CN114057178A - 纳米复合碳球的制备方法与应用 - Google Patents
纳米复合碳球的制备方法与应用 Download PDFInfo
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- CN114057178A CN114057178A CN202010778529.1A CN202010778529A CN114057178A CN 114057178 A CN114057178 A CN 114057178A CN 202010778529 A CN202010778529 A CN 202010778529A CN 114057178 A CN114057178 A CN 114057178A
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- water
- carbon
- nano composite
- soluble
- composite carbon
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 121
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 29
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005530 etching Methods 0.000 claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 9
- 238000004146 energy storage Methods 0.000 claims abstract description 7
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- 239000010865 sewage Substances 0.000 claims abstract description 5
- 238000009833 condensation Methods 0.000 claims abstract description 3
- 230000005494 condensation Effects 0.000 claims abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000002262 Schiff base Substances 0.000 claims description 16
- 150000004753 Schiff bases Chemical class 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 239000002077 nanosphere Substances 0.000 claims description 9
- 150000001299 aldehydes Chemical class 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-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
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- AIJULSRZWUXGPQ-UHFFFAOYSA-N Methylglyoxal Chemical compound CC(=O)C=O AIJULSRZWUXGPQ-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 4
- 229920000193 polymethacrylate Polymers 0.000 claims description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229940015043 glyoxal Drugs 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- -1 polyoxyethylene octylphenol Polymers 0.000 claims description 3
