CN102891017B - Hybrid super capacitor anode pole piece of carbon nano-tube compound and preparation method thereof - Google Patents
Hybrid super capacitor anode pole piece of carbon nano-tube compound and preparation method thereof Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 105
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 105
- 239000003990 capacitor Substances 0.000 title claims description 27
- -1 carbon nano-tube compound Chemical class 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000003292 glue Substances 0.000 claims abstract description 61
- 239000006258 conductive agent Substances 0.000 claims abstract description 49
- 239000002002 slurry Substances 0.000 claims abstract description 44
- 238000001035 drying Methods 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000002079 double walled nanotube Substances 0.000 claims abstract description 5
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 5
- 239000002109 single walled nanotube Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 229920006318 anionic polymer Polymers 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000004815 dispersion polymer Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000011267 electrode slurry Substances 0.000 claims 8
- 239000004568 cement Substances 0.000 claims 2
- 238000001291 vacuum drying Methods 0.000 claims 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 abstract description 66
- 239000000203 mixture Substances 0.000 abstract description 24
- 238000003756 stirring Methods 0.000 abstract description 15
- 239000006185 dispersion Substances 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000003825 pressing Methods 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 230000005055 memory storage Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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
- 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
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- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
碳纳米管复合的混合型超级电容器正极极片，包括集流体及其上压制的正极，所述正极的组分及其重量份比例为：正极材料70–89.5，碳纳米管0.5–20，导电剂5，胶5，所述碳纳米管为单壁、双壁或多壁碳纳米管。制作时，先将胶加入溶剂中搅拌混合均匀，再向其中加入导电剂、分散好的碳纳米管分散浆液搅拌混合均匀，然后加入正极材料搅拌混合均匀以得到正极材料浆液，再将正极材料浆液成型为多个形状一致的极片毛坯，然后将极片毛坯干燥以得到正极，最后将正极在10–25Mpa的压力下压制于集流体上以制得所述超级电容器正极极片。本设计不仅功率密度、能量密度较高，而且内阻较小、便于提高超级电容器的性能，其应用范围较广。
Carbon nanotube-composited hybrid supercapacitor positive electrode sheet, including a current collector and a positive electrode pressed on it, the components of the positive electrode and their weight ratios are: positive electrode material 70-89.5, carbon nanotubes 0.5-20, conductive Agent 5, glue 5, the carbon nanotubes are single-walled, double-walled or multi-walled carbon nanotubes. When making, first add the glue to the solvent and stir and mix evenly, then add the conductive agent and the dispersed carbon nanotube dispersion slurry to it, stir and mix evenly, then add the positive electrode material and stir and mix evenly to obtain the positive electrode material slurry, and then mix the positive electrode material slurry Forming a plurality of pole piece blanks with the same shape, then drying the pole piece blanks to obtain a positive electrode, and finally pressing the positive electrode on the current collector under a pressure of 10-25Mpa to obtain the supercapacitor positive pole piece. This design not only has high power density and energy density, but also has small internal resistance, which is convenient for improving the performance of the supercapacitor, and its application range is wide.
Description
技术领域 technical field
本发明涉及一种超级电容器正极极片，尤其涉及一种碳纳米管复合的混合型超级电容器正极极片及其制作方法，具体适用于提高超级电容器的能量密度和功率密度。 The invention relates to a positive pole piece of a supercapacitor, in particular to a positive pole piece of a hybrid supercapacitor composed of carbon nanotubes and a manufacturing method thereof, which is particularly suitable for improving the energy density and power density of a supercapacitor.
背景技术 Background technique
商用超级电容器是一种电能储存设备，在汽车辅助动力电源、能量回收、便携式仪器设备、数据记忆存储系统、应急后备电源灯等领域都有应用。商用超级电容器主要是以大比表面积的活性炭材料为储能电极，充放电过程中活性炭材料表面发生电荷吸附脱附。与商用锂离子电池相比较，商用超级电容器充放电速度快，能提供大电流，但其储存的电量少，限制了其应用领域。 Commercial supercapacitor is a kind of electric energy storage device, which has applications in automotive auxiliary power supply, energy recovery, portable instruments and equipment, data memory storage system, emergency backup power supply lamp and other fields. Commercial supercapacitors mainly use activated carbon materials with a large specific surface area as energy storage electrodes, and charge adsorption and desorption occurs on the surface of activated carbon materials during charging and discharging. Compared with commercial lithium-ion batteries, commercial supercapacitors charge and discharge quickly and can provide large currents, but their stored power is small, which limits their application fields.
目前，为提高超级电容器的能量密度，同时保持其较高的功率密度，开发高能量密度的超级电容器成为研究关注的热点。混合型超级电容器是最近发展的一种具有较高能量密度的储能器件，该器件的一电极材料是锂离子材料，另一电极材料是活性炭材料，在充放电过程中，含锂的电极发生锂离子晶格的插入脱出，而另一电极中的活性炭则发生电荷的吸附脱附，因此，这种电容器既可获得较高的能量密度，同时还保有较高的功率密度。 At present, in order to increase the energy density of supercapacitors while maintaining their high power density, the development of supercapacitors with high energy density has become a research focus. Hybrid supercapacitor is a recently developed energy storage device with high energy density. One electrode material of this device is lithium ion material, and the other electrode material is activated carbon material. During the charging and discharging process, the lithium-containing electrode generates The lithium ion lattice is inserted and extracted, while the activated carbon in the other electrode undergoes charge adsorption and desorption. Therefore, this capacitor can obtain high energy density while maintaining high power density.
