WO2013044684A1 - 一种高能镍碳超级电容器负极负极板浆料的制备方法 - Google Patents
一种高能镍碳超级电容器负极负极板浆料的制备方法 Download PDFInfo
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- WO2013044684A1 WO2013044684A1 PCT/CN2012/079634 CN2012079634W WO2013044684A1 WO 2013044684 A1 WO2013044684 A1 WO 2013044684A1 CN 2012079634 W CN2012079634 W CN 2012079634W WO 2013044684 A1 WO2013044684 A1 WO 2013044684A1
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- WIPO (PCT)
- Prior art keywords
- supercapacitor
- negative electrode
- preparing
- stir
- deionized water
- Prior art date
Links
- 239000002002 slurry Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000003860 storage Methods 0.000 claims abstract description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000000853 adhesive Substances 0.000 claims abstract description 6
- 230000001070 adhesive effect Effects 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 239000000839 emulsion Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000005054 agglomeration Methods 0.000 claims description 8
- 230000002776 aggregation Effects 0.000 claims description 8
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 8
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 8
- 239000011883 electrode binding agent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011267 electrode slurry Substances 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 10
- 238000004146 energy storage Methods 0.000 abstract description 8
- 238000007599 discharging Methods 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 239000003575 carbonaceous material Substances 0.000 abstract 1
- 239000004816 latex Substances 0.000 abstract 1
- 229920000126 latex Polymers 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 27
- 229910052759 nickel Inorganic materials 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- GDXTWKJNMJAERW-UHFFFAOYSA-J molybdenum(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mo+4] GDXTWKJNMJAERW-UHFFFAOYSA-J 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- 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
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
-
- 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
Definitions
- the invention belongs to the field of supercapacitors, in particular to a method for preparing a high energy nickel carbon supercapacitor negative plate slurry. Background technique
- a nickel hydroxide mixed supercapacitor and a preparation method thereof (CN200810111891.2), the capacitor comprises a cylindrical type and a square structure, and comprises a nickel hydroxide anode, an alkali metal hydroxide aqueous electrolyte and activated carbon fiber
- the cathode seal is constructed in a stainless steel or engineering plastic casing, and has a hybrid supercapacitor with high energy storage density and high discharge power.
- the nickel hydroxide anode is prepared by a chemical reaction method and an electrochemical reaction method, in which an appropriate amount of carbon nanotubes and nickel carbonyl are added as an additive, and foamed nickel is used as a matrix to produce an anode.
- the activated carbon cathode is made of electroplated nickel-treated activated carbon fiber as a raw material, and nickel foil is used as a current collector.
- the assembled capacitor has an operating voltage of 1.6V, a maximum energy storage density of 20Wh/kg, and a peak discharge power of 8KW/kg. Widely used in industrial, transportation, electronics, military and other fields.
- a vehicle start-up supercapacitor (CN03114837.9).
- the supercapacitor core is composed of a sintered nickel oxide positive electrode sheet enclosing a diaphragm, a continuous activated carbon fiber cloth negative electrode and a thin nickel plate supported by a current collector, and the capacitor core passes through After the current terminal is fabricated and welded, it is placed in a plastic case, and the electrolyte is injected, and the supercapacitor is obtained by sealing.
- the supercapacitor has high power density and energy density, and is light in weight, low in cost, long in life, and suitable for starting energy of various types of vehicles, and has good value for popularization and application.
- a carbon-based porous electrode film for a supercapacitor and a preparation method thereof (CN200410009580.7), wherein the content of each component of the film is: an activated carbon content of 72 mass S % to 99 mass S %, a conductive carbon black or a graphite content of O .lmass % ⁇ 20mass %, the content of zirconia nano powder is O.lmass % ⁇ 5mass %, the content of nano metal nickel powder is 0.1mass% ⁇ 3mass %; the void ratio is 45% ⁇ 75%, further preferred void The rate is 55 % ⁇ 65%.
- Preparing the film of the invention firstly mixing the deionized water, the organic monomer and the crosslinking agent uniformly; then adding the dispersing agent to the solution and stirring uniformly to obtain a premixed solution; then adding the raw material powder, ball milling and mixing to prepare a slurry; The slurry is added with a defoaming agent and vacuum defoaming; the initiator and the catalyst are added to the defoamed slurry, stirred uniformly, and then formed, solidified and stripped on a casting machine to obtain a green body, and then subjected to a weak oxidizing atmosphere. Heat treatment to obtain a target porous electrode film.
