CN117293286A - 硅碳预锂复层负极材料及其制备方法与应用 - Google Patents
硅碳预锂复层负极材料及其制备方法与应用 Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 167
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 239000002131 composite material Substances 0.000 title claims abstract description 79
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000010405 anode material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002153 silicon-carbon composite material Substances 0.000 claims abstract description 37
- 239000002086 nanomaterial Substances 0.000 claims abstract description 32
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000002210 silicon-based material Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 238000000265 homogenisation Methods 0.000 claims abstract description 8
- 238000007709 nanocrystallization Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 32
- 239000002052 molecular layer Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 7
- -1 alO 2 Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 4
- 229910018091 Li 2 S Inorganic materials 0.000 claims description 4
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 claims description 4
- 229910010093 LiAlO Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000001165 hydrophobic group Chemical group 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940080818 propionamide Drugs 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
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- 229910052786 argon Inorganic materials 0.000 description 3
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- 238000010586 diagram Methods 0.000 description 3
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- 239000011261 inert gas Substances 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 239000011866 silicon-based anode active material Substances 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
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- 239000012530 fluid Substances 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007908 dry granulation Methods 0.000 description 1
- 238000009760 electrical discharge machining Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011871 silicon-based negative electrode active material Substances 0.000 description 1
- 229910021435 silicon-carbon complex Inorganic materials 0.000 description 1
- 239000011867 silicon-carbon complex material Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005550 wet granulation Methods 0.000 description 1
Classifications
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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Abstract
本申请提供一种硅碳预锂复层负极材料的制备方法,包括以下步骤:对硅料进行纳米化得到纳米硅,向纳米硅中加入碳基材及高分子聚合物进行均质化处理,得到硅碳复合体;提供一预锂纳米材料;将硅碳复合体和预锂纳米材料混合后进行造粒,得到硅碳预锂复层前驱体;对所述硅碳预锂复层前驱体进行烧结,得到硅碳预锂复层负极材料。本申请还提供一种硅碳预锂复层负极材料及包括其的电池。本申请提供的硅碳预锂复层负极材料的比容量和循环性能大幅提升。
Description
技术领域
本发明涉及电池技术领域,尤其涉及一种硅碳预锂复层负极材料及其制备方法及包括该硅碳预锂复层负极材料的电池。
背景技术
目前,锂离子电池的预锂技术是提升电池能量密度和循环寿命的重要方法。预锂技术分为正极预锂及负极预锂。正极预锂化主要通过在正极中加入富锂氧化物,以补充首次活化过程中的锂源损失。而负极预锂化,主要通过将锂源如锂金属薄膜压制在负极活性物质层的表面上从而将锂离子嵌入负极活性物质中。这种方法虽然可以通过降低硅基负极活性材料的初始不可逆性来提高寿命,但是在锂源预锂化到硅基负极活性材料的过程中会有大量的副产物产生。同时,导电率低的氧化锂几乎只在硅基负极活性材料的表面产生,因此该方法减少不可逆性是有限度的。
现有技术的预锂方法,只能实现在首次活化中,对负极进行一次性补充以改善首次充电时造成的活性锂损失。但是,在一次性预锂后,大部分预锂材料,会以一种惰性物质的形式存在电池中,降低了整体能量密度和功率密度。所以,一次性预锂方法,对于锂离子电池在持续使用过程中,因为充放电循环所产生的锂损失,无法进行有效的补充,达不到循环中持续补充的效果。目前的解决方式主要是在负极预存一部分锂源,在循环过程中,随着锂的损失而逐步释放,但该方法在首次充电过程中存在极大的热失控风险。然同时,由于硅基负极活性材料在充放电过程中,不可避免会发生体积膨胀,造成固态电解质界面(SEI)反复形成,也会消耗电池体系内的锂量。
发明内容
有鉴于此,确有必要提供一种硅碳预锂复层负极材料的制备方法,以制备一种硅碳预锂复层负极材料,实现提高电池的容量及循环稳定性。
一种硅碳预锂复层负极材料的制备方法,所述制备方法包括以下步骤:对硅料进行纳米化得到纳米硅,向纳米硅中加入碳基材及高分子聚合物进行均质化处理,得到硅碳复合体;提供一预锂纳米材料;将硅碳复合体和预锂纳米材料混合后进行造粒,得到硅碳预锂复层前驱体;对所述硅碳预锂复层前驱体进行烧结,得到硅碳预锂复层负极材料。
一种硅碳预锂复层负极材料,所述硅碳预锂复层负极材料包括硅碳复合体及包覆在所述硅碳复合体表面的预锂纳米层,所述硅碳复合体包括纳米硅、高分子聚合物和碳基材;所述预锂纳米层包括一种或多种含锂化合物LiyM,其中,M为B、Si、Ge、Sn、N、O、F、Cl、I、S、P、AlO2、TiO2中的至少一种。
一种电池,包括正极极片、负极极片和隔膜,所述负极极片包括上述所述的硅碳预锂复层负极材料。
与现有技术相比,本发明的有益效果为:通过采用硅碳复合材料和预锂纳米材料混合均质后进行造粒和烧结的步骤,得到预锂纳米层包覆硅碳复合体的复合结构。该预锂纳米层可形成稳固的SEI膜,并提供硅材料体积膨胀时需要的缓冲空间,同时,所述预锂纳米层作为富锂相还可进行锂源补给,从而使得所述硅碳预锂复层负极材料的比容量和循环性能大幅提升。
附图说明