中国专利公开号为CN101221853A，公开日为2008年7月16日的发明专利公开一种半固态或全固态水系超级电容器，该发明中，正极采用含有包括锂离子、或者其他碱金属、碱土金属、稀土金属、铝或锌的一种或几种离子的混合物阳离子嵌入化合物材料，负极采用高比表面的活性炭、介孔碳或碳纳米管等，电解质采用含上述阳离子的水系聚合物凝胶电解质。虽然该发明提高了电容量，但其功率密度、能量密度仍旧较低，缩小了其应用范围。 The Chinese patent publication number is CN101221853A, and the invention patent published on July 16, 2008 discloses a semi-solid or all-solid water supercapacitor. In this invention, the positive electrode is made of lithium ions or other alkali metals, alkaline earth metals, A mixture of one or several ions of rare earth metals, aluminum or zinc is used as a cation intercalation compound material. The negative electrode uses activated carbon, mesoporous carbon or carbon nanotubes with a high specific surface area. The electrolyte uses a water-based polymer gel electrolyte containing the above-mentioned cations. Although the invention improves the capacitance, its power density and energy density are still low, which narrows its application range.
发明内容 Contents of the invention
本发明的目的是克服现有技术中存在的功率密度、能量密度较低，应用范围较窄的缺陷与问题，提供一种功率密度、能量密度较高，应用范围较广的碳纳米管复合的混合型超级电容器正极极片及其制作方法。 The purpose of the present invention is to overcome the defects and problems of low power density and energy density and narrow application range in the prior art, and provide a carbon nanotube composite composite material with high power density and energy density and wide application range. A hybrid supercapacitor positive electrode sheet and a manufacturing method thereof.
为实现以上目的，本发明的技术解决方案是：碳纳米管复合的混合型超级电容器正极极片，包括集流体及其上压制的正极，所述正极的组分包括正极材料、导电剂、胶，所述正极材料为锰酸锂、镍钴锰酸锂或钴酸锂； To achieve the above object, the technical solution of the present invention is: carbon nanotube composite hybrid supercapacitor positive electrode sheet, including current collector and the positive electrode pressed thereon, the components of the positive electrode include positive electrode material, conductive agent, glue , the positive electrode material is lithium manganese oxide, lithium nickel cobalt manganese oxide or lithium cobalt oxide;
所述正极的组分还包括碳纳米管； The components of the positive electrode also include carbon nanotubes;
所述正极的组分及其重量份比例为：正极材料70–89.5，碳纳米管0.5–20，导电剂5，胶5。 The components of the positive electrode and their weight ratios are: positive electrode material 70-89.5, carbon nanotubes 0.5-20, conductive agent 5, glue 5.
所述正极的组分及其重量份比例为：正极材料80，碳纳米管10，导电剂5，胶5。 The components of the positive electrode and their weight ratios are: 80 positive electrode materials, 10 carbon nanotubes, 5 conductive agents, and 5 glue.
所述碳纳米管为单壁、双壁或多壁碳纳米管。 The carbon nanotubes are single-walled, double-walled or multi-walled carbon nanotubes.
所述导电剂为乙炔黑、导电炭黑或碳黑导电剂。 The conductive agent is acetylene black, conductive carbon black or carbon black conductive agent.
所述胶包括水性胶或油性胶，所述水性胶包括聚四氟乙烯或阴离子型聚合物分散体，所述油性胶包括聚偏氟乙烯。 The glue includes water-based glue or oil-based glue, the water-based glue includes polytetrafluoroethylene or anionic polymer dispersion, and the oil-based glue includes polyvinylidene fluoride.
上述碳纳米管复合的混合型超级电容器正极极片的制作方法，所述制作方法依次包括以下步骤： The manufacturing method of the hybrid supercapacitor positive pole sheet composited by the above-mentioned carbon nanotubes, the manufacturing method comprises the following steps in sequence:
第一步：先将胶加入溶剂中搅拌混合，待混合均匀后，再向其中加入导电剂、分散好的碳纳米管分散浆液，继续进行搅拌混合，待混合均匀后，再向其中加入正极材料，继续进行搅拌混合，待混合均匀后，即可得到正极材料浆液； The first step: first add the glue into the solvent and stir and mix. After the mixture is uniform, add the conductive agent and the dispersed carbon nanotube dispersion slurry to it, continue to stir and mix, and then add the positive electrode material to it after the mixture is uniform. , continue to stir and mix, and after mixing evenly, the positive electrode material slurry can be obtained;
所述碳纳米管分散浆液中碳纳米管的含量为1–20 wt.%；所述正极材料浆液中正极材料、碳纳米管、导电剂、胶的重量份比例为：正极材料70–89.5，碳纳米管0.5–20，导电剂5，胶5； The content of carbon nanotubes in the carbon nanotube dispersion slurry is 1-20 wt.%; the weight ratio of the positive electrode material, carbon nanotubes, conductive agent, and glue in the positive electrode material slurry is: positive electrode material 70-89.5, Carbon nanotubes 0.5–20, conductive agent 5, glue 5;
第二步：先将上述混合均匀的正极材料浆液倒在不锈钢板上，再用不锈钢棒将正极材料浆液擀成均匀的薄片，然后用压片机将其成型为多个形状一致的极片毛坯，再将极片毛坯放入真空烘箱中进行干燥，干燥后，即可得到所述正极； The second step: first pour the above-mentioned homogeneously mixed positive electrode material slurry on the stainless steel plate, then roll the positive electrode material slurry into a uniform thin sheet with a stainless steel rod, and then use a tablet machine to shape it into multiple electrode blanks with the same shape , and then put the electrode sheet blank into a vacuum oven for drying, and after drying, the positive electrode can be obtained;
第三步：用油压机将上述正极在10–25Mpa的压力下压制于集流体上即可制得所述混合型超级电容器正极极片。 Step 3: Use a hydraulic press to press the above-mentioned positive electrode on the current collector under a pressure of 10-25Mpa to obtain the positive electrode sheet of the hybrid supercapacitor.
