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The mitigation of pitch-derived carbon with different structures on the volume expansion of silicon in Si/C composite anode

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Journal of Energy Chemistry 2023年第9期84卷 292-302页

作者： Xin Xue Xiao Liu Bin Lou Yuanxi Yang Nan Shi FuShan Wen Xiujie Yang Dong Liu State Key Laboratory of Heavy Oil Processing China University of PetroleumQingdao 266580ShandongChina Department of Chemical Engineering University College London Torrington Place London WC1E7JEUK

The microstructures of carbon precursors significantly affect the electrochemical performance of Si/C composite anodes.However,the interaction between Si and carbon materials with different structures is still unclear.Pitch-based materials undergoing different thermal treatments are superior sources for synthesizing carbons with different structures.Herein,different types of mesophase pitch(domain,flow-domain and mosaic structure) obtained from controllable thermal condensation are utilized to prepare Si/C composite materials and the corresponding models are established through finite element simulation to explore the correlation between the lithium storage properties of Si/C composites and the structures of carbon materials.The results indicate that the flow-domain texture pitch P2 has a better ability to buffer the volume expansion of silicon particles for its highly ordered arrangement of carbon crystallites inside could disperse the swelling stress uniformly alongside the particle surface.The sample Si@P2 exhibits the highest capacity of 1328 mA h/g after 200 cycles at a current density of 0.1 A/g as well as the best rate performance and stability.While sample Si@P3 in which the mosaic texture pitch P3 composed of random orientation of crystallites undergoes the fastest capacity decay.These findings suggest that highly ordered carbon materials are more suitable for the synthesis of Si/C composite anodes and provide insights for understanding the interaction between carbon and silicon during the charging/discharging process.

关键词： Si/C composite materials Mesophase pitch Finite element simulation volume expansion

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Structural Designs for Accommodating volume expansion in Sodium Ion Batteries

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Chinese Journal of Chemistry 2018年第9期36卷 866-874页

作者： Wenjie Wang Xiaohui Zhu Yujing Zhang Yongiun Liu Qin Zhang Lei Fu College of Chemistry and Molecular Science Wuhan University Wuhan Hubei 430072 China The Institute for Advanced Studies (IAS) Wuhan University WuhanHubei 430072 China

T At the forefront of energy storage field, developing sodium ion batteries （SIBs） has drew a wide concern due to relatively low cost and abundant resource, comparing with lithium ion batteries （LIBs）. Serious volume expansion constraints the electrochemical performance of the conver- sion/alloying materials, despite of their high reversible capacities or theoretical capacities. Here, from the perspective of structural designs, we systemat- ically study four types of routes to accommodate volume expansion. Delicate and peculiar nanostructures based on nanocrystallization engineering are widely focused on, covering nanosheet assembly and nanoarray construction. Robust materials such as carbon-based materials can be utilized as the buffer matrix, mitigating the mechanical stress during the charge/discharge process. Besides, recent studies have demonstrated void space reservation in nanostructures was also beneficial for adapting to volume changes. Moreover, for conversion materials, numerous works have confirmed the advanta- geous influence of interlayer spacing regulation. We also explained the superiority and challenges for further giving scope to structural designs. Sketching out the future studies in SIBs, in situ characterizations are supposed to be highlighted, as well as in-depth researches on the stress evolution caused by volume expansion.

关键词： sodium ion batteries volume expansion structural design buffer matrix void space

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Experimental evidence of pressure effects on spinel dissolution and peridotite serpentinization kinetics under shallow hydrothermal conditions

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Geoscience Frontiers 2024年第2期15卷 236-250页

作者： Yuri de Melo Portella Rommulo Vieira Conceição Tiago Abreu Siqueira Lucas Bonan Gomes Rodrigo Sebastian Iglesias Programa de Pós-Graduação em Geociências(PPGGEO) Universidade Federal do Rio Grande do SulPorto AlegreBrazil Petrobras–Petróleo Brasileiro S.A. Avenida Henrique Valadares 28CentroRio de Janeiro(RJ)20231-030Brazil Instituto do Petróleo e dos Recursos Naturais-PUCRS–Pontifícia Universidade Católica do Rio Grande do Sul 90619-900Porto AlegreBrazil Universidade Federal do Rio Grande do Sul Instituto de GeociênciasLaboratório de Difratometria de Raios XPorto AlegreBrazil Escola Politécnica–PUCRS-Pontifícia Universidade Católica do Rio Grande do Sul 90619-900 Porto AlegreBrazil

