CN117525372B - 一种基于金属有机骨架材料的锂电池负极材料 - Google Patents
一种基于金属有机骨架材料的锂电池负极材料 Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 49
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 26
- 239000010405 anode material Substances 0.000 title claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000011247 coating layer Substances 0.000 claims abstract description 6
- 239000007773 negative electrode material Substances 0.000 claims abstract description 4
- 239000011258 core-shell material Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- -1 methacryloxypropyl Chemical group 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 239000002096 quantum dot Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 10
- 238000010000 carbonizing Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 230000010355 oscillation Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 210000004940 nucleus Anatomy 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
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- 238000012546 transfer Methods 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 108010047956 Nucleosomes Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 210000001623 nucleosome Anatomy 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M10/052—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
本发明涉及锂电池技术领域,具体为一种基于金属有机骨架材料的锂电池负极材料,所述锂电池负极材料为核壳结构,核体为MOFs碳化产物,壳体为多孔碳包覆层,所述核体与壳体之间有空腔,本发明所制备的锂电池负极材料电化学性能良好,循环稳定性优异。
Description
技术领域
本发明涉及锂电池技术领域,具体为一种基于金属有机骨架材料的锂电池负极材料。
背景技术
近几年来,手机、平板、笔记本电脑等便携式电子产品的快速发展,以及新能源电动汽车的不断普及,对能量存储***的需求越来越大。与传统的铅酸电池等相比,锂离子电池具有能量密度大、毒性较低、循环寿命长等优点,因而广泛应用于电子消费产品领域。
金属有机骨架材料本身具有大比表面积、高孔隙率、孔径可调等优点,将其作为锂离子电池电极材料能够为充放电反应过程中锂离子的脱嵌提供有利通道及多的活性位点,从而有助于改善锂离子电池的电化学性能,2006年MOFs(MOF-177)材料首次被用作锂离子电池负极材料,研究发现,材料在50mA/g的电流密度下首次放电比容量为425mAh/g,但低的库伦效率导致容量的严重衰减,尽管MOF-177作为电极材料不太理想,但为MOFs电极材料的开发奠定了基础。
虽然经过长时间的不懈努力,金属有机骨架材料在锂离子电池电极上的应用性能得到了极大的改善。但现有材料仍存在首次放电比容量低,循环稳定性等缺陷。
