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Article(id=1240648794866504341, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1240648781595725960, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2024.05.034, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1714406400000, receivedDateStr=2024-04-30, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773723322835, onlineDateStr=2026-03-17, pubDate=1727712000000, pubDateStr=2024-10-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773723322835, onlineIssueDateStr=2026-03-17, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773723322835, creator=13701087609, updateTime=1773723322835, updator=13701087609, issue=Issue{id=1240648781595725960, tenantId=1146029695717560320, journalId=1235980550691926019, year='2024', volume='44', issue='5', pageStart='1', pageEnd='184', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773723319672, creator=13701087609, updateTime=1773824608750, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241073618831078097, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1240648781595725960, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241073618831078098, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1240648781595725960, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=168, endPage=173, ext={EN=ArticleExt(id=1240648795202048687, articleId=1240648794866504341, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Expanded Graphite-Loaded Bimetallic Sulfide Derived from Anode Materials of Spent Lithium-Ion Batteries, columnId=1236276108207902848, journalTitle=Mining and Metallurgical Engineering, columnName=MATERIALS, runingTitle=null, highlight=null, articleAbstract=

The expanded graphite (EG) derived from the graphite anodes of spent lithium-ion batteries was taken as conductive substrate, and then Sn/Co-based bimetallic sulfide was loaded by using a hydrothermal method to synthesize SnCoS4@EG nanocomposite. And such EG presents a cross-linked porous three-dimensional lattice, and the SnCoS4 nanocrystals in the synthesized composite are uniformly dispersed in the EG, which enhances electrical conductivity of electrode material and stability of metallic sulfide, but also increases the contact area between active sites and electrolyte, leading to a higher exchange rate of Li+ ions at electrode/electrolyte interface. It is shown that SnCoS4@EG electrode can exhibit a reversible specific capacity of 1 195.90 mAh/g at 1.0 A/g after 500 cycles, presenting excellent durability over a large number of cycles.

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利用废旧锂离子电池负极石墨衍生的膨胀石墨为支撑导电基体，采用水热法负载锡/钴双金属硫化物，合成SnCoS4@EG纳米复合材料。石墨衍生的膨胀石墨EG呈现交联多孔的三维网格，复合材料中SnCoS4纳米晶体均匀分散于膨胀石墨中，这种复合结构提升了电极材料的导电性和金属硫化物的稳定性，增加了活性位点与电解液的接触面积，提高了Li+在电极/电解液界面的交换速率。SnCoS4@EG电极在1.0 A/g电流密度下，经过500次循环后，可逆比容量为1 195.90 mAh/g，表现出优异的长循环耐久性。

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张晓辉（1985—），男，山东济宁人，博士，教授，主要研究方向为锂离子电池电极材料。E-mail：
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邓成情（1996—），女，云南昭通人，硕士研究生，主要研究方向为锂离子电池电极材料。E-mail：

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邓成情（1996—），女，云南昭通人，硕士研究生，主要研究方向为锂离子电池电极材料。E-mail：

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邓成情（1996—），女，云南昭通人，硕士研究生，主要研究方向为锂离子电池电极材料。E-mail：

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（a）SG，SEM；（b）EG，SEM；（c）SnCoS4，SEM；（d），（e）SnCoS4@EG，SEM；（f）SnCoS4@EG复合材料中Sn、Co、S、C元素的EDS元素图

, figureFileSmall=SSxeb2C35G1LH30EjThQ5A==, figureFileBig=VK6H4srVariry1hEjmf7yg==, tableContent=null), ArticleFig(id=1240648805385818376, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1240648794866504341, language=EN, label=null, caption=null, figureFileSmall=06bHBQpJiKhgbtSzgZ27kQ==, figureFileBig=84d0jxuP6P59iBj2pP3hIA==, tableContent=null), ArticleFig(id=1240648805545201939, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1240648794866504341, language=CN, label=图3, caption=SnCoS4@EG的XPS高分辨光谱

