CN112072098A - 一种锂电池用纳米管状硅基材料及其制备方法 - Google Patents
一种锂电池用纳米管状硅基材料及其制备方法 Download PDFInfo
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- 239000002210 silicon-based material Substances 0.000 title claims abstract description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 25
- 239000002070 nanowire Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000012298 atmosphere Substances 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000012686 silicon precursor Substances 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 9
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052734 helium Inorganic materials 0.000 claims description 8
- 239000001307 helium Substances 0.000 claims description 8
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 6
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- 239000010703 silicon Substances 0.000 claims description 6
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000378 calcium silicate Substances 0.000 claims description 4
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 4
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
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- 239000001257 hydrogen Substances 0.000 claims description 4
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- 239000011701 zinc Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 239000003502 gasoline Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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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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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
本发明公开了一种锂电池用纳米管状硅基材料及其制备方法，属于锂电池材料技术领域。其是先将金属纳米线分散于溶剂中，然后加入硅的前驱体，经搅拌、干燥、保护气氛下煅烧后，于酸溶液中搅拌反应一定时间，再经过滤、洗涤、干燥制得所述锂电池用纳米管状硅基材料。本发明所得纳米管状硅基材料在锂电池充放电过程中的体积膨胀较小，因而具有较好的稳定性。
Description
技术领域
本发明属于锂电池材料技术领域，具体涉及一种锂电池用纳米管状硅基材料及其制备方法。
背景技术
将硅基材料用作锂电池负极材料，可大幅提高锂电池的容量。1摩尔硅可与3.6摩尔的锂离子复合形成Li3.6Si化合物，这使得锂电池的理论容量可达1820 mA·g-1。但高纯度的Si材料在充放电过程中易发生膨胀而导致破碎、分解，最终破坏电池结构，导致其失效。