- the molding process of the invention is simple, the molding time is short, the operation is easy, the film thickness is controllable, and the middle hole is developed.
- a method for preparing a porous carbon electrode of a large-capacity charge-discharge performance supercapacitor comprising the following process, using a microporous zeolite molecular sieve as a template, using a gas block, methane or ethylene as a carbon source
- a high-period heating device is used for vapor deposition to obtain a porous carbon rich in micropores;
- the prepared large specific surface area carbon has a uniform pore structure; the porous carbon has low surface hydrophilicity and low oxygen content, and the prepared porous carbon electrode is particularly suitable for super rate charging and discharging performance super Capacitor.
- a nickel hydroxide mixed supercapacitor and a preparation method thereof (CN200810111891.2), the capacitor comprises a cylindrical type and a square structure, and comprises a nickel hydroxide anode, an alkali metal hydroxide aqueous electrolyte and activated carbon fiber
- the cathode seal constitutes a hybrid supercapacitor with high energy storage density and high discharge power in a stainless steel or engineering plastic casing.
- the nickel hydroxide anode is prepared by a chemical reaction method and an electrochemical reaction method, in which an appropriate amount of carbon nanotubes and nickel carbonyl are added as an additive, and a foamed nickel is used as a matrix to produce an anode.
- the activated carbon cathode is made of electroplated nickel-treated activated carbon fiber as a raw material, and a nickel foil is used as a current collector.
- the assembled capacitor has an operating voltage of 1.6V, a maximum storage density of 20Wh/kg, and a peak discharge power of 8KW/kg. Widely used in industrial, transportation, electronics, military and other fields.
- a hybrid supercapacitor and a preparation method thereof wherein the negative active material of the hybrid supercapacitor is one or more of a homomorphic ⁇ 02- ⁇ of nano-Ti02 or ⁇ 02, positive electrode active
- the material is one or more of carbon nanotubes, carbon nanofibers, graphite, conductive carbon black, nickel hydroxide, manganese hydroxide or molybdenum hydroxide.
- the hybrid supercapacitor is made of a positive and negative electrode active material, a binder, and a conductive agent, and is assembled into an analog battery to form a supercapacitor in a glove box.
- the preparation method provided by the invention has the characteristics of regulation, simple preparation process and easy operation, and the assembled hybrid supercapacitor model has high specific capacity, low potential, stable performance, high current charge and discharge, long cycle life, low cost and large-scale mechanization. Production is easy to achieve and so on.
- a method for preparing a supercapacitor which comprises the following steps: 1) placing a nickel foam substrate in a chemical vapor deposition reactor, introducing argon gas for 10 to 60 minutes, and exhausting the air in the furnace. Then, the temperature is raised to 450-75 CTC, the hydrocarbon gas is introduced at a flow rate of 25-40 ml/min in an argon atmosphere, and the reaction is carried out at 450-75 CTC for 30 seconds to 50 minutes. After the reaction is completed, carbon nanotubes are grown.
- Nickel foam After removing the surface loose layer product, directly use the foamed nickel substrate with carbon nanotubes grown as the supercapacitor electrode; 3) Dry the two electrodes of the same thickness and size obtained in step 2, using the electrolyte Soaking for 1 to 36 hours, and then separating them with a separator which is also saturated with electrolyte to assemble a supercapacitor; the hydrocarbon gas is a block, methane, ethylene, or propylene.
- the carbon nanotube of the invention is directly grown on the nickel foam substrate without using an adhesive; the nickel foam is a substrate, and the electrode material has a higher bulk density and a reasonable pore distribution. After comparison, the negative electrode materials involved in the above patent technologies are quite different from the patent application.
- An object of the present invention is to overcome the deficiencies of the prior art and to provide a method for preparing a negative electrode plate slurry of a high energy nickel carbon supercapacitor having a large energy storage density and a high discharge power.
- the present invention adopts the following technical solutions:
- a method for preparing a high energy nickel carbon supercapacitor negative plate slurry the steps of the preparation method are:
- the binder for the negative electrode is 20% to 38% of the total weight of the negative electrode binder and the main material.
