CN117410475B - 一种三维多孔负极材料及其制备方法、锂电池 - Google Patents
一种三维多孔负极材料及其制备方法、锂电池 Download PDFInfo
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- 239000010405 anode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 13
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 31
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 13
- 239000002923 metal particle Substances 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000004332 silver Substances 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 74
- 239000000243 solution Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 36
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000004005 microsphere Substances 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 235000012239 silicon dioxide Nutrition 0.000 claims description 21
- 229910052786 argon Inorganic materials 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 19
- 230000008961 swelling Effects 0.000 claims description 19
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- 150000003254 radicals Chemical class 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 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 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000007740 vapor deposition Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims description 2
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 claims description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 2
- 239000001433 sodium tartrate Substances 0.000 claims description 2
- 229960002167 sodium tartrate Drugs 0.000 claims description 2
- 235000011004 sodium tartrates Nutrition 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 238000005470 impregnation Methods 0.000 claims 1
- 239000007773 negative electrode material Substances 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 28
- 239000007789 gas Substances 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 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
- -1 diethyl silicate Chemical compound 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011366 tin-based material 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
- H01M4/366—Composites as layered products
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/023—Preparation by reduction of silica or free silica-containing 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/04—Processes of manufacture in general
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- H01M4/0428—Chemical vapour deposition
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- H01—ELECTRIC ELEMENTS
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- H01M4/04—Processes of manufacture in general
- 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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- 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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Abstract
本发明涉及锂电池技术领域,具体为一种三维多孔负极材料及其制备方法、锂电池,由内至外依次包括微米级三维多孔硅碳材料核体、金属粒子负载层和石墨烯包覆壳层,所述金属粒子负载层为银或铜,经过测试,本发明所制备三维多孔负极材料具有良好的电化学性能,在0.5A/g的电流密度下首次充电比容量大于1300mAh/g,首次库伦效率大于92%,800周循环容量保持率大于89%。
Description
技术领域
本发明涉及锂电池技术领域,具体为一种三维多孔负极材料及其制备方法、锂电池。
背景技术
由于锂离子电池具有高循环寿命、高比能量、体积小、质量轻、无记忆效应等优点,是目前综合性能最好的电池体系。在锂离子电池中负极材料起着至关重要的作用,常见的负极材料有锡基材料、碳材料和硅基材料等。
硅材料具有较大的理论比容量、电解液反应活性低,以及储量丰富,是新一代锂离子电池负极材料的理想选择。但是,硅材料在与锂的合金化反应过程中会产生巨大的体积膨胀,这容易导致活性材料粉化脱落,以及硅材料在电解液中所形成的SEI膜在锂的嵌脱过程中会发生破裂并不断生成,使得电池的循环性能较差、库仑效率较低。
发明内容
发明目的:针对上述技术问题,本发明提出了一种三维多孔负极材料及其制备方法、锂电池。
所采用的技术方案如下:
一种三维多孔负极材料,由内至外依次包括微米级三维多孔硅碳材料核体、金属粒子负载层和石墨烯包覆壳层。
进一步地,所述金属粒子负载层为银或铜。
本发明还提供了一种三维多孔负极材料的制备方法,包括如下步骤:
S1:利用聚合物模板法制备二氧化硅微球前驱体;
S2:将所述二氧化硅微球前驱体与金属镁在惰性气体保护下升温至700-900℃进行镁热还原,所得产物经酸洗、水洗、干燥后粉碎得到微米级三维多孔硅碳材料;
S3:将所述微米级三维多孔硅碳材料分散在乙醇中,滴加银氨溶液或铜氨溶液,将混匀后得到的混合溶液与还原液混合,40-60℃水浴加热下搅拌反应1-5h,收集产物洗涤后干燥得到中间体;
S4:利用化学气相沉积法在所述中间体上沉积石墨烯包覆壳层即可。
进一步地,S1具体如下:
将聚苯乙烯纳米种子微球加入到十二烷基硫酸钠的乙醇水溶液中,再加入氯代十二烷,超声分散后,搅拌溶胀10h以上得到种球乳化液,将苯乙烯、二乙烯基苯、含氮功能单体、甲苯和自由基引发剂加入到十二烷基硫酸钠的乙醇水溶液中并混匀,超声乳化后加入到种子乳化液中继续溶胀10h以上,氮气保护下,升温至70-80℃聚合反应18h以上,反应结束后,收集产物,洗涤、干燥得到多孔聚合物模板,用正硅酸乙酯对多孔聚合物模板进行浸渍处理,干燥后,加入到十二烷基硫酸钠的乙醇水溶液中,用酸液调节反应体系pH至3-4进行水解反应,最后将得到的产物洗涤、干燥即可。
进一步地,所述含氮功能单体为丙烯腈、丙烯酰胺或N-乙烯基咔唑中的任意一种或多种组合。
进一步地,所述苯乙烯、二乙烯基苯、含氮功能单体的重量比为1-3:1:0.1-0.5。
进一步地,S2中二氧化硅微球前驱体与金属镁的重量比为1.5-2.5:1。
进一步地,S3中所述还原液为葡萄糖溶液、酒石酸钠溶液、苹果酸溶液和丁二酸溶液。
进一步地,S4具体如下:
将中间体放置气相沉积设备的石英管内,在氩气和氢气的混合气氛下升温至750-850℃,通入甲烷进行裂解生长石墨烯,沉积25-50min后停止通入甲烷和氢气,在氩气保护下恢复室温即可。
本发明还提供了一种锂电池,由上述三维多孔负极材料制备而成。
本发明的有益效果:
本发明提供了一种三维多孔负极材料,利用聚合物模板法制备的微米级三维多孔硅碳材料具有丰富的三维孔洞结构,不仅能够提供足够的空隙,还能缓解在锂离子电池硅负极脱-嵌锂过程中发生的体积变化,有利于锂离子的快速传输;
聚合物模板还可以作为碳化原料形成嵌入型的硅碳复合结构来帮助构建形成稳定的SEI膜,对硅的膨胀起到一定的缓冲作用,使得SEI膜更加稳定,同时还抑制了硅的团聚;
而且本发明中通过引入含氮功能单体实现氮掺杂,通过改变硅碳材料的电荷密度和表面理化性质,提供更多活性位点,使其具有更优异的电化学性能;
金属粒子负载层的存在可以提高三维多孔硅碳材料的导电性,有利于硅碳材料之间以及硅碳材料与集流体之间的电接触,缓解硅碳材料在反复充放电过程中活性物质颗粒和导电网络之间可能出现的电接触丧失问题,同时与石墨烯包覆壳层一起作为缓冲层可以有效地降低内应力及体积变化对于材料结构的破坏;
经过测试,本发明所制备三维多孔负极材料具有良好的电化学性能,在0.5A/g的电流密度下首次充电比容量大于1300mAh/g,首次库伦效率大于92%,800周循环容量保持率大于89%。
附图说明
图1为实施例1中所制备三维多孔负极材料的结构示意图;
图中:1-石墨烯包覆壳层、2-银粒子、3-微米级三维多孔硅碳材料核体。
图2为实施例1中所制备三维多孔负极材料所组装CR2032型半电池的循环性能曲线;
图3为实施例1中所制备三维多孔负极材料的SEM照片。
图4为实施例1中所制备三维多孔负极材料的局部放大SEM照片。
具体实施方式
实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。本发明未提及的技术均参照现有技术,除非特别指出,以下实施例和对比例为平行试验,采用同样的处理步骤和参数。
实施例1:
一种三维多孔负极材料的制备方法:
将0.5g聚苯乙烯纳米种子微球(购自中科雷鸣(北京)科技有限公司,粒度25nm)加入到十二烷基硫酸钠的乙醇水溶液(m十二烷基硫酸钠、m乙醇、m水分别为0.125g、40g和10g)中,再加入0.5g氯代十二烷作为溶胀剂,超声振荡分散30min后,搅拌溶胀12h得到种球乳化液,将1.5g苯乙烯、0.75g二乙烯基苯、0.375g丙烯腈、3.5ml甲苯和0.17g自由基引发剂BPO加入到十二烷基硫酸钠的乙醇水溶液(m十二烷基硫酸钠、m乙醇、m水分别为0.125g、40g和10g)中并混匀,超声乳化后加入到种子乳化液中继续溶胀24h,向反应体系中通入氮气保护,升温至80℃聚合反应24h,反应结束后,收集产物,用乙醇和水反复洗涤,置于60℃烘箱中干燥过夜即可得到多孔聚合物模板,取1g多孔聚合物模板加入到10ml正硅酸乙酯中混匀,充分浸渍24h,离心,干燥,再加入到十二烷基硫酸钠的乙醇水溶液中(m十二烷基硫酸钠、m乙醇、m水分别为0.5g、160g和40g),用冰醋酸调节反应体系pH至4进行水解反应24h,收集产物用乙醇和水反复洗涤,置于60℃烘箱中干燥过夜得到二氧化硅微球前驱体,将重量比为1.8:1的二氧化硅微球前驱体与金属镁在氩气保护