发明内容
本发明的目的在于提供一种锂电池用纳米管状硅基材料及其制备方法。
为实现上述目的，本发明采用如下技术方案：
一种锂电池用纳米管状硅基材料的制备方法，其包括以下步骤：
1）将金属纳米线分散于溶剂中；
2）将硅的前驱体加入到步骤1）所得的溶液中，搅拌一段时间；
3）将步骤2）所得产物过滤后进行干燥；
4）将步骤3）烘干后的产物置于保护气氛下煅烧一定时间，之后冷却；
5）将步骤4）所得产物置于酸溶液中搅拌一定时间，过滤、洗涤并干燥后，即得所述纳米管状硅基材料。
步骤1）所述纳米线金属包括铝、铜、铅、锌、锡、钴、镍、铁、铬、锰、锑、镉、铋、钛、锆、铪、钒、铌、钽、钨、钼、镓、铟、铊、锗、铼中的一种或者几种。
步骤1）中所述溶剂为水、甲醇、乙醇、乙二醇、异丙醇、丙三醇、正丁醇、糠醇、乙醚、汽油、柴油中的一种或几种。
步骤2）中所加入的硅的前驱体与金属纳米线的质量比为1:1~10。所述硅的前驱体为正硅酸四乙酯、硅酸钙、硅烷偶联剂、硅酸钠、硅酮、氟硅酸或偏硅酸铝中的一种或几种。
步骤2）中搅拌的时间为60~120 min。
步骤4）中所述保护气氛包括氢气、氮气、氦气、氩气、一氧化碳、二氧化碳中的一种或几种；所述煅烧的温度为400~600℃，时间为10~24 h。
步骤5）中所述酸溶液为盐酸、硫酸、磷酸、硝酸、硒酸、碲酸、高氯酸、次氯酸中一种或几种的水溶液，其浓度为0.1~3 mol/L；用量按酸与金属元素的摩尔比为10~30:1进行换算；
搅拌的时间为10~24 h。
操作中所述干燥是于真空或惰性保护气氛下进行，干燥的温度为80~110 ℃，时间为10~24 h；所述惰性保护气氛包括氮气、氦气、氩气中的一种或几种。
本发明的有益效果在于：
本发明将氧化硅包裹在金属纳米线表面，并经煅烧及酸处理，使金属原子进入氧化硅内部而与硅原子和氧原子发生相互作用，从而使所得硅基材料可有效解决高纯度的硅材料在锂电池充放电过程中体积膨胀的问题，提高了电池的稳定性。
附图说明
图1为本发明实施例1所得纳米管状硅基材料的扫描电镜图。
图2为本发明实施例1所得纳米管状硅基材料制备的锂电池的充放电曲线。
图3为本发明实施例1所得纳米管状硅基材料制备的锂电池的充放电循环次数图。
图4为本发明实施例1-6所得纳米管状硅基材料制备的锂电池各充放电循环100次的性能曲线。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
实施例1
1）参照文献“Roll-to-roll-compatible, flexible, transparent electrodesbased on self-nanoembedded Cu nanowires using intense pulsed lightirradiation.”（ Z. Y. Zhong, K. Woo, I. Kim, H. Hwang, S. Kwon, Y.-M. Choi, Y.Lee, T.-M. Lee, K. Kim, J. Moon. Nanoscale 8 (2016) 8995-9003.）制备铜纳米线，其直径为10 nm，长度为150 nm；将制得的铜纳米线分散于10 mL水中；
2）将氟硅酸加入到步骤1）所得的溶液中，搅拌60 min，其中氟硅酸与铜纳米线的质量比为1:1；
3）将步骤2）所得产物过滤后于氮气氛围下80 ℃干燥24 h；
4）将步骤3）烘干后的产物置于氢气气氛下400℃煅烧24 h，之后冷却；
5）将步骤4）所得产物置于浓度为0.1 mol/L的盐酸溶液中搅拌24 h（所用盐酸与铜元素的摩尔比为10:1），过滤、洗涤，然后于氮气氛围下80 ℃干燥24 h，即得所述纳米管状硅基材料。
图1为所得纳米管状硅基材料的扫描电镜图。
将所得纳米管状硅基材料组装成锂电池，组装过程在氩气手套箱中进行，过程如下：将制备的纳米管状硅基材料、粘结剂PVDF以及导电剂乙炔黑按质量比8:1:1混合均匀，并加入适量N-甲基吡咯烷酮调制成粘稠的浆料并涂布在铜箔上。干燥后用冲片机将铜箔冲压成直径为15 mm的圆形电极片。采用CR2032纽扣电池作为模拟电池。以上述极片作为工作电极，金属锂片作为对电极。电解液采用1 mol·L的LiPF6的碳酸二甲酯/碳酸甲乙酯/碳酸乙烯酯 (质量比为1:1:1)有机溶液(LB315)。Celgard 2300PP/PE/PP三层微孔复合隔膜作为电池隔膜。用封口机将电池封口。性能测试采用蓝电测试系统进行，充放电电压为0~3.0V。同时以不进行煅烧和酸溶及煅烧后不进行酸溶的硅基材料样品进行对比。
