CN106848273B - 一种硅碳复合材料的制备方法 - Google Patents
一种硅碳复合材料的制备方法 Download PDFInfo
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- CN106848273B CN106848273B CN201710039430.8A CN201710039430A CN106848273B CN 106848273 B CN106848273 B CN 106848273B CN 201710039430 A CN201710039430 A CN 201710039430A CN 106848273 B CN106848273 B CN 106848273B
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000011856 silicon-based particle Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 239000005543 nano-size silicon particle Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 238000005202 decontamination Methods 0.000 claims description 7
- 230000003588 decontaminative effect Effects 0.000 claims description 7
- 238000002242 deionisation method Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 238000005554 pickling Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 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 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052743 krypton Inorganic materials 0.000 claims description 3
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052704 radon Inorganic materials 0.000 claims description 3
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- 239000002585 base Substances 0.000 description 5
- 229920002307 Dextran Polymers 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
- 206010016766 flatulence Diseases 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 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
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002409 silicon-based active material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
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- 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
- H01M4/364—Composites as mixtures
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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- H01—ELECTRIC ELEMENTS
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- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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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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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
一种硅碳复合材料的制备方法,包括以下步骤:步骤一:制备碳包覆纳米硅基氧化物;分别称取硅颗粒和碳源水溶液以硅碳摩尔比为5‑15:1的比例混合均匀成悬浮液;转移至容器中,在第一预设温度下水热反应第一预设时间后冷却至室温后取出,经水洗后真空干燥,制备出碳包覆纳米硅基氧化物;步骤二:制备硅碳复合材料;将步骤一得到的碳包覆纳米硅基氧化物与金属镁粉以质量比为1:0.6‑1.6的比例研磨混合形成混合物,然后将混合物混入无机盐中;将以上混合好的混合物及无机盐装入容器,且置于惰性气体下,在预设升温速率的情况下上升至第二预设温度,保持第二预设时间后冷却取出清洗除去杂质,再真空干燥即可得到硅碳复合材料。
Description
【技术领域】
本发明涉及锂电池负极材料技术领域,尤其涉及一种硅碳复合材料的制备方法。
【背景技术】
目前锂电池已广泛应用于3C数码、电动汽车的电力储能系统等方面。电力储能系统要求锂电池有更高的能量密度和更好的循环寿命,同时要求低成本且具有良好的安全性。然而传统锂电池的石墨基负极材料的理论质量比容量仅为372mAh/g,导致电池的重量能量密度较低,难以满足当前的要求。而非碳负极材料主要是具有高储锂性能的金属或合金类材料。其中,硅因具有较大的嵌锂比容量(常温下理论比容量可达约3600mAh/g)和嵌锂电位低(<0.5V)等特点而成为研究的热点。但是以硅为代表的金属或合金类材料的储锂原理是合金化过程,在脱嵌锂过程中会伴随着较大的体积变化效应,由其产生的较大的机械作用力会使硅活性材料粉化,并在多次循环后使电池电极活性材料与集流体间的脱落,引起电接触的减弱;并且体积变化效应导致硅在常规电解液中难以形成稳定的电解质界面膜(SEI膜),每次嵌脱锂后新暴露的硅界面上新的SEI膜会大量消耗锂离子和电解液,导致充放电效率降低,整体容量和循环性能迅速下降。而常规的制备硅材料的方法,如金属热还原二氧化硅,采用葡萄糖、石墨、石墨烯等碳源包覆已制好的纳米硅颗粒及采用化学气相沉积法等多步构架结构的碳/硅材料等,从材料本身的角度分析,面临着诸如纳米颗粒团聚,分布不均,体积膨胀效应难以彻底解决等问题,导致锂电池的实际循环性能差。
鉴于以上所述,实有必要提供一种新型的一种硅碳复合材料的制备方法来克服以上缺陷。
【发明内容】
本发明的目的是提供一种硅碳复合材料的制备方法,不仅能保证硅的高容量发挥,而且具有良好的充放电性能及循环性能。另外,应用本发明实施例制备的硅碳复合材料,颗粒均一,有利于电子和锂离子的快速脱嵌,提高电化学性能。
为了实现上述目的,本发明提供一种硅碳复合材料的制备方法,包括以下步骤:
步骤一:制备碳包覆的纳米硅基氧化物;
①分别称取一定量的硅颗粒和碳源的水溶液以硅碳摩尔比为5-15:1的比例混合均匀成悬浮液;
②转移至容器中,在第一预设温度下水热反应第一预设时间后冷却至室温后取出,经水洗和无水乙醇洗涤后真空干燥,制备出碳包覆的纳米硅基氧化物;步骤一中的所述第一预设温度为:180℃-220℃,所述第一预设时间为:3h-8h;
步骤二:制备硅碳复合材料;
①将步骤一得到的碳包覆的纳米硅基氧化物与金属镁粉以质量比为1:0.6-1.6的比例研磨混合形成混合物,然后将混合物混入在无机盐中;
②将以上混合好的混合物及无机盐装入容器,且放置于惰性气体下,在预设升温速率的情况下上升至第二预设温度,保持第二预设时间后冷却取出;所述第二预设温度为:400℃-700℃,所述第二预设时间为:5h-15h;
③依次用一定量的盐酸洗、去离子水洗、氢氟酸浸泡、去离子水洗除去杂质,再真空干燥即可得到硅碳复合材料。
具体的,步骤一中的所述硅颗粒为:一氧化硅或二氧化硅,所述硅颗粒的粒径为:50nm-200nm。
具体的,步骤一中的所述碳源的水溶液为葡萄糖溶液、蔗糖溶液、柠檬酸溶液、马来酸溶液及石墨烯分散液中的任意一种,所述碳源的水溶液的浓度为:0.1mol-1mol/L,所述石墨烯分散液的固含量为:0.3%-5%。
具体的,步骤二中的所述无机盐为无水氯化钠、无水氯化钾、无水氯化铝及无水氯化镁的一种或多种混合,所述混合物和无机盐的质量比为1:10-20。
具体的,步骤二中的所述预设升温速率为:3℃-5℃/min。
具体的,步骤二中的所述惰性气体为氮气、氖气、氩气、氪气、氙气及氡气中的一种。
与现有技术相比,本发明提供的一种硅碳复合材料的制备方法,不仅能保证硅的高容量发挥,而且具有良好的充放电性能及循环性能。另外,应用本发明实施例的制备的硅碳复合材料,颗粒均一,有利于电子和锂离子的快速脱嵌,提高电化学性能。
【附图说明】
图1为本发明实施例2制备的硅碳复合材料的XRD衍射谱图。
图2为本发明实施例2制备的硅碳复合材料的SEM图。
图3为本发明实施例2制备的硅碳复合材料在0.1C倍率下的充放电曲线图。
图4为本发明实施例2制备的硅碳复合材料在0.1C倍率下的循环曲线图。
【具体实施方式】
为了使本发明的目的、技术方案和有益技术效果更加清晰明白,以下结合附图和具体实施方式,对本发明进行进一步详细说明。应当理解的是,本说明书中描述的具体实施方式仅仅是为了解释本发明,并不是为了限定本发明。
本发明提供一种硅碳复合材料的制备方法,包括以下步骤:
步骤一:制备碳包覆的纳米硅基氧化物。
①分别称取一定量的硅颗粒和碳源的水溶液以硅碳摩尔比为5-15:1的比例混合均匀成悬浮液;