所述第一步中，所述溶剂为水或N–甲基吡咯烷酮。 In the first step, the solvent is water or N-methylpyrrolidone.
所述第二步中，所述压片机的压头直径为2cm，所述极片毛坯的形状是直径为9mm的圆形。 In the second step, the diameter of the press head of the tablet press is 2 cm, and the shape of the pole piece blank is a circle with a diameter of 9 mm.
所述第二步中，所述干燥的温度为120℃，干燥时间为8h。 In the second step, the drying temperature is 120° C., and the drying time is 8 hours.
所述第三步中，所述油压机的压力为12–15Mpa。 In the third step, the pressure of the hydraulic press is 12-15Mpa.
与现有技术相比，本发明的有益效果为： Compared with prior art, the beneficial effect of the present invention is:
1、本发明碳纳米管复合的混合型超级电容器正极极片及其制作方法中正极的组分中增添了碳纳米管，在正极中，该碳纳米管一方面能建立电子和锂离子的通道，提高电荷和离子的传输效率，增强正极材料的活性，另一方面，碳纳米管自身也能吸附脱附电荷，储存能量，从而提高超级电容器正极的性能，使得应用该正极的混合型超级电容器具有更高的能量密度和功率密度，其能量密度高达30–40 Wh/kg，功率密度高达1500–4000 W/kg，进而扩大其应用范围，适合发展为高性能储能器件。因此，本发明不仅功率密度、能量密度较高，而且应用范围较广。 1. Carbon nanotubes are added to the components of the positive electrode in the carbon nanotube-composited hybrid supercapacitor positive electrode sheet and its manufacturing method of the present invention. In the positive electrode, the carbon nanotubes can establish channels for electrons and lithium ions on the one hand. , improve the transmission efficiency of charges and ions, and enhance the activity of positive electrode materials. On the other hand, carbon nanotubes themselves can also absorb and desorb charges and store energy, thereby improving the performance of the positive electrode of supercapacitors, making hybrid supercapacitors that use this positive electrode It has higher energy density and power density, its energy density is as high as 30-40 Wh/kg, and its power density is as high as 1500-4000 W/kg, which further expands its application range and is suitable for the development of high-performance energy storage devices. Therefore, the present invention not only has high power density and energy density, but also has a wide application range.
2、本发明碳纳米管复合的混合型超级电容器正极极片及其制作方法中正极的组分及其重量份比例为：正极材料70–89.5，碳纳米管0.5–20，导电剂5，胶5；其中，碳纳米管的用量有严格的要求，其原因在于：随着碳纳米管在正极中含量增大，正极导电率会逐渐增大，但同时正极材料含量会下降，尽管碳纳米管表面可吸附电荷储存电量，但其吸附的电荷密度远低于正极材料体中储存电荷的密度，因此，当碳纳米管超过一定含量时会导致电容器的容量和能量密度下降，因而并不是碳纳米管加入的量越多电容器的电化学性能越好，为此，本发明选择的碳纳米管含量既然确保获得较高的能量密度和容量，又能获得较高的功率密度。因此，本发明不仅容量、能量密度较好，而且功率密度较高。 2. The carbon nanotube-composited hybrid supercapacitor positive electrode sheet of the present invention and the positive electrode components and their weight ratios in the manufacturing method are: positive electrode material 70-89.5, carbon nanotubes 0.5-20, conductive agent 5, glue 5; Among them, the amount of carbon nanotubes has strict requirements, the reason is: as the content of carbon nanotubes in the positive electrode increases, the conductivity of the positive electrode will gradually increase, but at the same time the content of the positive electrode material will decrease, although carbon nanotubes The surface can absorb charges to store electricity, but the density of the adsorbed charges is much lower than the density of charges stored in the positive electrode material. Therefore, when the carbon nanotubes exceed a certain content, the capacity and energy density of the capacitor will decrease, so it is not carbon nanotubes. The more the amount of tubes added, the better the electrochemical performance of the capacitor. Therefore, the content of carbon nanotubes selected in the present invention not only ensures higher energy density and capacity, but also can obtain higher power density. Therefore, the present invention not only has better capacity and energy density, but also has higher power density.
