CN102324317B - 一种用于柔性固态超级电容器的电极及其制备方法 - Google Patents
一种用于柔性固态超级电容器的电极及其制备方法 Download PDFInfo
- Publication number
- CN102324317B CN102324317B CN201110271179.0A CN201110271179A CN102324317B CN 102324317 B CN102324317 B CN 102324317B CN 201110271179 A CN201110271179 A CN 201110271179A CN 102324317 B CN102324317 B CN 102324317B
- Authority
- CN
- China
- Prior art keywords
- electrode
- active substance
- flexible solid
- oxide
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003990 capacitor Substances 0.000 title abstract description 10
- 239000007787 solid Substances 0.000 title abstract 5
- 238000002360 preparation method Methods 0.000 title description 9
- 239000013543 active substance Substances 0.000 claims abstract description 33
- 239000006258 conductive agent Substances 0.000 claims abstract description 10
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229920001940 conductive polymer Polymers 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229950000845 politef Drugs 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002322 conducting polymer Substances 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 229920000128 polypyrrole Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- CASZBAVUIZZLOB-UHFFFAOYSA-N lithium iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Li+] CASZBAVUIZZLOB-UHFFFAOYSA-N 0.000 claims description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 3
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920001197 polyacetylene Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 claims 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229920001400 block copolymer Polymers 0.000 claims 1
- 229910021393 carbon nanotube Inorganic materials 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 12
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 229920006254 polymer film Polymers 0.000 abstract 3
- 239000000853 adhesive Substances 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000013019 agitation Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- 238000005253 cladding Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
-
- 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
- H01G11/48—Conductive polymers
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
本发明涉及一种柔性固态超级电容器的电极，由活性物质、导电剂、粘结剂组成，其特征在于：活性物质、导电剂、粘结剂组分比为70～80：10～20：8～18；活性物质外层包覆离子－电子传导聚合物膜，其质量为活性物质质量的3～26%。其采用离子－电子传导聚合物膜包覆活性物质，制备柔性固态超级电容器电极，是新能源汽车用的一个理想储能器件，柔性轻薄利于储能单元与汽车的装配设计，降低储能单元重量，安全环保，针对柔性固态超级电容器的电极，在活性物质外层包覆兼具离子和电子传导性能的聚合物膜，改善电极与聚合物电解质之间的界面性能，降低接触电阻，提高离子传导率，提升超级电容器的储能能力。
Description
技术领域
本发明涉及一种用于柔性固态超级电容器的电极及其制备方法，属于超级电容器技术领域。
背景技术