- the raw material composition of the binder for the negative electrode and the weight ratio range thereof are respectively:
- the preparation method of the binder for the negative electrode is:
- Hydrogen storage alloy powder 70% ⁇ 85%
- Titanium oxide 0.5% ⁇ 5%
- the supercapacitor adopts a positive electrode material mainly composed of nickel hydroxide as a main active material, and a mixed negative electrode plate composed of an alkali metal hydroxide aqueous electrolyte and a hydrogen storage alloy powder and an activated carbon material as main active substances used in the patent application.
- the diaphragm seal is constructed in a stainless steel or engineering plastic casing, and has the characteristics of high energy storage density and high discharge power. 2.
- the working voltage of the supercapacitor prepared by the negative electrode plate slurry of the invention reaches 1.3V, and the maximum energy storage density reaches 65Wh/kg.
- the preparation method of the high-energy nickel-carbon supercapacitor negative plate slurry according to the present invention is divided into two steps. The first is to prepare a binder for the negative electrode, which needs to be prepared 3-6 hours in advance, and is mixed with the binder for the negative electrode and then mixed with the main material. The preparation of the negative plate slurry was carried out.
- a method for preparing a high energy nickel carbon supercapacitor negative plate slurry the specific steps are:
- the binder for the negative electrode is prepared, and the weight ratio of the raw materials is as follows:
- the steps of the preparation method are:
- the raw material composition and weight percentage range of the negative plate slurry are as follows:
- Hydrogen storage alloy powder 75% Hydrogen storage alloy powder 75% ;
- Titanium dioxide 3% Titanium dioxide
- PTFE emulsion After half an hour, add 4.9 kg of PTFE emulsion according to the weight ratio.
- the added PTFE emulsion is the commonly used concentration, the concentration is 60%, and the mixture can be evenly stirred.