3、本发明碳纳米管复合的混合型超级电容器正极极片及其制作方法中在制作正极时，进行了特殊设计以提高制作效果，具体为：首先，先加胶，再加导电剂、碳纳米管分散浆液，然后加正极材料是为了预防浆料混合不均匀；其次，干燥温度为120℃，时间为8h能够确保去除极片毛坯中所有的水份，以提高正极的质量；再次，先对极片进行干燥，再将其压制于集流体上能防止正极材料与集流体分离，有利于降低内阻，从而提高正极极片质量，增强电容器的电化学性能。因此，本发明有利于提高正极极片的质量，并增强超级电容器的电化学性能。 3. In the carbon nanotube-composited hybrid supercapacitor positive pole piece and its production method of the present invention, a special design is carried out to improve the production effect when making the positive pole. Specifically: first, add glue first, then add conductive agent, carbon Nanotubes are dispersed in the slurry, and then the positive electrode material is added to prevent uneven mixing of the slurry; secondly, the drying temperature is 120°C, and the drying time is 8 hours to ensure that all the water in the blank is removed to improve the quality of the positive electrode; again, first Drying the pole piece and then pressing it on the current collector can prevent the separation of the positive electrode material and the current collector, which is beneficial to reduce the internal resistance, thereby improving the quality of the positive pole piece and enhancing the electrochemical performance of the capacitor. Therefore, the invention is beneficial to improving the quality of the positive electrode sheet and enhancing the electrochemical performance of the supercapacitor.
4、本发明碳纳米管复合的混合型超级电容器正极极片及其制作方法中的正极在10–25Mpa的压力下压制于集流体上以制取超级电容器正极极片，其最佳压力范围为12–15Mpa，该压力范围既能确保电解液易渗透进正极中，不影响活性物质性能的发挥，从而进一步提高超级电容器的能量密度与功率密度，同时，又不会造成活性物质间接触电阻过大，避免内阻较大以影响电容器性能。因此，本发明不仅功率密度、能量密度较高，而且内阻较小。 4. The positive pole in the hybrid supercapacitor positive pole sheet composited with carbon nanotubes of the present invention and its manufacturing method is pressed on the current collector under a pressure of 10-25Mpa to produce the supercapacitor positive pole piece, and its optimum pressure range is 12–15Mpa, this pressure range can ensure that the electrolyte is easy to penetrate into the positive electrode without affecting the performance of the active material, thereby further improving the energy density and power density of the supercapacitor, and at the same time, it will not cause excessive contact resistance between the active materials Large, to avoid large internal resistance to affect the performance of the capacitor. Therefore, the present invention not only has high power density and energy density, but also has low internal resistance.
附图说明 Description of drawings
图1是本发明中正极的扫描电子显微镜照片。 Fig. 1 is a scanning electron micrograph of the positive electrode in the present invention.
图2是本发明应用的超级电容器的结构示意图。 Fig. 2 is a schematic structural diagram of a supercapacitor applied in the present invention.
图中：电源1、负极2、正极3、电解液4、集流体5、碳纳米管6、正极材料颗粒7。 In the figure: power supply 1, negative electrode 2, positive electrode 3, electrolyte solution 4, current collector 5, carbon nanotubes 6, and positive electrode material particles 7.
具体实施方式 detailed description
以下结合附图说明和具体实施方式对本发明作进一步详细的说明。 The present invention will be described in further detail below in conjunction with the accompanying drawings and specific embodiments.
参见图1–图2，碳纳米管复合的混合型超级电容器正极极片，包括集流体及其上压制的正极，所述正极的组分包括正极材料、导电剂、胶，所述正极材料为锰酸锂、镍钴锰酸锂或钴酸锂； Referring to Fig. 1-Fig. 2, the carbon nanotube composite hybrid supercapacitor positive electrode sheet includes a current collector and a positive electrode pressed thereon, the components of the positive electrode include positive electrode material, conductive agent, glue, and the positive electrode material is Lithium manganese oxide, lithium nickel cobalt manganese oxide or lithium cobalt oxide;
所述正极的组分还包括碳纳米管； The components of the positive electrode also include carbon nanotubes;
所述正极的组分及其重量份比例为：正极材料70–89.5，碳纳米管0.5–20，导电剂5，胶5。 The components of the positive electrode and their weight ratios are: positive electrode material 70-89.5, carbon nanotubes 0.5-20, conductive agent 5, glue 5.
所述正极的组分及其重量份比例为：正极材料80，碳纳米管10，导电剂5，胶5。 The components of the positive electrode and their weight ratios are: 80 positive electrode materials, 10 carbon nanotubes, 5 conductive agents, and 5 glue.
所述碳纳米管为单壁、双壁或多壁碳纳米管。 The carbon nanotubes are single-walled, double-walled or multi-walled carbon nanotubes.
所述导电剂为乙炔黑、导电炭黑或碳黑导电剂。 The conductive agent is acetylene black, conductive carbon black or carbon black conductive agent.
所述胶包括水性胶或油性胶，所述水性胶包括聚四氟乙烯或阴离子型聚合物分散体，所述油性胶包括聚偏氟乙烯。 The glue includes water-based glue or oil-based glue, the water-based glue includes polytetrafluoroethylene or anionic polymer dispersion, and the oil-based glue includes polyvinylidene fluoride.