图1为本发明提供的硅碳复合体和预锂纳米材料的造粒示意图。
图2为本发明提供的硅碳预锂复层负极材料的结构示意图。
图3为实施例1制备的硅碳预锂复层负极材料与单质硅的X射线衍射图。
图4为实施例1制备的硅碳预锂复层负极材料的扫描电镜图。
主要元件符号说明
硅碳预锂复层负极材料 100
硅碳复合体 10
预锂纳米层 20
如下具体实施例将结合上述附图进一步说明本发明。
具体实施方式
除非另有定义,本文所使用的所有的技术和科学术语与属于本申请实施例的技术领域的技术人员通常理解的含义相同。本文中所使用的术语只是为了描述具体的实施方式的目的,不是旨在于限制本申请实施例。
另外,在本申请中如涉及“第一”“第二”等的描述仅用于描述目的,而不能理解为指示或暗示其相对重要性或者隐含指明所指示的技术特征的数量。由此,限定有“第一”“第二”的特征可以明示或者隐含地包括至少一个该特征。在本申请的描述中,“多个”的含义是至少两个,例如两个,三个等,除非另有明确具体的限定。
下面结合附图,对本申请的一些实施方式作详细说明。在不冲突的情况下,下述的实施方式及实施方式中的特征可以相互组合。
本发明实施例提供一种硅碳预锂复层负极材料的制备方法,包括以下步骤:
步骤S1,对硅料进行纳米化得到纳米硅,向纳米硅中加入碳基材及高分子聚合物进行均质化处理,得到硅碳复合体;
步骤S2,提供一预锂纳米材料;
步骤S3,将硅碳复合体和预锂纳米材料混合后进行造粒,得到硅碳预锂复层前驱体;
步骤S4,对所述硅碳预锂复层前驱体进行烧结,烧结温度为500℃~1200℃,得到硅碳预锂复层负极材料。
上述步骤编号S1~S4仅是为了以下说明方便,并非限定步骤的先后顺序。此外,各步骤之间,亦可依所需包含其他步骤。
在步骤S1中,所述硅料可选择半导体等级的硅料,硅料的尺寸可选择微米等级,如大于等于10微米。纳米化的实现方式包括但不限于机械加工、机械球磨等,机械球磨可为干磨或湿磨。
所述纳米化的过程需要在保护性的环境中进行。其中,所述保护性的环境可为真空环境,或者所述保护性的环境可由通入惰性气体或者加入溶剂获得。所述惰性气体包括氩气(Ar)、氮气(N2)或氦气(He)中的至少一种。所述惰性气体可提供无氧环境,防止纳米硅被氧化,使后续制备出的硅碳预锂复层负极材料基本上无SiOx,有利于提升硅碳预锂复层负极材料的电化学性能和降低体积效应。所述溶剂可为二甘醇(DEG)、聚乙二醇(PEG)、丙二醇(PG)、二甲基亚砜(DMSO)或其组合。所述溶剂能防止纳米硅被氧化,使制备出的硅碳预锂复层负极材料基本上无SiOx,有利于提升硅碳预锂复层负极材料的电化学性能和降低体积效应。所述纳米硅的晶粒尺寸为10纳米-50纳米。将硅料纳米化后有利于与碳基材的均质化处理,并利于后续制备出合适粒径的硅碳预锂复层负极材料,以适合二次电池的制浆工艺。
所述高分子聚合物为两性高分子,同时具有疏水基和亲水基。所述高分子聚合物可为N-烯丙基-(2-乙基黄原酸基)丙酰胺(NAPA)、二甲基甲酰胺(DMF)或其组合。具体地,所述高分子聚合物是一种介质,含有例如氨基和羟基等。所述高分子聚合物一端具有亲水基和另一端具有疏水基的特性,能够改善纳米硅与碳基材之间的亲水性与疏水性差异。本实施例中,所述高分子聚合物中具有亲水基的一端与纳米硅键结,具有疏水基的一端与碳基材键结,从而使得纳米硅牢固地被包覆在碳基材上,且不容易与另外的纳米硅发生团聚。
所述碳基材可为沥青、石墨、石墨烯、碳黑、碳纳米管、纳米纤维等。在均质化处理过程中,颗粒逃逸现象会引发放热反应,所述碳基材可进行热扩散,避免发生团聚,并避免纳米硅因为放热现象而被氧化。
所述均质化处理可以是但不限于机械加工、放电加工或机械球磨等。其中,机械球磨可以是干磨或湿磨。所述均质化处理使得纳米硅、高分子聚合物和碳基材完成有序堆栈自组装包覆,得到层状的硅碳复合体。
在步骤S2中,所述预锂纳米材料(LiyM)可为Li5B4、Li22Si5、Li22Sn5、Li22Ge5、Li3N、Li2O、LiF、LiCl、LiI、Li2S、Li3PO4、LiAlO2、Li2TiO3等。优选地,所述预锂纳米材料为Li3N。进一步,所述预锂纳米材料可通过对锂原料和活性物进行混合后合成得到。所述锂原料可为氧化锂(Li2O)、锂粉、氢氧化锂(LiOH)、硝酸锂(LiNO3)、碳酸锂(LiCO3)等中的至少一种。所述活性物可为B、Si、Ge、Sn、N、O、F、Cl、I、S、P、AlO2、TiO2中的至少一种。根据选择的活性物的种类,即可得到相应的预锂纳米材料。
所述锂原料和活性物的合成反应需要在密封环境中进行。进一步,在所述密封环境中还可通入氮气或氩气进行内循环以用于散热。具体地,所述合成反应是在密封环境中将锂原料和活性物混合后进行研磨加工实现。经过研磨得到的所述预锂纳米材料的粒径为纳米级粒径,优选地,所述预锂纳米材料的粒径小于硅碳复合体的粒径,以易于在造粒过程中包覆在硅碳复合体上。进一步,在研磨过程中可加入溶剂以用于散热。所述溶剂可为己烷、庚烷、辛烷等烷烃类溶剂。所述溶剂可在反应后经真空干燥去除。