Serpentinization reactions are paramount to understand hydro-geothermal activity near plate boundaries and mafic–ultramafic massifs,as well as fluid and element transfer between the Earth’s mantle and crust.However,fluid-rock element exchange and serpentinization kinetics under shallow hydrothermal conditions is still largely unconstrained.Here we present two constant temperature(230℃)time-series of natural peridotite(77.5%olivine;13.7%enstatite;6.8%diopside;2%spinel)serpentinization experiments:at 13.4 MPa;and 20.7 MPa.Al-enriched lizardite was the main secondary mineral in all runs after olivine(olv)and orthopyroxene(opx)serpentinization(without any detectable brucite,talc or magnetite),while primary spinel and diopside partially dissolved during the experiments.Initial serpentinization stages comprises intrinsically coupled reactions between olivine and enstatite,as Al and Si are progressively transferred from orthopyroxene-derived to olivine-derived serpentine,while the opposite is true for Mg and Fe,with homogenization of serpentines compositions after 40 days.The Ni/Cr ratios of serpentines,however,remain diagnostic of the respective primary mineral.Estimated average serpentine content indicates fast serpentinization rates of 0.55 wt.%·day^(-1)(0.26 mmol·day^(-1))and 0.26 wt.%·day^(-1)(0.13 mmol·day^(-1))at 13.4 and 20.7 MPa,respectively.Approximately 2x faster serpentinization kinetics at lower pressure is likely linked to enhanced spinel dissolution leading to one order of magnitude higher available Al,which accelerates olivine serpentinization while delays orthopyroxene dissolution.Additionally,time-dependent increase in solid products masses suggests rock volume expands linearly 0.37%±0.01%per serpentine wt.%independently of pressure.Mass balance constrains suggests olv:opx react at~5:2 and~3:2 M ratios,resulting in Si-deficient and Si-saturated serpentines at the end of the low-pressure series(13.4 MPa)and high-pressure series(20.7 MPa),respectively.Elevated starting peridotite olv:opx ratio(7.94:1)the

关键词： Serpentine volume expansion Serpentinization fluids Lost City hydrothermal field Serpentinite-hosted hydrothermal systems Hydrogen(H_(2))generation

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Yolk-Shell P3-Type K_(0.5)[Mn_(0.85)Ni_(0.1)Co_(0.05)]O_(2):A Low-Cost Cathode for Potassium-Ion Batteries

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Energy & Environmental Materials 2022年第1期5卷 261-269页

作者： Jiaxin Hao Ke Xiong Jiang Zhou Apparao M.Rao Xianyou Wang Huan Liu Bingan Lu School of Physics and Electronics State Key Laboratory of Advanced Design and Manufacturing for Vehicle BodyHunan UniversityChangsha 410082China Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education Hunan Province Key Laboratory of Electrochemical Energy Storage and ConversionSchool of ChemistryXiangtan UniversityXiangtan 411105China School of Materials Science and Engineering Central South UniversityChangsha 410083China Department of Physics and Astronomy Clemson Nanomaterials InstituteClemson UniversityClemson SC 29634USA College of Materials Science and Engineering Hunan University of Scienceand TechnologyXiangtan 411201China Fujian Strait Research Institute of Industrial Graphene Technologies Quanzhou 362000China

Low-cost preparation methods for cathodes with high capacity and long cycle life are crucial for commercializing potassium-ion batteries(PIBs).Presently,the charging/discharging strain that develops in the active cathode material of PIBs causes cracks in the particles,leading to a sharp capacity fade.Here,to abate the strain release and the need for an industrially relevant process,a simple low-cost co-precipitation method for synthesizing yolk-shell P3-type K_(0.5)[Mn_(0.85)Ni_(0.1)Co_(0.05)]O_(2) (YS-KMNC)was reported.As cathode material for PIBs,the YS-KMNC delivers a high reversible capacity(96 mAh g^(-1) at 20 mA g^(-1))and excellent cycle stability(80.5%retention over 400 cycles at a high current density of 200 mA g^(-1)).More importantly,a full battery assembled with the YS-KMNC cathode and a commercial graphite anode exhibits a high operating voltage(0.5-3.4 V)and an excellent cycling performance(84.2%retention for 100 cycles at 100 mA g^(-1)).Considering the low-cost,simple production process and high performance of YS-KMNC cathode,this work could pave the way for the commercial development of PIBs.

