CN107706362A - 一种石墨烯复合电极材料的制备方法 - Google Patents
一种石墨烯复合电极材料的制备方法 Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 64
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000007772 electrode material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- -1 graphite alkene Chemical class 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 238000010494 dissociation reaction Methods 0.000 claims description 2
- 230000005593 dissociations Effects 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 238000000407 epitaxy Methods 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 238000004904 shortening Methods 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 229910009866 Ti5O12 Inorganic materials 0.000 description 1
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- QKBNDJRSDDTNDX-UHFFFAOYSA-N lithium;propan-2-one Chemical compound [Li].CC(C)=O QKBNDJRSDDTNDX-UHFFFAOYSA-N 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
本发明涉及一种石墨烯复合电极材料的制备方法,其特征在于:将石墨烯与聚乙二醇混合并超声分散到溶剂中,形成导电石墨烯分散液,然后在导电石墨烯分散液中加入钛源形成混合液A,将锂盐溶解于溶剂中形成溶液B,将溶液B缓慢滴加到混合液A中得到混合液C,经搅拌、干燥后,在保护气氛中进行热处理烧结得到纳米钛酸锂‑石墨烯复合材料。其使用了分散性较好的导电石墨烯分散液,解决了石墨烯在复合材料中分散性较差的问题,并且石墨烯可以抑制钛酸锂晶粒长大,缩短充放电时Li+的扩散路径,从而同时提高了钛酸锂复合材料的电子导电性和离子导电性,因而所得到的纳米钛酸锂‑石墨烯复合材料具有较好的倍率性能。
Description
技术领域
本发明涉及一种石墨烯复合电极材料的制备方法,属于锂离子电池和混合超级电容器技术领域。
背景技术
当今时代,煤、石油、天然气等不可再生资源日益枯竭,环境问题越来越受到人们的关注,开发和利用可再生资源成为解决人类生存和发展的重要问题。传统的铅酸蓄电池、镍氢蓄电池能量密度和功率密度已经不能满足未来储能系统的要求,特别是伴随着电动汽车及笔记本电脑、数码相机等各种便携式电子设备的广泛应用,对电池的可逆存储容量及稳定性要求更高,并要求具有较长的使用寿命,因此研究和开发具有更高性能的锂离子电池至关重要。新一代环境友好的锂离子二次电池具有能量密度高、工作电压高、自放电小、循环寿命长、无记忆效应、环境友好等优点,是继镍氢电池、镍镉电池之后的可充电绿色电池,近年来成为人们关注的重点。