- a method for preparing a high energy nickel carbon supercapacitor negative plate slurry the specific steps are:
- the binder for the negative electrode is prepared, and the weight ratio of the raw materials is as follows:
- the steps of the preparation method are:
- the main raw material composition and weight percentage range of the negative plate slurry are as follows:
- Electrostatic capacity 118.4% Storage energy: 71.3% Internal resistance: 1.67 times
- Electrostatic capacity 152.8% Storage energy: 91.0% Internal resistance: 1.86 times
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
一种高能镍碳超级电容器负极板浆料的制备方法,由负极用粘合剂和主料构成,其中负极用粘合剂为负极粘合剂和主料所形成的总重量的20%-38%,主料包括储氢合金粉、活性碳材料、亚氧化钛和PTFE乳液。超级电容器工作电压达到1.3V,最大储能密度达到65Wh/kg,具有储能密度大、放电功率高等特点,可广泛应用于电动公交车的动力电源、车辆低温启动用动力电源、军用装备的动力电源,如航空航天、歼击机、潜艇、舰艇等装备用电容器,也可应用在便携式设备用高容量动力电源,如笔记本电脑、手机、电动工具用电容器等。
Description
一种髙能镍碳超级电容器负极负极板浆料的制备方法
技术领域
本发明属于超级电容器领域,尤其是一种高能镍碳超级电容器负极板浆料的制备方法。 背景技术
随着国家新能源建设的逐步推进, 新能源的研究步入一个快速发展的轨道, 尤其超级 电容器的研究引起各国的重视。 通过检索, 发现如下有关超级电容器的公开专利文献:
1、 一种氢氧化亚镍混和式超级电容器及其制备方法 (CN200810111891.2), 该电容器 包括圆柱型和方型结构, 由氢氧化亚镍阳极, 碱金属氢氧化物水性电解液和活性碳纤维阴 极密封在不锈钢或工程塑料外壳内构成, 具有储能密度大、 放电功率高等特点的混和式超 级电容器。 氢氧化亚镍阳极采用化学反应法和电化学反应方法制备, 在其中掺加适量碳纳 米管及羰基镍作为添加剂, 发泡镍为基体制造出阳极。 活性碳阴极采用电镀镍处理过的活 性碳纤维作为原材料, 采用镍箔作为集流体。 所组装电容器工作电压达到 1.6V, 最大储能 密度达到 20Wh/kg, 峰值放电功率达到 8KW/kg。 在工业、 交通、 电子、 军事等领域广泛 应用。
2、 一种车用启动超级电容器 (CN03114837.9 ), 超级电容器芯子由包裹隔膜的烧结式 氧化镍正极片, 连续化活性碳纤维布 负极和集流支撑的薄镍片构成, 电容芯子通过制作、 焊接电流端子后置于塑料壳体内, 注入电解液, 封口便得超级电容器成品。 该超级电容器 具有较高的功率密度和能量密度, 且重量轻, 成本低, 寿命长, 适合做各种类型车辆的启 动能源, 推广应用具有很好价值。
3、 一种用于超级电容器的碳基多孔电极薄膜及其制备方法 (CN200410009580.7 ), 薄 膜各组分含量为: 活性炭含量为 72masS %〜 99masS %, 导电碳黑或石墨含量为 O.lmass %〜20mass %, 氧化锆纳米粉体的含量为 O.lmass %〜5mass %, 纳米金属镍粉体含量为 0.1mass %〜3mass % ; 空隙率为 45 %〜75 %, 进一步的优选空隙率为 55 %〜65 %。 制备本 发明薄膜首先将去离子水、 有机单体和交联剂混合均匀; 然后将分散剂加入溶液搅拌均匀 得到预混溶液; 再将原料粉体加入, 球磨混合, 制成浆料; 将所得浆料加入除泡剂并进行 真空除泡; 将引发剂和催化剂加入除泡后的浆料, 搅拌均匀后, 在流延机上经成型、 固化 和脱膜后得到生坯, 再经弱氧化气氛热处理, 得到目标多孔电极薄膜。 本发明成型工艺简 单、 成型时间短、 易操作, 薄膜厚度可控性好、 中孔发达。
4、一种大倍率充放电性能超级电容器的多孔炭电极的制备方法(CN200810053475.1 ), 该方法包括以下过程, 以微孔型沸石分子筛为模板, 以气体乙块、 甲烷或乙烯为碳源, 在
石英管反应器中, 利用高周波加热装置进行气相沉积得到富含微孔的多孔炭; 多孔炭再经