在步骤S3中,所述硅碳复合体和预锂纳米材料混合均匀后造粒,以制备出能用于后续制浆的实心球。具体地,所述预锂纳米材料与硅碳复合体的质量比为1%-5%。
所述造粒工艺包括但不限于二流体造粒、四流体造粒、旋风造粒、喷雾造粒、干式造粒或湿式造粒。请参阅图1,将硅碳复合体和预锂纳米材料均匀混合后,经过造粒工艺,所述预锂纳米材料在所述硅碳复合体的表面形成一稳定的膜层。所述预锂纳米材料形成的膜层包覆在所述硅碳复合体的表面,形成均匀的实心球结构,从而得到硅碳预锂复层前驱体。在所述造粒工艺中,造粒的温度和压差等造粒条件可根据需要进行调节控制,以防止预锂纳米材料在造粒过程中发生逸散。
造粒后,得到的所述硅碳预锂复层前驱体的粒径为5微米至15微米,以适合于现在锂二次电池制浆工艺的大小,同时也可避免后续烧结过程中的团聚。
在步骤S4中,所述烧结过程需要在保护性气氛下或低真空环境下进行,以增加所述预锂纳米材料作为包覆层的致密性及完整性。所述保护性气氛可为氮氢混合气氛。所述烧结温度为500℃~1200℃。
本发明实施例还提供一种硅碳预锂复层负极材料。请参阅图2,所述硅碳预锂复层负极材料100包括硅碳复合体10及包覆硅碳复合体10的预锂纳米层20。所述硅碳复合体10包括纳米硅、高分子聚合物和碳基材。在一个实施方式中,所述硅碳复合体10是由纳米硅、高分子聚合物和碳基材形成的复合结构。其中,所述纳米硅通过所述高分子聚合物键结在所述碳基材上,使得所述纳米硅被牢固地包覆在所述碳基材上,同时防止纳米硅颗粒之间发生团聚。所述预锂纳米层20包括一种或多种含锂化合物LiyM。其中,M为B、Si、Ge、Sn、N、O、F、Cl、I、S、P、AlO2、TiO2中的至少一种。所述含锂化合物LiyM的实例包含但不限于Li5B4、Li22Si5、Li22Sn5、Li22Ge5、Li3N、Li2O、LiF、LiCl、LiI、Li2S、Li3PO4、LiAlO2、Li2TiO3等。所述预锂纳米层20可以在所述硅碳复合体的表面形成稳固的SEI膜,并能在电池循环过程中进行锂源补给,含鋰化合物LiyM中的M是一种预留空位作为嵌锂使用,还可提供硅材料体积膨胀时需要的缓冲空间,从而使得负极材料的循环性能大幅提升。同时,由于所述硅碳预锂复层负极材料100中采用纳米化的硅,硅在纳米化后可有效降低首次因为锂嵌入硅而产生的应力效应。
本发明实施例还提供一种电池,包括正极极片、负极极片和隔膜,所述负极极片包括所述硅碳预锂复层负极材料。所述电池可为二次电池,例如锂离子二次电池、钠离子电池等,但并不限于此。
本申请提供的所述硅碳预锂复层负极材料的制备方法,通过采用硅碳复合材料和预锂纳米材料混合均质后进行造粒和烧结的步骤,得到预锂纳米层包覆硅碳复合体形成的复合结构。该预锂纳米层可在表面形成稳固的SEI膜,并提供硅材料体积膨胀时需要的缓冲空间,同时,所述预锂纳米层作为富锂相还可进行锂源补给,从而使得所述硅碳预锂复层负极材料的循环性能大幅提升。本申请提供的所述硅碳预锂复层负极材料,具有高的比容量(>1600mAh g-1)、所述硅碳预锂复层负极材料形成的半电池的法拉第效率可达90%以上及高的循环稳定性。
以下将结合具体实施例对本申请进行进一步说明。
实施例1
S1:将半导体等级的硅料(≥10μm)和二甘醇及5wt%高分子聚合物N-烯丙基-(2-乙基黄原酸基)丙酰胺放入研磨机中进行机械加工,其中,所述研磨机的转速为2400~3000rpm,所述硅料被加工成纳米硅,所述纳米硅的晶粒尺寸为15~50纳米;再添加10wt%片状天然石墨的碳基材,通过有序堆栈自组装工艺,使得纳米硅复合在碳基材表面,得到硅碳复合体。
S2:将符合LiyB原子比例的Li2O和B粉置于氩封环境内进行研磨加工,并加入辛烷作为散热溶剂,转速为2400~3000rpm,研磨24小时后取出并进行真空干燥,得到预锂纳米材料。
S3:将硅碳复合体与1%的LiyB预锂纳米材料进行混合均质处理,再进行共同造粒,得到硅碳预锂复层前驱体。
S4:将所述硅碳预锂复层前驱体放入含有氮氢混合气的烧结炉中,气体流速为2L/min,温度为550℃下热处理8小时,得到硅碳预锂复层负极材料。
请参阅图3,由实施例1制备的硅碳预锂复层负极材料与单质硅的XRD(X-RayDiffraction)图进行对比可知,所述硅碳预锂复层负极材料中硅的特征峰与单质硅的特征峰相同,并没有硅氧化物的特征峰,表明实施例1制备的硅碳预锂复层负极材料中的硅仍以单质硅的形式存在,而没有被氧化。