上述碳纳米管复合的混合型超级电容器正极极片的制作方法，所述制作方法依次包括以下步骤： The manufacturing method of the hybrid supercapacitor positive pole sheet composited by the above-mentioned carbon nanotubes, the manufacturing method comprises the following steps in sequence:
第一步：先将胶加入溶剂中搅拌混合，待混合均匀后，再向其中加入导电剂、分散好的碳纳米管分散浆液，继续进行搅拌混合，待混合均匀后，再向其中加入正极材料，继续进行搅拌混合，待混合均匀后，即可得到正极材料浆液； The first step: first add the glue into the solvent and stir and mix. After the mixture is uniform, add the conductive agent and the dispersed carbon nanotube dispersion slurry to it, continue to stir and mix, and then add the positive electrode material to it after the mixture is uniform. , continue to stir and mix, and after mixing evenly, the positive electrode material slurry can be obtained;
所述碳纳米管分散浆液中碳纳米管的含量为1–20 wt.%；所述正极材料浆液中正极材料、碳纳米管、导电剂、胶的重量份比例为：正极材料70–89.5，碳纳米管0.5–20，导电剂5，胶5； The content of carbon nanotubes in the carbon nanotube dispersion slurry is 1-20 wt.%; the weight ratio of the positive electrode material, carbon nanotubes, conductive agent, and glue in the positive electrode material slurry is: positive electrode material 70-89.5, Carbon nanotubes 0.5–20, conductive agent 5, glue 5;
第二步：先将上述混合均匀的正极材料浆液倒在不锈钢板上，再用不锈钢棒将正极材料浆液擀成均匀的薄片，然后用压片机将其成型为多个形状一致的极片毛坯，再将极片毛坯放入真空烘箱中进行干燥，干燥后，即可得到所述正极； The second step: first pour the above-mentioned homogeneously mixed positive electrode material slurry on the stainless steel plate, then roll the positive electrode material slurry into a uniform thin sheet with a stainless steel rod, and then use a tablet machine to shape it into multiple electrode blanks with the same shape , and then put the electrode sheet blank into a vacuum oven for drying, and after drying, the positive electrode can be obtained;
第三步：用油压机将上述正极在10–25Mpa的压力下压制于集流体上即可制得所述混合型超级电容器正极极片。 Step 3: Use a hydraulic press to press the above-mentioned positive electrode on the current collector under a pressure of 10-25Mpa to obtain the positive electrode sheet of the hybrid supercapacitor.
所述第一步中，所述溶剂为水或N–甲基吡咯烷酮。 In the first step, the solvent is water or N-methylpyrrolidone.
所述第二步中，所述压片机的压头直径为2cm，所述极片毛坯的形状是直径为9mm的圆形。 In the second step, the diameter of the press head of the tablet press is 2 cm, and the shape of the pole piece blank is a circle with a diameter of 9 mm.
所述第二步中，所述干燥的温度为120℃，干燥时间为8h。 In the second step, the drying temperature is 120° C., and the drying time is 8 hours.
所述第三步中，所述油压机的压力为12–15Mpa。 In the third step, the pressure of the hydraulic press is 12-15Mpa.
本发明的原理说明如下： Principle of the present invention is described as follows:
1、碳纳米管： 1. Carbon nanotubes:
本发明在正极的组分中增添了碳纳米管。在正极中，该碳纳米管一方面能建立电子和锂离子的通道，构建成导电网络（参见图1，图1是本发明中正极的扫描电子显微镜照片，该图中能清楚看出碳纳米管包裹在正极材料颗粒之间，并将正极材料颗粒连通，构建出导电网络），从而提高电荷和离子的传输效率，增强正极材料的活性，另一方面，碳纳米管自身也能吸附脱附电荷，储存能量，从而提高超级电容器正极的性能，使得应用该正极的混合型超级电容器具有更高的能量密度和功率密度，其能量密度高达30–40 Wh/kg，功率密度高达1500–4000 W/kg，进而扩大其应用范围，适合发展为高性能储能器件。 The present invention adds carbon nanotubes to the components of the positive electrode. In the positive electrode, on the one hand, the carbon nanotubes can establish channels for electrons and lithium ions, and form a conductive network (see Figure 1, which is a scanning electron microscope photo of the positive electrode in the present invention, and it can be clearly seen that the carbon nanotubes The tube is wrapped between the positive electrode material particles and connects the positive electrode material particles to form a conductive network), thereby improving the transmission efficiency of charges and ions, and enhancing the activity of the positive electrode material. On the other hand, carbon nanotubes themselves can also adsorb and desorb charge and store energy, thereby improving the performance of the positive electrode of the supercapacitor, so that the hybrid supercapacitor with the positive electrode has higher energy density and power density, the energy density is as high as 30–40 Wh/kg, and the power density is as high as 1500–4000 W /kg, and then expand its scope of application, suitable for the development of high-performance energy storage devices.
同时，本发明对碳纳米管的用量有严格要求，即所述正极的组分及其重量份比例为：正极材料70–89.5，碳纳米管0.5–20，导电剂5，胶5。碳纳米管采用该用量的原因在于：随着碳纳米管在正极中含量增大，正极导电率会逐渐增大，但同时正极材料含量会下降，尽管碳纳米管表面可吸附电荷储存电量，但其吸附的电荷密度远低于正极材料体中储存电荷的密度，因此，当碳纳米管超过一定含量时会导致电容器的容量和能量密度下降，因而并不是碳纳米管加入的量越多电容器的电化学性能越好。在制作极片的过程中，一般而言，正极在某个压力下，碳纳米管含量为10则电容器电化学性能较优。同时，碳纳米管含量低于0.5，则正极阻值较高，提高电化学性能不明显；高于20，则碳纳米管难以分散，且会降低电化学性能。 At the same time, the present invention has strict requirements on the amount of carbon nanotubes, that is, the components of the positive electrode and their weight ratios are: positive electrode material 70-89.5, carbon nanotubes 0.5-20, conductive agent 5, glue 5. The reason for using this amount of carbon nanotubes is that as the content of carbon nanotubes in the positive electrode increases, the conductivity of the positive electrode will gradually increase, but at the same time the content of the positive electrode material will decrease. Although the surface of carbon nanotubes can absorb charges to store electricity, but The charge density absorbed by it is much lower than the charge density stored in the positive electrode material body. Therefore, when the carbon nanotubes exceed a certain content, the capacity and energy density of the capacitor will decrease. Therefore, it is not the more carbon nanotubes that are added to the capacitor. The better the electrochemical performance. In the process of making the pole piece, generally speaking, the positive electrode is under a certain pressure, and the electrochemical performance of the capacitor is better if the carbon nanotube content is 10. At the same time, if the content of carbon nanotubes is lower than 0.5, the resistance of the positive electrode will be high, and the electrochemical performance will not be improved significantly; if it is higher than 20, the carbon nanotubes will be difficult to disperse, and the electrochemical performance will be reduced.