在锂离子电池中,电极材料的选择对电池的比能量、循环稳定性等有很大影响,因此选择合适的电极材料有望提高锂离子电池的综合性能。目前市场上锂离子电池负极材料使用的主要是各种嵌锂碳材料(石墨、中间相炭微球等),虽然采用碳材料的锂离子电池具有能量密度高的优点,但是其功率特性、循环寿命和安全性却受到了限制。近年来,钛酸锂(Li4Ti5O12)作为动力锂离子电池的负极材料日益受到重视,这是因为尖晶石型Li4Ti5O12在锂离子插入和脱出前后的晶格常数变化很小,被称为“零应变材料”,因而可以具有优异的循环稳定性,同时Li4Ti5O12的充放电平台电位约1.55 V(vs. Li+/Li),当用作锂离子电池负极时,比金属锂和碳类材料电位高很多,不但表面不形成固体电解质膜(SEI膜),而且在充放电过程中避免了可导致安全隐患的金属锂枝晶的形成,具有很好的安全性,另外Li4Ti5O12还具有倍率性能好、库伦效率高等特点,是一种优异的动力电池材料。
虽然Li4Ti5O12具有较高的理论比容量、较好的循环性能和安全性能,但是纯相Li4Ti5O12本身是绝缘体,其电子导电率仅为10-13 S·cm-1,在一定程度上限制了该材料倍率性能的表现,也限制了其在动力锂离子电池以及超级电容器领域的应用。因此,目前有较多的研究工作着眼于提高Li4Ti5O12的离子导电性和电子导电性。常用的方法有:(1)改进制备方法以获得颗粒较小且粒径分布较均匀的Li4Ti5O12,缩短Li+的扩散路径;(2)掺杂金属离子;(3)在Li4Ti5O12颗粒表面包覆碳或制备Li4Ti5O12与导电剂的复合物。
石墨烯是一种仅由碳原子以sp2杂化轨道组成六角型晶格且只有一个碳原子厚度的二维材料。由于石墨烯具有结构稳定、电导率高、比表面积大(理论可达2600 m2 g-1)等优点,作为锂离子电池负极材料添加剂时,可以明显提高电子导电性,使负极具有出色的高倍率充放电性能。但是由于石墨烯材料表面呈惰性状态,化学稳定性高,与其他介质的相互作用较弱,并且石墨烯片层间有较强的范德华力作用而容易发生聚集,因此如何在应用时保持石墨烯的有效分散也是一个亟待解决的难题。
发明内容
本发明的目的在于提供一种石墨烯复合电极材料的制备方法,一方面解决石墨烯在复合材料中分散性较差的问题,进而提高钛酸锂材料的电子导电性;另一方面减小钛酸锂颗粒的粒径,缩短充放电时Li+的扩散路径,从而获得具有高倍率性能的纳米钛酸锂-石墨烯复合材料。
本发明的技术方案是这样实现的:一种石墨烯复合电极材料的制备方法,其特征在于:将石墨烯与聚乙二醇混合并超声分散到溶剂中,形成导电石墨烯分散液,然后在导电石墨烯分散液中加入钛源形成混合液A,将锂盐溶解于溶剂中形成溶液B,将溶液B缓慢滴加到混合液A中得到混合液C,经搅拌、干燥后,在保护气氛中进行热处理烧结得到纳米钛酸锂-石墨烯复合材料。该工艺包括如下步骤:
(1)将粉末状石墨烯与聚乙二醇按1:1~2的重量比相混合,优选比例1:1,加入20~100倍聚乙二醇质量的溶剂,超生分散0.5~5h,优选2h,形成导电石墨烯分散液;
(2)按照质量比钛酸锂:石墨烯=80~99:1~20称取钛源化合物,并加入到步骤(1)中的导电石墨烯分散液中,高速搅拌0.5~5h,优选1h,形成混合液A;
(3)按照Li:Ti=4.0~4.8:5的摩尔比,优选4.4:5,将锂盐溶解到溶剂中,溶剂质量为锂盐质量的10~30倍,形成溶液B;
(4)将步骤(3)得到的溶液B缓慢滴加到步骤(2)得到的混合液A中,高速搅拌1~12h,优选3h,得到混合液C;
(5)将步骤(4)得到的混合液C在干燥箱中50~100℃干燥2~12h,得到钛酸锂-石墨烯复合材料前驱体;