下升温至850℃进行镁热还原,所得产物用1mol/L盐酸洗涤后再用水洗涤至中性,再经100℃烘箱中干燥过夜后粉碎至400目得到微米级三维多孔硅碳材料,将5ml浓度为0.15mol/L的硝酸银溶液,逐滴加入3%的氨水溶液,直至白色沉淀刚好消失得到银氨溶液,将0.2g微米级三维多孔硅碳材料分散在50ml乙醇中形成悬浮液,滴加配制好的银氨溶液,混匀后得到混合溶液,将混合溶液与50ml0.2mol/L葡萄糖溶液混合,50℃水浴加热下搅拌反应3h,收集产物用乙醇和水反复洗涤,置于60℃烘箱中干燥过夜得到中间体,利用化学气相沉积法在中间体上沉积石墨烯包覆壳层,具体是将中间体放置气相沉积设备的石英管内,在氩气和氢气的混合气氛下升温至800℃,氩气和氢气的流量保持在100sccm,升温速率为10℃/min,通入流量为20sccm的甲烷进行裂解生长石墨烯,沉积35min后停止通入甲烷和氢气,在氩气保护下冷却至室温即可。
图1为本实施例所制备的三维多孔负极材料的结构示意图,其中,1为石墨烯包覆壳层,2为银粒子,3为微米级三维多孔硅碳材料核体。
实施例2:
一种三维多孔负极材料的制备方法:
将0.5g聚苯乙烯纳米种子微球(购自中科雷鸣(北京)科技有限公司,粒度25nm)加入到十二烷基硫酸钠的乙醇水溶液(m十二烷基硫酸钠、m乙醇、m水分别为0.125g、40g和10g)中,再加入0.5g氯代十二烷作为溶胀剂,超声振荡分散30min后,搅拌溶胀12h得到种球乳化液,将1.5g苯乙烯、0.75g二乙烯基苯、0.375g丙烯腈、3.5ml甲苯和0.17g自由基引发剂BPO加入到十二烷基硫酸钠的乙醇水溶液(m十二烷基硫酸钠、m乙醇、m水分别为0.125g、40g和10g)中并混匀,超声乳化后加入到种子乳化液中继续溶胀24h,向反应体系中通入氮气保护,升温至80℃聚合反应24h,反应结束后,收集产物,用乙醇和水反复洗涤,置于60℃烘箱中干燥过夜即可得到多孔聚合物模板,取1g多孔聚合物模板加入到10ml正硅酸乙酯中混匀,充分浸渍24h,离心,干燥,再加入到十二烷基硫酸钠的乙醇水溶液中(m十二烷基硫酸钠、m乙醇、m水分别为0.5g、160g和40g),用冰醋酸调节反应体系pH至4进行水解反应24h,收集产物用乙醇和水反复洗涤,置于60℃烘箱中干燥过夜得到二氧化硅微球前驱体,将重量比为2.5:1的二氧化硅微球前驱体与金属镁在氩气保护下升温至900℃进行镁热还原,所得产物用1mol/L盐酸洗涤后再用水洗涤至中性,再经100℃烘箱中干燥过夜后粉碎至400目得到微米级三维多孔硅碳材料,将5ml浓度为0.15mol/L的硝酸银溶液,逐滴加入3%的氨水溶液,直至白色沉淀刚好消失得到银氨溶液,将0.2g微米级三维多孔硅碳材料分散在50ml乙醇中形成悬浮液,滴加配制好的银氨溶液,混匀后得到混合溶液,将混合溶液与50ml0.2mol/L葡萄糖溶液混合,60℃水浴加热下搅拌反应5h,收集产物用乙醇和水反复洗涤,置于60℃烘箱中干燥过夜得到中间体,利用化学气相沉积法在中间体上沉积石墨烯包覆壳层,具体是将中间体放置气相沉积设备的石英管内,在氩气和氢气的混合气氛下升温至850℃,氩气和氢气的流量保持在100sccm,升温速率为10℃/min,通入流量为20sccm的甲烷进行裂解生长石墨烯,沉积50min后停止通入甲烷和氢气,在氩气保护下冷却至室温即可。
实施例3:
一种三维多孔负极材料的制备方法:
将0.5g聚苯乙烯纳米种子微球(购自中科雷鸣(北京)科技有限公司,粒度25nm)加入到十二烷基硫酸钠的乙醇水溶液(m十二烷基硫酸钠、m乙醇、m水分别为0.125g、40g和10g)中,再加入0.5g氯代十二烷作为溶胀剂,超声振荡分散30min后,搅拌溶胀12h得到种球乳化液,将1.5g苯乙烯、0.75g二乙烯基苯、0.375g丙烯腈、3.5ml甲苯和0.17g自由基引发剂BPO加入到十二烷基硫酸钠的乙醇水溶液(m十二烷基硫酸钠、m乙醇、m水分别为0.125g、40g和10g)中并混匀,超声乳化后加入到种子乳化液中继续溶胀24h,向反应体系中通入氮气保护,升温至80℃聚合反应24h,反应结束后,收集产物,用乙醇和水反复洗涤,置于60℃烘箱中干燥过夜即可得到多孔聚合物模板,取1g多孔聚合物模板加入到10ml正硅酸乙酯中混匀,充分浸渍24h,离心,干燥,再加入到十二烷基硫酸钠的乙醇水溶液中(m十二烷基硫酸钠、m乙醇、m水分别为0.5g、160g和40g),用冰醋酸调节反应