至于正极材料的含量则根据最终的电化学性能效果来决定；胶和导电剂的用量则根据制作超级电容器的实验决定，实验显示，胶5、导电剂5是较佳的一个比例。 As for the content of the positive electrode material, it is determined according to the final electrochemical performance; the amount of glue and conductive agent is determined according to the experiment of making a supercapacitor. The experiment shows that glue 5 and conductive agent 5 are a better ratio.
此外，本发明在制作正极时采用了碳纳米管分散浆液，该碳纳米管分散浆液中碳纳米管的含量为1–20 wt.%，采取分散浆液的原因在于：使用碳纳米管分散浆液而不是直接用碳纳米管粉加入到正极材料浆液中，目的是使碳纳米管在正极材料浆液中更容易分散。 In addition, the present invention adopts the carbon nanotube dispersion slurry when making the positive electrode, and the content of carbon nanotubes in the carbon nanotube dispersion slurry is 1-20 wt.%. The reason for adopting the dispersion slurry is: use the carbon nanotube dispersion slurry instead Instead of directly adding carbon nanotube powder to the positive electrode material slurry, the purpose is to make the carbon nanotubes more easily dispersed in the positive electrode material slurry.
2、制作中材料的添加顺序： 2. The order of adding materials in production:
本发明中材料的添加顺序依次为：先将胶加入溶剂中搅拌混合，待混合均匀后，再向其中加入导电剂、分散好的碳纳米管分散浆液，继续进行搅拌混合，待混合均匀后，再向其中加入正极材料，继续进行搅拌混合，待混合均匀后，即可得到正极材料浆液。 The order of adding materials in the present invention is as follows: first add the glue into the solvent and stir and mix, and then add the conductive agent and the dispersed carbon nanotube dispersion slurry to it after the mixture is uniform, and continue to stir and mix, and after the mixture is uniform, Then add the positive electrode material therein, continue stirring and mixing, and after uniform mixing, the positive electrode material slurry can be obtained.
本发明采用胶、导电剂、碳纳米管分散浆液、正极材料这种添加顺序的原因在于：先加胶又称为打胶，胶加入到液体中，液体粘性大大增大，需先将胶分散，否则，胶会出现团簇，因此，需先打胶。导电剂和碳纳米管分散浆液加入的顺序则不限定，最后加入锂离子正极材料。这种顺序不能打乱，否则易造成浆料不均匀。 The reason why the present invention adopts the addition order of glue, conductive agent, carbon nanotube dispersion slurry, and positive electrode material is that the glue is added first, also known as glue beating, and the viscosity of the liquid is greatly increased when the glue is added to the liquid, so the glue needs to be dispersed first. , otherwise, the glue will appear in clusters, so the glue needs to be applied first. The order of adding the conductive agent and the carbon nanotube dispersion slurry is not limited, and the lithium ion cathode material is added last. This order cannot be disturbed, otherwise it is easy to cause uneven slurry.
3、正极的烘干： 3. Drying of positive electrode:
本发明中对正极进行烘干的操作为：将极片毛坯放入真空烘箱中进行干燥，干燥后，即可得到所述正极，优选干燥的温度为120℃，干燥时间为8h。其中，对干燥温度、时间都有要求，其原因在于：采用该干燥温度与时间能够确保去除极片毛坯中所有的水份，以提高正极的质量，确保电容器的使用效果。别的温度和时间要不达不到去除所有水份的效果，要不就是温度过高或时间过长，造成温度、时间配合不契合，浪费资源。 The operation of drying the positive electrode in the present invention is as follows: put the blank of the electrode sheet into a vacuum oven for drying, and after drying, the positive electrode can be obtained. The preferred drying temperature is 120° C. and the drying time is 8 hours. Among them, there are requirements for drying temperature and time. The reason is that the use of this drying temperature and time can ensure that all the water in the blank of the pole piece can be removed, so as to improve the quality of the positive electrode and ensure the use effect of the capacitor. Other temperature and time either cannot achieve the effect of removing all the water, or the temperature is too high or the time is too long, resulting in the mismatch of temperature and time, wasting resources.
此外，本发明是先对极片进行干燥，再将其压制于集流体上，而不是先压制于集流体再烘干，其原因在于：如果先压制后干燥，则易造成正极材料与集流体分离，不利于正极材料与集流体的结合，不利于降低内阻。 In addition, the present invention firstly dries the pole piece, and then presses it on the current collector, instead of pressing it on the current collector first and then drying it. The reason is that if it is pressed first and then dried, it is easy to cause the positive electrode material and the current collector to be damaged. Separation is not conducive to the combination of positive electrode material and current collector, and is not conducive to reducing internal resistance.