关键词： cathode materials K_(0.5)[Mn_(0.85)Ni_(0.1)Co_(0.05)]O_(2) strain release volume expansion yolk-shell structure

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Ni-P-SBR composite-electroless-plating enables Si anode with high conductivity and elasticity for high performance Li-ion batteries application

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Journal of Energy Chemistry 2023年第1期76卷 59-66,I0003页

作者： Yuxiao Wang Jian Gou Hongzhang Zhang Xiaofei Yang Huamin Zhang Xianfeng Li Dalian Institute of Chemical Physics Chinese Academy of SciencesDalian 116023LiaoningChina University of Chinese Academy of Sciences Beijing 100039China

Silica-based anode is widely employed for high energy density Li-ion batteries owing to their high theoretical specific capacity(4200 m A h g-1).However,it is always accompanied by a huge volume expansion(300%)and shrinks during the lithiation/delithiation process,further leading to low cycle stability.Efforts to mitigate the adverse effects caused by volume expansion such as robust binder matrix,Coreshell structure,etc.,inevitably affect the electronic conductivity within the electrode.Herein,a high conductivity and elasticity Si anode(Ni-P-SBR(styrene-butadiene rubber)@Si)was designed and fabricated via the Ni-P-SBR composite-electroless-plating process.In this design,the Si particles are surrounded by SBR polymer and Ni particles,where the SBR can adapt to the volume change and Ni particles can provide the electrode with high electronic conductivity.Therefore,the Ni-P-SBR@Si delivers a high initial capacity of 3470 m A h g-1and presents capacity retention of 49.4%within 200 cycles at 600 m A g-1.Additionally,a high capacity of 1153 m A h g-1can be achieved at 2000 m A g-1and can be cycled stably under bending conditions.This strategy provides feasible ideas to solve the key issues that limit the practical application of Si anodes.

关键词： Silicon anode volume expansion Composite-electroless-plating High elasticity High electronic conductivity

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Development and Field Application of Phosphogypsum-Based Soil Subgrade Stabilizers

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Journal of Renewable Materials 2022年第8期10卷 2247-2261页

作者： Hongfei Yue Aiguo Fang Sudong Hua Zenghuan Gu Yu Jia Cheng Yang College of Materials Science and Engineering Nanjing Tech UniversityNanjing211800China China Construction Installaction Engineering Co. Ltd.Nanjing210023China Jiangsu Subote New Material Co. Ltd.Nanjing211103China Sinoma Construction Co. Ltd.Suzhou215300China

A phosphogypsum-based subgrade stabilizer(PBSS)was formulated using industrial by-product phosphogypsum(PG),mixed with slag and calcium-silicon-rich active material(GSR).The active powder(AP)was used to modify PBSS,and PBSS-AP was obtained.PBSS and PBSS-AP were each mixed with 10%silty soil,and cement and lime(CAL:5%lime+2%cement)were used as the traditional material for comparative experiments.Samples were cured under standard conditions,and tested for unconfined compressive strength(UCS),water stability,volume expansion,and leachate,to explore the stabilization effect of the three solidified materials on silty soil.The results showed that the comprehensive performance of sility soil mixed with 12%PBSS-AP was the best.The CaO,SiO_(2)and Al_(2)O_(3)provided by PG,Slag and GSR will react with water to form a stable C-S-H gel,which is conducive to stabilizing the soil.Field application results showed that the compaction exceeded 95%,the deflection was 144.9 mm,and UCS was 2.5 MPa after 28 days.These findings indicated that PBSS-AP is an effective stabilizer for subgrade soils.