超级电容器是一种介于传统静电电容器和电池之间的新型储能元件，具有功率密度大、大充放电倍率、循环寿命长、耐温性好、环境友好等优点。可应用于小型电器电源、脉冲电源，近年来，与燃料电池、锂离子电池以及镍氢电池等组合成复合电源，满足了汽车的启动加速、爬坡、能量回收等要求，同时延长了电池的使用寿命，获得了广泛关注。
电极材料作为超级电容器的核心部分，直接影响到器件的性能。碳材料是目前研究时间最长，应用最广泛的电极材料。授权公告号CN 201323134Y 的中国专利报道了以高比表面稻壳活性炭和无硫膨胀石墨的复合物作电极材料，30% 的氢氧化钾溶液为电解液，极耳通过铆焊的方式与极柱相连组装的超级电容器成本低、寿命长。申请号为200910091711.3 的中国专利介绍了一种基于活性碳纤维布的超级电容器，采用喷涂或蒸镀的方法在活性碳纤维布的一侧附着一层微小金属铝颗粒作为导电层，然后采用导电粘合剂粘附在铝箔集流体两侧制成活性碳纤维电极，提高了超级电容器的工作电压，降低了内阻。
导电聚合物的分子结构可设计性及高的储能特性，为人们开发具有法拉第效应的新型活性材料开拓了思路。申请号200910060774.2 的中国专利报道了一类聚吡咯/ 聚噻吩衍生物复合导电高分子材料的制备方法，在大功率放电时，具有较高的比容量和较好的循环稳定性。申请号200510027782.9 的中国专利通过将具有双电层效应的碳材料与聚合物自由基材料复合，制备的超级电容器比容量高、功率密度大、循环寿命长。公开号为CN1290047A 的中国专利报道了一种聚合物涂布的锂混合氧化物，改善了材料的存储寿命和高温循环性能。专利号为US 7651 819 B2 的美国专利报道了一种多孔炭包覆一种氧化物后再包覆一层聚合物，具有较高的充放电倍率。公开号为CN 101016412A 的中国专利公开了一种用于超级电容器的锂盐掺杂态聚苯胺电极材料的制备方法，有效解决了苯胺材料在有机电解液中比电容小的问题。公开号为CN 101488400A 的中国专利报道了一种导电高分子修饰活性炭电极用于超级电容器的制备方法，制得的电极材料比电容比单纯的活性炭电极提高了2 ～ 3 倍。公开号为CN 1760226A 的中国专利报道了一种超级电容器用复合导电高分子电极材料，电位窗口大幅度提高。随着人们对离子－电子混合传导研究的深入，兼具离子、电子传导特性的聚合物或复合物用于电池电极、电池隔膜获得了广泛的关注。将电池材料引入到超级电容器体系中，开发电池电容，是储能器件发展的一个重要模式。由于目前使用的超级电容器多是液体电解液体系，给储能器件的维护、装配及安全带来很多问题，因此，采用聚合物电解质的柔性固态超级电容器成为车用理想储能器件之一。
发明内容
本发明的目的在于提供一种用于柔性固态超级电容器的电极及其制备方法，采用离子－电子传导聚合物膜包覆活性物质，制备柔性固态超级电容器电极。
本发明的技术方案是这样实现的：一种用于柔性固态超级电容器的电极，由活性物质、导电剂、粘结剂组成，其特征在于：活性物质、导电剂、粘结剂按照质量比70～80：10～20：8～18混合制成浆料，涂敷到隔膜上，得到柔性固态超级电容器电极，其中活性物质外层包覆离子－电子传导聚合物膜，且离子－电子传导聚合物膜的质量为活性物质质量的3～26%。
所述的离子－电子传导聚合物膜由导电聚合物以及聚合物电解质基体组成，通过溶液共混法成膜包覆活性物质，二者按15～22：78～85质量比混合；所述的导电聚合物为聚苯胺、聚吡咯、聚噻吩、聚乙炔、聚乙烯咔唑中的一种；所述的聚合物电解质基体为聚氧乙烯、聚丙烯腈、聚丙烯酸、聚乙二醇、聚甲基丙烯酸甲酯、聚乙烯醇、羧甲基纤维素、聚硅氧烷、聚偏氟乙烯－六氟丙烯、聚偏氟乙烯、聚四氟乙烯中的一种或几种；或所述的离子－电子传导聚合物膜是通过化学聚合反应，形成兼有导电聚合物链和聚合物电解质基体链的接枝共聚物，分子结构Ⅰ ，其中0 ≤ y ≤ 1，n 为聚合度或嵌段共聚物：分子结构Ⅱ， 0 ≤ y ≤ 1，n 为聚合度；且通过溶液共混法在活性物质外层成膜。
所述的活性物质为活性炭、中间相碳微球、碳纤维、碳纳米管、石墨烯、氧化锰、氧化镍、氧化铁、氧化锰锂、氧化镍锂、氧化钛锂、氧化铁锂、氧化钴锂中的一种；所述的导电剂为碳纳米纤维或碳纳米管。
其制备方法为：（1）将活性物质质量3 ～ 26% 的聚合物在共溶剂中机械搅拌2 ～8 小时，得到离子－电子传导聚合物溶液；（2）将计量好的活性物质在与步骤1 相同的溶剂中机械搅拌2 ～ 4 小时，然后与聚合物溶液混合，机械搅拌2 ～ 8 小时，除去溶剂得到混合传导膜包覆的活性物质；（3）将活性物质、导电剂及粘结剂按照组分比70 ～ 80 ：10 ～20 ：8 ～ 18，在溶剂中混合制成浆料，涂敷到隔膜上，得到柔性固态超级电容器电极；所述的活性物质为活性炭、中间碳相微球、碳纤维、碳纳米管、石墨烯、氧化锰、氧化镍、氧化铁、氧化锰锂、氧化镍锂、氧化钛锂、氧化铁锂、氧化钴锂中的一种；所述的导电剂为碳纳米纤维或碳纳米管。
本发明的积极效果是柔性固态超级电容器是新能源汽车用的一个理想储能器件，柔性轻薄利于储能单元与汽车的装配设计，降低储能单元重量，安全环保。本发明针对柔性固态超级电容器的电极，在活性物质外层包覆兼具离子和电子传导性能的聚合物膜，改善电极与聚合物电解质之间的界面性能，降低接触电阻，提高离子传导率，提升超级电容器的储能能力。
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85 份聚环氧乙烯，15 份的聚吡咯在乙腈溶液中机械搅拌2 小时，得到聚合物溶液；300 份的氧化钛锂在乙腈溶液中机械搅拌4 小时后与聚合物溶液混合，机械搅拌4小时，除去溶剂，真空烘箱中50℃干燥至恒重，得到聚合物膜包覆的活性物质；取75 份聚合物膜包覆的活性物质、15 份的碳纳米管、5 份的聚四氟乙烯，在去离子水中混合均匀制成浆料，涂覆到隔膜的一面，真空烘箱中50℃干燥至恒重；另一面涂覆由85 份活性炭、10 份碳纳米管、5 份聚四氟乙烯组成的浆料，50℃真空干燥至恒重，得到柔性固态超级电容器电极。
实施例2 ：