1000— 160CTC高温热处理调节表面性质制得大比表面积多孔炭; 大比表面积多孔炭与聚四 氟乙烯混合分散到乙醇中, 并调制为浆状, 均匀地涂敷在泡沫镍片上, 再经烘干压制制成 多孔炭电极。 本发明的优点在于: 所制得的大比表面积炭具有均一的孔隙结构; 多孔炭的 表面亲水性低, 氧含量低, 所制得的多孔炭电极特别适用于大倍率充放电性能的超级电容 器。
5、 一种氢氧化亚镍混和式超级电容器及其制备方法 (CN200810111891.2), 该电容器 包括圆柱型和方型结构, 由氢氧化亚镍阳极, 碱金属氢氧化物水性电解液和活性碳纤维阴 极密封在不锈钢或工程塑料外壳内构成具有储能密度大、 放电功率高等特点的混和式超级 电容器。 氢氧化亚镍阳极采用化学反应法和电化学反应方法制备, 在其中掺加适量碳纳米 管及羰基镍作为添加剂, 发泡镍为基体制造出阳极。 活性碳阴极采用电镀镍处理过的活性 碳纤维作为原材料, 采用镍箔作为集流体。 所组装电容器工作电压达到 1.6V, 最大储能密 度达到 20Wh/kg, 峰值放电功率达到 8KW/kg。 在工业、 交通、 电子、 军事等领域广泛应 用。
6、 一种混合型超级电容器及其制备方法 (CN200910079669.3), 混合型超级电容器的 负极活性材料为纳米 Ti02或 Ή02的同质异像体 Ή02-Β中的一种或几种, 正极活性材料 为碳纳米管、 碳纳米纤维、 石墨、 导电炭黑、 氢氧化镍、 氢氧化锰或氢氧化钼中的一种或 几种。 混合型超级电容器以正负极活性材料、 粘结剂和导电剂为原料制成电极, 在手套箱 中装配成模拟电池制成超级电容器。 本发明提供的制备方法具有可调控, 制备流程简单, 操作容易, 组装的混合超级电容器模型具有比容量高、 电位低、 性能稳定、 可大电流充放 电、 循环寿命长、 成本低廉、 机械化大规模生产容易实现等特点。
7、 一种超级电容器的制备方法 (CN200910063288.6), 它包括如下步骤: 1)将泡沫镍 基板放入化学气相沉积反应炉中, 通入氩气 10-60分钟, 排尽炉内空气, 然后, 加热升温 至 450-75CTC, 在氩气氛围中以 25-40ml/min的流量通入烃类气体, 450-75CTC下反应 30秒 至 50分钟, 反应完成后, 得到生长有碳纳米管的泡沫镍; 2)除去表面疏松层产物后, 直接 以生长有碳纳米管的泡沫镍基体直接用作超级电容器电极; 3)将步骤 2所得的两片厚度、 大小相同的电极干燥, 用电解液充分浸泡 1-36小时, 再用同样浸满电解液的隔膜隔开, 组 装得到超级电容器; 所述烃类气体是乙块、 甲烷、 乙烯、 或丙烯。 本发明碳纳米管是直接 生长在泡沫镍基板上, 无需使用粘合剂; 泡沫镍为基板, 电极物质体积密度更高, 孔分布 合理。
经过对比, 上述各项专利技术所涉及的负极材料与本专利申请有较大不同。
发明内容
本发明的目的在于克服现有技术的不足之处, 提供一种储能密度大、 放电功率高的高 能镍碳超级电容器的负极板浆料的制备方法。
为解决上述技术问题, 本发明采用下列技术方案:
一种高能镍碳超级电容器负极板浆料的制备方法, 制备方法的步骤是:
(1)将负极用粘合剂, 放在搅拌机上搅拌均匀;
(2)将活性碳材料、 亚氧化钛用去离子水溶解, 去离子水慢慢加入, 边加入边搅拌, 以 免粉料结块;
(3)加入储氢合金粉, 先少量加入十分之一, 搅拌均匀后, 继续分批加入到搅拌机内搅 拌;
(4)加完后再均匀搅拌半小时;
(5)半小时后按照重量配比加入 PTFE乳液, 搅拌均匀即成为负极板浆料;
负极用粘合剂为负极粘合剂和主料所形成的总重量的 20%-38%。
而且, 所述负极用粘合剂的原料构成及其重量配比范围分别为:
HPMC 2 %〜4%
去离子水 96%〜98%;
而且, 所述负极用粘合剂的配制方法是:
(1)加热去离子水, 温度控制在 60°C-80°C ;
(2)缓慢加入 HPMC, 边加入边搅拌;
(3)完全加入后, 放在搅拌机内搅拌搅拌至无结块、 溶液均匀为止, 降至室温备用。 而且, 所述各原料的重量百分比范围如下:
储氢合金粉 70%〜85%;
活性碳材料 5%〜15%;
亚氧化钛 0.5%〜5%;
PTFE乳液 2%〜8%。
本发明的优点及积极效果是:
1、本超级电容器采用氢氧化镍为主要活性物质的正极材料与本专利申请所采用的碱金 属氢氧化物水性电解液和储氢合金粉与活性碳材料为主要活性物质组成的混合负极板, 以 及隔膜密封在不锈钢或工程塑料外壳内构成, 具有储能密度大、 放电功率高等特点。
2、 本发明所发明的负极板浆料所制备的超级电容器工作电压达到 1.3V, 最大储能密 度达到 65Wh/kg。 可广泛应用于电动公交车的动力电源、 车辆低温启动用动力电源、 军用 装备的动力电源, 如航空航天、 歼击机、 潜艇、 舰艇等装备用电容器, 也可应用在便携式 设备用高容量动力电源, 如笔记本电脑、 手机、 电动工具用电容器等。 应用领域涉及到车 辆、 交通、 工业、 航空、 军事、 消费电子、 绿色能源等, 具有非常广泛的应用前景。