4、正极的压制压力： 4. The compression pressure of the positive electrode:
本发明要求将所述正极在10–25Mpa的压力下压制于集流体上以制得所述混合型超级电容器正极极片，优选压力范围是12–15Mpa。 The present invention requires that the positive electrode be pressed on the current collector under a pressure of 10-25Mpa to make the hybrid supercapacitor positive electrode sheet, and the preferred pressure range is 12-15Mpa.
选择该压力范围的原因在于：若压力过大，则易造成电解液难以渗透到正极中，从而影响活性物质性能发挥，降低电容器的能量密度与功率密度；若压力过小，则会造成活性物质间接触电阻过大，易导致内阻过大，影响电容器性能。 The reason for choosing this pressure range is that if the pressure is too high, it will be difficult for the electrolyte to penetrate into the positive electrode, thereby affecting the performance of the active material and reducing the energy density and power density of the capacitor; If the indirect contact resistance is too large, it will easily lead to too large internal resistance and affect the performance of the capacitor.
5、以正极材料浆液制作正极： 5. Make positive electrode with positive electrode material slurry:
本发明中先将正极材料浆液倒在不锈钢板上，再用不锈钢棒将正极材料浆液擀成均匀的薄片，然后用压片机将其成型为多个形状一致的极片毛坯，再对极片毛坯干燥以获得正极。这是做小电容器的操作过程，如果要做相应的大电容器，其制作浆料过程与做小电容器的相同，不同之处在于，制完浆料之后是对浆料涂布，获得正极。 In the present invention, the positive electrode material slurry is first poured on the stainless steel plate, and then the positive electrode material slurry is rolled into a uniform sheet with a stainless steel rod, and then it is formed into a plurality of pole piece blanks with the same shape with a tablet machine, and then the pole piece The blank was dried to obtain a positive electrode. This is the operation process of making a small capacitor. If a corresponding large capacitor is to be made, the process of making the slurry is the same as that of making a small capacitor. The difference is that after the slurry is prepared, the slurry is coated to obtain the positive electrode.
实施例1： Example 1:
碳纳米管复合的混合型超级电容器正极极片，包括集流体及其上压制的正极，所述正极的组分包括正极材料、导电剂、胶，所述正极材料为锰酸锂、镍钴锰酸锂或钴酸锂；所述正极的组分及其重量份比例为：正极材料85，碳纳米管5，导电剂5，胶5； The carbon nanotube composite hybrid supercapacitor positive electrode sheet includes a current collector and a positive electrode pressed on it. The components of the positive electrode include positive electrode materials, conductive agents, and glue. The positive electrode materials are lithium manganate, nickel cobalt manganese Lithium oxide or lithium cobaltate; The components of the positive electrode and their weight ratios are: positive electrode material 85, carbon nanotubes 5, conductive agent 5, glue 5;
所述碳纳米管为单壁、双壁或多壁碳纳米管，所述导电剂为乙炔黑、导电炭黑或碳黑导电剂，所述胶包括水性胶或油性胶，所述水性胶包括聚四氟乙烯或阴离子型聚合物分散体，所述油性胶包括聚偏氟乙烯。 The carbon nanotubes are single-wall, double-wall or multi-wall carbon nanotubes, the conductive agent is acetylene black, conductive carbon black or carbon black conductive agent, the glue includes water-based glue or oily glue, and the water-based glue includes Polytetrafluoroethylene or anionic polymer dispersion, the oily gum includes polyvinylidene fluoride.
上述碳纳米管复合的混合型超级电容器正极极片的制作方法，所述制作方法依次包括以下步骤： The manufacturing method of the hybrid supercapacitor positive pole sheet composited by the above-mentioned carbon nanotubes, the manufacturing method comprises the following steps in sequence:
第一步：先将胶加入溶剂中搅拌混合，待混合均匀后，再向其中加入导电剂、分散好的碳纳米管分散浆液，继续进行搅拌混合，待混合均匀后，再向其中加入正极材料，继续进行搅拌混合，待混合均匀后，即可得到正极材料浆液；所述溶剂为水或N–甲基吡咯烷酮； The first step: first add the glue into the solvent and stir and mix. After the mixture is uniform, add the conductive agent and the dispersed carbon nanotube dispersion slurry to it, continue to stir and mix, and then add the positive electrode material to it after the mixture is uniform. , continue to stir and mix, and after mixing evenly, a positive electrode material slurry can be obtained; the solvent is water or N-methylpyrrolidone;
所述碳纳米管分散浆液中碳纳米管的含量为1–20 wt.%；所述正极材料浆液中正极材料、碳纳米管、导电剂、胶的重量份比例为：正极材料85，碳纳米管5，导电剂5，胶5； The content of carbon nanotubes in the carbon nanotube dispersion slurry is 1-20 wt.%; the weight ratio of positive electrode material, carbon nanotubes, conductive agent, and glue in the positive electrode material slurry is: positive electrode material 85, carbon nanotubes Tube 5, conductive agent 5, glue 5;
第二步：先将上述混合均匀的正极材料浆液倒在不锈钢板上，再用不锈钢棒将正极材料浆液擀成均匀的薄片，然后用压片机将其成型为多个形状一致的极片毛坯，再将极片毛坯放入真空烘箱中进行干燥，干燥温度为120℃，干燥时间为8h，干燥后，即可得到所述正极；所述压片机的压头直径为2cm，所述极片毛坯的形状是直径为9mm的圆形； The second step: first pour the above-mentioned homogeneously mixed positive electrode material slurry on the stainless steel plate, then roll the positive electrode material slurry into a uniform thin sheet with a stainless steel rod, and then use a tablet machine to shape it into multiple electrode blanks with the same shape , and then put the electrode blank into a vacuum oven for drying, the drying temperature is 120°C, and the drying time is 8h. After drying, the positive electrode can be obtained; the diameter of the pressure head of the tablet press is 2cm, and the electrode The shape of the sheet blank is a circle with a diameter of 9 mm;
第三步：用油压机将上述正极在25Mpa的压力下压制于集流体上即可制得所述混合型超级电容器正极极片。 Step 3: Use a hydraulic press to press the above-mentioned positive electrode on the current collector under a pressure of 25Mpa to obtain the positive electrode sheet of the hybrid supercapacitor.