- FIADVASZMLCQIF-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octamethyl-1,3,5,7,2,4,6,8-tetrazatetrasilocane Chemical compound C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N[Si](C)(C)N1 FIADVASZMLCQIF-UHFFFAOYSA-N 0.000 claims description 2
- WGGNJZRNHUJNEM-UHFFFAOYSA-N 2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6-triazatrisilinane Chemical compound C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N1 WGGNJZRNHUJNEM-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- GBQYMXVQHATSCC-UHFFFAOYSA-N 3-triethoxysilylpropanenitrile Chemical compound CCO[Si](OCC)(OCC)CCC#N GBQYMXVQHATSCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- CPLASELWOOUNGW-UHFFFAOYSA-N benzyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CC1=CC=CC=C1 CPLASELWOOUNGW-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 1
- 229920013822 aminosilicone Polymers 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 239000010406 cathode material Substances 0.000 abstract description 7
- 239000000969 carrier Substances 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 19
- 239000000463 material Substances 0.000 description 19
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 15
- 229910052717 sulfur Inorganic materials 0.000 description 10
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
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- 238000010438 heat treatment Methods 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 7
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- 229910021392 nanocarbon Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
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- BSRGOPQVDCJHIW-UHFFFAOYSA-N 2-(2-aminophenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC=CC=C1N BSRGOPQVDCJHIW-UHFFFAOYSA-N 0.000 description 3
- 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 3
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- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- KQOATKAFTRNONV-UHFFFAOYSA-N oxolan-2-amine Chemical compound NC1CCCO1 KQOATKAFTRNONV-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C01B32/15—Nano-sized carbon materials
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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
- 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
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
本发明公开了一种纳米复合碳球的制备方法与应用,包括醛胺缩合、高温煅烧以及刻蚀后处理步骤,制备工艺简单,得到的纳米复合碳球的元素组成、比表面积、孔径结构、孔径分布具有可调控性,可以通过改变原料比例、添加非氨基有机硅氧烷和\或非有机硅类水溶性胺类物质、改变煅烧温度、刻蚀条件等进行调控,且得到纳米复合碳球粒径为50~200nm,碳元素含量为50~99wt%,复合了大量由Si、O、N等元素形成的基团,具有多孔结构,具有较大的比表面与孔体积,吸附能力强,可广泛用作锂离子电池负极材料、锂硫电池正极载体、储能与催化剂载体、污水处理吸附剂。
Description
技术领域:
本发明涉及纳米储能材料与器件技术领域,具体涉及纳米复合碳球的制备方法与应用。
背景技术:
目前在新能源领域中,锂离子电池具有工作电压高、能量密度高、循环寿命长、自放电小、无记忆效应等优点,已广泛应用到多个工作领域,例如智能移动设备、电动交通工具、电能存储等领域都采用它作为动力能源。从20世纪90年代开始,人们对其进行了大量的研究和发展,锂离子电池已逐渐取代了铅酸蓄电池、镍镉蓄电池。但是,锂离子电池相关技术也存在许多不足,例如电池的能量密度、功率密度、热稳定性、充电效率等有待继续改良。锂离子电池的性能主要取决于正负极材料,而发展更高能量密度的负极材料是当前的研究重点之一。现有石墨基碳负极的理论嵌锂容量仅为372mAh/g,这严重限制了锂离子电池能量密度的进一步提升。为了提高石墨负极的容量,人们常将其与Si、SiOC、氧化物、硫化物等高比量材料进行复合,用于提高石墨碳负极的放电比容量。现有专利主要是通过制备硅材料后再与碳材料复合,在专利CN 107863512中先制备得到SiO,进一步在SiO表面包覆碳制备得硅碳复合负极材料,而这种方法制备得到得材料组成与结构可控性较低,复合效果并不十分理想。
与此同时,在传统的锂离子电池之外,人们也研发了其它的电池体系。其中以锂硫电池为典型代表,锂硫电池被认为是最有产业化前景的下一代电池体系。不过,锂硫电池的产业化被一些严重的技术问题所阻碍,包括:(1)单质硫及其放电产物Li2S的绝缘特性导致硫的利用率低,(2)充放电中间产物多硫化锂存在严重的“穿梭效应”,导致电池容量迅速衰减,(3)锂负极存在严重的枝晶现象,易于产生各种安全隐患。为了解决锂硫电池的上述问题,通常采用多孔或空心碳作为载体负载硫。由于碳材料具有高电导率,将其与硫复合制备复合正极,可以提高硫正极的电导率、硫的利用率以及放电比容量。不过,由于碳与多硫化物之间发生的是物理吸附,作用强度低,无法彻底抑制“穿梭效应”。为了进一步抑制“穿梭效应”,人们通常使用使用其他元素掺杂碳材料,或者将碳与极性材料复合。其他元素或极性材料与多硫化物之间发生可以化学吸附,吸附强度比物理吸附高,将其他元素或极性材料组合在一起可以有效抑制穿梭效应,大范围提升锂硫电池的循环稳定性与电化学可逆性。