具体实肺式
下面将结合具体实施方式对本发明进行进一步阐述, 但本发明要求保护的范围并不局 限于下列实施方式。
本发明所涉及的高能镍碳超级电容器负极板浆料其配制方法分两步, 首先是配制负极 用粘合剂,需提前 3-6h配制,配好负极用粘合剂后再与主料混合而进行负极板浆料的配制。
实施例 1 :
一种高能镍碳超级电容器负极板浆料的制备方法, 具体步骤是:
一、 配制负极用粘合剂, 其原料的重量配比分别为:
HPMC 4%
去离子水 96%
配制方法的步骤是:
1、 加热去离子水, 温度控制在 80°C。
2、 缓慢加入 HPMC, 边加入边搅拌。
3、 完全加入后, 放在搅拌机内搅拌搅拌至无结块、 溶液均匀为止, 降至室温备用。 二、 负极板浆料的原料构成及重量百分比范围如下:
储氢合金粉 75% ;
活性碳材料 15% ;
亚氧化钛 3% ;
PTFE乳液 Ή。。
三、 配制负极板浆料, 以 100公斤为例, 其具体步骤如下:
1、 准备好已经配好的负极用粘合剂 30 公斤, 放在搅拌机上搅拌均匀, 配制后, 3-6 小时使用。
2、 将活性碳材料 10.5公斤、 亚氧化钛 2.1公斤用去离子水溶解, 注意去离子水要多次 少量慢慢加入, 边加入边搅拌, 以免粉料结块。
3、 按照重量配比加入储氢合金粉 52.5公斤, 先少量加入 5.3公斤, 搅拌均匀后, 分 3
批且每批 15.7公斤左右加入到搅拌机内搅拌。
4、 加完后再均匀搅拌半小时。
5、 半小时后按照重量配比加入 PTFE乳液 4.9公斤, 所加入的 PTFE乳液为常用的浓 度, 浓度为 60%, 搅拌均匀即可。
实施例 2:
一种高能镍碳超级电容器负极板浆料的制备方法, 具体步骤是:
一、 配制负极用粘合剂, 其原料的重量配比分别为:
HPMC 4%
去离子水 96%。
配制方法的步骤是:
1、 加热去离子水, 温度控制在 60°C。
2、 缓慢加入 HPMC, 边加入边搅拌。
3、 完全加入后, 放在搅拌机内搅拌搅拌至无结块、 溶液均匀为止, 降至室温备用。 二、 负极板浆料的主要原料构成及重量百分比范围如下:
储氢合金粉 85%;
活性碳材料 6%;
亚氧化钛 4%;
PTFE乳液 5%。
三、 配制负极板浆料的具体步骤如下
1、 将负极用粘合剂 25公斤放在搅拌机上搅拌均匀, 该负极用粘合剂需要 3-6小时使 用。
2、 将活性碳材料 4.5公斤、 亚氧化钛 3.0公斤用去离子水溶解, 注意去离子水要多次 少量慢慢加入, 边加入边搅拌, 以免粉料结块。
3、 加入储氢合金粉 63.75公斤, 先少量加入 6.4公斤, 搅拌均匀后, 分 3批每批 19.1 公斤左右加入到搅拌机内搅拌。
4、 加完后再均匀搅拌半小时。
5、 半小时后加入 PTFE乳液 3.75公斤, 所加入的 PTFE乳液为常用的浓度, 浓度一般 为 60%, 搅拌均匀即可。 由本负极板浆料制作的超级电容器的检测结果见下表:
检测单位: 信息产业部化学物理电源产品质量监督检验中心
110408- 08 静电容量: 152.8% 储存能量: 91.0% 内阻: 1.86倍
Claims
1、一种高能镍碳超级电容器负极板浆料的制备方法,其特征在于:制备方法的步骤是:
(1)将负极用粘合剂, 放在搅拌机上搅拌均匀;
(2)将活性碳材料、 亚氧化钛用去离子水溶解, 去离子水慢慢加入, 边加入边搅拌, 以 免粉料结块;
(3)加入储氢合金粉, 先少量加入十分之一, 搅拌均匀后, 继续分批加入到搅拌机内搅 拌;
(4)加完后再均匀搅拌半小时;
(5)半小时后按照重量配比加入 PTFE乳液, 搅拌均匀即成为负极板浆料;
负极用粘合剂为负极粘合剂和主料所形成的总重量的 20%-38%。
2、 根据权利要求 1所述的高能镍碳超级电容器负极板浆料的制备方法, 其特征在于: 所述负极用粘合剂的原料构成及其重量配比范围分别为:
HPMC 2 %〜4%
去离子水 96%〜98%;
3、 根据权利要求 2所述的高能镍碳超级电容器负极板浆料的制备方法, 其特征在于: 所述负极用粘合剂的配制方法是:
(1)加热去离子水, 温度控制在 60°C-80°C ;
(2)缓慢加入 HPMC, 边加入边搅拌;
(3)完全加入后, 放在搅拌机内搅拌搅拌至无结块、 溶液均匀为止, 降至室温备用。
4、根据权利要求 1所述的高能镍碳超级电容器负极负极板浆料的制备方法, 其特征在 于: 所述各原料的重量百分比范围如下:
储氢合金粉 70%〜85%;
活性碳材料 5%〜15%;
亚氧化钛 0.5%〜5%;
PTFE乳液 2%〜8%。
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