CN109428072A - 复合电极材料及其制作方法、复合电极、以及锂电池 - Google Patents
复合电极材料及其制作方法、复合电极、以及锂电池 Download PDFInfo
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- CN109428072A CN109428072A CN201710831979.0A CN201710831979A CN109428072A CN 109428072 A CN109428072 A CN 109428072A CN 201710831979 A CN201710831979 A CN 201710831979A CN 109428072 A CN109428072 A CN 109428072A
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- combination electrode
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- carbon
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- 239000007772 electrode material Substances 0.000 title claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000002131 composite material Substances 0.000 title abstract 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 52
- 239000004917 carbon fiber Substances 0.000 claims abstract description 52
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 45
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 45
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 5
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000011149 active material Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000005229 chemical vapour deposition Methods 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 238000002955 isolation Methods 0.000 claims description 8
- 238000002230 thermal chemical vapour deposition Methods 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 7
- 238000005253 cladding Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 230000007246 mechanism Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 38
- 239000011162 core material Substances 0.000 description 23
- 239000010703 silicon Substances 0.000 description 23
- 239000011863 silicon-based powder Substances 0.000 description 15
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 14
- 239000003990 capacitor Substances 0.000 description 11
- 239000005543 nano-size silicon particle Substances 0.000 description 11
- 239000011856 silicon-based particle Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 229910021392 nanocarbon Inorganic materials 0.000 description 10
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 9
- 241000723346 Cinnamomum camphora Species 0.000 description 9
- 229960000846 camphor Drugs 0.000 description 9
- 229930008380 camphor Natural products 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
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- 238000006062 fragmentation reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- DSSYKIVIOFKYAU-XVKPBYJWSA-N (1s,4r)-4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical compound C1C[C@@]2(C)C(=O)C[C@H]1C2(C)C DSSYKIVIOFKYAU-XVKPBYJWSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PPOCFSJSVCAFQQ-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical compound C1CC2(C)C(=O)CC1C2(C)C.C1CC2(C)C(=O)CC1C2(C)C PPOCFSJSVCAFQQ-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- -1 NaCMC) Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- QSCAXGGEMZIPTH-UHFFFAOYSA-N cyclopenta-1,3-diene iron iron(2+) Chemical compound [CH-]1C=CC=C1.[CH-]1C=CC=C1.[Fe+2].[Fe] QSCAXGGEMZIPTH-UHFFFAOYSA-N 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000010291 electrical method Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011176 pooling Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4418—Methods for making free-standing articles
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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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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- 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
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- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
本发明提供了一种新颖的复合电极材料及其制作方法、使用此复合电极材料制得的复合电极、及包含此复合电极的锂电池,其中,本发明的复合电极材料包含:一核心,该核心的材料为至少一选自由Sn、Sb、Si、Ge、C、及其化合物所组成的群组;以及一纳米碳管或一碳纤维,其中,该纳米碳管或该碳纤维成长于一表面,该表面包括该核心的表面。
Description