多孔或空心结构的掺杂型碳材料是理想的载体,但在目前的制备方法中,多采用以SiO2为模板包覆有机聚合物材料再经热处理、刻蚀制备得到。专利CN 109626355 A中提出了一种利用甲醛为碳源、含氨基酚类化合物为氮源通过酚醛缩合反应在二氧化硅硬模板进行表面包覆后,再经热处理、刻蚀制备得到空心氮掺杂碳球,由于二氧化硅模板本身是分散的,很难制备得到多孔碳球。此外,专利CN 107039191 B中虽然将酚醛树脂的缩聚和正硅酸四乙酯的水解过程同时进行反应得到复合纳米球,热处理刻蚀后得到氮功能化中空介孔碳球,但本质上仍是二氧化硅模板法,且由于反应过程中生成的二氧化硅模板较大形成了空心结构,很难形成微孔结构。
发明内容:
本发明的目的是提供一种纳米复合碳球的制备方法与应用,包括醛胺缩合、高温煅烧以及刻蚀后处理步骤,制备工艺简单,得到的纳米复合碳球为碳连续且均匀分布的多孔复合碳球,其元素组成、比表面积、孔径结构、孔径分布具有可调控性,可以通过改变原料比例、添加非氨基有机硅氧烷和\或非有机硅类水溶性胺类物质、改变煅烧温度、刻蚀条件等进行调控,且得到纳米复合碳球粒径为50~200nm,碳元素含量为50~99wt%,复合了大量由Si、O、N等元素形成的基团,具有多孔结构,具有较大的比表面与孔体积,吸附能力强,可广泛用作锂离子电池负极材料、锂硫电池正极载体、储能与催化剂载体、污水处理吸附剂。
本发明是通过以下技术方案予以实现的:
一种纳米复合碳球的制备方法,该方法包括以下步骤:
1)在分散剂的作用下,通过水溶性氨基有机硅和水溶性醛发生醛胺缩合反应制取席夫碱SiO2前驱体,反应温度为20~90℃,反应时间为1~12h,为控制产物组成可选择性添加非氨基有机硅氧烷和\或非有机硅类水溶性胺类物质;
2)将步骤1)制备的席夫碱SiO2前驱体分离烘干后,通过惰性气体保护下700~1300℃高温煅烧2~6h以及酸或碱刻蚀并经洗涤烘干后处理制备得到纳米复合碳球;刻蚀温度为20~100℃,刻蚀时间为0.5~48h;所述纳米复合碳球粒径为50~200nm,碳元素含量为50~99wt%,且所述纳米复合碳球的元素组成、比表面积与孔径结构和孔径分布等具有可调控性,通过改变原料比例、添加非氨基有机硅氧烷和\或非有机硅类水溶性胺类物质、改变煅烧温度或刻蚀条件进行调控。
所述水溶性氨基有机硅为γ-氨丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、N-[3-(三甲氧基硅基)丙基]乙二胺、六甲基二硅胺烷、2,2,4,4,6,6-六甲基环三硅氮烷、八甲基环四硅氮烷、八氨基丙基笼形聚倍半硅氧烷中的一种或多种。
所述水溶性醛为甲醛、乙二醛、丙酮醛、戊二醛、己二醛、水杨醛中的一种或多种。
非氨基有机硅氧烷为四甲氧基硅烷、四乙氧基硅烷、β-氰乙基三乙氧基硅烷、甲基三甲氧基硅烷、苯甲基三乙氧基硅烷、乙烯基三甲氧基硅烷、γ-氰乙基三乙氧基硅烷中的一种以上;非氨基有机硅氧烷的加入可以和水溶性氨基有机硅发生共水解缩聚反应,从而调控复合碳球中的硅氧含量,在刻蚀后可调控孔结构及比表面积。
所述非有机硅类水溶性胺类物质包括丁胺、一乙醇胺、乙二胺、二乙二胺、聚乙烯亚胺、苄基胺、四氢呋喃胺、氨基酸中的一种以上。非有机硅类水溶性胺类的加入可以和水溶性醛继续发生席夫碱反应,从而增加产物碳含量,改良导电性实现更优异的电化学性能。
优选地,步骤1)所述分散剂为聚乙烯吡咯烷酮、聚乙二醇辛基苯基醚、聚氧乙烯辛基苯酚醚-10、聚丙烯酸钠、聚甲基丙烯酸钠中的一种以上。分散剂的加入可有效防止纳米球体桥连进而制备单分散纳米球。
步骤1)中所述反应物原料水溶性氨基有机硅和水溶性醛的比例为1:0.5到1:4,选择性添加的非氨基有机硅氧烷和非有机硅类水溶性胺类物质的量均不超过水溶性氨基有机硅的物质的量。
惰性气体为氩气、氮气中的一种。
其中,酸或碱刻蚀,酸为氢氟酸,碱为氢氧化钠溶液、氢氧化钾溶液、四丙基氢氧化铵溶液中的一种。