图2为所得纳米管状硅基材料制备的锂电池的充放电曲线。由图2可见，所得纳米管状硅基材料制备的锂电池在充放电过程中可获得1800 mA h g−1以上的容量。相比之下，不进行煅烧和酸溶及煅烧后未酸溶的硅基材料所制备的锂电池在充放电过程中仅获得了较低的容量。
图3为所得纳米管状硅基材料制备的锂电池的充放电循环次数图。由图3可见，所得纳米管状硅基材料制备的锂电池在充放电循环过程中保持了较好的稳定性。
实施例2
1）参照文献“Growth of Single-Crystalline Ni and Co Nanowires viaElectrochemical Deposition and Their Magnetic Properties.”（ H. Pan, B. H.Liu, J. B. Yi, C. Poh, S. H. Lim, J. Ding, Y. P. Feng, C. H. A. Huan, J. Y.Lin. J. Phys. Chem. B 109 (2005) 3094-3098.）制备镍纳米线，其直径为50 nm，长度为500 nm；将制得的镍纳米线分散于1000 mL乙醇中；
2）将硅烷偶联剂加入到步骤1）所得的溶液中，搅拌120 min，其中硅烷偶联剂与镍纳米线的质量比为1:10；
3）将步骤2）所得产物过滤后于氦气氛围下110 ℃干燥10 h；
4）将步骤3）烘干后的产物置于氩气气氛下600℃煅烧10 h，之后冷却；
5）将步骤4）所得产物置于盐酸与硝酸的混合溶液中搅拌2 h（其中盐酸与硝酸的摩尔比为3:1，酸的浓度为3 mol/L，所用酸与镍元素的摩尔比为30:1），过滤、洗涤，然后于氦气氛围下110 ℃干燥10 h，即得所述纳米管状硅基材料。
实施例3
1）参照文献“Growth of Single-Crystalline Ni and Co Nanowires viaElectrochemical Deposition and Their Magnetic Properties.”（ H. Pan, B. H.Liu, J. B. Yi, C. Poh, S. H. Lim, J. Ding, Y. P. Feng, C. H. A. Huan, J. Y.Lin. J. Phys. Chem. B 109 (2005) 3094-3098.）制备镍钴纳米线，其中镍钴的摩尔比为1:1，纳米线的直径为30 nm，长度为300 nm；将制得的镍钴纳米线分散于500 mL汽油中；
2）将硅酮加入到步骤1）所得的溶液中，搅拌90 min，其中硅酮与镍钴纳米线的质量比为1:5；
3）将步骤2）所得产物过滤后于氩气氛围下100 ℃干燥17 h；
4）将步骤3）烘干后的产物置于氩气气氛下500 ℃煅烧17 h，之后冷却；
5）将步骤4）所得产物置于盐酸与硒酸的混合溶液中搅拌17 h（其中盐酸与硒酸的摩尔比为3:1，酸的浓度为1.5 mol/L，所用酸与镍钴两种元素的摩尔量之和的比例为20:1），过滤、洗涤，然后于氩气氛围下100 ℃干燥17 h，即得所述纳米管状硅基材料。
实施例4
1）参照文献“Nanomechanics of single crystalline tungsten nanowires”(V.Cimalla, C. C. Röhlig, J. Pezoldt, M. Niebelschütz, O. Ambacher, K. Brückner,M. Hein, J. Weber, S. Milenkovic, A. J. Smith, A. W. Hassel. J. Nanomater.2008, 638947.)制备钨纳米线，其直径为40 nm，长度为200 nm；将制得的钨纳米线分散于200 mL糠醇中；
2）将硅酸钙加入到步骤1）所得的溶液中，搅拌70 min，其中硅酸钙与钨纳米线的质量比为1:3；
3）将步骤2）所得产物过滤后于体积比为1:1的氩气/氮气混合气体氛围下80 ℃干燥15h；
4）将步骤3）烘干后的产物置于一氧化碳气氛下550℃煅烧11 h，之后冷却；
5）将步骤4）所得产物置于浓度为2 mol/L的硫酸溶液中搅拌2 h（所用硫酸与钨元素的摩尔比为14:1），过滤、洗涤，然后于体积比为1:1的氩气/氮气混合气体氛围下80 ℃干燥10h，即得所述纳米管状硅基材料。
实施例5
1）参照文献“Electrodeposition of Zinc-Copper and Zinc-Tin Films and Free-Standing Nanowire Arrays from Ionic Liquids”(Z. Liu, A. M. Elbasiony, S. Z.E. Abedin, F. Endres. ChemElectroChem 2 (2015) 389-395.)制备锌锡铜纳米线，其中锌锡铜的摩尔比为1:1:1，纳米线的直径为30 nm，长度为450 nm；将制得的锌锡铜纳米线分散于600 mL异丙醇中；