发明内容
发明目的:针对上述技术问题,本发明提出了一种基于金属有机骨架材料的锂电池负极材料。
所采用的技术方案如下:
一种基于金属有机骨架材料的锂电池负极材料:
所述锂电池负极材料为核壳结构,核体为MOFs碳化产物,壳体为多孔碳包覆层;
所述核体与壳体之间有空腔。
进一步地,所述核体为石墨烯量子点掺杂CuCo-MOFs的碳化产物。
进一步地,所述基于金属有机骨架材料的锂电池负极材料的备方法如下:
将2-甲基咪唑和石墨烯量子点加入到乙醇中并混匀,再将水溶性铜盐和水溶性钴盐加入,搅拌反应12h以上,收集产物,洗涤后干燥得到石墨烯量子点掺杂CuCo-MOFs,将石墨烯量子点掺杂CuCo-MOFs加入到水与乙醇组成的共混溶液中,超声振荡分散后,滴加正硅酸乙酯,再将反应体系的pH调节至3-4,搅拌反应30min以上,再将反应体系的pH调节至8-9,继续搅拌反应1h以上,收集产物,干燥得到中间体,将中间体和乳化剂加入到水中,超声振荡分散后,加入丙烯酸酯单体、丙烯腈和POSS单体,搅拌升温至60-80℃,加入自由基引发剂,反应1-5h后收集产物,洗涤后干燥得到前驱体,将前驱体在惰性气氛下一次碳化后蚀刻再在惰性气氛下进行二次碳化即可。
进一步地,所述石墨烯量子点的用量为2-甲基咪唑重量的1-10%。
进一步地,所述水溶性铜盐和水溶性钴盐的摩尔比为1:1-5。
进一步地,所述丙烯酸酯单体为丙烯酸、甲基丙烯酸、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸异丁酯、甲基丙烯酸异丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯中的任意一种或多种组合。
进一步地,所述POSS单体为甲基丙烯酰氧丙基七异丁基POSS、甲基丙烯酰氧丙基七苯基POSS、甲基丙烯酸甲酯基七异辛基POSS、甲基丙烯酰氧丙基七环戊基POSS、甲基丙烯酰氧丙基七环己基POSS中的任意一种或多种组合。
进一步地,所述丙烯酸酯单体、丙烯腈和POSS单体的重量比为70-90:5-10:1-5。
进一步地,一次碳化温度为650-750℃,一次碳化时间为1-3h,二次碳化温度为850-950℃,二次碳化时间为1-3h。
进一步地,蚀刻所使用的蚀刻液为质量浓度为1-15%的氢氟酸溶液。
本发明的有益效果:本发明提供了一种基于金属有机骨架材料的锂电池负极材料,将MOFs进行热解,形成碳/氧化物复合材料,可改变MOFs本身导电性和稳定性差的缺点,石墨烯量子点的引入一方面有利于提高所合成CuCo-MOFs的比表面积和孔体积,另一方面可以提高碳化产物的导电性,提高电子的转移速度,丙烯酸酯单体、丙烯腈和POSS单体的共聚物碳化后形成氮掺杂含SiOx包覆炭层,再利用蚀刻法除去SiOx和核体与壳体之间的SiO2,在核体与壳体之间形成空腔,并且在包覆炭层上形成多孔结构,这种特殊的结构有助于Li+的扩散和电解液的浸润,促进电解液和电子的快速传递,增强储锂能力,也可以缓解放电/充电过程中的体积膨胀,增强负极材料的循环稳定性,本发明所制备的锂电池负极材料电化学性能良好,循环稳定性优异。
附图说明
图1为实施例1中所制备锂电池负极材料的TEM图。
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
一种基于金属有机骨架材料的锂电池负极材料的制备方法:
将1.97g 2-甲基咪唑和98.5mg石墨烯量子点加入到25ml乙醇中并混匀,再将0.24g硝酸铜和0.58g硝酸钴加入,室温下搅拌反应24h,离心,收集产物,用去离子水和乙醇反复洗涤后置于60℃真空烘箱中干燥10h得到石墨烯量子点掺杂CuCo-MOFs,将石墨烯量子点掺杂CuCo-MOFs加入到20ml去离子水与8ml乙醇组成的共混溶液中,超声振荡分散30min后,滴加6ml正硅酸乙酯,再滴加0.05M盐酸溶液使反应体系的pH调节至3,搅拌反应45min,再滴加氨水使反应体系的pH调节至8.5,继续搅拌反应2h,收集得到的凝胶状产物,置于80℃真空烘箱中干燥10h得到中间体,将中间体和0.5g乳化剂SDS加入到100ml去离子水中,超声振荡分散30min后,加入8g甲基丙烯酸甲酯、1g丙烯腈和0.25g甲基丙烯酰氧丙基七异丁基POSS,搅拌升温至70℃,加入0.01g 自由基引发剂AIBN,反应4h后滤出产物,用去离子水洗涤后置于80℃真空烘箱中干燥10h得到前驱体,将前驱体置于马弗炉中,通入氩气保护,以1℃/min的速度升温至700℃一次碳化2h后自然冷却至室温,置于100ml质量浓度为10%的氢氟酸溶液中蚀刻10min后滤出去离子水洗涤至中性后置于80℃真空烘箱中干燥10h,再转移至马弗炉中,通入氩气保护,以1℃/min的速度升温至950℃二次碳化2h后自然冷却至室温即可得到以MOFs碳化产物为核体,多孔碳包覆层为壳体,核体与壳体之间有空腔的锂电池负极材料。