本发明还保护所述纳米复合碳球的应用,纳米复合碳球用作锂离子电池负极材料、锂硫电池正极载体、储能与催化剂载体、污水处理吸附剂。
本发明的有益效果如下:
1、本发明作为硅烷偶联剂的水溶性氨基有机硅含有Si-C键,通过醛胺缩合反应将有机聚合物和无机硅氧化合物良好地结合在一起,在复合碳球内部形成了连续且均匀分布的碳结构,可大大提高复合材料的性能。
2、本发明制备的纳米复合碳球是碳在材料中连续且均匀分布的多孔复合碳球,其元素组成、比表面积、孔径结构、孔径分布等材料特性具有可调控性,可以通过改变原料比例、添加非氨基有机硅氧烷和\或非有机硅类水溶性胺类物质、改变煅烧温度、刻蚀条件等因素进行调节,当硅氧含量较少时易形成微孔碳球,硅氧含量适中时易形成微介多级孔纳米碳球,硅氧含量较高时形成介孔纳米碳球;
3、本发明制备的纳米碳球可以作为锂离子电池负极材料,通过硅烷偶联剂将硅碳二者良好地复合在了一起,较高的碳含量赋予材料高电导率(0.1S/cm~6.6S/cm),大量的Si、O、N等元素组成则使其有较高容量;
4、本发明通过醛胺缩合反应将有机聚合物和无机硅氧化合物良好地结合在一起,再经热处理刻蚀后,可以形成可控的微介多级孔结构,具有较大的比表面与孔体积,这赋予其较强的物理吸附能力,在作为锂硫电池硫载体时会有更好固硫效果和更好的电化学性能,应用于催化以及吸附领域也有更好的效果。可广泛用作锂硫电池正极载体、储能与催化剂载体、污水处理吸附剂。
5、本发明制备的纳米复合碳球含有一定量的Si、O、N等掺杂元素,这赋予其较强的多硫化物化学吸附能力。总之,在用作锂硫电池正极载体时,所述纳米碳球可以通过物理-化学吸附双重限制作用固定多硫化物,有效抑制多硫化物的穿梭效应,这有助于锂硫电池实现较高的放电比容量与循环稳定性,显著提高锂硫电池的电化学性能。
6、本发明采用了水性反应体系制备前驱体,反应条件温和,是一种简单绿色的材料制备工艺。
附图说明:
图1为通过煅烧刻蚀席夫碱SiO2前驱体制备多孔纳米复合碳球的原理示意图,所述席夫碱SiO2为通过醛胺缩合反应制备的无机-有机复合材料;
图2为实施例1中制备的纳米复合碳球的SEM图片;
图3为实施例1中制备的纳米复合碳球负极的放电比容量(0.2A/g循环充放电);
图4为实施例2中制备的纳米复合碳球的TEM图片;
图5为实施例2中制备的纳米复合碳球负极的放电比容量(0.5A/g循环充放电);
图6为实施例3中制备的纳米复合碳球的SEM图片;
图7为实施例3中制备的硫/碳正极的放电比容量(0.2C循环充放电);
图8为实施例4中制备的纳米复合碳球的TEM图片;
图9为实施例4中制备的硫/碳正极的放电比容量(0.5C循环放电)。
具体实施方式:
以下是对本发明的进一步说明,而不是对本发明的限制。
实施例1:纳米复合碳球材料的制备及其在锂离子电池负极中的应用
按照以下步骤进行的:
(1)准备反应原材料
称取1.0010g聚乙烯吡咯烷酮、1.5422g的γ-氨丙基三甲氧基硅烷、0.6090g的2-氨基苯丙酸、1.8432g的40%甲醛水溶液、500ml水备用,γ-氨丙基三甲氧基硅烷:2-氨基苯丙酸:甲醛物质的量比为0.7:0.3:2。
(2)制备席夫碱SiO2前驱体
将步骤1称取的聚乙烯吡咯烷酮、γ-氨丙基三甲氧基硅烷、2-氨基苯丙酸溶解到水中,搅拌1h至均匀后,滴加40%甲醛水溶液,在20℃反应12h后,得到席夫碱SiO2前驱体悬浮液,将悬浮液离心水洗之后得到前驱体,使用热风烘箱在80℃烘干24h。
(3)纳米复合碳球的制备
在氩气保护下,将烘干的前驱体放入刚玉坩埚并在管式炉中于900℃煅烧3h,煅烧升温速度为2℃/min,制得中间体并研磨。
将中间体放置到四氟乙烯容器中,加入20wt%浓度的氢氧化钠溶液并在20℃刻蚀2h,将制备的碳球抽滤洗涤至滤液中性后放置到真空烘箱中烘干,烘干温度60℃,烘干时间为12h。
(4)纳米复合碳球的表征
将制备的纳米复合碳球进行XRD、XPS测试,结果显示该纳米碳球为无定型结构,由Si、O、C、N四种元素组成;高分辨XPS图谱显示材料含有Si-O、SiOxCyNz、C-N键等基团;热重分析(TGA)测试表明,Si、O、N等元素含量为48.5wt%;BET分析表明,其比表面积可达403.5m2/g,所述纳米复合碳球平均粒径约为140nm。