体系pH至4进行水解反应24h,收集产物用乙醇和水反复洗涤,置于60℃烘箱中干燥过夜得到二氧化硅微球前驱体,将重量比为1.8:1的二氧化硅微球前驱体与金属镁在氩气保护下升温至800℃进行镁热还原,所得产物用1mol/L盐酸洗涤后再用水洗涤至中性,再经100℃烘箱中干燥过夜后粉碎至400目得到微米级三维多孔硅碳材料,将5ml浓度为0.15mol/L的硝酸银溶液,逐滴加入3%的氨水溶液,直至白色沉淀刚好消失得到银氨溶液,将0.2g微米级三维多孔硅碳材料分散在50ml乙醇中形成悬浮液,滴加配制好的银氨溶液,混匀后得到混合溶液,将混合溶液与50ml0.2mol/L葡萄糖溶液混合,40℃水浴加热下搅拌反应2.5h,收集产物用乙醇和水反复洗涤,置于60℃烘箱中干燥过夜得到中间体,利用化学气相沉积法在中间体上沉积石墨烯包覆壳层,具体是将中间体放置气相沉积设备的石英管内,在氩气和氢气的混合气氛下升温至800℃,氩气和氢气的流量保持在100sccm,升温速率为10℃/min,通入流量为20sccm的甲烷进行裂解生长石墨烯,沉积25min后停止通入甲烷和氢气,在氩气保护下冷却至室温即可。
对比例1:
与实施例1基本相同,区别在于,不含金属粒子负载层,制备方法如下:
将0.5g聚苯乙烯纳米种子微球(购自中科雷鸣(北京)科技有限公司,粒度25nm)加入到十二烷基硫酸钠的乙醇水溶液(m十二烷基硫酸钠、m乙醇、m水分别为0.125g、40g和10g)中,再加入0.5g氯代十二烷作为溶胀剂,超声振荡分散30min后,搅拌溶胀12h得到种球乳化液,将1.5g苯乙烯、0.75g二乙烯基苯、0.375g丙烯腈、3.5ml甲苯和0.17g自由基引发剂BPO加入到十二烷基硫酸钠的乙醇水溶液(m十二烷基硫酸钠、m乙醇、m水分别为0.125g、40g和10g)中并混匀,超声乳化后加入到种子乳化液中继续溶胀24h,向反应体系中通入氮气保护,升温至80℃聚合反应24h,反应结束后,收集产物,用乙醇和水反复洗涤,置于60℃烘箱中干燥过夜即可得到多孔聚合物模板,取1g多孔聚合物模板加入到10ml正硅酸乙酯中混匀,充分浸渍24h,离心,干燥,再加入到十二烷基硫酸钠的乙醇水溶液中(m十二烷基硫酸钠、m乙醇、m水分别为0.5g、160g和40g),用冰醋酸调节反应体系pH至4进行水解反应24h,收集产物用乙醇和水反复洗涤,置于60℃烘箱中干燥过夜得到二氧化硅微球前驱体,将重量比为1.8:1的二氧化硅微球前驱体与金属镁在氩气保护下升温至850℃进行镁热还原,所得产物用1mol/L盐酸洗涤后再用水洗涤至中性,再经100℃烘箱中干燥过夜后粉碎至400目得到微米级三维多孔硅碳材料,利用化学气相沉积法在微米级三维多孔硅碳材料上沉积石墨烯包覆壳层,具体是将微米级三维多孔硅碳材料放置在气相沉积设备的石英管内,在氩气和氢气的混合气氛下升温至800℃,氩气和氢气的流量保持在100sccm,升温速率为10℃/min,通入流量为20sccm的甲烷进行裂解生长石墨烯,沉积35min后停止通入甲烷和氢气,在氩气保护下冷却至室温即可。
对比例2:
与实施例1基本相同,区别在于,不含石墨烯包覆壳层,制备方法如下:
将0.5g聚苯乙烯纳米种子微球(购自中科雷鸣(北京)科技有限公司,粒度25nm)加入到十二烷基硫酸钠的乙醇水溶液(m十二烷基硫酸钠、m乙醇、m水分别为0.125g、40g和10g)中,再加入0.5g氯代十二烷作为溶胀剂,超声振荡分散30min后,搅拌溶胀12h得到种球乳化液,将1.5g苯乙烯、0.75g二乙烯基苯、0.375g丙烯腈、3.5ml甲苯和0.17g自由基引发剂BPO加入到十二烷基硫酸钠的乙醇水溶液(m十二烷基硫酸钠、m乙醇、m水分别为0.125g、40g和10g)中并混匀,超声乳化后加入到种子乳化液中继续溶胀24h,向反应体系中通入氮气保护,升温至80℃聚合反应24h,反应结束后,收集产物,用乙醇和水反复洗涤,置于60℃烘箱中干燥过夜即可得到多孔聚合物模板,取1g多孔聚合物模板加入到10ml正硅酸乙酯中混匀,充分浸渍24h,离心,干燥,再加入到十二烷基硫酸钠的乙醇水溶液中(m十二烷基硫酸钠、m乙醇、m水分别为0.5g、160g和40g),用冰醋酸调节反应体系pH至4进行水解反应24h,收集产物用乙醇和水反复洗涤,置于60℃烘箱中干燥过夜得到二氧化硅微球前驱体,将重量比为1.8:1的二氧化硅微球前驱体与金属镁在氩气保护下升温至850℃进行镁热还原,所得产物用1mol/L盐酸洗涤后再用水洗涤至中性,再经100℃烘箱中干燥过夜后粉碎至400目得到微米级三维多孔硅碳材料,将5ml浓度为0.15mol/L的硝酸银溶液,逐滴加入3%的氨水溶液,直至白色沉淀刚好消失得到银氨溶液,将0.2g微米级三维多孔硅碳材料分散在50ml乙醇中形成悬浮液,滴加配制好的银氨溶液,混匀后得到混合溶液,将混合溶液与50ml0.2mol/L葡萄糖溶液混合,50℃水浴加热下搅拌反应3h,收集产物用乙醇和水反复洗涤,置于60℃烘箱中干燥过夜即可。
