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Mitigating volume expansion of silicon-based anode through interfacial engineering based on intermittent discharge strategy

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Journal of Energy Chemistry 2024年第11期98卷 680-691页

作者： Chunlei Li Yu Zhu Yin Quan Feifei Zong Jie Wang Dongni Zhao Ningshuang Zhang Peng Wang Xiaoling Cui Shiyou Li School of Petrochemical Technology Lanzhou University of TechnologyLanzhou 730050GansuChina Key laboratory of Low Carbon Energy and Chemical engineering of gansu Province Lanzhou 730050GansuChina gansu engineering laboratory of cathode material for lithium-ion battery Baiyin 730900GansuChina

Silicon is considered to be one of the most promising anode materials for lithium-ion batteries(LIBs),but its application is limited by the large volume expansion during alloying and *** constructing of a high-performance solid electrolyte interface(SEI) film on the surface of the anode material is considered to be one of the effective strategies to mitigate volume expansion of silicon-based *** this study,an intermittent discharge strategy which helps to improve the utilization efficiency of electrolyte additive of lithium difluorobisoxalate phosphate(LiDFBOP) is proposed to construct a highly conductive and dense SEI *** results of electrochemical and physical characterization and theoretical calculations show that the intermittent discharge in the voltage range from open circuit voltage(OCV) to 1.8 V facilitates the diffusion of the soluble products,creates the conditions for the repeated direct contact between Si@C anode and LiDFBOP additive,increases the decomposition of LiDFBOP additive,and thus produces a uniform,dense and inorganics-rich(Li_(2)C_(2)O_(4),LiF and Li_(x)PO_yF_z) SEI ***,this SEI film helps to ensure the even intercalation/de-intercalation of Li^(+) in the SEI film and the homogeneous diffusion of Li^(+) inside the Si particles,decreasing the internal stresses and anisotropic phase transitions,maintaining the integrity of Si particles,inhibiting the volume expansion and thu s improving the electrochemical performance of *** study not only improves the utilization efficiency of expensive additives through a simply and low-cost method,but also enriches the strategy to improve the electrochemical performance of Si@C anode through interfacial engineering.

关键词： Si@C anode lithium difluoro(bisoxalato)phosphate Intermittent discharge Solid electrolyte interface Volume expansion

Adjusting the solvation structure with tris(trimethylsilyl)borate additive to improve the performance of LNCM half cells

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Journal of Energy Chemistry 2022年第4期31卷 55-64页

作者： Jie Wang Hong Dong Peng Wang Xiao-Lan Fu Ning-Shuang Zhang Dong-Ni Zhao Shi-You Li Xiao-Ling Cui School of Petrochemical Technology Lanzhou University of TechnologyLanzhou 730050GansuChina gansu Key laboratory of Low-Carbon Energy and Chemical engineering Lanzhou 730050GansuChina gansu engineering laboratory of Electrolyte material for lithium-ion battery Lanzhou 730050GansuChina

Tris(trimethylsilyl)borate(TMSB) has been intensively studied to improve the performances of lithiumion batteries. However, it is still an interesting issue needed to be resolved for the research on the Li^(+) solvation structure affected by TMSB additive. Herein, the electrochemical tests, quantum chemistry calculations, potential-resolved in-situ electrochemical impedance spectroscopy measurements and surface analyses were used to explore the effects of Li^(+) solvation structure with TMSB additive on the formation of the cathode electrolyte interface(CEI) film in LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/Li half cells. The results reveal that the TMSB additive is easy to complex with Li^(+) ion, thus weaken the intermolecular force between Li^(+) ions and ethylene carbonate solvent, which is benefit for the cycle performance. Besides, the changed Li^(+) solvation structure results in a thin and dense CEI film containing compounds with Si–O and B–O bonds which is favorable to the transfer of Li^(+) ions. As a result, the performances of the LNCM811/Li half cells are effectively improved. This research provides a new idea to construct a high-performance CEI film by adjusting the Li^(+) solvation structures.

关键词： lithium-ion battery Solvation structure Tris(trimethylsilyl)borate Si-containing additive LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) cathode electrolyte interface film

3D-printed hierarchical porous and multidimensional conductive network based on conducting polymer/graphene oxide

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Journal of Materiomics 2024年第1期10卷 234-244页

作者： Cankun Gao Xiaoling Cui Caiyun Wang Mengya Wang Shumin Wu Yin Quan Peng Wang Dongni Zhao Shiyou Li School of Petrochemical Technology Lanzhou University of TechnologyLanzhou730050China Key laboratory of Low Carbon Energy and Chemical engineering of gansu Province Lanzhou730050China gansu engineering laboratory of cathode material for lithium-ion battery Baiyin730900China ARC Centre of Excellence for Electromaterials Science Intelligent Polymer Research InstituteUniversity of WollongongAIIM FacilityInnovation CampusNorth WollongongNSW2500Australia