(6)将步骤(5)中得到的前驱体放在气氛炉中,在无氧的惰性气体保护下进行烧结,升温速度为1~20℃/min,优选10℃/min;烧结温度为700~900℃,优选800℃;烧结时间为8~24h,优选12h;即可得到纳米钛酸锂-石墨烯复合材料。
所述的石墨烯分散液中所分散的粉末状石墨烯可由机械剥离法、直流电弧法、取向附生法、加热SiC法、化学还原法、化学解离法、CVD法等方法制备得到或复配。
所述的石墨烯分散液中所用的溶剂为乙醇、甲醇、丁醇、N-甲基吡咯烷酮、异丙醇中的一种,优选乙醇。
所述的钛源化合物为钛酸四丁酯、钛酸四异丙酯、四氯化钛、乙酰丙酮钛中的一种,优选钛酸四丁酯、钛酸四异丙酯中的一种。
所述的锂盐为醋酸锂、异丙醇锂、硝酸锂、氯化锂、碳酸锂、柠檬酸锂、草酸锂、乙酰丙酮锂中的一种,优选醋酸锂、乙酰丙酮锂、异丙醇锂中的一种。
所述的溶液B中所用的溶剂为醇、水、酸组成的溶液,其中醇:水:酸=60~95:5~20:0~5,醇为乙醇、异丙醇、甲醇、丁醇、乙二醇中的一种,酸为醋酸、硝酸、草酸、柠檬酸、盐酸中的一种。
所述惰性气体为氩气、氮气、氦气中的一种,优选氩气。
本发明积极效果是使用了分散性较好的导电石墨烯分散液,解决了石墨烯在复合材料中分散性较差的问题,并且石墨烯可以抑制钛酸锂晶粒长大,缩短充放电时Li+的扩散路径,从而同时提高了钛酸锂复合材料的电子导电性和离子导电性,因而所得到的纳米钛酸锂-石墨烯复合材料具有较好的倍率性能,适合作为动力锂离子电池和超级电容器的负极材料。
附图说明
图1为本发明实施例1的纳米钛酸锂-石墨烯复合材料的SEM图片。
图2为本发明实施例1的纳米钛酸锂-石墨烯复合材料的XRD衍射图。
图3为本发明实施例2的纳米钛酸锂-石墨烯复合材料的SEM图片。
图4为本发明实施例2的纳米钛酸锂-石墨烯复合材料在0.1C的充放电曲线。
图5为本发明实施例2的纳米钛酸锂-石墨烯复合材料的倍率性能曲线。
具体实施方式
下面通过具体实施例对本发明进行具体描述,所述的实施例只是对本发明的权利要求的具体描述,权利要求包括但不限于所述的实施例内容。
实施例1:
将0.11g粉末状石墨烯(宁波墨西科技公司)与0.11g聚乙二醇混合,加入10.0g乙醇,超生分散2h,形成导电石墨烯分散液;加入7.41g钛酸四丁酯,搅拌1h,形成混合液A;将1.96g醋酸锂溶解到32.7g乙醇、4g水和0.5g醋酸组成的混合溶剂中,形成溶液B;将溶液B缓慢滴加到混合液A中,高速搅拌3h,得到混合液C;将混合液C在干燥箱中65℃干燥10h,得到钛酸锂-石墨烯复合材料前驱体;将前驱体放在气氛炉中,在氩气保护下进行烧结,升温速度为10℃/min,烧结温度为800℃;烧结时间为12h;即可得到纳米钛酸锂-石墨烯复合材料如图1-2所示。
实施例2:
将0.11g粉末状石墨烯(北京清大际光公司)与0.11g聚乙二醇混合,加入7.41g乙醇,超生分散2h,形成导电石墨烯分散液;加入7.41g钛酸四丁酯,搅拌1h,形成混合液A;将1.96g醋酸锂溶解到36g乙醇、4g水和0.5g醋酸组成的混合溶剂中,形成溶液B;将溶液B缓慢滴加到混合液A中,高速搅拌3h,得到混合液C;将混合液C在干燥箱中65℃干燥10h,得到钛酸锂-石墨烯复合材料前驱体;将前驱体放在气氛炉中,在氩气保护下进行烧结,升温速度为10℃/min,烧结温度为800℃;烧结时间为12h;即可得到纳米钛酸锂-石墨烯复合材料如图3所示。
按照质量比85:10:5依次称取纳米钛酸锂-石墨烯复合材料、气相生长碳纤维和聚偏氟乙烯,在N-甲基吡咯烷酮中制成浆料,涂敷在铜箔上,经真空干燥,裁切成直径为8mm的极片,与金属锂片(作为负极)组成扣式半电池,在不同倍率下进行充放电测试如图4所示。