性能测试:
将本发明实施例1-3及对比例1-2中所制备的三维多孔负极材料、碳导电剂(SuperP)、粘合剂(海藻酸钠)以质量比(7:2:1)混合,去离子水作为溶剂加入,研磨成浆料状态,再将浆料涂布到铜箔上以制备工作电极;
将制备得到的工作电极电极在80℃下真空干燥24h,活性材料的负载质量约为1.0mg·cm-2,将1mol·L-1的LiPF6溶于电解液(V碳酸乙烯酯:V碳酸二甲酯:V碳酸甲乙酯=1:1:1)中,在氩气填充的手套箱中组装成CR2032型半电池,锂片用作参比电极和对电极,将密封电池在室温下静置24h后使用新威电池测试仪系统在0.5A/g的电流密度下充放电,充放电电压范围为0.01-1.5V,测试结果如表1所示:
表1:
由上表1可知,本发明所制备三维多孔负极材料具有良好的电化学性能;
通过实施例1和对比例1的数据对比可知,负载银粒子对于改善负极材料的电化学性能起到了积极作用,究其原因,可能是银粒子的存在可以提高三维多孔硅碳材料的导电性,有利于硅碳材料之间以及硅碳材料与集流体之间的电接触;
通过实施例1和对比例2的数据对比可知,石墨烯包覆壳层对于改善负极材料的电化学性能也起到了积极作用,究其原因,可能是石墨烯包覆壳层提高了三维多孔硅碳材料与电解液的相容性,有利于其在电解液中稳定进行充放电。
以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (7)
1.一种三维多孔负极材料,其特征在于,由内至外依次包括微米级三维多孔硅碳材料核体、金属粒子负载层和石墨烯包覆壳层;
所述金属粒子负载层为银或铜;
上述三维多孔负极材料的制备方法,包括如下步骤:
S1:将聚苯乙烯纳米种子微球加入到十二烷基硫酸钠的乙醇水溶液中,再加入氯代十二烷,超声分散后,搅拌溶胀10h以上得到种球乳化液,将苯乙烯、二乙烯基苯、含氮功能单体、甲苯和自由基引发剂加入到十二烷基硫酸钠的乙醇水溶液中并混匀,超声乳化后加入到种球乳化液中继续溶胀10h以上,氮气保护下,升温至70-80℃聚合反应18h以上,反应结束后,收集产物,洗涤、干燥得到多孔聚合物模板,用正硅酸乙酯对多孔聚合物模板进行浸渍处理,干燥后,加入到十二烷基硫酸钠的乙醇水溶液中,用酸液调节反应体系pH至3-4进行水解反应,最后将得到的产物洗涤、干燥即可得到二氧化硅微球前驱体;
S2:将所述二氧化硅微球前驱体与金属镁在惰性气体保护下升温至700-900℃进行镁热还原,所得产物经酸洗、水洗、干燥后粉碎得到微米级三维多孔硅碳材料;
S3:将所述微米级三维多孔硅碳材料分散在乙醇中,滴加银氨溶液或铜氨溶液,将混匀后得到的混合溶液与还原液混合,40-60℃水浴加热下搅拌反应1-5h,收集产物洗涤后干燥得到中间体;
S4:利用化学气相沉积法在所述中间体上沉积石墨烯包覆壳层即可。
2.如权利要求1所述的三维多孔负极材料,其特征在于,所述含氮功能单体为丙烯腈、丙烯酰胺或N-乙烯基咔唑中的任意一种或多种组合。
3.如权利要求1所述的三维多孔负极材料,其特征在于,所述苯乙烯、二乙烯基苯、含氮功能单体的重量比为1-3:1:0.1-0.5。
4.如权利要求1所述的三维多孔负极材料,其特征在于,S2中二氧化硅微球前驱体与金属镁的重量比为1.5-2.5:1。
5.如权利要求1所述的三维多孔负极材料,其特征在于,S3中所述还原液为葡萄糖溶液、酒石酸钠溶液、苹果酸溶液和丁二酸溶液。
6.如权利要求1所述的三维多孔负极材料,其特征在于,S4具体如下:
将中间体放置气相沉积设备的石英管内,在氩气和氢气的混合气氛下升温至750-850℃,通入甲烷进行裂解生长石墨烯,沉积25-50min后停止通入甲烷和氢气,在氩气保护下恢复室温即可。
7.一种锂电池,其特征在于,由权利要求1所述的三维多孔负极材料制备而成。
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