(5)电化学性能
将制备的纳米复合碳球、乙炔黑、羧甲基纤维素钠按照8:1:1的比例混合均匀制成浆料后,涂布在铜箔上,在80℃条件下真空烘干12h,经辊压、裁切以及称量后得到锂离子电池负极极片,极片上纳米复合碳球的负载量为0.6mg/cm2。将负极极片组装成锂离子电池,锂离子电池电解液为浓度1M LiPF6/DMC/DEC/EMC,其中DMC/DEC/EMC体积比为1:1:1,隔膜采用Celgard-2325,采用锂片作为对电极。电化学测试表明,在0.2A/g电流密度下循环充放电120圈,放电比容量仍保持在561.2mAh/g,其余效率保持在99.8%以上。其中锂离子电池的放电比容量按照有效物质(即纳米复合碳球)的质量计算。
对比例1:
不加入实施例1中的分散剂,其他步骤与实施例1相同,无法得到均匀且单分散席夫碱SiO2球。
对比例2:
将实施例1中的刻蚀时间增加到48h,其他步骤与实施例1相同,材料无法保持球状结构。
实施例2:纳米复合碳球材料的制备及其在锂离子电池负极中的应用
按照以下步骤进行的:
(1)准备反应原材料
称取0.2402g聚乙烯吡咯烷酮、0.4484g的γ-氨丙基三甲氧基硅烷、0.5210g的四乙氧基硅烷,0.2854g的己二醛、700ml水备用,γ-氨丙基三甲氧基硅烷:四乙氧基硅烷:己二醛物质的量比为1:1:1。
(2)制备席夫碱SiO2前驱体
将步骤1称取的己二醛溶解到200ml水中,将称取的聚乙烯吡咯烷酮、γ-氨丙基三甲氧基硅烷、四乙氧基硅烷溶解到500ml水中搅拌6h后滴加上述己二醛溶液,在30℃反应3h后,得到席夫碱SiO2前驱体悬浮液,将悬浮液离心水洗之后得到前驱体,使用热风烘箱在60℃烘干24h。
(3)纳米复合碳球的制备
在氮气保护下,将烘干的前驱体放入刚玉坩埚并在管式炉中于800℃煅烧5h,煅烧升温速度为2℃/min,制得中间体并研磨。
将中间体放置到四氟乙烯容器中,加入质量百分比5wt%浓度的氢氧化钠溶液并在40℃刻蚀1h,将制备的碳球抽滤洗涤至滤液中性后放置到真空烘箱中烘干,烘干温度90℃,烘干时间为12h。
(4)纳米复合碳球的表征
将制备的纳米复合碳球进行XRD、XPS测试,结果显示所制备的碳球为无定型结构,由Si、O、C、N四种元素组成;高分辨XPS图谱显示材料含有SiO2、SiOxCyNz、C-N键等基团;热重分析(TGA)测试表明,Si、O、N等杂元素含量为49.8wt%;BET分析表明,其比表面积可达354.7m2/g,所述纳米复合碳球平均粒径为95nm。
(5)电化学性能
将制备的纳米复合碳球、乙炔黑、羧甲基纤维素钠按照8:1:1的比例混合均与制成浆料后,涂布在铜箔上,在80℃条件下真空烘干12h,经辊压、裁切以及称量后得到锂离子电池负极极片,极片上纳米碳球的负载量为0.6mg/cm2。将负极极片组装成锂离子电池,锂离子电池电解液为浓度1M LiPF6/DMC/DEC/EMC,其中DMC/DEC/EMC体积比为1:1:1,电解液中添加10wt%的FEC,隔膜采用Celgard-2325,采用锂片作为对电极与参比电极。电化学实验发现,在0.5A/g电流密度下循环充放电120圈,放电比容量仍保持在423.2mAh/g,其余效率保持在99.5%以上。其中锂离子电池的放电比容量按照有效物质(即纳米复合碳球)的质量计算。
实施例3:纳米复合碳球材料的制备及其锂硫电池中的应用
按照以下步骤进行的:
(1)准备反应原材料
称取0.8054g聚甲基丙烯酸钠分散剂,称取2.0735g的γ-氨丙基三甲氧基硅烷、1.8526g的50%戊二醛水溶液、600ml水备用,γ-氨丙基三甲氧基硅烷与戊二醛物质的量比为1:0.8。
(2)制备席夫碱SiO2前驱体
将步骤(1)称取的聚甲基丙烯酸钠、γ-氨丙基三甲氧基硅烷溶解到水中,搅拌0.5h至均匀后,滴加50%戊二醛,在80℃反应1h后,得到席夫碱SiO2前驱体悬浮液,将悬浮液离心水洗之后得到前驱体,使用热风烘干箱在80℃烘干24h。
(3)纳米复合碳球的制备与表征
在氩气保护下,将烘干的前驱体放入刚玉坩埚并置入管式炉中于700℃煅烧5h,煅烧升温速度为2℃/min,制得中间体并研磨。