Designing ultrathick and hierarchical electrodes is effective to deal with the challenge of high areal capacity and high power density for lithium-ion batteries(LIBs)***,a thick electrode with hierarchical porous and multidimensional conductive network is fabricated by 3D printing tech-nology,in which both the conducting polymer of poly(3,4-ethylene dioxythiophene):polystyrene sul-fonate(PEDOT:PSS)and graphene oxide(GO)play the dual roles as binders and conductive *** a consequence,the 3D-printed thick electrode(~900 mm)with a mass loading of~47 mg/cm^(2) exhibits a good rate capability of 122 mA·h/g at 2 C,a high areal capacity of up to 5.8 mA·h/cm^(2),and stable cycling performance of~95%capacity retention after 100 ***,the C-O-S bond is further confirmed by the spectral analysis and the DFT calculation,which not only hinders the stack of nanosheets but enhances the mechanical stability and electronic conductivity of electrodes.A stable covalent multidi-mensional conductive network constructed by 3D-printing technology provides a new design strategy to improve the performance of LIBs.

关键词： 3D printing PEDOT:PSS Thick electrodes Areal capacity lithium-ion batteries

In-situ magnetic field enhanced performances in ferromagnetic FeCo_(2)O_(4) nanofibers-based rechargeable Zinc-air batteries

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Journal of Energy Chemistry 2023年第3期78卷 447-453,I0013页

作者： Zhengmei Zhang Lei Jia Tong Li Jinmei Qian Xiaolei Liang Desheng Xue Daqiang Gao Key laboratory for Magnetism and Magnetic materials of Ministry of Education Lanzhou UniversityLanzhou 730000GansuChina Key laboratory of Atomic and Molecular Physics&Function material of gansu Province Northwest Normal UniversityLanzhou 730070GansuChina Department of Obstetrics and Gynecology Key Laboratory for Gynecologic Oncology Gansu Provincethe First Hospital of Lanzhou UniversityLanzhou 730000GansuChina

Field-assisted electrocatalytic reactions are demonstrated to be sufficient strategies in enhancing the electrocatalyst activities for oxygen evolution reaction(OER).Here,we report the in-situ magnetic field enhanced electrocatalytic activity in ferromagnetic FeCo_(2)O_(4)*** results demonstrate that the overpotential of FeCo_(2)O_(4)nanofibers at 10 mA cm^(-2)shows a left-shift of 40 mV for the OER by applying an external magnetic field,and no obvious change has been observed in the non-ferromagnetic-order *** results indicate that there are more overlaps between the density of states for Co3d and O 2p by applying an external magnetic ***,the spin hybridization of 3d-2p and the kinetics of spin charge transfer are optimized in ferromagnetic FeCo_(2)O_(4),which can promote the adsorption of oxygen-intermediates and electron transfer,significantly improving its electrocatalytic ***’s more,the maximum power density of the FeCo_(2)O_(4)nanofibers based Zn-air battery(ZAB)increases from 97.3 mW cm^(-2)to 108.2 mW cm^(-2)by applying an external magnetic field,providing a new idea for the application of magnetic cathode electrocatalysts in ZABs.

关键词： In-situ magneticﬁeld Oxygen evolution reaction Spin hybridization Zn-air battery

Recent advances and perspectives of metal/covalent-organic frameworks in metal-air batteries

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Journal of Energy Chemistry 2021年第12期30卷 113-129,I0003页

作者： Ming Zhong Ming Liu Na Li Xian-He Bu School of materials Science and engineering Tianjin Key Laboratory of Metal and Molecule-Based Material ChemistryNankai UniversityTianjin 300350China State Key laboratory of Advanced Processing and Recycling of Nonferrous Metals Lanzhou University of TechnologyLanzhou 730050GansuChina College of Chemistry Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education)Nankai UniversityTianjin 300071China

Metal-air batteries(MABs)have attracted considerable attention as a novel energy technology that can alleviate the severe energy crisis and environmental *** primary processes,including oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)occur on the air cathode and dominate the battery performance during battery charging and ***,metal-organic frameworks(MOFs)and covalent-organic frameworks(COFs)emerge as promising cathode catalysts due to their structure and composition *** unique characteristics of MOFs and COFs contribute to improved *** review mainly summarizes the recent applications of MOFs and COFs in a series of MABs,mainly including lithium-and zinc-air ***,some critical issues are emphasized regarding MOFs and COFs used in other MABs limited progress,their fabrication and alternatives to potential problems.

关键词： Metal-organic frameworks Covalent-organic frameworks Li-air batteries Zn-air batteries Active sites

Aqueous Zn-MnO_(2) battery: Approaching the energy storage limit with deep Zn^(2+) pre-intercalation and revealing the ions insertion/extraction mechanisms

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Journal of Energy Chemistry 2022年第4期31卷 225-232页

作者： Yaxiong Zhang Xiaosha Cui Yupeng Liu Situo Cheng Peng Cui Yin Wu Zhenheng Sun Zhipeng Shao Jiecai Fu Erqing Xie Key laboratory for Magnetism and Magnetic materials of the Ministry of Education School of Physical Science and TechnologyLanzhou UniversityLanzhou 730000GansuChina