（a）Sn3d；（b）Co2p；（c）C1s；（d）S2p

, figureFileSmall=06bHBQpJiKhgbtSzgZ27kQ==, figureFileBig=84d0jxuP6P59iBj2pP3hIA==, tableContent=null), ArticleFig(id=1240648805645865239, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1240648794866504341, language=EN, label=null, caption=null, figureFileSmall=Y1s+tk9BFIzqaHJCfETwAg==, figureFileBig=XnjZu2O361UJsfqfegepBw==, tableContent=null), ArticleFig(id=1240648805914300702, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1240648794866504341, language=CN, label=图4, caption=SnCoS4和SnCoS4@EG的CV曲线和充放电曲线

（a）SnCoS4，CV曲线；（b）SnCoS4@EG，CV曲线；（c）SnCoS4，充放电曲线；（d）SnCoS4@EG，充放电曲线

, figureFileSmall=Y1s+tk9BFIzqaHJCfETwAg==, figureFileBig=XnjZu2O361UJsfqfegepBw==, tableContent=null), ArticleFig(id=1240648806023352608, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1240648794866504341, language=EN, label=null, caption=null, figureFileSmall=M+LzNTbfFEkNndEp3h8q7A==, figureFileBig=U8gv16uRYdP+tM26SlZN3A==, tableContent=null), ArticleFig(id=1240648806136598823, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1240648794866504341, language=CN, label=图5, caption=EG、SnCoS4和SnCoS4@EG的电化学性能

（a）循环稳定性；（b）倍率性能；（c）EIS测试；（d）低频Z′与ω-0.5的关系

, figureFileSmall=M+LzNTbfFEkNndEp3h8q7A==, figureFileBig=U8gv16uRYdP+tM26SlZN3A==, tableContent=null), ArticleFig(id=1240648806262427950, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1240648794866504341, language=EN, label=null, caption=null, figureFileSmall=g/gU5x8owowCUVibVtZIZQ==, figureFileBig=Kq/wkII0oF39aUIx4beuMg==, tableContent=null), ArticleFig(id=1240648806409228592, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1240648794866504341, language=CN, label=图6, caption=SnCoS4@EG复合材料的循环性能

（a）CV曲线；（b）lgi-lgv关系曲线；（c）SnCoS4@EG在0.8 mV/s时的CV曲线和相应的电容贡献；（d）不同扫描速率下的扩散和电容贡献

, figureFileSmall=g/gU5x8owowCUVibVtZIZQ==, figureFileBig=Kq/wkII0oF39aUIx4beuMg==, tableContent=null), ArticleFig(id=1240648806518280505, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1240648794866504341, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
样品名称Re/ΩRct/ΩD（Li+）/（cm2·s-1）
SnCoS42.26088.826.92×10-17
SnCoS4@EG1.54848.692.04×10-16
EG3.901461.603.52×10-17
), ArticleFig(id=1240648806673469757, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1240648794866504341, language=CN, label=表1, caption=

拟合阻抗参数

, figureFileSmall=null, figureFileBig=null, tableContent=
样品名称Re/ΩRct/ΩD（Li+）/（cm2·s-1）
SnCoS42.26088.826.92×10-17
SnCoS4@EG1.54848.692.04×10-16
EG3.901461.603.52×10-17
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废旧锂离子电池负极衍生膨胀石墨负载双金属硫化物负极材料
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邓成情 1, 2 , 陈慧 2 , 刘文涛 2 , 雷艾莹 1 , 赖飞燕 1, 2 , 张晓辉 1, 2
矿冶工程杂志 | 材料 2024,44(5): 168-173
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矿冶工程杂志 | 材料 2024, 44(5): 168-173
废旧锂离子电池负极衍生膨胀石墨负载双金属硫化物负极材料
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邓成情1, 2 , 陈慧2, 刘文涛2, 雷艾莹1, 赖飞燕1, 2, 张晓辉1, 2
作者信息
  • 1.桂林电子科技大学　材料科学与工程学院，广西　桂林　541004
  • 2.贺州学院　广西碳酸钙资源综合利用重点实验室，广西　贺州　542899

    • 邓成情（1996—），女，云南昭通人，硕士研究生，主要研究方向为锂离子电池电极材料。E-mail：

通讯作者:

张晓辉（1985—），男，山东济宁人，博士，教授，主要研究方向为锂离子电池电极材料。E-mail：
Expanded Graphite-Loaded Bimetallic Sulfide Derived from Anode Materials of Spent Lithium-Ion Batteries
Chengqing DENG1, 2 , Hui CHEN2, Wentao LIU2, Aiying LEI1, Feiyan LAI1, 2, Xiaohui ZHANG1, 2
Affiliations
  • 1.School of Materials Science and Engineering, Guilin University of Electronic Technology, Guilin 541004, Guangxi, China
  • 2.Guangxi Key Laboratory of Comprehensive Utilization of Calcium Carbonate Resources, Hezhou University, Hezhou 542899, Guangxi, China
出版时间: 2024-10-01 doi: 10.3969/j.issn.0253-6099.2024.05.034
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摘要
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利用废旧锂离子电池负极石墨衍生的膨胀石墨为支撑导电基体，采用水热法负载锡/钴双金属硫化物，合成SnCoS4@EG纳米复合材料。石墨衍生的膨胀石墨EG呈现交联多孔的三维网格，复合材料中SnCoS4纳米晶体均匀分散于膨胀石墨中，这种复合结构提升了电极材料的导电性和金属硫化物的稳定性，增加了活性位点与电解液的接触面积，提高了Li+在电极/电解液界面的交换速率。SnCoS4@EG电极在1.0 A/g电流密度下，经过500次循环后，可逆比容量为1 195.90 mAh/g，表现出优异的长循环耐久性。

锂离子电池  /  负极材料  /  回收再利用  /  膨胀石墨  /  双金属硫化物

The expanded graphite (EG) derived from the graphite anodes of spent lithium-ion batteries was taken as conductive substrate, and then Sn/Co-based bimetallic sulfide was loaded by using a hydrothermal method to synthesize SnCoS4@EG nanocomposite. And such EG presents a cross-linked porous three-dimensional lattice, and the SnCoS4 nanocrystals in the synthesized composite are uniformly dispersed in the EG, which enhances electrical conductivity of electrode material and stability of metallic sulfide, but also increases the contact area between active sites and electrolyte, leading to a higher exchange rate of Li+ ions at electrode/electrolyte interface. It is shown that SnCoS4@EG electrode can exhibit a reversible specific capacity of 1 195.90 mAh/g at 1.0 A/g after 500 cycles, presenting excellent durability over a large number of cycles.