将中间体放置到四氟乙烯容器中,加入质量百分比10wt%氢氟酸并在80℃刻蚀24h,将制备的碳球抽滤洗涤至滤液中性后放置到真空烘箱中烘干,烘干温度100℃,烘干时间为12h。
使用材料分析仪器对上述制备的纳米复合碳球进行表征。复合碳球平均粒径约为70nm。BET测试表明,实施例3制备的碳材料在0.50~36.00nm范围内具有微-介孔孔径分布,比表面为724.08m2/g,孔体积为1.05cm3/g,平均孔径为0.70nm。XPS测试表明,制备的纳米复合碳球为Si、O、N杂元素掺杂,其元素组成为:Si含量为3.43%,O含量为14.27%,碳含量为78.29%,氮含量为4.01%(以mol%表示)。
(4)电化学性能
将制备的纳米复合碳球与升华硫按照3:7质量比混合均匀,并置于密封玻璃瓶中,将样品瓶放置到管式炉中,在氩气保护下于155℃加热12h制备硫/碳正极材料。将制备的S/C正极材料与乙炔黑、羧甲基纤维素钠按照7:2:1的比例混合均与制成浆料后,涂布在碳纸上,在60℃条件下真空烘干12h,经裁切、称量后得到锂硫电池正极极片,极片上S的负载量为1.2mg/cm2。将S正极极片组装成二次锂硫电池,锂硫电池电解液为浓度1M LiTFSI/DOL/DME,其中DOL与DME体积比为1:1,电解液中添加0.2M的LiNO3,隔膜为Celgard-2325,采用锂片作为对电极与参比电极。
将锂硫电池放置到电池性能测试架上,测试电池的电化学性能。实验发现,将电池在0.1C下活化3圈,然后在0.2C下循环充放电100圈,锂硫电池的放电比容量保持在816.38mAh/g,库伦效率保持在98.92%以上。其中1C=1675mA/g,电池的放电比容量按照单质硫的质量计算。
实施例4:组成与结构可调控纳米复合碳球的制备及其在Li-S电池中的应用
按照以下步骤进行的:
(1)准备反应原材料
称取0.8475g聚丙烯酸钠分散剂,称取2.7870g的γ-氨丙基三乙氧基硅烷、0.8626g的己二醛、0.1343g的乙二胺、0.3807g的四甲氧基硅烷、700ml水备用,γ-氨丙基三乙氧基硅烷与戊二醛、乙二胺:四甲氧基硅烷物质的量比为1:0.6:0.2:1。
(2)制备席夫碱SiO2前驱体
将步骤(1)称取的乙二醛、己二醛溶解到200ml水中,将称取的聚丙烯酸钠、γ-氨丙基三乙氧基硅烷溶解到500ml水中搅拌0.5h均匀后滴加上述制备的乙二醛-己二醛混合溶液,在40℃反应6h后,得到席夫碱SiO2前驱体悬浮液;将悬浮液离心水洗之后得到前驱体,使用热风烘箱在80℃烘干24h。
(3)纳米复合碳球的制备与表征
在氮气保护下,将烘干的前驱体放入刚玉坩埚并置入管式炉中于1100℃煅烧2h,煅烧升温速度为2℃/min,制得中间体并研磨筛分。
将中间体放置到四氟乙烯容器中,加入质量百分比20wt%的氢氧化钠溶液并在80℃刻蚀24h,将制备的碳球抽滤洗涤至滤液中性后放置到真空烘箱中烘干,烘干温度100℃,烘干时间为12h。
使用材料分析仪器对上述制备的纳米复合碳球进行表征。复合碳球平均粒径约为105nm。BET测试表明,实施例4制备的纳米碳球在0.50~36.00nm范围内具有微-介孔孔径分布,比表面为1423.38m2/g,孔体积为1.05cm3/g。XPS测试表明,制备的纳米复合碳球含有Si、O、N杂元素掺杂,其元素组成为:Si含量为1.43%,O含量为5.27%,碳含量为89.29%,氮含量为4.01%(以mol%表示)。
(4)电化学性能
将制备的纳米复合碳球与升华硫按照3:7质量比混合均匀并置于密封玻璃瓶中,将样品瓶放置到管式炉中,在氩气保护下于155℃加热12h制备硫/碳正极材料。将制备的S/C正极材料与乙炔黑、海藻酸钠按照7:2:1的比例混合均与制成浆料后,涂布在碳纸上,在60℃条件下真空烘干12h,经裁切、称量后得到锂硫电池正极极片,极片上S的负载量为1.0mg/cm2。将S正极极片组装成二次锂硫电池,锂硫电池电解液为浓度1M LiTFSI/DOL/DME,其中DOL与DME体积比为1:1,电解液中添加0.2M的LiNO3,隔膜为Celgard-2325,采用锂片作为对电极与参比电极。
