CN111029538B - 一种碳包覆硅复合硅酸盐材料及其制备方法和应用 - Google Patents
一种碳包覆硅复合硅酸盐材料及其制备方法和应用 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 52
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 52
- 239000010703 silicon Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 12
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- 238000000034 method Methods 0.000 claims description 12
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- YTHCQFKNFVSQBC-UHFFFAOYSA-N magnesium silicide Chemical compound [Mg]=[Si]=[Mg] YTHCQFKNFVSQBC-UHFFFAOYSA-N 0.000 claims description 5
- 229910021338 magnesium silicide Inorganic materials 0.000 claims description 5
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- 239000011261 inert gas Substances 0.000 claims description 4
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 claims description 3
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- JUZTWRXHHZRLED-UHFFFAOYSA-N [Si].[Cu].[Cu].[Cu].[Cu].[Cu] Chemical compound [Si].[Cu].[Cu].[Cu].[Cu].[Cu] JUZTWRXHHZRLED-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910021360 copper silicide Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920000779 poly(divinylbenzene) Polymers 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
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- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 229910021332 silicide Inorganic materials 0.000 claims description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
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- 238000001291 vacuum drying Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
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- FSBVERYRVPGNGG-UHFFFAOYSA-N dimagnesium dioxido-bis[[oxido(oxo)silyl]oxy]silane hydrate Chemical compound O.[Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O FSBVERYRVPGNGG-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 239000002210 silicon-based material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010661 Li22Si5 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- FZXTYMGSDGWHLI-UHFFFAOYSA-N O.[Si].[Fe] Chemical compound O.[Si].[Fe] FZXTYMGSDGWHLI-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/386—Silicon or alloys based on silicon
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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Abstract
本发明公开了一种碳包覆硅复合硅酸盐材料及其制备方法和应用,材料的制备方法为:将金属硅化合物和碳源加入溶剂中搅拌混匀,超声分散后得到前驱体溶液,前驱体溶液放置到高温反应釜中,经过烧结得到碳包覆硅复合硅酸盐材料。本发明利用金属硅化合物作为前驱体,实现了硅酸盐在硅颗粒内部合成,可以有效缓解硅的体积膨胀;并且通过碳包覆可显著地增强材料的导电性,增加库伦效率。本制备方法简单,对环境无污染,适合工业化大规模生产。本发明还公开了所述碳包覆硅复合硅酸盐材料在锂离子电池中的应用,其可作为锂离子电池的负极材料,从而在电池电极、超级电容器及后端新能源电动汽车领域中具有广阔的应用前景。
Description
技术领域
本发明涉及复合材料技术领域,尤其涉及一种碳包覆硅复合硅酸盐材料及其制备方法和应用。
背景技术
锂离子电池因其具有工作电压高、比能量高、容量大、自放电小、循环性好、使用寿命长、重量轻、体积小等突出优点而成为移动电话、笔记本电脑、汽车等的理想电源。为了满足使用要求,高容量、长寿命锂离子电池成为锂离子电池发展的一个重要研究方向。
随着新能源电动汽车的发展以及国家政策的推动,市场对高能量密度锂离子电池的需求也日益增加。传统石墨作为锂电池负极,对其的研发已接近其理论比容量372mAh/g,很难满足未来需求。因此寻找替代碳的高容量负极材料成为一个重要的研究方向。
相比于传统石墨在嵌入锂之后形成LiC6插层化合物,硅作为负极材料,通常与锂合金化形成Li22Si5金属间化合物,其理论比容量达3572mAh/g。
但硅作为锂离子电池负极材料也有缺点:硅材料在脱嵌锂离子的过程中,会使材料体积发生300%以上的膨胀与收缩,重复破坏和生成新的SEI膜;产生的机械作用力会使材料逐渐粉化,造成结构坍塌,最终导致电极活性物质与集流体脱离,丧失电接触,导致电池循环性能大大降低;且硅是半导体材料,自身的电导率较低。
由于硅自身存在的缺陷,严重制约硅负极材料的产业化道路。为适应现代社会对高容量、高密度锂离子电池的需要,需采用很多技术用来改善硅负极材料的上述缺陷。
发明内容
基于背景技术存在的技术问题,本发明的目的是提供一种碳包覆硅复合硅酸盐材料及其制备方法和应用,本发明利用金属硅化合物作为前驱体,实现了硅酸盐在硅颗粒内部生成,并通过对材料进行碳包覆,有效提高了材料的导电性,缓解了在充放电过程中硅的体积膨胀,能有效降低锂电池充放电极化,提高锂电池的容量、寿命和倍率性能;且制备方法简便、操作容易、易实现规模化生产。
为实现上述目的,本发明采用的技术方案为:
一种碳包覆硅复合硅酸盐材料的制备方法,包括如下步骤:将金属硅化合物和碳源加入溶剂中搅拌混匀,超声分散后得到前驱体溶液,将前驱体溶液放置到高温反应釜中,在惰性气体氛围下,烧结得到碳包覆硅复合硅酸盐材料。
进一步方案,所述金属硅化合物为硅化铝、硅化镁、硅化铁或硅化铜中的至少一种。
进一步方案,所述碳源为柠檬酸、葡萄糖、纤维素、蔗糖、糖、糖聚合物、多糖、聚酰亚胺、聚丙烯腈、聚苯乙烯、聚二乙烯基苯、聚乙烯基吡啶、聚吡咯、聚噻吩、聚苯胺中的至少一种。
进一步方案,所述金属硅化合物中硅元素的含量与碳源中的碳元素的含量的质量比为1:2-50。
进一步方案,所述溶剂为乙醇、甲醇中的至少一种。
进一步方案,所述烧结为梯度烧结,首先在200-500℃烧结2-5h后,升温至700-1000℃,继续烧结2-24h;所述升温的速度为2.5-5℃/min。
进一步方案,所述超声的功率为100W-300W,超声的时间为0.5-4h。
进一步方案,所述惰性气体为氮气、氦气、氖气、氩气、氪气和氙气中的至少一种。
本发明的第二个目的是提供上述所述的制备方法制得的碳包覆硅复合硅酸盐材料。
本发明的第三个目的是提供上述所述的碳包覆硅复合硅酸盐材料在锂离子电池中的应用。所述碳包覆硅复合硅酸盐材料可作为锂离子电池的负极材料。从而在电池电极、超级电容器及后端新能源电动汽车领域中具有广阔的应用前景。
本发明具有如下有益效果:
(1)本发明通过将金属硅化合物和碳源分散在溶剂中混合后梯度烧结,使得碳均匀的包覆在硅复合硅酸盐材料表面且无团聚;
(2)本发明利用金属硅化合物作为前驱体,实现了硅酸盐在硅颗粒内部合成,硅酸盐作为缓冲层,在提高电池首效的同时可以有效缓解硅的体积膨胀。
(3)本发明碳包覆硅复合硅酸盐材料的碳包覆层薄且均匀,可与显著地增强硅材料的导电性的同时,也增加了库伦效率;
(4)本发明采用的金属硅化合物和碳源原料,均为常用的化工原料,具有价格低廉、无毒无害的优点,工艺简单,适合大规模的工业化生产。
(5)用本发明制作电池电极,应用在电池负极等物质中时,提高了充放电比容量和首效,并且具有更加稳定的循环性能,在电池电极、超级电容器及后端新能源电动汽车领域中具有广阔的应用前景。
附图说明
图1为实施例1制备的碳包覆硅复合硅酸盐材料的SEM图片;
图2为实施例1制备的碳包覆硅复合硅酸盐材料的XRD图片;
图3为实施例1制备的碳包覆硅复合硅酸盐材料以及商业SiO制成的扣式电池的首次充放电曲线。
具体实施方式
下面结合实施例对本发明作更进一步的说明。显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
一种碳包覆硅复合硅酸盐材料的制备方法,包括如下步骤:将1mol硅化镁加入200ml甲醇中,再加入0.008mol的葡萄糖,经磁力搅拌1h,超声0.5h分散均匀得到前驱体溶液;将前驱体溶液倒入高压反应釜中并放入管式炉中,在氮气氛围中,以5℃/min的速度升温至200℃,烧结2h,再以5℃/min的速度升温至700℃,烧结2h,然后取出用去离子水交替洗涤3次至中性,于80℃真空干燥24h得到碳包覆硅复合硅酸盐材料。