实施例3:
将0.11g粉末状石墨烯(青岛东正石墨公司)与0.11g聚乙二醇混合,加入6.17g异丙醇,超生分散2h,形成导电石墨烯分散液;加入6.17g钛酸四异丙酯,搅拌1h,形成混合液A;将1.15g异丙醇锂溶解到20.6g异丙醇、2.4g水和0.2g醋酸组成的混合溶剂中,形成溶液B;将溶液B缓慢滴加到混合液A中,高速搅拌3h,得到混合液C;将混合液C在干燥箱中65℃干燥10h,得到钛酸锂-石墨烯复合材料前驱体;将前驱体放在气氛炉中,在氩气保护下进行烧结,升温速度为10℃/min,烧结温度为800℃;烧结时间为12h;即可得到纳米钛酸锂-石墨烯复合材料。
Claims (7)
1.一种石墨烯复合电极材料的制备方法,其特征在于:将石墨烯与聚乙二醇混合并超声分散到溶剂中,形成导电石墨烯分散液,然后在导电石墨烯分散液中加入钛源形成混合液A,将锂盐溶解于溶剂中形成溶液B,将溶液B缓慢滴加到混合液A中得到混合液C,经搅拌、干燥后,在保护气氛中进行热处理烧结得到纳米钛酸锂-石墨烯复合材料;
该工艺包括如下步骤:
(1)将粉末状石墨烯与聚乙二醇按1:1~2的重量比相混合,优选比例1:1,加入20~100倍聚乙二醇质量的溶剂,超生分散0.5~5h,优选2h,形成导电石墨烯分散液;
(2)按照质量比钛酸锂:石墨烯=80~99:1~20称取钛源,并加入到步骤(1)中的导电石墨烯分散液中,高速搅拌0.5~5h,优选1h,形成混合液A;
(3)按照Li:Ti=4.0~4.8:5的摩尔比,优选4.4:5,将锂盐溶解到溶剂中,溶剂质量为锂盐质量的10~30倍,形成溶液B;
(4)将步骤(3)得到的溶液B缓慢滴加到步骤(2)得到的混合液A中,高速搅拌1~12h,优选3h,得到混合液C;
(5)将步骤(4)得到的混合液C在干燥箱中50~100℃干燥2~12h,得到钛酸锂-石墨烯复合材料前驱体;
(6)将步骤(5)中得到的前驱体放在气氛炉中,在无氧的惰性气体保护下进行烧结,升温速度为1~20℃/min,优选10℃/min;烧结温度为700~900℃,优选800℃;烧结时间为8~24h,优选12h;即可得到纳米钛酸锂-石墨烯复合材料。
2.根据权利要求1所述的一种石墨烯复合电极材料的制备方法,其特征在于所述的石墨烯分散液中所分散的粉末状石墨烯可由机械剥离法、直流电弧法、取向附生法、加热SiC法、化学还原法、化学解离法、CVD法等方法制备得到或复配。
3.根据权利要求1所述的一种石墨烯复合电极材料的制备方法,其特征在于所述的石墨烯分散液中所用的溶剂为乙醇、甲醇、丁醇、N-甲基吡咯烷酮、异丙醇中的一种,优选乙醇。
4.根据权利要求1所述的一种石墨烯复合电极材料的制备方法,其特征在于所述的钛源化合物为钛酸四丁酯、钛酸四异丙酯、四氯化钛、乙酰丙酮钛中的一种,优选钛酸四丁酯、钛酸四异丙酯中的一种。
5.根据权利要求1所述的一种石墨烯复合电极材料的制备方法,其特征在于所述的锂盐为醋酸锂、异丙醇锂、硝酸锂、氯化锂、碳酸锂、柠檬酸锂、草酸锂、乙酰丙酮锂中的一种,优选醋酸锂、乙酰丙酮锂、异丙醇锂中的一种。
6.根据权利要求1所述的一种石墨烯复合电极材料的制备方法,其特征在于所述的溶液B中所用的溶剂为醇、水、酸组成的溶液,其中醇:水:酸=60~95:5~20:0~5,醇为乙醇、异丙醇、甲醇、丁醇、乙二醇中的一种,酸为醋酸、硝酸、草酸、柠檬酸、盐酸中的一种。
7.根据权利要求1所述的一种石墨烯复合电极材料的制备方法,其特征在于所述的惰性气体为氩气、氮气、氦气中的一种,优选氩气。
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