Rechargeable aqueous zinc ion batteries(AZIBs)were considered as one of the most promising candidates for large-scale energy storage due to the merits of high safety and *** AZIBs cathode material,Mn O_(2)possesses great merits but was greatly hindered due to the sluggish diffusion kinetic of Zn^(2+) during electrochemical ***,deep Zn^(2+) ions intercalatedδ-Mn O_(2)(Zn-Mn O_(2))was achieved by the in situ electrochemical deposition route,which significantly enhanced the diffusion ability of Zn^(2+) due to the synergistic effects of Zn^(2+) pillars and structural H;*** resultant Zn-Mn O_(2)based AZIBs delivers a record capacity of 696 m Ah/g(0.5 m Ah/cm^(2))based on the initial mass loading,which is approaching the theoretical capacity of Mn O_(2)with a two-electrons ***-situ Raman studies reveal highly reversible Zn^(2+)ions insertion/extraction behaviors and here the Zn-Mn O_(2)plays the role of a container during the charge–discharge *** charge storage mechanism investigations point out the insertion/extraction of Zn^(2+) and H^(+) coincides,and such process is significantly facilitated results from superior interlayered configurations of Zn-Mn O_(2)The excellent electrochemical performance of Zn-Mn O_(2)achieved in this work suggests the deep ions pre-intercalation strategy may aid in the future development of advanced cathodes for AZIBs.

关键词： Aqueous zinc ion batteries Deep Zn^(2+)intercalated MnO_(2) Interlayer distance engineering ions insertion/extraction mechanisms

The roles of graphene in advanced Li-ion hybrid supercapacitors

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Journal of Energy Chemistry 2018年第1期27卷 43-56页

作者： Junwei Lang Xu Zhang Bao Liu RutaoWang Jiangtao Chen Xingbin Yan laboratory of Clean Energy Chemistry and materials State Key Laboratory of Solid LubricationLanzhou Institute of Chemical PbysicsLanzhou 730000GansuChina Qingdao Center of Resource Chemistry&New materials Qingdao 266071SbandongChina

lithium-ion hybrid supercapacitors （LIHSs）, also called Li-ion capacitors, are electrochemical energy stor- age devices that combining the advantages of high power density of supercapacitor and high energy density of Li-ion battery. However, high power density and long cycle life are still challenges for the cul~ rent LIHSs due to the imbalance of charge-storage capacity and electrode kinetics between capacitor-type cathode and battery-type anode. Therefore, great efforts have been made on designing novel cathode materials with high storage capacity and anode material with enhanced kinetic behavior for LIHSs. With unique two-dimensional form and numerous appealing properties, for the past several years, the rational designed graphene and its composites materials exhibit greatly improved electrochemical performance as cathode or anode for LIHSs. Here, we summarized and discussed the latest advances of the state- of-art graphene-based materials for LIHSs applications. The major roles of graphene are highlighted as （1） a superior active material, （2） ultrathin 2D flexible support to remedy the sluggish reaction of the metal compound anode, and （3） good 2D building blocks for constructing macroscopic 3D pOFOUS car- bonjgraphene hybrids. In addition, some high performance aqueous LIHSs using graphene as electrode were also summarized. Finally, the perspectives and challenges are also proposed for further develop- ment of more advanced graphene-based LIHSs.

关键词： Graphene Li-ion hybrid supercapacitors Supercapacitor lithium ion batteries Carbon materials Metal oxide Naoocomposites

A high-capacity and long-lifespan SnO_(2)@K-MnO_(2) cathode material for aqueous zinc-ion batteries

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Frontiers of materials Science 2024年第3期18卷 45-57页

作者： Xiaoqing Jin Yae Qi Yongyao Xia College of Chemistry and Chemical engineering Key Laboratory of Hexi Corridor Resources Utilization of GansuHexi UniversityZhangye 734000China Department of Chemistry Shanghai Key Laboratory of Molecular Catalysis and Innovative MaterialsInstitute of New EnergyiChEM(Collaborative Innovation Center of Chemistry for Energy Materials)Fudan UniversityShanghai 200433China

Aqueous Zn/MnO_(2) rechargeable zinc-ion batteries(ZIBs)possess potential applications in electrochemical energy storage due to their safety,low cost,and environmental ***,manganese dioxide as the cathode material has poor cycle stability and low *** this work,the SnO_(2)@K-MnO_(2)(SMO)composite was prepared using the hydrothermal method followed by the treatment with SnCl_(2) sensitization,and its electrochemical characteristics were examined using SMO as the cathode material for *** reversible specific capacity reaches 298.2 mA·h-g^(-1) at 0.5A·g^(-1),and an excellent capacity retention of 86%is realized after 200 cycles,together with a high discharge capacity of 105 mA·h·g^(-1) at 10 A·g^(-1) and a long-term cycling life of over 8000 cycles with no apparent capacity *** cathode exhibits a long cycle life up to 2000 cycles at 2 Ag^(-1) with the mass loading of 5 mg·cm^(-2),and the battery maintains the capacity of 80%.The reversible co-embedding mechanism of H^(+)/Zn^(2+) in such a ZnlSMO battery was confirmed by XRD and SEM during the chargeldischarge *** work can enlighten and promote the development of advanced cathode materialsforZIBs.

关键词： zinc ion battery SnO_(2)@K-MnO_(2) cathode material energy storage mechanism