结果分析
取实施例1制得的碳包覆硅复合硅酸盐材料进行电子显微镜扫描,结果参见图1,图1为本发明制备的碳包覆硅复合硅酸盐材料的SEM图片。由图1可以看出碳均匀的包覆在硅复合硅酸盐表面,呈块状结构。在硅复合硅酸盐表面均匀包覆碳可以有效的提高材料的电导率和缓解体积膨胀。
取实施例1制得的碳包覆硅复合硅酸盐材料进行XRD扫描,结果参见图2,图2为本发明制备的碳包覆硅复合硅酸盐材料的XRD图片。由图2可以看出出现了硅酸镁和碳的XRD峰,说明材料存在一定量的硅酸镁,同时表面包覆了碳。
实施例2
一种碳包覆硅复合硅酸盐材的制备方法,包括如下步骤:将1mol硅化镁加入200ml甲醇中,再加入0.008mol的葡萄糖,经磁力搅拌1h,超声0.5h分散均匀得到前驱体溶液;将前驱体溶液倒入高压反应釜中并放入管式炉中,在氮气氛围中,以5℃/min的速度升温至300℃,烧结2h,再以5℃/min的速度升温至1000℃,烧结2h,然后取出用去离子水交替洗涤3次至中性,于80℃真空干燥24h得到碳包覆硅复合硅酸盐材料。
实施例3
一种碳包覆硅复合硅酸盐材料的制备方法,包括如下步骤:将1mol硅化镁加入200ml甲醇中,再加入0.016mol葡萄糖,经磁力搅拌1h,超声0.5h分散均匀得到前驱体溶液;将前驱体溶液倒入高压反应釜中并放入管式炉中,在氮气氛围中,以3℃/min的速度升温至300℃,烧结2h,再以3℃/min的速度升温至700℃,烧结12h,然后取出用去离子水交替洗涤3次至中性,于80℃真空干燥24h得到碳包覆硅复合硅酸盐材料。
实施例4
一种碳包覆硅复合硅酸盐材料的制备方法,包括如下步骤:将1mol硅化铝加入200ml乙醇中,再加入0.01ml聚丙烯腈,经磁力搅拌1h,超声4h分散均匀得到前驱体溶液;将前驱体溶液倒入高压反应釜中并放入管式炉中,在氩气氛围中,以5℃/min的速度升温至300℃,烧结3h,再以2.5℃/min的速度升温至700℃,烧结4h,然后取出用去离子水交替洗涤3次至中性,于60℃真空干燥48h得到碳包覆复合硅酸盐材料。
实施例5
一种碳包覆硅复合硅酸盐材料的制备方法,包括如下步骤:将1mol硅化铁水合物加入200ml乙醇中,再加入0.015mol聚吡咯,经磁力搅拌1h,超声2h分散均匀得到前驱体溶液;将前驱体溶液倒入高压反应釜中并放入管式炉中,在空气氛围中,以2.5℃/min的速度升温至250℃,烧结2.5h,再以5℃/min的速度升温至900℃,烧结3h,然后取出用去离子水交替洗涤3次至中性,于70℃真空干燥36h得到碳包覆硅复合硅酸盐材料。
应用例1
试验组:将实施例1制得的碳包覆硅复合硅酸盐材料、导电剂super-p、粘结剂CMC+SBR按质量比8:1:1混合均匀涂敷于铜箔上制作成电极片;接着将通过压片得到的负极膜片在110℃恒温干燥箱中干燥24h,再于80℃下真空干燥12h,并用冲头冲成直径为12mm的极片转入真空手套箱中备用。扣式锂离子电池的组装是以金属锂片作负极,以(LiPF6/EC+EMC+DMC)作电解液,以上述直径为12mm的极片为正极极片,全部操作均在手套箱中进行;记作试验组扣式锂离子电池。
常温恒温箱中,0.1C充放电检测试验组扣式锂离子电池的性能,结果参见图3,图3为用本发明制备的碳包覆硅复合硅酸盐材料组装成的扣式电池在电压区间为0.05-1.5V条件下的首次充放电曲线。从图3中可看出:由普通SiO制成的电池首次放电比容量为1011.15mAh/g充电比容量为1180.7mAh/g首次库伦效率仅为85.64%。而由碳包覆硅复合硅酸盐材料制成的电池首次放电比容量为1407.61mAh/g充电比容量为1586.73mAh/g首次库伦效率88.71%;可知与商业SiO制成的扣式电池相比,由本发明制备得到的材料组装成的电池的容量明显提高,表现出较高的首次库伦效率和首次充电比容量,这对于提高电池的容量和首次库伦效率具有很大的意义。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (8)
1.一种碳包覆硅复合硅酸盐材料的制备方法,其特征在于:包括如下步骤:将金属硅化合物和碳源加入溶剂中搅拌混匀,超声分散后得到前驱体溶液,将前驱体溶液放置到高温反应釜中,在惰性气体氛围下,烧结得到碳包覆硅复合硅酸盐材料;
所述碳源为柠檬酸、糖、聚酰亚胺、聚丙烯腈、聚苯乙烯、聚二乙烯基苯、聚乙烯基吡啶、聚吡咯、聚噻吩、聚苯胺中的至少一种;
所述烧结为梯度烧结,首先在200-500℃烧结2-5h后,升温至700-1000℃,继续烧结2-24h;所述升温的速度为2.5-5℃/min。
2.根据权利要求1所述的制备方法,其特征在于:所述金属硅化合物为硅化铝、硅化镁、硅化铁或硅化铜中的至少一种。
3.根据权利要求1所述的制备方法,其特征在于:所述金属硅化合物中硅元素的含量与碳源中的碳元素的含量的质量比为1:2-50。
4.根据权利要求1所述的制备方法,其特征在于:所述溶剂为乙醇、甲醇中的至少一种。
5.根据权利要求1所述的制备方法,其特征在于:超声的功率为100W-300W,超声的时间为0.5-4h。
6.根据权利要求1所述的制备方法,其特征在于:所述惰性气体为氮气、氦气、氖气、氩气、氪气和氙气中的至少一种。
7.如权利要求1-6任一所述的制备方法制得的碳包覆硅复合硅酸盐材料。
8.如权利要求7所述的碳包覆硅复合硅酸盐材料在锂离子电池中的应用。
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