2）将偏硅酸铝加入到步骤1）所得的溶液中，搅拌110 min，其中偏硅酸铝与锌锡铜纳米线的质量比为1:6；
3）将步骤2）所得产物于体积比为1:1:1的氩气/氮气/氦气混合气体氛围下90 ℃干燥11 h；
4）将步骤3）烘干后的产物置于二氧化碳气氛下530℃煅烧15 h，之后冷却；
5）将步骤4）所得产物置于浓度为1.7 mol/L的硝酸溶液中搅拌110 min（所用硝酸与锌锡铜三种元素的摩尔量之和的比例为14:1），过滤、洗涤，然后于体积比为1:1:1的氩气/氮气/氦气混合气体氛围下90 ℃干燥11 h，即得所述纳米管状硅基材料。
实施例6
1）参照文献“Fabrication of rhenium nanowires by selective etching ofeutectic alloys”(A. W. Hassel, B. B. Rodriguez, S. Milenkovic, A. Schneider.Electrochimi. Acta 51 (205) 795-801.)制备铼纳米线，其直径为25 nm，长度为400 nm；将制得的铼纳米线分散于600 ml水和异丙醇按体积比1:2混合的溶液中；
2）将正硅酸四乙酯加入到步骤1）所得的溶液中，搅拌30 min，其中正硅酸四乙酯与铼纳米线的质量比为1:7；
3）将步骤2）所得产物于氮气氛围下90 ℃干燥20 h；
4）将步骤3）烘干后的产物置于体积比为1:2的氢气/一氧化碳混合气体气氛下450℃煅烧18 h，之后冷却；
5）将步骤4）所得产物置于浓度为盐酸与碲酸的混合溶液中搅拌8 h（其中盐酸与碲酸的摩尔比为3:1，酸的浓度为2.6 mol/L，所用酸与铼元素的摩尔比为10:1），过滤、洗涤，然后于氮气氛围下70 ℃干燥20 h，即得所述纳米管状硅基材料。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (9)
1.一种锂电池用纳米管状硅基材料的制备方法，其特征在于：包括以下步骤：
1）将金属纳米线分散于溶剂中；
2）将硅的前驱体加入到步骤1）所得的溶液中，搅拌一段时间；
3）将步骤2）所得产物过滤后进行干燥；
4）将步骤3）烘干后的产物置于保护气氛下煅烧一定时间，之后冷却；
5）将步骤4）所得产物置于酸溶液中搅拌一定时间，过滤、洗涤并干燥后，即得所述纳米管状硅基材料。
2.根据权利要求1所述的锂电池用纳米管状硅基材料的制备方法，其特征在于：步骤1）中所述金属纳米线包括铝、铜、铅、锌、锡、钴、镍、铁、铬、锰、锑、镉、铋、钛、锆、铪、钒、铌、钽、钨、钼、镓、铟、铊、锗、铼中的一种或者几种。
3.根据权利要求1所述的锂电池用纳米管状硅基材料的制备方法，其特征在于：步骤1）中所述溶剂为水、甲醇、乙醇、乙二醇、异丙醇、丙三醇、正丁醇、糠醇、乙醚、汽油、柴油中的一种或几种。
4.根据权利要求1所述的锂电池用纳米管状硅基材料的制备方法，其特征在于：步骤2）中所加入的硅的前驱体与金属纳米线的质量比为1:1~10。
5.根据权利要求1或4所述的锂电池用纳米管状硅基材料的制备方法，其特征在于：所述硅的前驱体为正硅酸四乙酯、硅酸钙、硅烷偶联剂、硅酸钠、硅酮、氟硅酸或偏硅酸铝中的一种或几种。
6. 根据权利要求1所述的锂电池用纳米管状硅基材料的制备方法，其特征在于：步骤2）中搅拌的时间为60~120 min。
7.根据权利要求1所述的锂电池用纳米管状硅基材料的制备方法，其特征在于：步骤4）中所述保护气氛包括氢气、氮气、氦气、氩气、一氧化碳、二氧化碳中的一种或几种；
所述煅烧的温度为400~600℃，时间为10~24 h。
8. 根据权利要求1所述的锂电池用纳米管状硅基材料的制备方法，其特征在于：步骤5）中所述酸溶液为盐酸、硫酸、磷酸、硝酸、硒酸、碲酸、高氯酸、次氯酸中一种或几种的水溶液，其浓度为0.1~3 mol/L；用量按酸与金属元素的摩尔比为10~30:1进行换算；
搅拌的时间为10~24 h。
9. 根据权利要求1所述的锂电池用纳米管状硅基材料的制备方法，其特征在于：操作中所述干燥是于真空或惰性保护气氛下进行，干燥的温度为80~110 ℃，时间为10~24 h；
所述惰性保护气氛包括氮气、氦气、氩气中的一种或几种。
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| CN112072098B (zh) | 2021-06-29 |
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