实施例2
一种基于金属有机骨架材料的锂电池负极材料的制备方法:
将1.97g 2-甲基咪唑和197mg石墨烯量子点加入到25ml乙醇中并混匀,再将0.24g硝酸铜和0.58g硝酸钴加入,室温下搅拌反应24h,离心,收集产物,用去离子水和乙醇反复洗涤后置于60℃真空烘箱中干燥10h得到石墨烯量子点掺杂CuCo-MOFs,将石墨烯量子点掺杂CuCo-MOFs加入到20ml去离子水与8ml乙醇组成的共混溶液中,超声振荡分散30min后,滴加6ml正硅酸乙酯,再滴加0.05M盐酸溶液使反应体系的pH调节至3,搅拌反应45min,再滴加氨水使反应体系的pH调节至8.5,继续搅拌反应2h,收集得到的凝胶状产物,置于80℃真空烘箱中干燥10h得到中间体,将中间体和0.5g乳化剂SDS加入到100ml去离子水中,超声振荡分散30min后,加入9g甲基丙烯酸甲酯、1g丙烯腈和0.5g甲基丙烯酰氧丙基七异丁基POSS,搅拌升温至80℃,加入0.01g 自由基引发剂AIBN,反应5h后滤出产物,用去离子水洗涤后置于80℃真空烘箱中干燥10h得到前驱体,将前驱体置于马弗炉中,通入氩气保护,以1℃/min的速度升温至750℃一次碳化2h后自然冷却至室温,置于100ml质量浓度为15%的氢氟酸溶液中蚀刻10min后滤出去离子水洗涤至中性后置于80℃真空烘箱中干燥10h,再转移至马弗炉中,通入氩气保护,以1℃/min的速度升温至950℃二次碳化2h后自然冷却至室温即可得到以MOFs碳化产物为核体,多孔碳包覆层为壳体,核体与壳体之间有空腔的锂电池负极材料。
实施例3
一种基于金属有机骨架材料的锂电池负极材料的制备方法:
将1.97g 2-甲基咪唑和19.7mg石墨烯量子点加入到25ml乙醇中并混匀,再将0.24g硝酸铜和0.58g硝酸钴加入,室温下搅拌反应24h,离心,收集产物,用去离子水和乙醇反复洗涤后置于60℃真空烘箱中干燥10h得到石墨烯量子点掺杂CuCo-MOFs,将石墨烯量子点掺杂CuCo-MOFs加入到20ml去离子水与8ml乙醇组成的共混溶液中,超声振荡分散30min后,滴加6ml正硅酸乙酯,再滴加0.05M盐酸溶液使反应体系的pH调节至3,搅拌反应45min,再滴加氨水使反应体系的pH调节至8.5,继续搅拌反应2h,收集得到的凝胶状产物,置于80℃真空烘箱中干燥10h得到中间体,将中间体和0.5g乳化剂SDS加入到100ml去离子水中,超声振荡分散30min后,加入7g甲基丙烯酸甲酯、0.5g丙烯腈和0.1g甲基丙烯酰氧丙基七异丁基POSS,搅拌升温至60℃,加入0.01g 自由基引发剂AIBN,反应2h后滤出产物,用去离子水洗涤后置于80℃真空烘箱中干燥10h得到前驱体,将前驱体置于马弗炉中,通入氩气保护,以1℃/min的速度升温至650℃一次碳化2h后自然冷却至室温,置于100ml质量浓度为10%的氢氟酸溶液中蚀刻10min后滤出去离子水洗涤至中性后置于80℃真空烘箱中干燥10h,再转移至马弗炉中,通入氩气保护,以1℃/min的速度升温至850℃二次碳化2h后自然冷却至室温即可得到以MOFs碳化产物为核体,多孔碳包覆层为壳体,核体与壳体之间有空腔的锂电池负极材料。
对比例1:与实施例1基本相同,区别在于,不加入石墨烯量子点。
对比例2:与实施例1基本相同,区别在于,用相同物质的量的硝酸钴代替硝酸铜。
对比例3:与实施例1基本相同,区别在于,核体与壳体之间没有空腔,制备方法如下:
将1.97g 2-甲基咪唑和98.5mg石墨烯量子点加入到25ml乙醇中并混匀,再将0.24g硝酸铜和0.58g硝酸钴加入,室温下搅拌反应24h,离心,收集产物,用去离子水和乙醇反复洗涤后置于60℃真空烘箱中干燥10h得到石墨烯量子点掺杂CuCo-MOFs,将石墨烯量子点掺杂CuCo-MOFs和0.5g乳化剂SDS加入到100ml去离子水中,超声振荡分散30min后,加入8g甲基丙烯酸甲酯、1g丙烯腈和0.25g甲基丙烯酰氧丙基七异丁基POSS,搅拌升温至70℃,加入0.01g 自由基引发剂AIBN,反应4h后滤出产物,用去离子水洗涤后置于80℃真空烘箱中干燥10h得到前驱体,将前驱体置于马弗炉中,通入氩气保护,以1℃/min的速度升温至700℃一次碳化2h后自然冷却至室温,置于100ml质量浓度为10%的氢氟酸溶液中蚀刻10min后滤出去离子水洗涤至中性后置于80℃真空烘箱中干燥10h,再转移至马弗炉中,通入氩气保护,以1℃/min的速度升温至950℃二次碳化2h后自然冷却至室温即可得到以MOFs碳化产物为核体,多孔碳包覆层为壳体,核体与壳体之间有空腔的锂电池负极材料。