关键词： Phosphogypsum solidified material unconfined compressive strength water stability volume expansion leachate

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温度调控制备锡或二氧化锡@中空多孔碳纳米纤维电极用于个性化定制锂离子电池

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Science China Materials 2023年第5期66卷 1736-1746页

作者：梁芳华董慧龙季朱玉张伟张海峰曹春艳李恒刘宏超张克勤赖跃坤汤育欣葛明政 School of Textile and Clothing Nantong UniversityNantong 226019China School of Materials Engineering Changshu Institute of TechnologyChangshu 215500China Department of Biomedical Sciences City University of Hong KongHong Kong 999077China Institute of Applied Physics and Materials Engineering University of MacaoMacao 999078China National Engineering Laboratory for Modern Silk College of Textile and Clothing EngineeringSoochow UniversitySuzhou 215123China College of Chemical Engineering Fuzhou UniversityFuzhou 350116China

锂离子电池广泛应用于电动汽车、混合动力汽车、便携式电子设备等储能系统,但由于电荷在活性材料中传输缓慢以及活性材料易粉碎等缺点,开发同时具有高容量以及快充性能的电极材料仍然是一个极大的挑战.针对这一问题,本文通过温度调控将S... 详细信息

锂离子电池广泛应用于电动汽车、混合动力汽车、便携式电子设备等储能系统,但由于电荷在活性材料中传输缓慢以及活性材料易粉碎等缺点,开发同时具有高容量以及快充性能的电极材料仍然是一个极大的挑战.针对这一问题,本文通过温度调控将SnO_(2)量子点或Sn纳米团簇均匀负载在中空多孔碳纳米纤维(HPCNFs)的内部,用于制备个性化定制锂离子电池.一方面,高度互联的碳纳米纤维形成三维网络,加快了电子传输,提高了电子导电性.另一方面,中空多孔结构缩短了锂离子传输路径,促进了锂离子的快速扩散,同时,抑制了Sn和SnO_(2)的体积膨胀.由于具有较高的锂离子吸附性能以及快的离子扩散速率,低碳化温度下(450℃)合成的SnO_(2)@HPCNFs复合电极在0.1 A g^(-1)的小电流密度下具有较高的放电比容量(899.3 mA h g~(-1)).此外,由于在大的电流密度下,Sn的大孔结构能够储存更多的锂离子,以及具有较高的电子电导率,因此,高碳化温度下(850℃)制备的Sn@HPCNFs复合电极展现出优异的快充性能,同时,在5 A g^(-1)(~10 C)的高电流密度下具有238.8 mA h g^(-1)的放电容量.本文通过调控碳化温度来研究SnO_(2)和Sn电极之间的电化学行为,为构建高性能储能器件提供了新的思路.

关键词： Sn-based electrodes large energy storage high rate performance volume expansion lithium-ion batteries

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Effect of Systolic Cardiac Function on Passive Leg Raising for Predicting Fluid Responsiveness： A Prospective Observational Study

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Chinese Medical Journal 2018年第3期131卷 253-261页

作者： Xiang Si Dai-Yin Cao Juan Chen Jian-Feng Wu Zi-Meng Liu Hai-Lin Xu Min-Ying Chen Yong-Jun Liu Xiang-Dong Guan Department of SICU The First Affiliated Hospital of Sun Yat-sen University Guangzhou Guangdong 510080 China Department of Critical Care Medicine The Sixth Affiliated Hospital of Sun Yat-sen University Guangzhou Guangdong 510655 China

Background：Passive leg raising （PLR） represents a ＂self-volume expansion （VE）＂ that could predict fluid responsiveness,but the influence of systolic cardiac function on PLR has seldom been reported.This study aimed to investigate whether systolic cardiac function,estimated by the global ejection fraction （GEF） from transpulmonary-thermodilution,could influence the diagnostic value of PLR.Methods：This prospective,observational study was carried out in the surgical Intensive Care Unit of the First Affiliated Hospital of Sun Yat-sen University from December 2013 to July 2015.Seventy-eight mechanically ventilated patients considered for VE were prospectively included and divided into a low-GEF （〈20%） and a near-normal-GEF （〉20%） group.Within each group,baseline hemodynamics,after PLR and after VE （250 ml 5% albumin over 30 min）,were recorded.PLR-induced hemodynamic changes （PLR-△） were calculated.Fluid responders were defined by a 15% increase of stroke volume （SV） after VE.Results：Twenty-five out of 38 patients were responders in the GEF 〈20% group,compared to 26 out of 40 patients in the GEF 〉20% group.The thresholds of PLR-△SV and PLR-△ cardiac output （PLR-△CO） for predicting fluid responsiveness were higher in the GEF 〉20% group than in the GEF 〈20% group （△SV：12% vs.8%;△CO：7% vs.6%）,with increased sensitivity （△SV：92% vs.92%;△CO：81% vs.80%） and specificity （△SV：86% vs.70%;△CO：86% vs.77%）,respectively PLR-△ heart rate could predict fluid responsiveness in the GEF 〉20% group with a threshold value of-5% （sensitivity 65%,specificity 93%） but could not in the GEF 〈20% group.The pressure index changes were poor predictors.Conclusions：In the critically ill patients on mechanical ventilation,the diagnostic value of PLR for predicting fluid responsiveness depends on cardiac systolic function.Thus,cardiac systolic function must be considered when using PLR.Trial Registration：Chinese Clinical Trial Register,ChiCTR-OCH-13004027;http：//***/showproj.aspx？proj=5540.