以本发明为正极极片，活性炭为负极极片，1Mol/L的硫酸锂溶液为电解液，组装成混合型超级电容器。将正极极片、负极极片插入电解液中，并与电化学工作站连接测试混合型超级电容器电化学性能（参见图2）。室温下在0–1.8 V电压范围，电流密度为200 mA/g（以正负极活性物质总质量计算）恒流充放电测试和交流阻抗测试，测得该混合型超级电容器的比容量为73.4F/g，能量密度为33.0Wh/kg，功率密度为1.5 KW/kg。 A hybrid supercapacitor is assembled by using the present invention as a positive pole piece, activated carbon as a negative pole piece, and a 1Mol/L lithium sulfate solution as an electrolyte. Insert the positive and negative pole pieces into the electrolyte, and connect them to the electrochemical workstation to test the electrochemical performance of the hybrid supercapacitor (see Figure 2). In the voltage range of 0-1.8 V at room temperature, the current density is 200 mA/g (calculated based on the total mass of positive and negative active materials), constant current charge and discharge test and AC impedance test, the measured specific capacity of the hybrid supercapacitor is 73.4 F/g, the energy density is 33.0Wh/kg, and the power density is 1.5 KW/kg.
实施例2： Example 2:
基本内容同实施例1，不同之处在于： Basic content is the same as embodiment 1, the difference is:
所述正极的组分及其重量份比例为：正极材料80，碳纳米管10，导电剂5，胶5；所述油压机的压力为12Mpa； The components of the positive electrode and their weight ratios are: positive electrode material 80, carbon nanotubes 10, conductive agent 5, glue 5; the pressure of the hydraulic press is 12Mpa;
所述混合型超级电容器的比容量为82.5F/g，能量密度为37.1 Wh/kg，功率密度为2.0KW/kg。 The specific capacity of the hybrid supercapacitor is 82.5F/g, the energy density is 37.1 Wh/kg, and the power density is 2.0KW/kg.
实施例3： Example 3:
基本内容同实施例1，不同之处在于： Basic content is the same as embodiment 1, the difference is:
所述正极的组分及其重量份比例为：正极材料75，碳纳米管15，导电剂5，胶5；所述油压机的压力为15Mpa； The components of the positive electrode and their weight ratios are: positive electrode material 75, carbon nanotubes 15, conductive agent 5, glue 5; the pressure of the hydraulic press is 15Mpa;
所述混合型超级电容器的比容量为68.9F/g，能量密度为31.0 Wh/kg，功率密度为4.0KW/kg。 The specific capacity of the hybrid supercapacitor is 68.9F/g, the energy density is 31.0 Wh/kg, and the power density is 4.0KW/kg.
实施例4： Example 4:
基本内容同实施例1，不同之处在于： Basic content is the same as embodiment 1, the difference is:
所述正极的组分及其重量份比例为：正极材料89，碳纳米管1，导电剂5，胶5；所述油压机的压力为15Mpa； The components of the positive electrode and their weight ratios are: positive electrode material 89, carbon nanotube 1, conductive agent 5, glue 5; the pressure of the hydraulic press is 15Mpa;
所述混合型超级电容器的比容量为85.9F/g，能量密度为38.2 Wh/kg，功率密度为2.6KW/kg。 The specific capacity of the hybrid supercapacitor is 85.9F/g, the energy density is 38.2 Wh/kg, and the power density is 2.6KW/kg.
实施例5： Example 5:
基本内容同实施例1，不同之处在于： Basic content is the same as embodiment 1, the difference is:
所述正极的组分及其重量份比例为：正极材料89.5，碳纳米管0.5，导电剂5，胶5；所述油压机的压力为10Mpa； The components of the positive electrode and their weight ratios are: positive electrode material 89.5, carbon nanotubes 0.5, conductive agent 5, glue 5; the pressure of the hydraulic press is 10Mpa;
所述混合型超级电容器的比容量为80F/g，能量密度为32 Wh/kg，功率密度为2.0 KW/kg。） The specific capacity of the hybrid supercapacitor is 80F/g, the energy density is 32 Wh/kg, and the power density is 2.0 KW/kg. )
实施例6： Embodiment 6:
基本内容同实施例1，不同之处在于： Basic content is the same as embodiment 1, the difference is:
所述正极的组分及其重量份比例为：正极材料70，碳纳米管20，导电剂5，胶5；所述油压机的压力为20Mpa； The components of the positive electrode and their weight ratios are: positive electrode material 70, carbon nanotubes 20, conductive agent 5, glue 5; the pressure of the hydraulic press is 20Mpa;
所述混合型超级电容器的比容量为70F/g，能量密度为32 Wh/kg，功率密度为3.8 KW/kg。 The specific capacity of the hybrid supercapacitor is 70F/g, the energy density is 32 Wh/kg, and the power density is 3.8 KW/kg.
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