对比例4:与实施例1基本相同,区别在于,不含甲基丙烯酰氧丙基七异丁基POSS。
性能测试:分别将本发明实施例1-3及对比例1-4中所制备的锂电池负极材料作为试样进行性能测试;
将试样、导电剂(导电炭黑)、粘结剂(聚偏氟乙烯)按照8:1:1的质量比进行混合研磨。研磨充分后,加入适量的N-甲基吡咯烷酮(NMP)进行充分搅拌,形成固含量在50%的浆料;
然后将浆料涂覆在铜箔表面并在真空中于60℃干燥12h。将处理后的铜箔进行切片处理得到用于组装电池的电极片。材料的电化学性能通过以金属锂作为正极,使用Celgard隔膜,制备的电极片作为负极,1mol/L的LiPF6的氟代乙酸酯(FEC)/碳酸二甲酯(DMC)/碳酸甲乙酯(EMC)(体积比为1:1:1)为电解液组成CR2032纽扣电池;
将制备的CR2032纽扣电池静置20h后进行恒流充放电测试,电流密度200mA/g。
测试结果如表1所示:
表1:
;
由上表1可知,本发明所制备的锂电池负极材料电化学性能良好,循环稳定性优异。
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 (8)
1.一种基于金属有机骨架材料的锂电池负极材料,其特征在于,所述锂电池负极材料为核壳结构,核体为石墨烯量子点掺杂CuCo-MOFs的碳化产物,壳体为多孔碳包覆层;
所述核体与壳体之间有空腔;
上述基于金属有机骨架材料的锂电池负极材料的制备方法如下:
将2-甲基咪唑和石墨烯量子点加入到乙醇中并混匀,再将水溶性铜盐和水溶性钴盐加入,搅拌反应12h以上,收集产物,洗涤后干燥得到石墨烯量子点掺杂CuCo-MOFs,将石墨烯量子点掺杂CuCo-MOFs加入到水与乙醇组成的共混溶液中,超声振荡分散后,滴加正硅酸乙酯,再将反应体系的pH调节至3-4,搅拌反应30min以上,再将反应体系的pH调节至8-9,继续搅拌反应1h以上,收集产物,干燥得到中间体,将中间体和乳化剂加入到水中,超声振荡分散后,加入丙烯酸酯单体、丙烯腈和POSS单体,搅拌升温至60-80℃,加入自由基引发剂,反应1-5h后收集产物,洗涤后干燥得到前驱体,将前驱体在惰性气氛下一次碳化后蚀刻再在惰性气氛下进行二次碳化即可。
2.如权利要求1所述的基于金属有机骨架材料的锂电池负极材料,其特征在于,所述石墨烯量子点的用量为2-甲基咪唑重量的1-10%。
3.如权利要求1所述的基于金属有机骨架材料的锂电池负极材料,其特征在于,所述水溶性铜盐和水溶性钴盐的摩尔比为1:1-5。
4.如权利要求1所述的基于金属有机骨架材料的锂电池负极材料,其特征在于,所述丙烯酸酯单体为丙烯酸、甲基丙烯酸、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸异丁酯、甲基丙烯酸异丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯中的任意一种或多种组合。
5.如权利要求1所述的基于金属有机骨架材料的锂电池负极材料,其特征在于,所述POSS单体为甲基丙烯酰氧丙基七异丁基POSS、甲基丙烯酰氧丙基七苯基POSS、甲基丙烯酸甲酯基七异辛基POSS、甲基丙烯酰氧丙基七环戊基POSS、甲基丙烯酰氧丙基七环己基POSS中的任意一种或多种组合。
6.如权利要求1所述的基于金属有机骨架材料的锂电池负极材料,其特征在于,所述丙烯酸酯单体、丙烯腈和POSS单体的重量比为70-90:5-10:1-5。
7.如权利要求1所述的基于金属有机骨架材料的锂电池负极材料,其特征在于,一次碳化温度为650-750℃,一次碳化时间为1-3h,二次碳化温度为850-950℃,二次碳化时间为1-3h。