技术领域
本发明涉及一种复合电极材料及其制作方法、包含该复合电极材料的复合电极、以及包含该复合电极的锂电池,尤其涉及一种以纳米碳管或碳纤维成长于硅表面并包覆的硅纳米颗粒作为复合电极材料及其制作方法、包含该复合电极材料的复合电极、以及包含该复合电极的锂电池。
背景技术
锂离子电池因具有高工作电压、高能量密度、高功率、存储寿命长、和多次充电和放电等优点,被视为现今最有效存储能源的方式之一。目前,商业上所使用的锂离子电池阳极材料大多为石墨,其理论电容值约为372mAhg-1,然而,因首次充电后表面会形成固态电解质膜(solid electrolyte interphase,SEI),造成不可逆的电容流失,因此实际上电容值会低于理论值。重复充电和放电的过程,也会造成层和层石墨结构间的缝隙,以致分离破碎,失去电容量。随着科技发展,单纯的石墨电极已无法符合大众需求。硅因具有高达4200mAhg-1的理论电容值,近年来尤其受到重视,然而,硅的充放电过程造成约高达420%的体积变化率,因此容易造成硅本身粉化(pulverization)碎裂,破碎硅之间失去导电性接触,导致锂离子无法顺利嵌入和脱嵌,电容量因而减少。同时,碎裂的硅所形成新的表面会消耗电解液并与之反应生成新的SEI膜,多次充放电后,电池内部电解液持续消耗并不断累积新的SEI膜,导致电池寿命缩短。
因此,目前急需要发展一种复合电极材料,还能克服重复充放电后带来的缺陷,以提升锂离子电池的电池寿命,也需要能拥有高电容值。
发明内容
本发明主要提供了一种新颖的复合电极材料及其制作方法、包含该复合电极材料的复合电极、以及包含该复合电极的锂电池。其中,本发明的新颖复合电极材料使用一种以纳米碳管(carbon nanotubes,CNT)或碳纤维(carbon fibers,CF)包覆的硅或以硅为主要成分的化合物的纳米颗粒,使锂电池经过多次充放电后仍能维持良好的电池容量、效率及循环寿命。
本发明提供了一种复合电极材料,包含:一核心,该核心的材料为至少一选自由Sn、Sb、Si、Ge、C、及其化合物所组成的群组;以及一纳米碳管或一碳纤维,其中,该纳米碳管或该碳纤维成长于一表面,该表面包含该核心的表面,该表面也可包含其他纳米碳管或碳纤维的表面,形成包覆核心的多孔洞三度空间的碳结构。
本发明提供了一种复合电极材料的制作方法,包含下列步骤:提供一核心,该核心的材料为至少一选自由Sn、Sb、Si、Ge、C、及其化合物所组成的群组;以一催化剂通过化学气相沉积法(chemical vapor deposition),于一表面成长一纳米碳管或一碳纤维,其中,该表面包括该核心的表面。
该纳米碳管或该碳纤维的表面,可通过该催化剂通过化学气相沉积法,再成长另一纳米碳管或另一碳纤维,形成包覆核心的多孔洞三度空间的碳结构。
在本发明的复合电极材料及其制作方法中,所使用的核心材料较佳为Si,如此可提供高电容值。核心的形状和大小并无特别限制,较佳为该核心为一扁平状颗粒,因扁平状硅颗粒较具弹性、可挠性,在充放电过程中不易破碎;且扁平状硅颗粒的表面积远小于将该扁平状硅颗粒碎裂后所形成的总体积相同的其他形状的多数硅颗粒,例如圆形、方形等,因此消耗用于硅表面形成SEI膜的电解液较少,有利延长电池寿命。核心的尺寸并无特别限制,其中该扁平状核心厚度可为50nm至500nm,较佳为50nm至250nm,和/或该核心长宽平均可为100nm至9μm,较佳为500nm至1200nm。
此外,该纳米碳管或该碳纤维垂直或以各种角度直立成长于该核心的表面,且多余的纳米碳管或碳纤维也可成长于其他纳米碳管或碳纤维上,形成包覆硅颗粒的纳米碳管或碳纤维的三度空间(3D)多孔(porous)网状或海绵状(sponge)结构。该3D多孔纳米碳管或碳纤维的结构具有多重、多方向膨胀收缩的缓冲功能,可以减少硅颗粒在充放电循环中因硅体积变化所导致的破碎。且因电子可以沿着导电的纳米碳管或碳纤维传导而提升传导路径的效率,因此即使硅颗粒在充放电循环中破碎成更小的颗粒,破碎颗粒上的纳米碳管或碳纤维也可提供额外所需的导电路径,使硅颗粒连接至相邻的硅颗粒及电池的集电器(current collector)。同时,纳米碳管或碳纤维也可保护硅避免其过度与电解液反应,可维持高电极容量及提升电池循环寿命。
在本发明的复合电极材料的制作方法中,该化学气相沉积法可包含:以一旋转或搅拌机构均匀混合,使纳米碳管或碳纤维更均匀地成长于各个核心上。在此,旋转或搅拌的速率无特殊限制,可依照所使用的旋转或搅拌机构而改变,只要能使纳米碳管或碳纤维可均匀成长于各个核心上即可。此外,该化学气相沉积法的实施条件并无特殊限制,可以依据所欲成长出的纳米碳管或碳纤维的外型及尺寸进行调整。