将锂硫电池放置到电池性能测试架上,测试电池的电化学性能。实验发现,将电池在0.1C下活化3圈,然后在0.5C下循环80圈,Li-S电池的放电比容量保持在780.97mAh/g,库伦效率保持在98.12%。其中1C=1675mA/g,电池的放电比容量按照单质硫的质量计算。
以上仅是本发明的优选实施方式,本发明的保护范围并不仅限于上述实施例,与本发明构思无实质性差异的各种技术方案均在本发明的保护范围内。
Claims (10)
1.一种纳米复合碳球,其特征在于,所述纳米复合碳球为碳连续且均匀分布的实心多孔复合碳球,含有Si、O、N元素,碳元素含量为50~99wt%,纳米复合碳球粒径为50~200nm,具有多孔结构,采用水溶性氨基有机硅和水溶性醛发生醛胺缩合、高温煅烧以及刻蚀后处理步骤制备获得;其元素组成、比表面积、孔径结构、孔径分布具有可调控性,通过改变原料比例、添加非氨基有机硅氧烷和\或非有机硅类水溶性胺类物质、改变煅烧温度、刻蚀条件进行调控。
2.一种纳米复合碳球的制备方法,其特征在于,该方法包括以下步骤:
1)在分散剂的作用下,水溶性氨基有机硅和水溶性醛发生醛胺缩合反应制取席夫碱SiO2前驱体,反应温度为20~90℃,反应时间为1~12h;
2)将步骤1)制备的席夫碱SiO2前驱体分离烘干后,通过惰性气体保护下700~1300℃高温煅烧2~6h以及酸或碱刻蚀并经洗涤烘干后处理制备得到纳米复合碳球;刻蚀温度为20~100℃,刻蚀时间为0.5~48h;所述纳米复合碳球粒径为50~200nm,碳元素含量为50~99wt%。
3.根据权利要求2所述的纳米复合碳球的制备方法,其特征在于,所述纳米复合碳球的元素组成、比表面积与孔径结构和孔径分布具有可调控性,通过改变原料比例、在步骤1)添加非氨基有机硅氧烷和\或非有机硅类水溶性胺类物质、改变煅烧温度或刻蚀条件进行调控,水溶性氨基有机硅和水溶性醛的比例为1:0.5到1:4,选择性添加的非氨基有机硅氧烷或非有机硅类水溶性胺类的物质的量不超过水溶性氨基有机硅的物质的量。
4.根据权利要求2或3所述的纳米复合碳球的制备方法,其特征在于,所述水溶性氨基有机硅为γ-氨丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、N-[3-(三甲氧基硅基)丙基]乙二胺、六甲基二硅胺烷、2,2,4,4,6,6-六甲基环三硅氮烷、八甲基环四硅氮烷、八氨基丙基笼形聚倍半硅氧烷中的一种以上;所述水溶性醛为甲醛、乙二醛、丙酮醛、戊二醛、己二醛、水杨醛中的一种以上。
5.根据权利要求2或3所述的纳米复合碳球的制备方法,其特征在于,非氨基有机硅氧烷为四甲氧基硅烷、四乙氧基硅烷、β-氰乙基三乙氧基硅烷、甲基三甲氧基硅烷、苯甲基三乙氧基硅烷、乙烯基三甲氧基硅烷、γ-氰乙基三乙氧基硅烷中的一种以上。
6.根据权利要求2或3所述的纳米复合碳球的制备方法,其特征在于,所述非有机硅类水溶性胺类物质包括丁胺、一乙醇胺、乙二胺、二乙二胺、聚乙烯亚胺、苄基胺、四氢呋喃胺、氨基酸中的一种以上。
7.根据权利要求2或3所述的纳米复合碳球的制备方法,其特征在于,步骤1)所述分散剂为聚乙烯吡咯烷酮、聚乙二醇辛基苯基醚、聚氧乙烯辛基苯酚醚-10、聚丙烯酸钠、聚甲基丙烯酸钠中的一种以上。
8.根据权利要求2或3所述的纳米复合碳球的制备方法,其特征在于,惰性气体为氩气、氮气中的一种。
9.根据权利要求2或3所述的纳米复合碳球的制备方法,其特征在于,酸或碱刻蚀,酸为氢氟酸,碱为氢氧化钠溶液、氢氧化钾溶液、四丙基氢氧化铵溶液中的一种。
10.权利要求1所述纳米复合碳球的制备方法得到的纳米复合碳球的应用,其特征在于,纳米复合碳球用作锂离子电池负极材料、锂硫电池正极载体、储能与催化剂载体、污水处理吸附剂。
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CN115246638A (zh) * | 2022-08-22 | 2022-10-28 | 东北大学秦皇岛分校 | 一种内表面褶皱的中空介孔碳球的制备方法及应用 |
CN115246638B (zh) * | 2022-08-22 | 2023-11-17 | 东北大学秦皇岛分校 | 一种内表面褶皱的中空介孔碳球的制备方法及应用 |
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