8.如权利要求1所述的基于金属有机骨架材料的锂电池负极材料,其特征在于,蚀刻所使用的蚀刻液为质量浓度为1-15%的氢氟酸溶液。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20160060378A (ko) * | 2014-11-20 | 2016-05-30 | 한국과학기술연구원 | 일체형 핵-껍질 구조를 가진 코발트산화물-탄소나노복합체 양자점과 이를 이용한 리튬이차전지용 음극 활물질 조성물 및 그 제조방법 |
GB2586562A (en) * | 2020-06-01 | 2021-02-24 | Hangzhou Debiao New Energy Equipment Co Ltd | A lithium-ion battery and preparation methods thereof |
CN113422055A (zh) * | 2021-05-27 | 2021-09-21 | 复旦大学 | 亲锂性石墨烯量子点/锂复合材料及其制备方法和应用 |
CN114597358A (zh) * | 2021-12-29 | 2022-06-07 | 昆明理工大学 | 一种双金属MOF衍生的Si@CoCu-ZIF复合负极材料及其制备方法和应用 |
KR20220106403A (ko) * | 2021-01-22 | 2022-07-29 | 계명대학교 산학협력단 | 그래핀 양자점/실리콘/탄소나노소재 복합체의 제조방법 및 이를 이용한 이차전지 제조방법 |
CN116598459A (zh) * | 2023-05-26 | 2023-08-15 | 广东工业大学 | 一种钾离子电池负极材料及其制备方法和应用 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20200185788A1 (en) * | 2017-02-07 | 2020-06-11 | Ford Cheer International Limited | Electrodes having electrode additive for high performance batteries and applications of same |
-
2024
- 2024-01-05 CN CN202410018686.0A patent/CN117525372B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20160060378A (ko) * | 2014-11-20 | 2016-05-30 | 한국과학기술연구원 | 일체형 핵-껍질 구조를 가진 코발트산화물-탄소나노복합체 양자점과 이를 이용한 리튬이차전지용 음극 활물질 조성물 및 그 제조방법 |
GB2586562A (en) * | 2020-06-01 | 2021-02-24 | Hangzhou Debiao New Energy Equipment Co Ltd | A lithium-ion battery and preparation methods thereof |
KR20220106403A (ko) * | 2021-01-22 | 2022-07-29 | 계명대학교 산학협력단 | 그래핀 양자점/실리콘/탄소나노소재 복합체의 제조방법 및 이를 이용한 이차전지 제조방법 |
CN113422055A (zh) * | 2021-05-27 | 2021-09-21 | 复旦大学 | 亲锂性石墨烯量子点/锂复合材料及其制备方法和应用 |
CN114597358A (zh) * | 2021-12-29 | 2022-06-07 | 昆明理工大学 | 一种双金属MOF衍生的Si@CoCu-ZIF复合负极材料及其制备方法和应用 |
CN116598459A (zh) * | 2023-05-26 | 2023-08-15 | 广东工业大学 | 一种钾离子电池负极材料及其制备方法和应用 |
Non-Patent Citations (1)
Title |
---|
A highly flexible and self-healable rechargeable fibrous Zn-MnO2 battery;Bingtian Zhao等;Sustainable Energy & Fuels;20210421;第5卷(第11期);第2907-2915页 * |
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