本发明的化学气相沉积法并无特别限制,可使用本领域已知的任何化学气相沉积法,例如热化学气相沉积法(thermal chemical vapor deposition)、等离子体辅助化学气相沉积法(plasma chemical vapor deposition)等,只要能使纳米碳管或碳纤维成长于各个核心上即可。
在本发明的一实施方案中,将二茂铁(ferrocene)蒸气渗透进硅纳米颗粒的间隙,覆盖在硅表面作为催化剂,再以樟脑(camphor)蒸气作为碳源渗透至附有二茂铁的硅纳米颗粒的间隙,通过热化学气相沉积法在硅纳米颗粒表面经催化剂协助下成长纳米碳管或碳纤维。本发明的另一实施方案中,预先均匀混合硅纳米颗粒及二茂铁粉末,并将其放入腔体(chamber)中使硅纳米颗粒镀上二茂铁,再将镀有二茂铁的硅纳米颗粒与樟脑粉末混合,在腔体中使纳米碳管或碳纤维成长于硅纳米颗粒上。本发明的另一实施方案中,硅纳米颗粒、二茂铁粉末、及樟脑粉末三者也可预先均匀混合,并将其放入腔体(chamber)中,在腔体中使纳米碳管或碳纤维成长于硅纳米颗粒上。
其中,可使用Fe、Mo、Ni、Pt、Co等来源作为催化剂,较佳为使用铁源作为催化剂;且更佳为室温下为固体,且具有低温下高挥发度的含铁源,在加热后可以气态方式存在于反应腔体中,例如氯化铁、二茂铁等,但本发明并不局限于此,只要能作为纳米碳管或碳纤维成长的催化剂即可。其中,本发明的碳源并无特别限制,可使用本领域已知的任何气体、固体、或液体碳源,例如甲烷、乙炔、樟脑等,只要能作为成长纳米碳管或碳纤维的碳源即可。较佳为室温下为固体,且具有低温下高挥发度的含碳源。
在本发明还提供了一种复合电极,包含:一基板,其上方设置一活性材料层,其中,该活性材料层包含:前述的复合电极材料、以及一粘着剂。
在本发明的复合电极中,基板可为一导电金属基板,其中,导电金属基板的材料并无特别限制,例如可为本技术领域常用的铜箔。且该铜箔的厚度亦无特别限制,可视需要进行调整。
在本发明的复合电极中,粘着剂并无特别限制,可为本领域常用的羧甲基纤维素钠(sodium carboxymethyl cellulose,NaCMC)、聚丙烯酸(poly acrylic acid,PAA)等,在本发明的一实施方案中,使用NaCMC作为粘着剂。
在本发明的复合电极中,复合电极材料由前述方法所制得,故在此不在赘述。
通常在制作硅基电极时,需要额外加入例如碳黑(carbon black)等辅助导电材料来帮助提升电子传导于硅颗粒之间和传导至集电器,然而,额外添加的碳黑会使电极增加更多的重量和体积,却不能像纳米碳管或碳纤维一样,提供硅颗粒体积膨胀收缩的缓冲功能。反之因为电子可以沿着纳米碳管或碳纤维传导,可以提供额外的导电路径,故在本发明的一实施例中,在制作复合电极时,即使不加入碳黑作为辅助导电路径,在定电容2000mAhg-1下,该复合电极经过100次的充放电仍能维持电容量,没有像未经成长纳米碳管或碳纤维的硅电极一样,电容量严重下降。
本发明还提供了一种锂电池,包含:前述的复合电极;一锂对电极;一隔离膜,设置于该复合电极与该锂对电极之间;以及一电解液,设置于该复合电极与该锂对电极之间,且设置于该隔离膜的两侧。
如前所述,本发明的复合电极材料具有一特殊结构,通过纳米碳管或碳纤维直接成长于该核心,并形成包覆硅纳米颗粒的3D多孔的纳米碳管或碳纤维,可缓冲核心材料充放电时的体积变化应力,且可避免核心与电解液过度反应,以提升电池的循环寿命,同时纳米碳管或碳纤维可以提供导电路径,使电子沿着纳米碳管或碳纤维传导而提升传导路径的效率,故在制作复合电极时,即使不加入碳黑也能维持良好的充放电特性。因此,本发明提供的锂电池具有高电池循环寿命及高电容量,在多次循环下仍具有良好的充放电特性及库伦效率。
附图说明
图1A及1B为本发明的一实施例的工艺示意图。
图2为本发明的另一实施例的工艺示意图。
图3A为本发明一较佳实施例的硅粉的SEM图。
图3B为本发明一较佳实施例的复合电极材料的SEM图。
图3C为本发明一较佳实施例的复合电极材料的拉曼光谱图。
图4为本发明一较佳实施例的锂电池的示意图。
图5A及5B为定电容下硅电极的充放电电容量与循环次数的关系图。
图6A及6B为定电容下复合电极的充放电电容量与循环次数的关系图。
图7A及7B为定电容且不添加碳黑下复合电极的充放电电容量与循环次数的关系图。
【符号说明】
100 | 热化学气相沉积*** | 1 | 腔体 |
11 | 第一区域 | 12 | 第二区域 |
2 | 硅粉 | 3 | 二茂铁 |
4 | 樟脑 | 5 | 锂电池 |
51 | 下金属盖 | 52 | 复合电极 |
53 | 隔离膜 | 54 | 锂对电极 |
55 | 金属垫片 | 56 | 金属弹簧 |
57 | 上金属盖 | 58 | 电解液 |
A | 气体通入方向 |
具体实施方式
以下通过特定的具体实施例说明本发明的实施方式,且以下具体实施例应被解释为仅仅是说明性的,而不以任何方式限制本说明书所揭示的其余部分,本领域的技术人员可由本说明书所揭示的内容轻易地了解本发明的其他优点与功效。本发明也可通过其他不同的具体实施例加以施行或应用,本说明书中的各项细节也可针对不同观点与应用,在不悖离本发明的精神下进行各种修饰与变更。
复合电极材料的制备-工艺1
图1A及1B为本实施例的工艺示意图。将厚度为100nm、长宽平均约850nm的硅粉2(1.86g)置于热化学气相沉积***100的第二区域12的腔体(chamber)1中,并将二茂铁3(3g)作为铁源置于腔体1的第一区域11中,先将腔体1抽至高真空后,再将氩气(600sccm,4分钟)以A方向回填腔体1,使腔体1维持于1大气压力。保持氩气(600sccm)从A方向通入下,开启高温炉确保第一区域11加热至约160℃、第二区域12加热至约850℃,使二茂铁3分解挥发,铁颗粒可以以蒸汽方式渗透到硅粉2间隙之间,沉积时间约为15分钟,最后关闭高温炉,并将腔体1冷却至室温,以获得沉积铁及铁化合物的硅粉。接着将樟脑4(13g)作为碳源置于第一区域11,再次将腔体1抽至真空,并将氩气(600sccm,4分钟)以A方向回填至1大气压。保持氩气(600sccm)从A方向通入下,开启高温炉加热第一区域11至约160℃、第二区域12加热至约850℃,使樟脑分解挥发,碳源(樟脑)可以渗透到硅粉之间以成长纳米碳管或碳纤维,沉积时间约为15-60分钟,最后关闭高温炉,将腔体冷却至室温,获得纳米碳管或碳纤维包覆的硅纳米颗粒。在本发明的另一实施方案中,可在第二区域12设置一旋转或搅拌机构(图未示)均匀混合,使纳米碳管或碳纤维更均匀地成长于该核心上。
复合电极材料的制备-工艺2
图2为本实施例的工艺示意图。将厚度为100nm、长宽平均约850nm的硅粉2(1.86g)、二茂铁3(3g)、及樟脑4(13g)置于热化学气相沉积***100的腔体1中,将腔体稀释去除腔体内的空气,以氩气或氮气从A方向回填腔体至约1大气压力后,关闭腔体的气体的入口和出口。开启高温炉加热腔体至约850℃,使二茂铁3、及樟脑4挥发,并保留气相二茂铁、及樟脑在腔体内,在铁源(二茂铁)催化下于硅粉上成长纳米碳管或碳纤维,沉积时间约为30分钟。最后关闭高温炉,将腔体冷却至室温,获得纳米碳管或碳纤维包覆的硅纳米颗粒。在本发明的另一实施方案中,可以设置一旋转或搅拌机构(图未示)以均匀混合硅粉2、二茂铁3、及樟脑4三者,使纳米碳管或碳纤维更均匀地成长于该核心上。
在前述的工艺1及工艺2中,在常压下成长纳米碳管或碳纤维。成长纳米碳管或碳纤维的气压不限,在本发明的其他实施方案中,也可在低真空,例如1Torr至1000Torr压力、或较高气压下成长纳米碳管或碳纤维。
复合电极材料
图3A为本实施例的硅粉的SEM图,其中,使用厚度约100nm、长宽平均约850nm的硅粉,且具有不规则外型。图3B为本实施例的复合电极材料的SEM图,由图中可明显看出通过热化学气相沉积后的硅粉,具有纳米碳管或碳纤维直立成长于硅粉上。图3C为本实施例的复合电极材料的拉曼光谱图,其为使用绿光雷射(λ=532nm)的拉曼光谱分析,从图中可看到1346cm-1的D带、1575cm-1的G带、以及证明硅表面成长纳米碳管或碳纤维的2682cm-1的2D带。通过上述实验结果证实,本实施例的复合电极材料确实具有纳米碳管或碳纤维成长于硅粉上。
复合电极的制备
将前述制得的本发明的复合电极材料、导电碳黑、粘着剂NaCMC以重量比6∶3∶1混合,加入去离子水,以直流搅拌机搅拌至均匀,制成活性材料。将搅拌均匀的活性材料放入真空腔中抽至低压,使内部的气泡去除,接着使用刮刀将30μm厚的活性材料涂布至10μm的铜箔上,以获得一电极。将涂布完的电极放入真空烘箱抽至真空,并在65℃下烘烤8-12小时以移除多余溶剂。待降温后,以滚压机滚压烘烤完的电极,以提升电极的封装密度。最后以裁刀裁出所需要的电极大小。在本发明的一实施方案中,用于制备复合电极的活性材料可不包含导电碳黑。本发明的涂布活性材料厚度及滚压施加的压力不限于本实施例。
锂半电池的制备
图4为本实施例的锂电池5的示意图。在此,将前述所制得的复合电极(作为阳极)52、一下金属盖51、一锂对电极54、一隔离膜(Celgard2352)53、一金属垫片55、一金属弹簧56、一上金属盖57置于一手套箱中,并使用溶于EC/DEC(1∶1v/v)的1M的LiPF6溶液作为电解液58,依据图4依序组装成钮扣型电池,使用电池封装机将电池密封,以形成本实施例的锂半电池。然而此实施例仅为例示性的说明,本发明的锂半电池并不局限于此。
如图4所示,本实施例的锂电池包含:如前述所制得的复合电极52;一锂对电极54;一隔离膜53,设置于该复合电极52与该锂对电极54之间;以及一电解液58,设置于该复合电极52与该锂对电极54之间,且设置于该隔离膜53的两侧。
循环充放电分析
本实施例使用定电流充放电法,前三圈的充放电速率为0.02C,之后充放电速率改为0.1C完成整个试验。复合电极材料和复合电极由前述方法所制得,故在此不再赘述。
图5A和5B分别为硅电极在定电容1200mAhg-1及2000mAhg-1下的电容量与循环次数的关系图。由图5A可发现硅电极在1200mAhg-1定电容下,可以充放电循环80圈;若将电容提高至2000mAhg-1,硅电极仅能维持10圈的充放电循环,如图5B。
图6A和6B分别为复合电极在定电容1200mAhg-1及2000mAhg-1下的电容量与循环次数的关系图。由图6A及6B可看出,复合电极不管是在低电容1200mAhg-1或高电容2000mAhg-1下,均能稳定维持100圈的充放电循环。证明具有纳米碳管或碳纤维成长的硅粉可以缓冲硅粉于充放电时的体积膨胀收缩,减少硅粉破碎的发生,因而延长循环寿命。
图7A和7B分别为本发明的另一实施例的复合电极在定电容1200mAhg-1及2000mAhg-1下的电容量与循环次数的关系图。其中,本实施例的用于制备复合电极的活性材料不包含导电碳黑,其余复合电极材料和复合电极由前述方法所制得,故在此不再赘述。一般在制作电极的活性材料时,会加入导电碳黑作为导电途径,然而由实验结果可以发现,本实施例的复合电极即使不加入导电碳黑,在高电容下仍然可维持100圈的充放电循环。因此证明纳米碳管或碳纤维确实可以提供额外的导电路径,而提升传导路径的效率。
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (19)
1.一种复合电极材料,包含:
一核心,该核心的材料为至少一选自由Sn、Sb、Si、Ge、C、及其化合物所组成的群组;以及
一纳米碳管或一碳纤维,
其中,该纳米碳管或该碳纤维成长于一表面,该表面包含该核心的表面。
2.如权利要求1所述的复合电极材料,其中,该纳米碳管或该碳纤维直立成长于该表面。
3.如权利要求1所述的复合电极材料,其中,该核心为一扁平状颗粒。
4.如权利要求1所述的复合电极材料,其中,该核心厚度为50nm至500nm。
5.如权利要求1所述的复合电极材料,其中,该核心长宽平均为100nm至9μm。
6.如权利要求1所述的复合电极材料,其中,该纳米碳管或该碳纤维具有包覆该核心的3D多孔网状或海绵状结构。
7.一种复合电极材料的制作方法,包含下列步骤:
提供一核心,该核心的材料为至少一选自由Sn、Sb、Si、Ge、C、及其化合物所组成的群组;以及
以一催化剂通过一化学气相沉积法,于一表面成长一纳米碳管或一碳纤维,
其中,该表面包含该核心的表面。
8.如权利要求7所述的制作方法,其中,该化学气相沉积法包含:以一旋转或搅拌机构均匀混合。
9.如权利要求7所述的制作方法,其中,该化学气相沉积法为热化学气相沉积法。
10.如权利要求7所述的制作方法,其中,该催化剂为一铁源催化剂。
11.如权利要求7所述的制作方法,其中,该纳米碳管或该碳纤维直立成长于该表面。
12.如权利要求7所述的制作方法,其中,该核心为一扁平状颗粒。
13.如权利要求7所述的制作方法,其中,该核心厚度为50nm至500nm。
14.如权利要求7所述的制作方法,其中,该核心长宽平均为100nm至9μm。
15.如权利要求7所述的复合电极材料,其中,该纳米碳管或该碳纤维具有包覆该核心的3D多孔网状或海绵状结构。
16.一种复合电极,包含:
一基板,其上方设置一活性材料层,其中,该活性材料层包含:一如权利要求1至6任一所述的复合电极材料、以及一粘着剂。
17.如权利要求16所述的复合电极,其中,该基板为一导电金属板。
18.如权利要求16所述的复合电极,其中,该复合电极不包含碳黑。
19.一种锂电池,包含:
一如权利要求16至18任一所述的复合电极;
一锂对电极;
一隔离膜,设置于该复合电极与该锂对电极之间;以及
一电解液,设置于该复合电极与该锂对电极之间,且设置于该隔离膜的两侧。
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