②转移至容器中,在第一预设温度下水热反应第一预设时间后冷却至室温后取出,经水洗和无水乙醇洗涤后真空干燥,制备出碳包覆的纳米硅基氧化物;步骤一中的所述第一预设温度为:180℃-220℃,所述第一预设时间为:3h-8h。
步骤二:制备硅碳复合材料。
①将步骤一得到的碳包覆的纳米硅基氧化物与金属镁粉以质量比为1:0.6-1.6的比例研磨混合形成混合物,然后将混合物混入在无机盐中;
②将以上混合好的混合物及无机盐装入容器,且放置于惰性气体下,在预设升温速率的情况下上升至第二预设温度,保持第二预设时间后冷却取出;所述第二预设温度为:400℃-700℃,所述第二预设时间为:5h-15h。
③依次用一定量的盐酸洗、去离子水洗、氢氟酸浸泡、去离子水洗除去杂质,再真空干燥即可得到硅碳复合材料。
具体的,步骤一中的所述硅颗粒为:一氧化硅或二氧化硅,所述硅颗粒的粒径为:50nm-200nm。
具体的,步骤一中的所述碳源的水溶液为葡萄糖溶液、蔗糖溶液、柠檬酸溶液、马来酸溶液及石墨烯分散液中的任意一种,所述碳源的水溶液的浓度为:0.1mol-1mol/L,所述石墨烯分散液的固含量为:0.3%-5%。
具体的,步骤二中的所述无机盐为无水氯化钠、无水氯化钾、无水氯化铝及无水氯化镁的一种或多种混合,所述混合物和无机盐的质量比为1:10-20。
具体的,步骤二中的所述预设升温速率为:3℃-5℃/min。
具体的,步骤二中的所述惰性气体为氮气、氖气、氩气、氪气、氙气及氡气中的一种。
实施例:
实施例1:
①称取5.00g的SiO2颗粒搅拌分散于40mL去离子水中,加入1.51g葡萄糖颗粒水合物后搅拌均匀混合,转移到50mL的容器中,在180℃温度下水热反应4h后冷却至室温后取出,经水洗后真空干燥,制备出碳包覆的SiO2;
②将碳包覆纳米硅基氧化物及金属镁粉以质量比为1:0.88的比例研磨混合形成混合物,然后将混合物混入无水氯化钠和无水氯化钾的混合无机盐(1:1wt%)中,所述碳包覆纳米硅碳基氧化物、金属镁粉及混合无机盐的质量比为1:0.88:20,接着将混合好的混合物及无机盐装入容器中,且放置于惰气体性中,在3℃/min的升温速率下升至700℃,保持10h后冷却取出,并依次用一定量的盐酸洗、去离子水洗、氢氟酸浸泡、去离子水洗除去杂质后,再真空干燥即可得到硅碳复合材料。
实施例2:
①称取5.00g的SiO2颗粒搅拌分散于40mL去离子水中,加入1.70g葡萄糖颗粒水合物后搅拌混合均匀,转移到50mL的容器中,在190℃温度下水热反应6h后冷却至室温后取出,经水洗后真空干燥,制备出碳包覆的纳米SiO2;
②将碳包覆的纳米SiO2及金属镁粉以质量比为1:0.84的比例研磨混合形成混合物,然后将混合物混入无水氯化钠和无水氯化镁的混合无机盐(1:1.23wt%)中,所述碳包覆纳米硅碳基氧化物、金属镁粉及混合无机盐的质量比为1:0.84:20,接着将混合好的混合物及无机盐装入容器中,且放置于惰气体性中,在3℃/min的升温速率下升至650℃,保持8h后冷却取出,并依次用一定量的盐酸洗、去离子水洗、氢氟酸浸泡、去离子水洗除去杂质后,再真空干燥即可得到硅碳复合材料。
实施例3:
①称取5.00g的SiO2颗粒搅拌分散于40mL去离子水中,加入1.95g葡萄糖颗粒水合物后搅拌混合均匀,转移到50mL的容器中,在200℃温度下水热反应5h后冷却至室温后取出,经水洗后真空干燥,制备出碳包覆的纳米SiO2;
②将碳包覆纳米SiO2及金属镁粉以质量比为1:1的比例研磨混合形成混合物,然后将混合物混入无水氯化钠和氯化铝的混合无机盐(1:2.79wt%)中,所述碳包覆纳米硅碳基氧化物、金属镁粉及混合无机盐的质量比为1:1:20,接着将混合好的混合物及无机盐装入容器中,且放置于惰气体性中,在5℃/min的升温速率下升至550℃,保持10h后冷却取出,依次用一定量的盐酸洗、去离子水洗、氢氟酸浸泡、去离子水洗除去杂质后,再真空干燥即可得到硅碳复合材料。
实施例4:
①称取5.00g的纳米SiO2搅拌分散于40mL去离子水中,加入2.27g葡萄糖颗粒水合物后搅拌混合均匀,转移到50mL的容器中,在200℃下水热反应6h后冷却至室温后取出,经水洗后真空干燥,制备出碳包覆的纳米SiO2;
②将碳包覆纳米SiO2及金属镁粉以质量比为1:0.84的比例研磨混合形成混合物,然后将混合物混入无水氯化钠和无水氯化镁的混合无机盐(1:1.23wt%)中,所述碳包覆纳米硅碳基氧化物、金属镁粉及混合无机盐的质量比为1:0.84:20,接着将混合好的混合物及无机盐装入容器中,且放置于惰气体性中,在3℃/min的升温速率下升至650℃,保持10h后冷却取出,依次用一定量的盐酸洗、去离子水洗、氢氟酸浸泡、去离子水洗除去杂质后,再真空干燥即可得到硅碳复合材料。
本发明硅碳复合材料实施例1-4的各项性能参数如下表1:
表1
图1为本发明实施例2制备的硅碳复合材料的XRD衍射谱图;图2为本发明实施例2制备的硅碳复合材料的SEM图;图3为本发明实施例2制备的硅碳复合材料在0.1C倍率下的充放电曲线图;图4为本发明实施例2制备的硅碳复合材料在0.1C倍率下的循环曲线图。
由图1-图4可知,硅碳复合材料的颗粒均一,且整体有一定的空隙通道,有利于电子和锂电子的快速脱嵌;硅碳复合材料在0.1V左右的电压平台主要对应硅的放电反应,硅碳复合材料的首周放电容量达2800mAh/g,在100周循环后充电容量仍保持在1600mAh/g,且100周循环内的库伦效率维持在100%左右,性能良好。