将18 份的聚乙烯醇在去离子水中机械搅拌3 小时，加入160 份的氧化锰锂，机械搅拌2 小时，除去水， 50℃真空干燥至恒重；将得到的试样在1M 的苯胺的盐酸溶液中，浸泡2 小时后立即取出，与1M 的过硫酸胺的盐酸溶液，0℃反应3.5 小时，洗涤干净后，自然干燥至恒重，得到聚合物包覆的活性物质；取80 份聚合物膜包覆的活性物质、15 份的碳纳米管、5份的聚四氟乙烯，混合均匀制成浆料，涂覆到隔膜的一面，真空烘箱中50℃干燥24小时至恒重；另一面涂覆由85 份活性炭、10 份碳纳米管、5 份聚四氟乙烯组成的浆料，真空烘箱中50℃干燥至恒重，得到柔性固态超级电容器电极。
实施例3 ：
称取120 份的中间碳相微球在去离子水中机械搅拌4 小时，氩气氛围下，加入12份的三氯化铁，7 份的对甲苯磺酸，机械搅拌2 小时，加入2 份吡咯单体，机械搅拌24 小时，去离子水中反复洗涤至中性， 50℃真空干燥至恒重，得到粉末样品；将粉末样品加入到1g/200ml 的聚偏氟乙烯－六氟丙烯的丙酮中，机械搅拌4 小时， 50℃真空干燥至恒重，得到聚合物膜包覆的活性物质；取70 份聚合物膜包覆的活性物质、20 份的碳纳米管、10 份的聚四氟乙烯，在去离子水中混合均匀制成浆料，涂覆到隔膜的一面，真空烘箱中50℃干燥至恒重；另一面涂覆由110 克活性炭、30 克碳纳米管、22 克聚四氟乙烯组成的浆料，真空烘箱中50℃干燥至恒重，得到柔性固态超级电容器电极。
实施例4 ：
将10 份合成的聚苯胺与聚乙二醇的三嵌段化合物（PAn-PEG-PAn，物理化学报，2005年，21（6）：627 ～ 631）在去离子水中机械搅拌2 小时，得到聚合物溶液；称取100 份氧化铁锂在去离子水中机械搅拌3 小时后，与聚合物溶液混合，机械搅拌4 小时， 50℃真空干燥至恒重，得到聚合物包覆的活性物质；取75 份聚合物膜包覆的活性物质、15 份碳纳米管、10份的聚偏氟乙烯在N －甲基吡咯烷酮中混合均匀制成浆料，涂覆到隔膜的一面， 80℃真空干燥至恒重；另一面涂覆由80 克活性炭、15 份碳纳米管、5 份的聚偏氟乙烯在N －甲基吡咯烷酮中混合均匀制成的浆料，80℃真空干燥至恒重，得到柔性固态超级电容器电极。
Claims (3)
1.一种用于柔性固态超级电容器的电极，由活性物质、导电剂、粘结剂组成，其特征在于：活性物质、导电剂、粘结剂按照质量比70～80：10～20：8～18混合制成浆料，涂敷到隔膜上，得到柔性固态超级电容器电极，其中活性物质外层包覆离子－电子传导聚合物膜，且离子－电子传导聚合物膜的质量为活性物质质量的3～26%。
2.根据权利要求1所述的一种用于柔性固态超级电容器的电极，其特征在于所述的离子－电子传导聚合物膜由导电聚合物以及聚合物电解质基体组成，通过溶液共混法成膜包覆活性物质，二者按15～22：78～85质量比混合；所述的导电聚合物为聚苯胺、聚吡咯、聚噻吩、聚乙炔、聚乙烯咔唑中的一种；所述的聚合物电解质基体为聚氧乙烯、聚丙烯腈、聚丙烯酸、聚乙二醇、聚甲基丙烯酸甲酯、聚乙烯醇、羧甲基纤维素、聚硅氧烷、聚偏氟乙烯－六氟丙烯、聚偏氟乙烯、聚四氟乙烯中的一种或几种；或所述的离子－电子传导聚合物膜是通过化学聚合反应，形成兼有导电聚合物链和聚合物电解质基体链的接枝共聚物，分子结构Ⅰ，其中0 ≤ y ≤ 1，n 为聚合度或嵌段共聚物：分子结构Ⅱ， 0 ≤ y ≤ 1，n 为聚合度；且通过溶液共混法在活性物质外层成膜。
3.根据权利要求1所述的一种用于柔性固态超级电容器的电极，其特征在于所述的活性物质为活性炭、中间相碳微球、碳纤维、碳纳米管、石墨烯、氧化锰、氧化镍、氧化铁、氧化锰锂、氧化镍锂、氧化钛锂、氧化铁锂、氧化钴锂中的一种；所述的导电剂为碳纳米纤维或碳纳米管。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110271179.0A CN102324317B (zh) | 2011-09-14 | 2011-09-14 | 一种用于柔性固态超级电容器的电极及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110271179.0A CN102324317B (zh) | 2011-09-14 | 2011-09-14 | 一种用于柔性固态超级电容器的电极及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102324317A CN102324317A (zh) | 2012-01-18 |
| CN102324317B true CN102324317B (zh) | 2017-04-19 |
Family
ID=45452037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110271179.0A Active CN102324317B (zh) | 2011-09-14 | 2011-09-14 | 一种用于柔性固态超级电容器的电极及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102324317B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013148051A1 (en) | 2012-03-30 | 2013-10-03 | Linda Zhong | Electrode for energy storage devices and method for making same |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674813B (zh) * | 2012-04-27 | 2014-05-21 | 陕西华星电子开发有限公司 | 一种制作固态储能电容器的材料 |
| CN102881451A (zh) * | 2012-10-08 | 2013-01-16 | 中国科学院化学研究所 | 一种全固态储能器件 |
| WO2014072877A2 (en) * | 2012-11-08 | 2014-05-15 | Basf Se | Graphene based screen-printable ink and its use in supercapacitors |
| CN103366970B (zh) * | 2013-06-27 | 2016-02-10 | 暨南大学 | 基于MnO2与Fe2O3纳米结构的柔性非对称超级电容器及其制备方法和应用 |