关键词： Fluid Responsiveness Passive Leg Raising Systolic Cardiac Function volume expansion

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Enhanced electrochemical performance of Si/C electrode through surface modification using SrF_(2) particle

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International Journal of Minerals,Metallurgy and Materials 2021年第10期28卷 1621-1628页

作者： Jun Yang Yuan-hua Lin Bing-shu Guo Ming-shan Wang Jun-chen Chen Zhi-yuan Ma Yun Huang Xing Li School of New Energy and Materials Southwest Petroleum UniversityChengdu 610500China

The silicon-based material exhibits a high theoretical specific capacity and is one of the best anode for the next generation of advanced lithium-ion batteries(LIBs).However,it is difficult for the silicon-based anode to form a stable solid-state interphase(SEI)during Li alloy/de-alloy process due to the large volume change(up to 300%)between silicon and Li4.4Si,which seriously limits the cycle life of the LIBs.Herein,we use strontium fluoride(SrF_(2))particle to coat the silicon-carbon(Si/C)electrode(SrF_(2)@Si/C)to help forming a stable and high mechanical strength SEI by spontaneously embedding the SrF_(2) particle into SEI.Meanwhile the formed SEI can inhibit the volume expansion of the silicon-carbon anode during the cycle.The electrochemical test results show that the cycle performance and the ionic conductivity of the SrF_(2)@Si/C anode has been significantly improved.The X-ray photoelectron spectroscopy(XPS)analysis reveals that there are fewer electrolyte decomposition products formed on the surface of the SrF_(2)@Si/C anode.This study provides a facile approach to overcome the problems of Si/C electrode during the electrochemical cycling,which will be beneficial to the industrial application of silicon-based anode materials.

关键词： silicon-based anode volume expansion strontium fluoride solid electrolyte interface cycling stability

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Preparation and lithium storage performances of g-C_(3)N_(4)/Si nanocomposites as anode materials for lithium-ion battery

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Frontiers in Energy 2020年第4期14卷 759-766页

作者： Zhengxu BIAN Zehua TANG Jinfeng XIE Junhao ZHANG Xingmei GUO Yuanjun LIU Aihua YUAN Feng ZHANG Qinghong KONG School of Environmental and Chemical Engineering Jiangsu University of Science and TechnologyZhenjiang 212003China Marine Equipment and Technology Institute Jiangsu University of Science and TechnologyZhenjiang 212003China Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province Yancheng Institute of TechnologyYancheng 224051China School of the Environment and Safety Engineering Jiangsu UniversityZhenjiang 212013China

As the anode material of lithium-ion battery,silicon-based materials have a high theoretical capacity,but their volume changes greatly in the charging and discharging process.To ameliorate the volume expansion issue of silicobased anode materials,g-C_(3)N_(4)/Si nanocomposites are prepared by using the magnesium thermal reduction technique.It is well known that g-C_(3)N_(4)/Si nanocomposites can not only improve the electronic transmission ability,but also ameliorate the physical properties of the material for adapting the stress and strain caused by the volume expansion of silicon in the lithiation and delithiation process.When g-C_(3)N_(4)/Si electrode is evaluated,the initial discharge capacity of g-C_(3)N_(4)/Si nanocomposites is as high as 1033.3 mAh/g at 0.1 A/g,and its reversible capacity is maintained at 548 mAh/g after 400 cycles.Meanwhile,the improved rate capability is achieved with a relatively high reversible specific capacity of 218 mAh/g at 2.0 A/g.The superior lithium storage performances benefit from the unique g-C_(3)N_(4)/Si nanostructure,which improves electroconductivity,reduces volume expansion,and accelerates lithiumion transmission compared to pure silicon.

关键词： magnesium thermal reduction g-C_(3)N_(4)/Si nanocomposites volume expansion electroconductivity lithium-ion battery

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