lithium-ion battery  /  anode material  /  recycling  /  expanded graphite  /  bimetallic sulfide
邓成情, 陈慧, 刘文涛, 雷艾莹, 赖飞燕, 张晓辉. 废旧锂离子电池负极衍生膨胀石墨负载双金属硫化物负极材料. 矿冶工程杂志, 2024 , 44 (5) : 168 -173 . DOI: 10.3969/j.issn.0253-6099.2024.05.034
Chengqing DENG, Hui CHEN, Wentao LIU, Aiying LEI, Feiyan LAI, Xiaohui ZHANG. Expanded Graphite-Loaded Bimetallic Sulfide Derived from Anode Materials of Spent Lithium-Ion Batteries[J]. Mining and Metallurgical Engineering, 2024 , 44 (5) : 168 -173 . DOI: 10.3969/j.issn.0253-6099.2024.05.034
正文
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锂离子电池因能量密度高、循环寿命长、自放电低等优点，被广泛应用于各种电子设备和电动汽车中[1-2]。然而，锂离子电池有一定的使用寿命，目前每年有大量锂离子电池面临报废处理的问题[3-4]。废旧锂离子电池中含有有价金属、易燃电解质、塑料外壳以及大量的石墨材料等，若处理不当，不仅浪费资源，而且会严重污染环境[5-6]。因此，对废旧锂离子电池的有效处理不仅可以实现资源回收利用，而且可解决由此造成的环境污染问题。已有研究表明，从废旧电池中回收的石墨通常保持良好的晶体结构，初始容量可以基本满足重复使用的要求[7-8]。另外，经过长时间循环使用后，废旧石墨（spent graphite，SG）的层间距扩大，有利于锂离子的脱嵌过程，也容易将其制成膨胀石墨（expanded graphite，EG）或者剥离出石墨烯等石墨衍生物[9]。EG是一种新型碳材料，与天然鳞片石墨相比，具有比表面积大、导电性好及纯度高等优势[10]，常将其作为金属氧化物、金属硫化物等导电性能差的活性材料的负载基体[11-12]。
过渡金属硫化物因具有形貌可控、理论容量大、价态变化丰富和电化学活性优异等优点而被用作负极材料[13]，然而，其固有电导率低、在充放电过程中易发生体积膨胀和离子扩散缓慢等问题[14]，极大限制了其在锂离子电池领域的应用，为此，通常将其与具有高电子导电性和结构稳定性的碳材料复合，得到具有协同优势的复合材料，以克服这些缺陷。
本文基于以上理论基础，以膨胀石墨EG为导电基体，与高容量的双金属硫化物进行复合，复合材料各组分之间的协同效应可弥补单一组分性能上的缺陷，从而提高电极材料的导电性和金属硫化物的稳定性，实现废旧电池的综合利用。
1　实验
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1.1　实验原料及方法
高锰酸钾（KMnO4）、乙二醇（C2H6O2）、L-半胱氨酸（C3H7NO2S，99%）、二水氯化锡（SnCl4·2H2O，99%）和六水硝酸钴（Co（NO3）2·6H2O）均购自上海阿拉丁生化科技股份有限公司，均为分析纯。
膨胀石墨EG的制备[15]：采用硫酸磷酸混合溶液和KMnO4对废旧石墨进行氧化膨胀，用去离子水稀释反应溶液，过滤得到氧化石墨；然后在N2保护下，将氧化石墨加热到800 ℃保持3 h，获得膨胀石墨EG。
SnCoS4@EG的制备：首先，用超声波将EG分散在35 mL乙二醇中，得到均匀的溶液；然后，加入1.5 mmol SnCl4·2H2O、1.5 mmol Co（NO3）2·6H2O和6 mmol C3H7NO2S，搅拌1 h，移至聚四氟乙烯高压反应釜，180 ℃加热8 h，自然冷却后，用去离子水和乙醇洗涤黑色沉淀，冷冻干燥，得到SnCoS4@EG。同时，在其他条件不变的情况下合成了不添加EG的纯SnCoS4。
1.2　材料表征
采用X射线衍射仪（XRD，Rigaku，日本理学公司）分析物相结构；采用扫描电子显微镜（SEM，JSM-7610F，日本电子株式会社）观察材料的微观形貌；采用X射线光电子能谱分析仪（XPS，PHI QUANTERA-II SXM，日本真空公司）测试材料元素价态信息。
1.3　电化学性能测试
将活性材料、导电炭黑（SP）、聚偏氟乙烯（PVDF）按质量比7∶2∶1称量，以适量N-甲基吡咯烷酮（NMP）为分散剂，搅拌混合均匀后涂布在铜箔上，放入真空干燥箱中80 ℃下干燥12 h，辊压后，裁剪为直径1.2 cm的负极极片。在充满氩气的手套箱中将上述电极片组装成扣式电池，对电极为锂片，电解液采用体积比为1∶1∶1的碳酸二甲酯（DMC）、碳酸乙烯酯（EC）和碳酸甲乙酯（EMC）混合溶液，电解质是浓度1 mol/L的六氟磷酸锂（LiPF6）。采用LAND-CT2001A电池测试系统（武汉市蓝电电子股份有限公司）于室温下对材料进行测试，循环伏安测试（CV）和交流阻抗测试（EIS）在电化学工作站（CHI650E，上海辰华仪器有限公司）上进行。CV的扫描电压区间为0～3.0 V，扫描速率为0.1 mV/s。EIS测试频率为10-3～105 Hz，振幅为5 mV。