| CN105609328A (zh) * | 2015-09-06 | 2016-05-25 | 广东风华高新科技股份有限公司 | 电极片的制备方法 |
| CN105977047A (zh) * | 2016-05-24 | 2016-09-28 | 宁波墨西科技有限公司 | 一种石墨烯/活性炭复合电极材料及其制备方法 |
| GB2561253B (en) * | 2017-04-07 | 2022-10-12 | Zapgo Ltd | Self-supporting carbon electrode |
| CN108417408A (zh) * | 2018-01-17 | 2018-08-17 | 莆田市超维二维科技发展有限公司 | 一种超级电容器及其制备方法 |
| CN109192521B (zh) * | 2018-08-08 | 2020-07-03 | 厦门大学 | 一种柔性电极及其制备方法和应用 |
| TWI735017B (zh) | 2019-08-05 | 2021-08-01 | 輝能科技股份有限公司 | 活性材料球複合層 |
| CN112331906B (zh) * | 2019-08-05 | 2022-08-05 | 辉能科技股份有限公司 | 活性材料球极层结构 |
| TWI756556B (zh) * | 2019-08-05 | 2022-03-01 | 輝能科技股份有限公司 | 活性材料球極層結構 |
| CN110676059B (zh) * | 2019-08-14 | 2021-07-30 | 湖南艾华集团股份有限公司 | 聚苯胺基固态电解电容器电极材料的制备方法 |
| US11508956B2 (en) | 2020-09-08 | 2022-11-22 | Licap Technologies, Inc. | Dry electrode manufacture with lubricated active material mixture |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1776848A (zh) * | 2004-11-15 | 2006-05-24 | 三菱瓦斯化学株式会社 | 电极片和采用它的双电荷层电容器 |
| CN101814379A (zh) * | 2010-04-28 | 2010-08-25 | 复旦大学 | 一种超级电容器 |
-
2011
- 2011-09-14 CN CN201110271179.0A patent/CN102324317B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1776848A (zh) * | 2004-11-15 | 2006-05-24 | 三菱瓦斯化学株式会社 | 电极片和采用它的双电荷层电容器 |
| CN101814379A (zh) * | 2010-04-28 | 2010-08-25 | 复旦大学 | 一种超级电容器 |
Non-Patent Citations (2)
| Title |
|---|
| "Preparation of graphene nanosheet/carbon nanotube/polyaniline composite as electrode material for supercapacitors";Jun Yan 等;《Journal of Power Sources》;20091111;第195卷;第3041-3045页 * |
| "基于聚氧化乙烯的离子-电子混合传导聚合物";柳娜等;《化学通报》;20030930;第66卷(第9期);第2页第7-11行，第3页第19-21行及分子式a，第5页结束语第2段及分子式d * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013148051A1 (en) | 2012-03-30 | 2013-10-03 | Linda Zhong | Electrode for energy storage devices and method for making same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102324317A (zh) | 2012-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102324317B (zh) | 一种用于柔性固态超级电容器的电极及其制备方法 | |
| Abdah et al. | Fabrication of PEDOT coated PVA-GO nanofiber for supercapacitor | |
| Salinas-Torres et al. | Asymmetric hybrid capacitors based on activated carbon and activated carbon fibre–PANI electrodes | |
| Li et al. | Freestanding bacterial cellulose–polypyrrole nanofibres paper electrodes for advanced energy storage devices | |
| Xinping et al. | A new nanocomposite: Carbon cloth based polyaniline for an electrochemical supercapacitor | |
| Bavio et al. | Flexible symmetric and asymmetric supercapacitors based in nanocomposites of carbon cloth/polyaniline-carbon nanotubes | |