图4为实施例1制备的硅碳预锂复层负极材料的扫描电镜图,从图中可以看出,实施例1制备的硅碳预锂复层负极材料的颗粒表面光滑且覆层紧密,颗粒的比表面积得以有效控制,这说明通过本申请的均质、研磨、造粒工艺可得到尺寸合适的颗粒且颗粒表面得到有效的预锂纳米层的保护。
将实施例1制备的预锂纳米层为LiyB的硅碳预锂复层负极材料记为样品1,再根据实施例1的制备方法分别制备出预锂纳米层为LiySi的硅碳预锂复层负极材料和预锂纳米层为LiyN的硅碳预锂复层负极材料,并分别记为样品2和样品3。将不含预锂纳米层的硅碳负极材料作为对比例,并记为样品4。分别将四份样品与导电剂和黏结剂按照质量比88:1:11溶解在水中得到混合物,调配成固含量为50%的浆料。将所述浆料涂覆在铜箔集流体上并真空干燥以获得负极极片。然后采用常规生产工艺组装三元正极极片、锂盐浓度为1mol/L的电解液(组成为LiPF6/EC+DMC+EMC)、Celgard2400隔膜进行软包电池堆叠及5Ah组装。由样品1组装得到的电池记为电池1,由样品2组装得到的电池记为电池2,由样品3组装得到的电池记为电池3,由样品4组装得到的电池记为电池4。将电池1、电池2、电池3和电池4分别进行如下性能测试。
负极锂离子引出容量测试:电流密度0.1C、电压下降到2.0V,然后根据以下公式进行负极课电容量换算,得到引出容量。
上述性能测试结果请见表1。
表1
由表1可知,本申请制备方法所制备的硅碳预锂复层负极材料组装得到的电池,其引出容量和引出容量保持率都明显高于没有预锂复层的负极材料制备的电池,这表明本申请制备的含预锂纳米层的硅碳预锂复层负极材料提升了电池的导电性和循环稳定性。
本申请提供的硅碳预锂复层负极材料,由于预锂纳米材料LiyM可在硅碳复合体表面形成稳固的SEI膜,并可以在电池循环过程中,进行锂源补给,且还能够提供硅材料体积膨胀时需要的缓冲空间,从而使得硅碳预锂复层负极材料的循环性能大幅提升。同时,M可作为预留空位嵌锂使用,而且当硅碳预锂复层负极发生体积变化时,能够作为缓冲。本申请提供的硅碳预锂复层负极材料的制备方法工艺简单,易于控制流程,适合工业化生产。
另外,本领域技术人员还可在本发明精神内作其它变化,当然这些依据本发明精神所作的变化,都应包含在本发明所要求保护的范围内。
Claims (10)
1.一种硅碳预锂复层负极材料的制备方法,所述制备方法包括以下步骤:
对硅料进行纳米化得到纳米硅,向纳米硅中加入碳基材及高分子聚合物进行均质化处理,得到硅碳复合体;
提供一预锂纳米材料;
将硅碳复合体和预锂纳米材料混合后进行造粒,得到硅碳预锂复层前驱体;
对所述硅碳预锂复层前驱体进行烧结,得到硅碳预锂复层负极材料。
2.如权利要求1所述的硅碳预锂复层负极材料的制备方法,其特征在于,所述碳基材包括沥青、石墨、石墨烯、碳黑、碳纳米管、纳米纤维中的至少一种。
3.如权利要求1所述的硅碳预锂复层负极材料的制备方法,其特征在于,所述高分子聚合物具有疏水基和亲水基,所述高分子聚合物包括N-烯丙基-(2-乙基黄原酸基)丙酰胺、二甲基甲酰胺中的至少一种。
4.如权利要求1所述的硅碳预锂复层负极材料的制备方法,其特征在于,所述纳米硅的晶粒尺寸为10纳米-50纳米。
5.如权利要求1所述的硅碳预锂复层负极材料的制备方法,其特征在于,所述预锂纳米材料为Li5B4、Li22Si5、Li22Sn5、Li22Ge5、Li3N、Li2O、LiF、LiCl、LiI、Li2S、Li3PO4、LiAlO2、Li2TiO3中的至少一种。
6.如权利要求1所述的硅碳预锂复层负极材料的制备方法,其特征在于,所述预锂纳米材料与硅碳复合体的质量比为1%-5%。
7.如权利要求1所述的硅碳预锂复层负极材料的制备方法,其特征在于,所述硅碳预锂复层前驱体是由所述预锂纳米材料包覆在所述硅碳复合体的表面形成的实心球结构,所述硅碳预锂复层前驱体的粒径为5微米至15微米。
8.一种硅碳预锂复层负极材料,其特征在于,所述硅碳预锂复层负极材料包括硅碳复合体及包覆在所述硅碳复合体表面的预锂纳米层,所述硅碳复合体包括纳米硅、高分子聚合物和碳基材;所述预锂纳米层包括一或多种含锂化合物LiyM,其中,M为B、Si、Ge、Sn、N、O、F、Cl、I、S、P、AlO2、TiO2中的至少一种。
9.如权利要求8所述的硅碳预锂复层负极材料,其特征在于,所述含锂化合物LiyM为Li5B4、Li22Si5、Li22Sn5、Li22Ge5、Li3N、Li2O、LiF、LiCl、LiI、Li2S、Li3PO4、LiAlO2、Li2TiO3中的至少一种。
10.一种电池,包括正极极片、负极极片和隔膜,其特征在于,所述负极极片包括权利要求8或9所述的硅碳预锂复层负极材料。
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