2　结果与讨论
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图1为SnCoS4和SnCoS4@EG样品的XRD图谱。SnCoS4样品在18.02°、29.54°、51.22°和59.90°有特征峰，分别对应SnS2的（001）、（101）、（110）和（201）晶面，29.54°处的衍射峰与CoS2的（200）晶面相对应[16]，表明合成了SnCoS4。SnCoS4@EG和SnCoS4的特征峰位置基本一致，说明添加适量的膨胀石墨对SnCoS4晶体结构影响较小；此外，SnCoS4@EG复合材料的XRD在26.56°处有个尖锐强烈的峰，为EG的特征峰，这与石墨材料的（002）晶面有关[15]，证明成功合成了SnCoS4@EG复合材料。
图2为SG、EG、SnCoS4和SnCoS4@EG的SEM图谱和SnCoS4@EG的EDS元素图谱。从图2可以观察到：SG样品含有粗糙的块状结构、不规则的表面和大量杂质，这是长时间循环后金属杂质和分解副产物的附着所致；废旧石墨经氧化膨胀后，杂质随之被去除，这种松散、多孔、弯曲的蠕虫状结构具有比表面积大、导电性好及纯度高等优点[10]，有利于提高材料的化学反应活性位点；SnCoS4呈花状结构，直径约1 μm，尽管该颗粒具有独特的片层结构，但分散性欠佳；添加适量膨胀石墨可以抑制SnCoS4颗粒的堆积和团聚，使多层SnCoS4均匀负载在EG上，形成有机黏合的整体，提高了其结构的稳定性；Sn、Co、S和C元素均匀分布在EG的表面。综上所述，可以证实SnCoS4生长在膨胀石墨表面，并形成了紧密的纳米片结构网。
利用X射线光电子能谱（XPS）进一步研究了SnCoS4@EG中各元素的化学键态，见图3。Sn3d光谱中，以486.08 eV和494.48 eV为中心的2个峰分别归属于Sn3d5/2和Sn3d3/2，证明Sn以4价形式存在[17]。SnCoS4@EG的Co2p光谱在778.98 eV和796.48 eV处的峰可归因于Co2+的2p3/2和2p1/2，而在776.78 eV和793.88 eV处的峰与Co3+的2p3/2和2p1/2一致[18]，证实了Co2+和Co3+的存在；此外，在781.78 eV和801.88 eV探测到的2个弱峰属于Co的卫星峰[19]，证明CoS2的存在。对C1s拟合了3个峰，包括C—C（284.88 eV），C—O（286.28 eV）和（288.78 eV）键。SnCoS4@EG的S2p光谱位于160.88 eV、162.08 eV和163.38 eV的3个峰分别对应S2-、S22-和Sn2-的化学状态[20]。由此可以看出，成功制备了纯SnCoS4包覆在膨胀石墨表面的SnCoS4@EG结构，这种独特结构可以提高电池循环稳定性。
在扫描速度0.1 mV/s、电压0～3.0 V条件下对材料进行了CV测试，结果见图4。
从图4（a）～（b）可以看出，SnCoS4和SnCoS4@EG的CV曲线中均出现了氧化峰和还原峰，表明在充放电过程中均发生了氧化还原反应，说明SnCoS4和SnCoS4@EG反应机理几乎相同。在第1圈循环曲线中，SnCoS4电极在1.12 V和1.55 V处显示2个还原峰，这是由于锂离子插入SnCoS4中，形成了金属Co和Li2S合金。在0.10 V左右出现了一个还原峰与LixSn合金（0≤x≤4.4）和SEI膜的形成有关。位于0.55 V左右出现的氧化峰对应于Li-Sn的脱合金和Sn纳米颗粒或纳米晶体的重组，在1.15 V和1.50 V左右的2个氧化峰可能是Li2S合金的脱锂反应，总的反应为：
此外，第2圈和第3圈循环曲线基本重合，而第1圈循环曲线与后两圈未重合，这是因为第1圈循环过程中生成了SEI膜，发生了不可逆反应。SnCoS4@EG在第2圈和第3圈循环相较于纯SnCoS4重叠性更好，揭示了SnCoS4@EG具有更好的循环稳定性。
从图4（c）～（d）可以看出，初始充放电平台曲线与CV分析结果一致。由图4（d）可以看出，SnCoS4@EG电极的首次放电容量为1 741.96 mAh/g，远高于SnCoS4的相应值（1 197.49 mAh/g）。SnCoS4、SnCoS4@EG的首次库仑效率分别为53.56%、58.06%。第1圈循环的容量损失归因于SEI膜的不可逆形成和不完全转化反应[21]。在随后的循环中，库仑效率提高到94%以上。SnCoS4@EG第2圈和第3圈循环曲线重叠良好，表明SnCoS4@EG电极具有较高的可逆性。
不同材料的电化学性能测试结果见图5。由图5（a）可见，电流密度1 A/g时SnCoS4@EG电极具有优异的电化学性能，经过500次循环后可逆比容量仍有1 195.90 mAh/g；EG和SnCoS4循环500次后的可逆比容量仅为602.96 mAh/g和535.88 mAh/g。从图5（b）可以看出，电流密度0.1、0.2、0.5、1、2 A/g和5 A/g时，SnCoS4@EG的比容量分别为1 058.80、805.20、676.80、578.10、474.00 mAh/g和316.40 mAh/g，在相同条件下，EG的比容量分别为820.81、618.87、492.77、338.66、217.36 mAh/g和120.72 mAh/g，SnCoS4的比容量分别为798.50、568.00、452.40、353.90、262.00 mAh/g和117.80 mAh/g，均低于SnCoS4@EG复合材料。电流密度回归到0.2 A/g时，SnCoS4@EG的比容量回到696.00 mAh/g，证明SnCoS4@EG电极结构具有良好的可逆性。
采用图5（c）中的等效电路模型拟合阻抗参数，其中高频区域Z′轴截距表示欧姆电阻（Re），高频到中频的半圆对应电极反应的电荷转移阻抗（Rct），低频区斜直线对应低频区Li+的扩散过程。图5（d）中低频处的斜线表示Warburg阻抗[22]，拟合阻抗参数见表1。可以看出，SnCoS4@EG的Re和Rct明显低于SnCoS4，证明EG可以提高复合材料的导电性。另外，Li+的扩散系数（D（Li+））通过以下公式[9]计算：
式中：R为气体常数；T为绝对温度；A为电极面积；n为Li+的转移电子数，n=1；F为法拉第常数；c为锂离子质量浓度；σ为Warburg因子（可由式（3）拟合得到）。
表1中SnCoS4@EG的扩散系数明显高于EG和SnCoS4，表明其导电性更好。
SnCoS4@EG复合材料的循环性能测试结果见图6。
峰值电流（i）与扫描速率（v）的关系可通过式（5）进行量化，直线的斜率可通过对数计算进行拟合：
式中a和b均为可变常数。一般来说，b越接近1，电容行为越占主导地位。
图6（b）中，拟合的b值分别为0.83和0.89，表明电容起了重要作用。此外，使用式（6）进一步分析电容贡献的比例：
前一部分（k1v）为赝电容的贡献，后一部分（k1v1/2）为离子扩散控制的贡献。
如图6（c）～（d）阴影区域所示，扫描速率0.2、0.4、0.6、0.8 mV/s和1.0 mV/s时的电容贡献分别为56%、60%、65%、69%和74%，表明赝电容的贡献随着扫描速率增加而增加。
3　结论
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1）废旧锂离子电池负极石墨衍生的膨胀石墨EG呈现交联多孔的三维网格结构。
2）通过简单的水热法将锡/钴双金属硫化物负载在膨胀石墨上，形成了紧密的纳米片结构网，获得SnCoS4@EG纳米复合材料，该复合结构提高了金属硫化物的导电性和稳定性。
3）SnCoS4@EG复合材料在1 A/g电流密度下，经过500次长循环后，可逆比容量为1 195.90 mAh/g，具有优异的长循环稳定性。
基金
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  • 广西自然科学基金(2024GXNSFAA010515; 2022GXNSFAA035610)
  • 广西科技基地和人才专项(桂科AD23026038; 桂科AD23023008)
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2024年第44卷第5期
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doi: 10.3969/j.issn.0253-6099.2024.05.034
  • 接收时间：2024-04-30
  • 首发时间：2026-03-17
  • 出版时间：2024-10-01
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  • 收稿日期：2024-04-30
基金
广西自然科学基金(2024GXNSFAA010515; 2022GXNSFAA035610)
广西科技基地和人才专项(桂科AD23026038; 桂科AD23023008)
作者信息
    1.桂林电子科技大学　材料科学与工程学院，广西　桂林　541004
    2.贺州学院　广西碳酸钙资源综合利用重点实验室，广西　贺州　542899

通讯作者:

张晓辉（1985—），男，山东济宁人，博士，教授，主要研究方向为锂离子电池电极材料。E-mail：
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2种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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