid under the compression as originated from the surface defect dipole-dipole interactions;and(3) new functions achieved through extending the defect chemistry concept to the assembled architectures or multi-component oxide nanoparticles,in which defect surfaces enable the localized electrons or intermediate levels to produce giant dielectric performance or tunable light *** is concluded that understandings of defect chemistry provide diverse possibilities to manipulate electrons in oxide nanoparticles for functionalities in energy-relevant applications.

关键词： nanoparticles defect chemistry surfaces functionalities

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

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CCS Chemistry 2023年第1期5卷 95-105页

作者： Ying Yan Kai Niu Wenbo Zhang Weiming Sun Yue Jiang Zhonghao Jiang lijuan Zhao Ming Yang Baosheng li Ying Hou guangshe li Ming Yang Shouhua Feng State Key Laboratory of Inorganic Synthesis and Preparative Chemistry Jilin UniversityChangchun 130012 Department of Otorhinolaryngology Head and Neck Surgery The First Hospital of Jilin UniversityChangchun 130021 Key Laboratory of Automobile Materials College of Materials Science and EngineeringJilin UniversityChangchun 130025 Key Laboratory of Bionic Engineering of Ministry of Education College of Biological and Agricultural EngineeringJilin UniversityChangchun 130022 Department of Molecular Biology College of Basic Medical SciencesJilin UniversityChangchun 130021 Department of Dental Implantology Hospital of StomatologyJilin UniversityChangchun 130021

Hard materials typically lack the mechanism of energy dissipation and cannot *** addresses this challenge by creating multiscale interfaces between high-contrast materials,namely minerals and *** by the enamel-dentin junction in nature,an enamel-like crown consisting ofβFeOOH nanocolumns is interdigitated with a flexible self-healing *** iron oxide top layer has exceptionally high modulus and hardness,which is more resistant to cyclic deformation than the bottom *** latter however provides an additional pathway for viscous and plastic energy dissipation and enables self-healing by allowing upward polymer diffusion to seal the ***-frame crack patterns were observed under large loading conditions using microindentation,which localizes the damage at the indentation *** 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 *** biomimetic tooth replicate is highly adhesive to a ceramic surface and shows an obvious inhibition effect against Streptococcus mutans,a significant contributor to tooth *** with ultralow thermal diffusivity,this has great potential as dental *** from nature,our work thus provides a powerful pathway to broadening the scope of synthetic materials for dental replicates.

关键词： biomimetics molecular assembly enamel-dentin interface mechanical properties self-healing