综上所述,本发明提供的一种硅碳复合材料的制备方法,不仅能保证硅的高容量发挥,而且具有良好的充放电性能及循环性能。另外,应用本发明实施例的制备的硅碳复合材料,颗粒均一,有利于电子和锂离子的快速脱嵌,提高电化学性能。
本发明并不仅仅限于说明书和实施方式中所描述,因此对于熟悉领域的人员而言可容易地实现另外的优点和修改,故在不背离权利要求及等同范围所限定的一般概念的精神和范围的情况下,本发明并不限于特定的细节、代表性的设备和这里示出与描述的图示示例。
Claims (6)
1.一种硅碳复合材料的制备方法,其特征在于,包括以下步骤:
步骤一:制备碳包覆的纳米硅基氧化物;
①分别称取一定量的硅颗粒和碳源的水溶液以硅碳摩尔比为5-15:1的比例混合均匀成悬浮液;
②转移至容器中,在第一预设温度下水热反应第一预设时间后冷却至室温后取出,经水洗和无水乙醇洗涤后真空干燥,制备出碳包覆的纳米硅基氧化物;步骤一中的所述第一预设温度为:180℃-220℃,所述第一预设时间为:3h-8h;
步骤二:制备硅碳复合材料;
①将步骤一得到的碳包覆的纳米硅基氧化物与金属镁粉以质量比为1:
0.6-1.6的比例研磨混合形成混合物,然后将混合物混入在无机盐中;
②将以上混合好的混合物及无机盐装入容器,且放置于惰性气体下,在预设升温速率的情况下上升至第二预设温度,保持第二预设时间后冷却取出;所述第二预设温度为:400℃-700℃,所述第二预设时间为:
5h-15h;
③依次用一定量的盐酸洗、去离子水洗、氢氟酸浸泡、去离子水洗除去杂质,再真空干燥即可得到硅碳复合材料。
2.根据权利要求1所述的硅碳复合材料的制备方法,其特征在于:步骤一中的所述硅颗粒为:一氧化硅或二氧化硅,所述硅颗粒的粒径为:50nm-200nm。
3.根据权利要求1所述的硅碳复合材料的制备方法,其特征在于:步骤一中的所述碳源的水溶液为葡萄糖溶液、蔗糖溶液、柠檬酸溶液、马来酸溶液及石墨烯分散液中的任意一种,所述碳源的水溶液的浓度为:0.1mol-1mol/L,所述石墨烯分散液的固含量为:0.3%-5%。
4.根据权利要求1所述的硅碳复合材料的制备方法,其特征在于:步骤二中的所述无机盐为无水氯化钠、无水氯化钾、无水氯化铝及无水氯化镁的一种或多种混合,所述混合物和无机盐的质量比为1:10-20。
5.根据权利要求1所述的硅碳复合材料的制备方法,其特征在于:步骤二中的所述预设升温速率为:3℃-5℃/min。
6.根据权利要求1所述的硅碳复合材料的制备方法,其特征在于:步骤二中的所述惰性气体为氮气、氖气、氩气、氪气、氙气及氡气中的一种。
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CN102157731B (zh) * | 2011-03-18 | 2015-03-04 | 上海交通大学 | 一种锂离子电池硅碳复合负极材料及其制备方法 |
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CN103165862B (zh) * | 2013-03-22 | 2015-10-21 | 浙江瓦力新能源科技有限公司 | 一种高性能锂离子电池负极材料及其制备方法 |
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WO2015180189A1 (zh) * | 2014-05-30 | 2015-12-03 | 西安交通大学 | 一种碳负载的纳米硅颗粒结构及其制备方法和应用 |
CN104466185A (zh) * | 2014-11-12 | 2015-03-25 | 中国科学院深圳先进技术研究院 | 硅/碳复合负极材料及其制备方法、锂离子电池及其负极 |
CN104681798B (zh) * | 2015-02-12 | 2017-12-08 | 中南大学 | 一种锂离子电池硅基复合负极材料的制备方法 |
CN107710464B (zh) * | 2015-06-15 | 2020-10-02 | 罗伯特·博世有限公司 | 多孔硅颗粒及生产硅颗粒的方法 |
CN105140487B (zh) * | 2015-09-10 | 2017-05-10 | 中天储能科技有限公司 | 一种锂离子电池负极材料硅碳复合物及其制备方法 |
CN105576209B (zh) * | 2016-02-04 | 2017-11-24 | 中南大学 | 一种高容量锂离子电池硅基负极材料及其制备方法、锂离子电池 |
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CN106099113B (zh) * | 2016-06-30 | 2019-07-02 | 中南大学 | 一种核壳结构硅碳复合材料及其制备方法 |
CN106328909B (zh) * | 2016-11-18 | 2020-01-24 | 深圳市贝特瑞新能源材料股份有限公司 | 纳米二氧化硅-硅基复合材料、制备方法及包含该复合材料的锂离子电池 |
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