| Abidin et al. | Electropolymerization of poly (3, 4-ethylenedioxythiophene) onto polyvinyl alcohol-graphene quantum dot-cobalt oxide nanofiber composite for high-performance supercapacitor | |
| Huang et al. | Sewable and cuttable flexible zinc-ion hybrid supercapacitor using a polydopamine/carbon cloth-based cathode | |
| Zhou et al. | Highly stable multi-wall carbon nanotubes@ poly (3, 4-ethylenedioxythiophene)/poly (styrene sulfonate) core–shell composites with three-dimensional porous nano-network for electrochemical capacitors | |
| Sadak et al. | Facile fabrication of highly ordered polyaniline–exfoliated graphite composite for enhanced charge storage | |
| CN104466134B (zh) | 自支撑石墨烯/碳纳米管杂化物泡沫负载氨基蒽醌类聚合物的制备方法 | |
| Soni et al. | Realizing high capacitance and rate capability in polyaniline by enhancing the electrochemical surface area through induction of superhydrophilicity | |
| JP5999367B2 (ja) | 高電子伝導性高分子及びこれを用いた高用量／高出力電気エネルギー貯蔵素子 | |
| Wang et al. | Porous polylactic acid/carbon nanotubes/polyaniline composite film as flexible free-standing electrode for supercapacitors | |
| JP2015079966A (ja) | 伝導性高分子複合体を用いた高容量／高出力の電気化学エネルギー貯蔵素子 | |
| Abdah et al. | Ternary functionalised carbon nanofibers/polypyrrole/manganese oxide as high specific energy electrode for supercapacitor | |
| Cevik et al. | High performance flexible supercapacitors including redox active molybdate incorporated Poly (vinylphosphonic acid) hydrogels | |
| Liu et al. | Synchronous-ultrahigh conductive-reactive N-atoms doping strategy of carbon nanofibers networks for high‐performance flexible energy storage | |
| Abdah et al. | Enhancement of electrochemical performance based on symmetrical poly-(3, 4-ethylenedioxythiophene) coated polyvinyl alcohol/graphene oxide/manganese oxide microfiber for supercapacitor | |
| Ji et al. | All-in-one energy storage devices supported and interfacially cross-linked by gel polymeric electrolyte | |
| Li et al. | Three-dimensional stretchable fabric-based electrode for supercapacitors prepared by electrostatic flocking | |
| Shendkar et al. | Hybrid composite polyaniline-nickel hydroxide electrode materials for supercapacitor applications | |
| Ma et al. | Asymmetric hybrid capacitors based on novel bearded carbon fiber cloth–pinhole polyaniline electrodes with excellent energy density | |
| Miao et al. | Performance comparison of electro-polymerized polypyrrole and polyaniline as cathodes for iodine redox reaction in zinc-iodine batteries | |
| Wesling et al. | Enhanced Electrochemical Performance of Nanocellulose/PPy· CuCl 2 Electrodes for All-Cellulose-Based Supercapacitors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |