WO2012146046A1 - 一种聚酰亚胺电容电池及其制作方法 - Google Patents

一种聚酰亚胺电容电池及其制作方法 Download PDF

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WO2012146046A1
WO2012146046A1 PCT/CN2011/085136 CN2011085136W WO2012146046A1 WO 2012146046 A1 WO2012146046 A1 WO 2012146046A1 CN 2011085136 W CN2011085136 W CN 2011085136W WO 2012146046 A1 WO2012146046 A1 WO 2012146046A1
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Prior art keywords
negative electrode
positive electrode
electrode sheet
polyimide
capacitor battery
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English (en)
French (fr)
Inventor
吕晓义
王�琦
桑玉贵
匡晓明
任金生
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SHENZHEN HIFUTURE ELECTRIC CO Ltd
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SHENZHEN HIFUTURE ELECTRIC CO Ltd
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Priority to EP11864507.6A priority Critical patent/EP2704248A4/en
Priority to KR1020137030526A priority patent/KR20140004773A/ko
Priority to JP2014506722A priority patent/JP2014517507A/ja
Priority to US14/113,790 priority patent/US20140043727A1/en
Publication of WO2012146046A1 publication Critical patent/WO2012146046A1/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the invention belongs to the technical field of capacitors and batteries, and relates to a supercapacitor, and in particular to a polyimide capacitor battery and a manufacturing method thereof.
  • Supercapacitor is a new type of electrochemical energy storage device between traditional capacitors and batteries. It has higher energy density than traditional capacitors, and its electrostatic capacity can reach tens of thousands of terahertz; it is higher than battery. Its power density and long cycle life make it a combination of traditional capacitors and batteries. It is a promising chemical power source. It has the characteristics of high specific capacity, high power, long life, wide working temperature limit and maintenance-free.
  • supercapacitors can be divided into three categories: electric double layer capacitors (EDLC), Faraday quasi-capacitor supercapacitors and hybrid supercapacitors, in which electric double layer capacitors are mainly formed by electrode/electrolyte interface charge separation.
  • EDLC electric double layer capacitors
  • Faraday quasi-capacitor supercapacitors Faraday quasi-capacitor supercapacitors
  • hybrid supercapacitors in which electric double layer capacitors are mainly formed by electrode/electrolyte interface charge separation.
  • the electric double layer is used to realize the storage of charge and energy;
  • the Faraday quasi-capacitor supercapacitor mainly realizes the storage of charge and energy by means of the Faraday "quasi-capacitance" generated by the rapid redox reaction of the electrode surface;
  • the hybrid supercapacitor is a
  • the extremely non-polarized electrode of the battery such as nickel hydroxide
  • the polarized electrode of the electric double layer capacitor such as activated carbon
  • Supercapacitors can be divided into three kinds of supercapacitors: inorganic electrolyte, organic electrolyte and polymer electrolyte.
  • the inorganic electrolytes are mostly used in high concentration acidic (such as H 2 S0 4 ) or alkaline (such as KOH) aqueous solutions. Neutral aqueous electrolytes are less used; organic electrolytes generally use a quaternary ammonium salt or a lithium salt to form a mixed electrolyte with a high-conductivity organic solvent (such as acetonitrile), while polymer electrolytes are now only in the laboratory stage. There are no commercial products.
  • Today, mature organic supercapacitors generally use a symmetrical structure, that is, the same carbon material is used for the positive and negative electrodes, and the electrolyte consists of an ammonium salt and a high-conductivity organic solvent such as acetonitrile.
  • the power density of this capacitor is very high. High, can reach 5000-6000W/Kg, but its energy density is low, only 3-5Wh/Kg. Therefore, in order to further improve the energy density of organic supercapacitors, people use a hybrid structural design, that is, positive Different active materials are used for the negative electrode.
  • an object of the present invention is to provide a polyimide capacitor battery, which greatly increases the energy density and cycle life of the capacitor battery, and further broadens the application field of the battery capacitor.
  • Another object of the present invention is to provide a method of fabricating a polyimide capacitor battery to achieve higher performance of a capacitor battery.
  • An organic capacitor polyimide battery consisting of a positive electrode, a negative electrode, a polymer separator interposed therebetween, and an electrolyte
  • the positive electrode material is a mixture of a lithium ion intercalation compound and a porous carbon material
  • the negative electrode material is A mixture of a modified graphite and a porous activated carbon material
  • the polymer separator is a polyimide separator
  • the electrolyte solution is an organic solvent electrolyte containing lithium ions.
  • the components and weight percentages of the negative electrode material are:
  • the lithium ion intercalation compounds as LiCo0 2, LiMn 2 04, LiFeP0 4, LiFeMnP0 4, LiNio.8CoQ.2O2, LiNii / 3 C01 / 3 Mni 3 0 2 of one / or two or more mixed.
  • the intercalation-deintercalation of lithium ions in these lithium ion intercalation compounds is good in reversibility, fast in diffusion rate, and small in volume change accompanying the reaction, so that the battery has good cycle characteristics and high current characteristics.
  • the modified graphite is a high-density modified graphite having a density of > 2.2 g/cm 3 , and includes at least one or a mixture of two or more of a resin carbon and an organic polymer pyrolytic carbon, and a soft carbon solid phase carbonized material.
  • This type of high-density modified graphite has a high specific capacity of 300-700 mAh/g. Lithium-ion-embedded ionic compounds and such high-density modified graphite materials do not cause significant structural expansion, and have good charge-discharge cycle performance. .
  • the porous carbon should include one or a mixture of two or more of activated carbon, carbon cloth, carbon fiber, carbon felt, carbon aerogel, and carbon nanotube.
  • the polyimide membrane is a curved membrane having a thickness of 10-30 ⁇ m, a pore diameter of 0.03 to 0.05 ⁇ m, a porosity of 90% to 95%, a dielectric constant of 4.0 at 103 Hz, and a decomposition temperature of 400 ° C or higher. , the material insulation coefficient is 3.4.
  • the use of this polyimide membrane can effectively solve the safety problems caused by lithium ion dendrites in lithium battery and capacitor battery products.
  • the electrolyte solution includes a lithium ion compound, and the lithium ion compound is one or two of LiC10 4 , LiBF 4 , LiPF 6 , LiCF 3 S0 3 , LiN(CF 3 S0 2 ), LiBOB, LiAsF 6 .
  • the phase transfer catalyst is Me 3 EtNBF 4 , Me 2 Et 2 NBF 4 , MeEt 3 NBF 4 , Et 4 NBF 4 , Pr 4 NBF 4 , MeBu 3 NBF 4 , Bu 4 NBF 4 , Hex 4 NBF 4 , Me 4 PBF 4 , Et 4 PBF 4 , Pr 4 PBF 4 .
  • One or more of BU 4 PBF 4 are mixed; an organic solvent, the organic solvent is ethylene carbonate, propylene carbonate, Y-butyl One or two of lactone, dinonyl carbonate, diethyl carbonate, butylene carbonate, cesium carbonate, propyl propyl carbonate, sulfite, propylene sulfite, ethyl acetate, acetonitrile
  • an organic solvent is ethylene carbonate, propylene carbonate, Y-butyl
  • lactone dinonyl carbonate, diethyl carbonate, butylene carbonate, cesium carbonate, propyl propyl carbonate, sulfite, propylene sulfite, ethyl acetate, acetonitrile
  • lithium-containing organic electrolytes have high ionic conductivity, provide fast moving channels for lithium ion migration during charge and discharge, and increase the rate of reaction; at the same time, in a wide potential range (0-5V) It has good electrochemical stability, good thermal stability and wide temperature range, which makes the stability of charge and discharge reaction of supercapacitor battery greatly improved, which is beneficial to the improvement of cycle life of capacitor battery.
  • a method for manufacturing a polyimide capacitor battery comprising the following steps:
  • Preparation of positive electrode sheet First, lithium ion intercalation compound, porous carbon material, conductive agent, and binder are mixed, adjusted into a slurry, and then coated on a positive electrode current collector, dried, rolled, and cut. Prepared into a positive electrode sheet by vacuum drying;
  • the prepared positive and negative electrode sheets are laminated or wound into electric cells, placed in an aluminum plastic film, aluminum shell, plastic shell or steel shell, and then sealed and injected with lithium in an organic solvent. Ionic electrolyte.
  • the lithium ion intercalation compound, the porous carbon material, the conductive agent, and the binder are mixed in the following weight percentages:
  • the high density modified graphite, the porous activated carbon, and the binder are mixed in the following weight percentages:
  • the conductive agent includes one or more of natural graphite powder, artificial graphite, carbon black, acetylene black, mesophase carbon: ball, high density modified graphite, petroleum coke, carbon nanotube, graphene. mixing.
  • the binder is one or a mixture of two or more of polytetrafluoroethylene, polyvinylidene fluoride, hydroxypropylmethylcellulose, carboxymethylcellulose, and styrene-butadiene rubber.
  • the current collector of the positive electrode sheet is an aluminum foil or an aluminum mesh
  • the current collector of the negative electrode sheet is a copper foil or a copper mesh
  • the present invention has the beneficial effects that: the invention utilizes a polyimide material as a separator material of a capacitor battery, and a high-density, high-power mixed material of a modified graphite and a porous carbon material is used on the anode, and the anode is Porous activated carbon with an endless cycle life can be used as part of the mixed cathode material.
  • the capacitor battery is greatly improved. Energy density and cycle life further expand the field of application of battery capacitors.
  • the specific capacity of the polyimide capacitor battery capacitor battery of the invention can be as high as 90 Wh/Kg, the specific power is up to 6000 W/Kg, and the capacity retention rate is as high as 95% after 15,000 cycles of 50A charge and discharge cycles.
  • the manufacturing method of the polyimide capacitor battery of the invention has the advantages of simple process and high drying temperature, which greatly shortens the production time and improves the working efficiency.
  • the product of the invention can be widely applied to electric vehicles. Power tools, solar energy storage, wind energy storage, portable appliances and other fields.
  • a method for manufacturing a polyimide capacitor battery comprising the following steps:
  • Preparation of positive electrode sheet First, lithium ion intercalation compound, porous carbon material, conductive agent, and binder are mixed, adjusted into a slurry, and then coated on a positive electrode current collector, dried, rolled, and cut. Prepared into a positive electrode sheet by vacuum drying;
  • the prepared positive and negative electrode sheets are laminated or wound into electric cells, placed in an aluminum plastic film, aluminum shell, plastic shell or steel shell, and then sealed and injected in a non-aqueous organic solvent.
  • An electrolyte containing lithium ions An electrolyte containing lithium ions.
  • the current collector of the positive electrode sheet is an aluminum foil or an aluminum mesh having a thickness of 20 ⁇ m; and the current collector of the negative electrode sheet is a copper foil or a copper mesh having a thickness of 16 ⁇ m.
  • the temperature of the oven during the drying process is set to 110 ⁇ 120 °C; the temperature of the vacuum drying oven in vacuum drying is set at 120 ⁇ 130 °C.
  • Preparation of positive electrode sheet A total of 500 g of LiM 0 4 , activated carbon, conductive carbon black, and PVDF were mixed at a mass ratio of 45%: 45%: 5%: 5%, and adjusted with NMP (N-methylpyrrolidone). Slurry, then coated on aluminum foil with a thickness of 20 ⁇ m (coating weight: 140 g/m 2 ), dried at 110 ° C > further laminated, cut into pieces (size: 100 * 154) *0.135mm), dried at 130 ° C for 24 h under vacuum to prepare a positive electrode sheet.
  • NMP N-methylpyrrolidone
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, porous activated carbon, and PVDF were mixed at a mass ratio of 45:45:10, slurried with NMP, and then coated on a copper foil having a thickness of 16 ⁇ m ( The coating weight gain is: 90g/m 2 ), dried at 110 ° C, milled, cut into pieces (size: 100*154*0.09mm 2 ), vacuum dried at 130 ° C for 24 h. Made into a negative electrode sheet.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel ear, and the welded cell is placed in the formed aluminum plastic film, and the concentration of LiPF 6 is injected into 1 mol/L, EC (ethylene carbonate) / DEC (diethyl carbonate).
  • the concentration ratio of the substance is 80g of 1:1 electrolyte, assembled into Square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (ie, the activation of the performance of the capacitor battery), the performance test is performed. The test system is charged to 4.2V for 30A, left for 5min, 50A for 2.5V, and the specific energy of the capacitor battery is 50 Wh/Kg. The specific power is 5000 W/Kg. After 15000 cycles of 50A charge and discharge, the capacity retention rate is 90%.
  • Example 2
  • Preparation of positive electrode sheet A total of 500 g of LiMn 2 0 4 , activated carbon, conductive carbon black, and PVDF were mixed at a mass ratio of 20:70:5:5, and a slurry was prepared by NMP, and then coated to a thickness of 20 ⁇ m.
  • Aluminum foil (coating weight gain: 140g/m 2 ), dried at 120 ° C, milled, cut pieces (size: 100* 154*0.135mm), vacuum at 120 ° C After drying for 24 hours, a positive electrode sheet was produced.
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, porous activated carbon, and PVDF were mixed at a mass ratio of 45:45:10, slurried with NMP, and then coated on a copper foil having a thickness of 16 ⁇ m ( The coating weight gain is: 90g/m 2 ), dried at 120 ° C, milled, cut into pieces (size: 100* 154*0.09mm 2 ), vacuum dried at 120 ° C for 24 h , made into a negative electrode sheet.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel ear, and the welded cell is placed in the formed aluminum plastic film, and the concentration of LiPF 6 is injected into 1 mol/L, EC (ethylene carbonate) / DEC (diethyl carbonate).
  • the amount of the substance was 80 g of the electrolyte with a concentration ratio of 1:1, and assembled into a square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (that is, the activation of the performance of the capacitor battery), the performance test is performed. The test system is charged to 4.2V for 30A, left for 5min, 50A for 2.5V, and the specific energy of the capacitor battery is 25 Wh/Kg. The specific power is 5200 W/Kg. After 15000 cycles of 50A charge and discharge, the capacity retention rate is 90%.
  • Example 3 After the capacitor battery is formed (that is, the activation of the performance of the capacitor battery), the performance test is performed. The test system is charged to 4.2V for 30A, left for 5min, 50A for 2.5V, and the specific energy of the capacitor battery is 25 Wh/Kg. The specific power is 5200 W/Kg. After 15000 cycles of 50A charge and discharge, the capacity retention rate is 90%.
  • Preparation of positive electrode sheet A total of 500 g of LiM 0 4 , activated carbon, conductive carbon black, and PVDF were mixed at a mass ratio of 85 : 5 : 5 : 5 , and slurried with NMP, and then coated to a thickness of 20 ⁇ m.
  • Aluminum foil (coating weight gain: 140g/m 2 ), dried at 120 ° C, laminated, and cut into pieces (size: 100* 154*0.135mm), dried under vacuum at 130 ° C for 24 h, and then made into a positive electrode sheet.
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, porous activated carbon, and PVDF were mixed at a mass ratio of 45:45:10, slurried with NMP, and then coated on a copper foil having a thickness of 16 ⁇ m ( The coating weight gain is: 90g/m 2 ), dried at 120 ° C, milled, cut into pieces (size: 100* 154*0.09mm 2 ), vacuum dried at 130 ° C for 24 h. , made into a negative electrode sheet.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel ear, and the welded cell is placed in the formed aluminum plastic film, and the concentration of LiPF 6 is injected into 1 mol/L, EC (ethylene carbonate) / DEC (diethyl carbonate).
  • the amount of the substance was 80 g of the electrolyte with a concentration ratio of 1:1, and assembled into a square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (ie, the activation of the performance of the capacitor battery), the performance test is performed. The test system is charged to 4.2V for 30A, left for 5min, 50A for 2.5V, and the specific energy of the capacitor battery is 50Wh/Kg. The specific power is 4000 W/Kg, and after 15,000 cycles of 50A charge and discharge, the capacity retention rate is 90%.
  • Example 4
  • Preparation of positive electrode sheet A total of 500 g of LiCo0 2 , porous carbon, conductive carbon black, PVDF (polyvinylidene fluoride) were mixed at a mass ratio of 45:45:5:5, and the slurry was adjusted with NMP, and then Coated on aluminum foil with a thickness of 20 ⁇ m (coating weight gain: 140 g/m 2 ), dried at 120 ° C, laminated, cut, laminated, and cut into pieces (size: 100*) After 154*0.135 mm) and vacuum drying at 120 ° C for 24 h, a positive electrode sheet was prepared.
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, porous activated carbon, and PVDF were mixed at a mass ratio of 45:45:10, slurried with NMP, and then coated on a copper foil having a thickness of 16 ⁇ m ( The coating weight gain is: 90g/m 2 ), dried at 120 ° C, milled, cut into pieces (size: 100* 154*0.09mm 2 ), vacuum dried at 120 ° C for 24 h , made into a negative electrode sheet.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel ear, and the welded cell is placed in the formed aluminum plastic film, and the concentration of LiPF 6 is injected into 1 mol/L, EC (ethylene carbonate) / DEC (diethyl carbonate). 80g of electrolyte with a mass ratio of 1:1, assembled into Square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (ie, the activation of the performance of the capacitor battery), the performance test is performed. The test system is charged to 4.2V for 30A, left for 5min, 50A for 2.5V, and the specific energy of the capacitor battery is 60Wh/Kg. The specific power is 4000 W/Kg, and after 15,000 cycles of 50A charge and discharge, the capacity retention rate is 95%.
  • Preparation of positive electrode sheet A total of 500 g of LiCo0 2 , porous carbon, conductive carbon black, and PVDF were mixed at a mass ratio of 20:70:5:5, slurried with NMP, and then coated at a thickness of 20 ⁇ m.
  • Aluminum foil (coating weight gain: 140g/m 2 ), dried at 120 ° C, laminated, cut into pieces (size: 100* 154*0.135mm), vacuum dried at 120 ° C After 24 hours, a positive electrode sheet was produced.
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, porous activated carbon, and PVDF were mixed at a mass ratio of 45:45:10, slurried with NMP, and then coated on a copper foil having a thickness of 16 ⁇ m ( The coating weight gain is: 90g/m 2 ), dried at 120 ° C, milled, cut into pieces (size: 100* 154*0.09mm 2 ), vacuum dried at 120 ° C for 24 h , made into a negative electrode sheet.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel ear, and the welded cell is placed in the formed aluminum plastic film, and the concentration of LiPF 6 is injected into 1 mol/L, EC (ethylene carbonate) / DEC (diethyl carbonate).
  • the amount of the substance was 80 g of the electrolyte with a concentration ratio of 1:1, and assembled into a square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (ie, the activation of the performance of the capacitor battery), the performance test is performed. The test system is charged to 4.2V for 30A, left for 5min, 50A for 2.5V, and the specific energy of the capacitor battery is 31Wh/Kg. The specific power is 5200 W/Kg, and after 15,000 cycles of 50 A charge and discharge cycles, the capacity retention rate is 95%.
  • Example 6
  • Preparation of positive electrode sheet A total of 500 g of LiCo0 2 , porous carbon, conductive carbon black, and PVDF were mixed at a mass ratio of 85:5:5:5, slurried with NMP, and then coated to a thickness of 20 ⁇ m.
  • Aluminum foil (coating weight gain: 140g/m 2 ), dried at 120 ° C, laminated, and cut into pieces (100* 154*0.135mm), After drying under vacuum at 120 ° C for 24 h, a positive electrode sheet was prepared.
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, porous activated carbon, and PVDF were mixed at a mass ratio of 45:45:10, slurried with NMP, and then coated on a copper foil having a thickness of 16 ⁇ m ( The coating weight gain is: 90g/m 2 ), dried at 120 ° C, milled, cut into pieces (size: 100* 154*0.09mm 2 ), vacuum dried at 120 ° C for 24 h , made into a negative electrode sheet.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel ear, and the welded cell is placed in the formed aluminum plastic film, and the concentration of LiPF 6 is injected into 1 mol/L, EC (ethylene carbonate) / DEC (diethyl carbonate).
  • the amount of the substance was 80 g of the electrolyte with a concentration ratio of 1:1, and assembled into a square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (ie, the activation of the performance of the capacitor battery), the performance test is performed. The test system is charged to 4.2V for 30A, left for 5min, 50A for 2.5V, and the specific energy of the capacitor battery is 71Wh/Kg. The specific power is 5200 W/Kg, and after 15,000 cycles of 50 A charge and discharge cycles, the capacity retention rate is 95%.
  • Example 7
  • Preparation of positive electrode sheet A total of 500 g of LiFeMnP ⁇ 4, porous carbon, conductive carbon black, and PVDF were mixed at a mass ratio of 45:45:5:5, and slurried with NMP, and then coated to a thickness of 20 ⁇ m.
  • Aluminum foil (coating weight gain: 140g/m 2 ), dried at 120 ° C, milled, cut pieces (size: 100* 154*0.135mm), vacuum at 120 ° C After drying for 24 hours, a positive electrode sheet was produced.
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, porous activated carbon, and PVDF were mixed at a mass ratio of 45:45:10, and the slurry was prepared by NMP, and then coated on a copper foil having a thickness of 16 ⁇ m (coating) The weight gain of the cloth is: 90g/m 2 ), dried at 120 °C, then laminated, cut into pieces (size: 100* 154*0.09mm 2 ), vacuum dried at 120 ° C for 24 hours, Made into a negative electrode sheet.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel ear, and the welded cell is placed in the formed aluminum plastic film, and the concentration of LiPF 6 is injected into 1 mol/L, EC (ethylene carbonate) / DEC (diethyl carbonate).
  • the amount of the substance was 80 g of the electrolyte with a concentration ratio of 1:1, and assembled into a square super polyimide capacitor battery. Performance test: After the capacitor battery is formed (ie, the activation of the performance of the capacitor battery), the performance test is performed.
  • the test system is charged to 4.2V for 30A, left for 5min, 50A for 2.5V, and the specific energy of the capacitor battery is 75Wh/Kg.
  • the specific power is 5600 W/Kg, and after 15,000 cycles of 50 A charge and discharge cycles, the capacity retention rate is 95%.
  • Preparation of positive electrode sheet A total of 500 g of LiFeMnP ⁇ 4, porous carbon, conductive carbon black, and PVDF were mixed at a mass ratio of 20:70:5:5, and a slurry was prepared by NMP, and then coated to a thickness of 20 ⁇ m.
  • Aluminum foil (coating weight gain: 140g/m 2 ), dried at 120 ° C, then laminated, cut into pieces (size: 100* 154*0.135mm), vacuum at 120 ° C After drying for 24 hours, a positive electrode sheet was produced.
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, porous activated carbon, and PVDF were mixed at a mass ratio of 45:45:10, slurried with NMP, and then coated on a copper foil having a thickness of 16 ⁇ m ( The coating weight gain is: 90g/m 2 ), dried at 120 ° C, milled, cut into pieces (size: 100* 154*0.09mm 2 ), vacuum dried at 120 ° C for 24 h , made into a negative electrode sheet.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel ear, and the welded cell is placed in the formed aluminum plastic film, and the concentration of LiPF 6 is injected into 1 mol/L, EC (ethylene carbonate) / DEC (diethyl carbonate).
  • the amount of the substance was 80 g of the electrolyte with a concentration ratio of 1:1, and assembled into a square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (ie, the activation of the performance of the capacitor battery), the performance test is performed. The test system is charged to 4.2V for 30A, left for 5min, 50A for 2.5V, and the specific energy of the capacitor battery is 40Wh/Kg. The specific power is 6000W/Kg, and after 15,000 cycles of 50A charge and discharge, the capacity retention rate is 90%.
  • Example 9
  • Preparation of positive electrode sheet A total of 500 g of LiFeMnP0 4 , porous carbon, conductive carbon black, and PVDF were mixed at a mass ratio of 85 : 5 : 5 : 5 , and slurried with NMP, and then coated at a thickness of 20 ⁇ m.
  • Aluminum foil (coating weight gain: 140g/m 2 ), dried at 120 ° C, laminated, cut into pieces (size: 100* 154*0.135mm), vacuum dried at 120 ° C After 24 hours, a positive electrode sheet was produced.
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, porous activated carbon, and PVDF were mixed at a mass ratio of 45:45:10, and the slurry was prepared by NMP, and then coated on a copper foil having a thickness of 16 ⁇ m (coating) The weight gain of the cloth is: 90g/m 2 ), dried at 120 °C, then laminated, cut into pieces (size: 100* 154*0.09mm 2 ), vacuum dried at 120 ° C for 24 hours, Made into a negative electrode sheet.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel ear, and the welded cell is placed in the formed aluminum plastic film, and the concentration of LiPF 6 is injected into 1 mol/L, EC (ethylene carbonate) / DEC (diethyl carbonate).
  • the amount of the substance was 80 g of the electrolyte with a concentration ratio of 1:1, and assembled into a square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (ie, the activation of the performance of the capacitor battery), the performance test is performed.
  • the test system is charged to 4.2V for 30A, left for 5min, 50A for 2.5V, and the specific energy of the capacitor battery is 90Wh/Kg.
  • the specific power is 4,500 W/Kg, and after 15,000 cycles of 50 A charge and discharge cycles, the capacity retention rate is 85%.
  • Preparation of positive electrode sheet A total of 500 g of LiFeP0 4 , porous carbon, conductive carbon black, and PVDF were mixed at a mass ratio of 45:45:5:5, slurried with NMP, and then coated to a thickness of 20 ⁇ m.
  • Aluminum foil (coating weight gain: 140g/m 2 ), dried at 110 ° C, milled, cut into pieces (100 * 154 * 0.135mm), vacuum dried at 130 ° C for 24 h, Made into a positive electrode.
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, porous activated carbon, and PVDF were mixed at a mass ratio of 45:45:10, and the slurry was prepared by NMP, and then coated on a copper foil having a thickness of 16 ⁇ m (coating) The weight gain of the cloth is: 90g/m 2 ), dried at 110 °C, then laminated, cut into pieces (size: 100* 154*0.09mm 2 ), vacuum dried at 130 ° C for 24 hours, Made into a negative electrode sheet.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel ear, and the welded cell is placed in the formed aluminum plastic film, and the concentration of LiPF 6 is injected into 1 mol/L, EC (ethylene carbonate) / DEC (diethyl carbonate).
  • the amount of the substance was 80 g of the electrolyte with a concentration ratio of 1:1, and assembled into a square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (ie, the activation of the performance of the capacitor battery), the performance test is performed.
  • the test system is charged to 30V to 4.2V, left for 5min, 50A to 2.5V, and the specific energy of the capacitor battery. It is 56Wh/Kg, the specific power is 4600W/Kg, and after 15000 cycles of 50A charge and discharge, the capacity retention rate is 87%.
  • Preparation of positive electrode sheet A total of 500 g of LiFeP0 4 , porous carbon, conductive carbon black, and PVDF were mixed at a mass ratio of 20:70:5:5, slurried with NMP, and then coated to a thickness of 20 ⁇ m.
  • Aluminum foil (coating weight gain: 140g/m 2 ), dried at 120 ° C, laminated, cut into pieces (size: 100* 154*0.135mm), vacuum dried at 130 ° C After 24 hours, a positive electrode sheet was produced.
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, porous activated carbon, and PVDF were mixed at a mass ratio of 45:45:10, slurried with NMP, and then coated with a copper foil having a thickness of 16 ⁇ m (coating) The weight gain of the cloth is: 90g/m 2 ), dried at 120 °C, then laminated, cut into pieces (size: 100*154*0.09mm 2 ), vacuum dried at 130 ° C for 24 hours, Made into a negative electrode sheet.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel ear, and the welded cell is placed in the formed aluminum plastic film, and the concentration of LiPF 6 is injected into 1 mol/L, EC (ethylene carbonate) / DEC (diethyl carbonate).
  • the amount of the substance was 80 g of the electrolyte with a concentration ratio of 1:1, and assembled into a square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (ie, the activation of the performance of the capacitor battery), the performance test is performed. The test system is charged to 4.2V for 30A, left for 5min, 50A for 2.5V, and the specific energy of the capacitor battery is 26Wh/Kg. The specific power is 5000W/Kg, and after 15,000 cycles of 50A charge and discharge, the capacity retention rate is 95%.
  • Preparation of positive electrode sheet A total of 500 g of LiFeP0 4 , porous carbon, conductive carbon black, and PVDF were mixed at a mass ratio of 85:5:5:5, slurried with NMP, and then coated to a thickness of 20 ⁇ m.
  • Aluminum foil (coating weight gain: 140g/m 2 ), dried at 110 ° C, milled, cut into pieces (size: 100* 154*0.135mm), vacuum dried at 130 ° C After 24 hours, a positive electrode sheet was produced.
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, porous activated carbon, and PVDF were mixed at a mass ratio of 45:45:10, slurried with NMP, and then coated with a copper foil having a thickness of 16 ⁇ m (coating) The weight gain of the cloth is: 90g/m 2 ), dried at 110 °C, then laminated, cut into pieces (size: 100*154*0.09mm 2 ), vacuum dried at 130 ° C for 24 hours, Made into a negative electrode sheet.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel ear, and the welded cell is placed in the formed aluminum plastic film, and the concentration of LiPF 6 is injected into 1 mol/L, EC (ethylene carbonate) / DEC (diethyl carbonate).
  • the amount of the substance was 80 g of the electrolyte with a concentration ratio of 1:1, and assembled into a square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (ie, the activation of the performance of the capacitor battery), the performance test is performed. The test system is charged to 4.2V for 30A, left for 5min, 50A for 2.5V, and the specific energy of the capacitor battery is 65Wh/Kg. The specific power is 5000W/Kg, and after 15,000 cycles of 50A charge and discharge, the capacity retention rate is 91%.
  • Preparation of positive electrode sheet LiNi 8 Co 2 0 2 , carbon fiber, conductive carbon black, and PVDF in a total amount of 500 g were mixed at a mass ratio of 45:45:5:5, slurried with NMP, and then coated in thickness. It is 20 ⁇ aluminum foil (coating weight gain: 140g/m 2 ), dried at 110°C, laminated, cut into pieces (100* 154*0.135mm), vacuum dried at 130°C After 24 hours, a positive electrode sheet was produced.
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, carbon nanotubes, and PVDF were mixed at a mass ratio of 45:45:10, slurried with NMP, and then coated on a copper foil having a thickness of 16 ⁇ m ( The coating weight gain is: 90g/m 2 ), dried at 110 °C, milled, cut into pieces (size: 100*154*0.09mm 2 ), vacuum dried at 130 ° C for 24 h , made into a negative electrode sheet.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel ear, and the welded cell is placed in the formed aluminum plastic film, and the concentration of LiC10 4 is 1 mol/L, and the concentration ratio of the propylene carbonate/acetonitrile material is 1: 80 g of electrolyte solution was assembled into a square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (ie, the activation of the performance of the capacitor battery), the performance test is performed.
  • the test system is charged to 4.0V for 30A, left for 5min, 50A for discharge to 2.3V, and the specific energy of the capacitor battery is 50Wh/Kg.
  • the specific power is 4200 W/Kg, and after 15,000 cycles of 50 A charge and discharge cycles, the capacity retention rate is 82%.
  • positive electrode sheet a total of 500g of LiNi 8 Co 2 0 2 , carbon fiber, conductive carbon black, PVDF Mixing at a mass ratio of 20:70:5:5, slicing with NMP, then coating on an aluminum foil (coating weight gain: 140 g/m 2 ) with a thickness of 20 ⁇ m, and baking at 120 ° C Dry, then milled, cut pieces (size: 100* 154*0.135mm), vacuum dried at 120 ° C for 24 h, then made into a positive electrode sheet.
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, carbon nanotubes, and PVDF were mixed at a mass ratio of 20:70:10, slurried with NMP, and then coated on a copper foil having a thickness of 16 ⁇ m. (Coating weight gain: 90g/m 2 ), drying at 120 °C, rolling, cutting (size: 100*154*0.09mm 2 ), vacuum drying at 120 °C for 24h After that, it was made into a negative electrode sheet.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel ear, and the welded cell is placed in the formed aluminum plastic film, and the concentration of LiPF 6 is 1 mol/L, and the concentration ratio of the propylene carbonate/acetonitrile material is 1: 80 g of electrolyte solution was assembled into a square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (ie, the activation of the performance of the capacitor battery), the performance test is performed.
  • the test system is charged to 4.0V for 30A, left for 5min, 50A for discharge to 2.3V, and the specific energy of the capacitor battery is 38Wh/Kg.
  • the specific power is 5800 W/Kg, and after 15,000 cycles of 50 A charge and discharge cycles, the capacity retention rate is 89%.
  • Example 15 Preparation of Positive Electrode Sheet: A total of 500 g of LiNi 8 Co 2 0 2 , carbon fibers, conductive carbon black, and PVDF were mixed at a mass ratio of 85:5:5:5, and a slurry was prepared by NMP, and then coated. The cloth was coated on an aluminum foil (coating weight gain: 140 g/m 2 ) having a thickness of 20 ⁇ m, dried at 120 ° C, laminated, and cut into pieces (size: 100* 154*0.135 mm), 120 After drying under vacuum at °C for 24 h, a positive electrode sheet was prepared.
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, carbon nanotubes, and PVDF were mixed at a mass ratio of 45:45:10, slurried with NMP, and then coated on a copper foil having a thickness of 16 ⁇ m. (Coating weight gain: 90g/m 2 ), drying at 120 °C, rolling, cutting (size: 100*154*0.09mm 2 ), vacuum drying at 120 °C for 24h After that, it was made into a negative electrode sheet.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel ear, and the welded cell is placed in the formed aluminum plastic film, and the concentration of LiPF 6 is injected into 1 mol/L, propylene carbonate.
  • the 80% electrolytic solution having a concentration ratio of acetonitrile or acetonitrile was assembled into a square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (ie, the activation of the performance of the capacitor battery), the performance test is performed.
  • the test system is charged to 4.0V for 30A, left for 5min, 50A for discharge to 2.3V, and the specific energy of the capacitor battery is 65Wh/Kg.
  • the specific power is 4700 W/Kg, and after 20,000 cycles of 50A charge and discharge, the capacity retention rate is 89%.
  • positive electrode sheet LiNii/ 3 Coi/3 ⁇ 1/3 0 2 , carbon nanotubes, conductive carbon black, and PVDF in a total amount of 500 g were mixed at a mass ratio of 45:45:5:5, and were mixed with NMP.
  • the slurry is then coated on an aluminum foil (coating weight gain: MOg/m 2 ) having a thickness of 20 ⁇ m, dried at 110 ° C, laminated, and cut into pieces (100*154*0.135 mm). After drying under vacuum at 130 ° C for 24 h, a positive electrode sheet was prepared.
  • Preparation of negative electrode sheets A total of 500 g of high-density modified graphite, carbon aerogel, and PVDF were mixed at a mass ratio of 45:45:10, slurried with NMP, and then coated on a copper foil having a thickness of 16 ⁇ m. (Coating weight gain: 90g/m 2 ), drying at 110 °C, rolling, and cutting (size:
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel ear, and the welded cell is placed in the formed aluminum plastic film, and the same amount of LiAsFe/LiBOB, ⁇ _butyrolactone/carbonic acid, with a total concentration of lithium ions of 1 mol/L is injected.
  • the amount of the propyl propyl ester was 80 g of the electrolyte of 1:1, and assembled into a square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (ie, the activation of the performance of the capacitor battery), the performance test is performed.
  • the test system is charged to 4.1V for 30A, left for 5min, 50A for discharge to 2.2V, and the specific energy of the capacitor battery is 50Wh/Kg.
  • the specific power is 4200 W/Kg, and after 15,000 cycles of 50 A charge and discharge cycles, the capacity retention rate is 82%.
  • Preparation of positive electrode sheet A total of 500 g of LiNii / 3 Coi / 3 Mm / 3 0 2 , carbon nanotubes, conductive carbon black, PVDF were mixed at a mass ratio of 20:70:5:5, and slurried with NMP. Then, coated on aluminum foil with a thickness of 20 ⁇ m (coating weight gain: 140 g/m 2 ), dried at 120 ° C, laminated, and cut into pieces (size: 100*154*0.135) Mm), vacuum drying at 120 ° C for 24 h, then made into a positive electrode sheet.
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, carbon aerogel, and PVDF were mixed at a mass ratio of 20:70:10, and a slurry was prepared by NMP, and then a copper foil having a thickness of 16 ⁇ m was applied. on (Coating weight gain: 90g/m 2 ), drying at 120 °C, rolling, cutting (size: 100*154*0.09mm 2 ), vacuum drying at 120 °C for 24h After that, it was made into a negative electrode sheet.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel tabs, and the welded cells are placed in the formed aluminum plastic film, and the same amount of LiAsFe/LiBOB with a total concentration of lithium ions of 1 mol/L is injected, and the propylene carbonate/acetonitrile material is used.
  • 80 g of electrolyte with a concentration ratio of 1:1 was assembled into a square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (that is, the activation of the performance of the capacitor battery), the performance test is performed.
  • the test system is charged to 4.1V for 30A, left for 5min, 50A for discharge to 2.2V, and the specific energy of the capacitor battery is 38Wh/Kg.
  • the specific power is 5800 W/Kg, and after 15,000 cycles of 50 A charge and discharge cycles, the capacity retention rate is 89%.
  • Preparation of positive electrode sheet A total of 500 g of LiNii/ 3 Coi/3 Mm/ 3 0 2 , carbon nanotubes, conductive carbon black, and PVDF were mixed at a mass ratio of 85:5:5:5, and pulverized with mash. Then, coated on aluminum foil with a thickness of 20 ⁇ m (coating weight gain: 140 g/m 2 ), dried at 120 ° C, laminated, and cut into pieces (size: 100*154*0.135) Mm), vacuum drying at 120 ° C for 24 h, then made into a positive electrode sheet.
  • Preparation of negative electrode sheet A total of 500 g of high-density modified graphite, carbon aerogel, and PVDF were mixed at a mass ratio of 45:45:10, slurried with NMP, and then coated with a copper foil having a thickness of 16 ⁇ m. Top (coating weight gain: 90g/m 2 ), drying at 120 ° C, crushing, cutting (size: 100*154*0.09mm 2 ), vacuum drying at 120 ° C After 24 hours, a negative electrode sheet was produced.
  • Polyimide is used as the separator, and the positive electrode sheet (22 pieces), the separator and the negative electrode sheet (23 pieces) are laminated into a battery core, and then the positive electrode group of the laminated battery core is welded on the aluminum tab and the negative electrode.
  • the group is welded on the nickel tabs, and the welded cells are placed in the formed aluminum plastic film, and the same amount of LiAsFe/LiBOB with a total concentration of lithium ions of 1 mol/L is injected, and the propylene carbonate/acetonitrile material is used.
  • 80 g of electrolyte with a concentration ratio of 1:1 was assembled into a square super polyimide capacitor battery.
  • Performance test After the capacitor battery is formed (ie, the activation of the performance of the capacitor battery), the performance test is performed.
  • the test system is charged to 4.1V for 30A, left for 5min, 50A for discharge to 2.2V, and the specific energy of the capacitor battery is 65Wh/Kg.
  • the specific power is 4700 W/Kg, and after 20,000 cycles of 50A charge and discharge, the capacity retention rate is 89%.
  • the polyimide capacitor battery of the invention realizes the combination of the principle and the technology of the lithium ion battery and the super capacitor in an electrolytic cell, and uses the polyimide membrane as the insulator, through electrochemical calculation and electrochemical design,
  • the combination of ion-embedded deintercalation reaction and fast reversible two-dimensional quasi-two-dimensional Faraday reaction organically enables high-energy capacitor cells to greatly increase specific energy while maintaining high specific power, long life and fast charging characteristics of supercapacitors. At the same time, it has the performance characteristics of supercapacitors and lithium-ion batteries.

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Description

一种聚酰亚胺电容电池及其制作方法
技术领域
本发明属于电容器和电池技术领域， 涉及超级电容器， 具体涉及一种聚酰亚 胺电容电池及其制作方法。
背景技术
超级电容器是介于传统电容器与电池之间的一种新型电化学储能器件，它相 比传统电容器有着更高的能量密度，静电容量能达千法拉至万法拉级； 相比电池 有着更高的功率密度和超长的循环寿命， 因此它结合了传统电容器与电池的优 点， 是一种应用前景广阔的化学电源。 它具有比容量高、 功率大、 寿命长、 工作 温限宽、 免维护等特点。
按照储能原理的不同， 超级电容器可以分为三类： 双电层电容器 （EDLC ), 法拉第准电容超级电容器和混合型超级电容器，其中双电层电容器主要是利用电 极 /电解质界面电荷分离所形成的双电层来实现电荷和能量的储存； 法拉第准电 容超级电容器主要是借助电极表面快速的氧化还原反应所产生的法拉第 "准电 容"来实现电荷和能量的储存； 而混合型超级电容器是一极釆用电池的非极化电 极（如氢氧化镍）， 另一极釆用双电层电容器的极化电极（如活性炭）， 这种混合 型的设计可以大幅度提高超级电容器的能量密度。
超级电容器按电解质分可分为无机电解质、有机电解质、 聚合物电解质三种 超级电容器，其中无机电解质应用较多的为高浓度的酸性（如 H2S04 )或碱性（如 KOH ) 的水溶液， 中性水溶液电解质应用的较少； 有机电解质则一般釆用季胺 盐或锂盐与高电导率的有机溶剂（如乙腈）组成混合电解液， 而聚合物电解质如 今只停留在实验室阶段， 尚无商业化产品的出现。
超级电容器釆用有机电解质， 可以大幅度提高电容器的工作电压， 根据 E=1/2CV2可知， 对提高电容器能量密度有很大的帮助。 如今， 成熟的有机超级 电容器一般都釆用对称型结构， 即正负极使用相同的炭材料， 电解液由铵盐和高 电导率的有机溶剂 （如乙腈） 组成， 这种电容器的功率密度很高， 能达到 5000-6000W/Kg, 但其能量密度偏低， 只能达到 3-5Wh/Kg, 因此， 为了进一步 提高有机超级电容器的能量密度，人们釆用了混合型的结构设计， 即正负极使用 不同的活性材料。 近年来， 有机混合型超级电容器的研究不断增多， 出现了如正 极釆用活性炭、 负极釆用钛酸裡和正极釆用聚 p塞吩， 负极釆用钛酸裡等有机超级 电容器。 在申请号为 200510110461.5的专利中， 正极釆用 LiMn2-xMx04, 负极 釆用活性炭， 该超级电容器的比能量最高可达 50Wh/Kg (基于正、 负极活性物 质总质量计算的）。 但是， 此类有机混合型超级电容器的能量密度与功率密度都 不理想， 电化学稳定性差、 热稳定性差以及使用温度范围小， 电容电池循环寿命 短， 不能满足目前人们对于电容电池有要求； 此外， 目前生产这类电容器的方法 繁瑣，工作效率低，不能满足对电容器产品高性能的要求以及大规模生产的要求。 发明内容
为克服现有技术的不足， 本发明的目的在于提供一种聚酰亚胺电容电池，大 幅度提高电容电池的能量密度和循环寿命， 进一步拓宽电池电容的应用领域。
本发明的另一目的在于提供一种聚酰亚胺电容电池的制作方法，以实现电容 器电池的更高性能。
为达到上述目的， 本发明所釆用的技术方案如下：
一种有机体系的聚酰亚胺电容电池， 由正极、 负极、 介于两者之间的聚合物 隔膜及电解液组成， 其中正极材料为锂离子嵌入化合物和多孔碳材料的混合物， 负极材料为改性石墨和多孔活性碳材料的混合物，所述聚合物隔膜为聚酰亚胺隔 膜， 所述电解液釆用含有锂离子的有机溶剂电解液。
其中所述正极材料各组分及重量百分比为：
锂离子嵌入化合物 20 - 85 %
多孔炭材料 5 _ 70 %
导电剂 5 %
粘结剂 5%;
所述负极材料各组分及重量百分比为：
高密度改性石墨 45 %
多孔活性炭 45 %
粘结剂 5 %。
所述锂离子嵌入化合物为 LiCo02、 LiMn204、 LiFeP04、 LiFeMnP04、 LiNio.8CoQ.2O2、 LiNii/3 C01/3 Mni/302 中的一种或者两种以上混合。 这些锂离子嵌 入化合物中锂离子的嵌入-脱嵌可逆性好、扩散速度快，伴随反应的体积变化小， 使电池具有良好的循环特性和大电流特性。 所述的改性石墨为高密度改性石墨， 密度 > 2.2g/cm3 , 包括树脂碳和有机聚 合物热解碳， 以及软碳固相碳化材料中的至少一种或者两种以上混合。这类高密 度改性石墨比容量高， 为 300-700mAh/g, 锂离子嵌入裡离子化合物与这类高密 度改性石墨材料同时使用不会引起结构显著膨胀， 具有很好的充放电循环性能。
所述多孔碳应包括活性炭、 碳布、 碳纤维、 碳毡、 碳气凝胶、 碳纳米管中的 一种或者两种以上混合。
所述聚酰亚胺隔膜为曲孔膜， 其厚度为 10-30μηι, 孔径为 0.03 -0.05μηι, 孔 隙率为 90% - 95%, 103 赫下介电常数 4.0, 分解温度在 400°C以上， 材料绝缘 系数为 3.4。 釆用这种聚酰亚胺隔膜可以有效解决锂电、 电容电池产品中由于锂 离子枝晶所带来的安全问题。
所述的电解液中包括锂离子化合物， 所述锂离子化合物为 LiC104、 LiBF4、 LiPF6、 LiCF3S03、 LiN(CF3S02)、 LiBOB、 LiAsF6中的一种或两种以上混合； 相 转移催化剂， 所述相转移催化剂为 Me3EtNBF4、 Me2Et2NBF4、 MeEt3NBF4、 Et4NBF4、 Pr4NBF4、 MeBu3NBF4、 Bu4NBF4、 Hex4NBF4、 Me4PBF4、 Et4PBF4、 Pr4PBF4. BU4PBF4中的一种或两种以上混合； 有机溶剂， 所述有机溶剂为碳酸乙 烯酯、 碳酸丙烯酯、 Y -丁内酯、 碳酸二曱酯、 碳酸二乙酯、 碳酸丁烯酯、 碳酸 曱乙酯、 碳酸曱丙酯、 亚硫酸乙烯酯、 亚硫酸丙烯酯、 乙酸乙酯、 乙腈中的一种 或两种以上混合； 其中所述电解液中锂离子的摩尔浓度保持 lmol/L, 相转移催 化剂占电解质总重量的 1-5%。 这些含有锂盐的有机电解液具有较高的离子电导 率， 能为充放电过程中锂离子的迁移提供快速移动的通道， 提高反应的速率；同 时， 在较宽的电位范围 （0-5V ) 内具有很好的电化学稳定性、 热稳定性好、 使用 温度范围宽等特点，使得超级电容电池充放电反应的稳定性大大提高，有利于电 容电池循环寿命的提升。
一种聚酰亚胺电容电池的制作方法， 包括一下步骤：
( 1 )正极片的制备： 首先将锂离子嵌入化合物、 多孔炭材料、 导电剂、 粘 结剂混合， 调成浆料， 然后涂布在正极集流体上， 经烘干、 碾压、 裁切、 真空干 燥制备成正极片；
( 2 ) 负极片的制备： 首先将高密度改性石墨、 多孔碳材料、 粘结剂混合， 调成浆料， 然后涂布在负极集流体上， 经烘干、 碾压、 裁切、 真空干燥制备成负 极片；
( 3 )组装： 将制备好的正、 负极片经叠片或卷绕成电芯，放入铝塑膜、铝壳， 塑料壳或钢壳中， 然后进行封口、 注入在有机溶剂中含有锂离子的电解液。
所述正极在制备步骤中锂离子嵌入化合物、 多孔炭材料、 导电剂、 粘结剂按 以下重量百分比混合：
锂离子嵌入化合物 20 - 85 %
多孔炭材料 5 _ 70 %
导电剂 5 %
粘结剂 5%;
所述负极制作步骤中高密度改性石墨、 多孔活性炭、粘结剂按以下重量百分 比混合：
改性石墨 45 %
多孔活性炭 45 %
粘结剂 5 %。
所述的导电剂包括天然石墨粉、 人造石墨、 炭黑、 乙炔黑、 中间相炭^:球、 高密度改性石墨、 石油焦、 碳纳米管、 石墨烯、 中的一种或两种以上混合。
所述的粘结剂为聚四氟乙烯、 聚偏氟乙烯、 羟丙基曱基纤维素、羧曱基纤维 素纳和丁苯橡胶中的一种或两种以上混合。
所述的正极片的集流体为铝箔或者铝网，所述的负极片的集流体为铜箔或者 铜网。
本发明相比现有技术， 其有益效果在于： 本发明利用聚酰亚胺材料作为电 容电池的隔膜材料， 负极上使用高密度、 高功率改性石墨与多孔碳材料的混合材 料，并且在正极上使用循环寿命能达到无限次的多孔活性炭作为混合正极材料的 一部分， 在保持电容电池高功率、 循环寿命长、 无污染、 高安全性、 免维护等特 性的前提下， 大幅度提高电容电池的能量密度和循环寿命， 进一步拓宽电池电容 的应用领域。 本发明聚酰亚胺电容电池电容电池的比能量可高达 90 Wh/Kg, 比 功率高达 6000 W/Kg,在经过 50A充放电循环 15000次后，容量保持率高达 95%。 本发明的聚酰亚胺电容电池的制作方法， 工艺简单， 釆用较高的干燥温度， 大大 缩短了制作时间，从而提高了工作效率。 本发明的产品可广泛应用于电动汽车， 电动工具、 太阳能储能、 风能储能、 便携式家电等领域。
具体实施方式
下面结合具体的实施方式对本发明作进一步详细说明。
一种聚酰亚胺电容电池的制作方法， 包括一下步骤：
( 1)正极片的制备： 首先将锂离子嵌入化合物、 多孔炭材料、 导电剂、 粘 结剂混合， 调成浆料， 然后涂布在正极集流体上， 经烘干、 碾压、 裁切、 真空干 燥制备成正极片；
(2) 负极片的制备： 首先将改性石墨、 多孔碳材料、 粘结剂混合， 调成浆 料， 然后涂布在负极集流体上， 经烘干、 碾压、 裁切、 真空干燥制备成负极片；
(3)组装： 将制备好的正、 负极片经叠片或卷绕成电芯，放入铝塑膜、铝壳， 塑料壳或钢壳中， 然后进行封口、 注入在非水有机溶剂中含有锂离子的电解液。
所述的正极片的集流体为铝箔或者铝网， 厚度为 20μηι; 所述的负极片的集 流体为铜箔或者铜网， 厚度为 16μηι。
其中， 烘干过程中烘箱的温度设置为 110~ 120°C; 真空干燥中真空干燥箱 的温度设置在 120~ 130°C。
实施例 1：
正极片的制作： 将总量为 500g的 LiM 04、 活性碳、 导电炭黑、 PVDF按 质量比为 45%: 45% :5% :5%混合， 用 NMP (N-甲基吡咯烷酮 ）调成浆料， 然后涂布在厚度为 20μηι的铝箔（涂布增重为： 140g/m2)上，在 110°C温度下烘干 > 再经碾压、 裁片（尺寸为： 100*154*0.135mm)、 130°C温度下真空干燥 24h, 制作 成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 多孔活性炭、 PVDF 按 质量比为 45: 45: 10混合， 用 NMP调成浆料， 然后涂布厚度为 16μηι的铜箔 上（涂布增重为： 90g/m2), 在 110°C温度下烘干、 再经碾压、 裁片（尺寸为： 100*154*0.09mm2)、 130°C温度下真空干燥 24h, 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入 LiPF6浓度为 lmol/L, EC (碳 酸乙烯酯） /DEC (碳酸二乙酯） 物质的量浓度比为 1: 1的电解液 80g, 组装成 方型超级聚酰亚胺电容电池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.2V, 静置 5min, 50A放电至 2.5V, 电容电池的比能量 为 50 Wh/Kg, 比功率为 5000 W/Kg, 经过 50A充放电循环 15000次后， 容量保 持率在 90%。 实施例 2
正极片的制作： 将总量为 500g的 LiMn204、 活性碳、 导电炭黑、 PVDF按 质量比为 20: 70 : 5 : 5混合， 用 NMP调成浆料， 然后涂布在厚度 20μηι的铝箔 (涂布增重为： 140g/m2)上， 在 120°C温度下烘干、 再经碾压、 裁片（尺寸为： 100* 154*0.135mm), 120°C温度下真空干燥 24h后， 制作成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 多孔活性炭、 PVDF 按 质量比为 45:45 : 10混合， 用 NMP调成浆料， 然后涂布厚度为 16μηι的铜箔上 (涂布增重为： 90g/m2) , 在 120°C温度下烘干、 再经碾压、 裁片（尺寸为： 100* 154*0.09mm2)、 120°C温度下真空干燥 24h后， 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入 LiPF6浓度为 lmol/L , EC (碳 酸乙烯酯） /DEC (碳酸二乙酯） 物质的量浓度比为 1 : 1的电解液 80g, 组装成 方型超级聚酰亚胺电容电池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.2V, 静置 5min, 50A放电至 2.5V, 电容电池的比能量 为 25 Wh/Kg, 比功率为 5200 W/Kg , 经过 50A充放电循环 15000次后， 容量保 持率在 90%。 实施例 3
正极片的制作： 将总量为 500g的 LiM 04、 活性碳、 导电炭黑、 PVDF按 质量比为 85 : 5 : 5 : 5混合， 用 NMP调成浆料， 然后涂布在厚度为 20μηι的铝 箔（涂布增重为： 140g/m2)上， 在 120°C温度下烘干、 再经碾压、 裁片（尺寸为： 100* 154*0.135mm), 130°C温度下真空干燥 24h后， 制作成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 多孔活性炭、 PVDF 按 质量比为 45 : 45: 10混合， 用 NMP调成浆料， 然后涂布厚度为 16μηι的铜箔 上（涂布增重为： 90g/m2) , 在 120°C温度下烘干、 再经碾压、 裁片（尺寸为： 100* 154*0.09mm2)、 130°C温度下真空干燥 24h后， 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入 LiPF6浓度为 lmol/L , EC (碳 酸乙烯酯） /DEC (碳酸二乙酯） 物质的量浓度比为 1 : 1的电解液 80g, 组装成 方型超级聚酰亚胺电容电池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.2V, 静置 5min, 50A放电至 2.5V, 电容电池的比能量 为 50Wh/Kg, 比功率为 4000 W/Kg , 经过 50A充放电循环 15000次后， 容量保 持率在 90%。 实施例 4:
正极片的制作： 将总量为 500g的 LiCo02、 多孔碳、 导电炭黑、 PVDF (聚 偏二氟乙烯）按质量比为 45: 45： 5： 5混合，用 NMP调成浆料， 然后涂布在 厚 度为 20μηι的铝箔（涂布增重为： 140g/m2)上， 在 120°C温度下烘干、 再经碾压、 裁片、 碾压、 裁片（尺寸为： 100* 154*0.135mm)、 120°C温度下真空干燥 24h后， 制作成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 多孔活性炭、 PVDF 按 质量比为 45:45 : 10混合， 用 NMP调成浆料， 然后涂布厚度为 16μηι的铜箔上 (涂布增重为： 90g/m2) , 在 120°C温度下烘干、 再经碾压、 裁片（尺寸为： 100* 154*0.09mm2)、 120°C温度下真空干燥 24h后， 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入 LiPF6浓度为 lmol/L , EC (碳 酸乙烯酯） /DEC (碳酸二乙酯） 物质的量浓度比为 1 : 1的电解液 80g, 组装成 方型超级聚酰亚胺电容电池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.2V, 静置 5min, 50A放电至 2.5V, 电容电池的比能量 为 60Wh/Kg, 比功率为 4000 W/Kg , 经过 50A充放电循环 15000次后， 容量保 持率在 95%。 实施例 5:
正极片的制作： 将总量为 500g的 LiCo02、 多孔碳、 导电炭黑、 PVDF按质 量比为 20: 70： 5： 5混合， 用 NMP调成浆料， 然后涂布在 厚度为 20μηι的铝 箔（涂布增重为： 140g/m2)上， 在 120°C温度下烘干、 再经碾压、 裁片（尺寸为： 100* 154*0.135mm), 120°C温度下真空干燥 24h后， 制作成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 多孔活性炭、 PVDF 按 质量比为 45:45 : 10混合， 用 NMP调成浆料， 然后涂布厚度为 16μηι的铜箔上 (涂布增重为： 90g/m2) , 在 120°C温度下烘干、 再经碾压、 裁片（尺寸为： 100* 154*0.09mm2)、 120°C温度下真空干燥 24h后， 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入 LiPF6浓度为 lmol/L , EC (碳 酸乙烯酯） /DEC (碳酸二乙酯） 物质的量浓度比为 1 : 1的电解液 80g, 组装成 方型超级聚酰亚胺电容电池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.2V, 静置 5min, 50A放电至 2.5V, 电容电池的比能量 为 31Wh/Kg, 比功率为 5200W/Kg, 经过 50A充放电循环 15000次后， 容量保持 率在 95%。 实施例 6:
正极片的制作： 将总量为 500g的 LiCo02、 多孔碳、 导电炭黑、 PVDF按质 量比为 85 : 5: 5： 5混合，用 NMP调成浆料，然后涂布在 厚度为 20μηι的铝箔 (涂 布增重为： 140g/m2)上，在 120°C温度下烘干、再经碾压、裁片（100* 154*0.135mm)、 120°C温度下真空干燥 24h后， 制作成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 多孔活性炭、 PVDF 按 质量比为 45:45 : 10混合， 用 NMP调成浆料， 然后涂布厚度为 16μηι的铜箔上 (涂布增重为： 90g/m2) , 在 120°C温度下烘干、 再经碾压、 裁片（尺寸为： 100* 154*0.09mm2)、 120°C温度下真空干燥 24h后， 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入 LiPF6浓度为 lmol/L , EC (碳 酸乙烯酯） /DEC (碳酸二乙酯） 物质的量浓度比为 1 : 1的电解液 80g, 组装成 方型超级聚酰亚胺电容电池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.2V, 静置 5min, 50A放电至 2.5V, 电容电池的比能量 为 71Wh/Kg, 比功率为 5200W/Kg, 经过 50A充放电循环 15000次后， 容量保持 率在 95%。 实施例 7:
正极片的制作： 将总量为 500g的 LiFeMnP〇4、 多孔碳、 导电炭黑、 PVDF 按质量比为 45 : 45： 5： 5混合， 用 NMP调成浆料， 然后涂布在 厚度为 20μηι 的铝箔 (涂布增重为： 140g/m2)上， 在 120°C温度下烘干、 再经碾压、 裁片（尺寸 为： 100* 154*0.135mm)、 120°C温度下真空干燥 24h后， 制作成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 多孔活性炭、 PVDF 按 质量比为 45:45 : 10混合， 用 NMP调成浆料， 然后涂布厚度 16μηι的铜箔上 (涂 布增重为： 90g/m2) , 在 120°C温度下烘干、 再经碾压、 裁片（尺寸为： 100* 154*0.09mm2)、 120°C温度下真空干燥 24h后， 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入 LiPF6浓度为 lmol/L , EC (碳 酸乙烯酯） /DEC (碳酸二乙酯） 物质的量浓度比为 1 : 1的电解液 80g, 组装成 方型超级聚酰亚胺电容电池。 性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.2V, 静置 5min, 50A放电至 2.5V, 电容电池的比能量 为 75Wh/Kg, 比功率为 5600W/Kg, 经过 50A充放电循环 15000次后， 容量保持 率在 95%。 实施例 8
正极片的制作： 将总量为 500g的 LiFeMnP〇4、 多孔碳、 导电炭黑、 PVDF 按质量比为 20: 70： 5： 5混合， 用 NMP调成浆料， 然后涂布在厚度为 20μηι的 铝箔 (涂布增重为： 140g/m2)上， 在 120°C温度下烘干、再经碾压、 裁片 （尺寸为： 100* 154*0.135mm), 120°C温度下真空干燥 24h后， 制作成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 多孔活性炭、 PVDF 按 质量比为 45:45 : 10混合， 用 NMP调成浆料， 然后涂布厚度为 16μηι的铜箔上 (涂布增重为： 90g/m2) , 在 120°C温度下烘干、 再经碾压、 裁片（尺寸为： 100* 154*0.09mm2)、 120°C温度下真空干燥 24h后， 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入 LiPF6浓度为 lmol/L , EC (碳 酸乙烯酯） /DEC (碳酸二乙酯） 物质的量浓度比为 1 : 1的电解液 80g, 组装成 方型超级聚酰亚胺电容电池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.2V, 静置 5min, 50A放电至 2.5V, 电容电池的比能量 为 40Wh/Kg, 比功率为 6000W/Kg, 经过 50A充放电循环 15000次后， 容量保持 率在 90%。 实施例 9
正极片的制作： 将总量为 500g的 LiFeMnP04、 多孔碳、 导电炭黑、 PVDF 按质量比为 85 : 5 : 5 : 5混合， 用 NMP调成浆料， 然后涂布在 厚度为 20μηι的 铝箔 (涂布增重为： 140g/m2)上， 在 120°C温度下烘干、 再经碾压、 裁片（尺寸为： 100* 154*0.135mm ), 120°C温度下真空干燥 24h后， 制作成正极片。 负极片的制作： 将总量为 500g的高密度改性石墨、 多孔活性炭、 PVDF 按 质量比为 45:45 : 10混合， 用 NMP调成浆料， 然后涂布厚度 16μηι的铜箔上 (涂 布增重为： 90g/m2) , 在 120 °C温度下烘干、 再经碾压、 裁片（尺寸为： 100* 154*0.09mm2)、 120°C温度下真空干燥 24h后， 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入 LiPF6浓度为 lmol/L , EC (碳 酸乙烯酯） /DEC (碳酸二乙酯） 物质的量浓度比为 1 : 1的电解液 80g, 组装成 方型超级聚酰亚胺电容电池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.2V, 静置 5min, 50A放电至 2.5V, 电容电池的比能量 为 90Wh/Kg, 比功率为 4500W/Kg, 经过 50A充放电循环 15000次后， 容量保持 率在 85%。
实施例 10:
正极片的制作： 将总量为 500g的 LiFeP04、 多孔碳、 导电炭黑、 PVDF按质 量比为 45: 45： 5： 5混合， 用 NMP调成浆料， 然后涂布在 厚度为 20μηι的铝 箔（涂布增重为： 140g/m2)上， 在 110°C温度下烘干、 再经碾压、 裁片 (100* 154*0.135mm), 130°C温度下真空干燥 24h后， 制作成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 多孔活性炭、 PVDF 按 质量比为 45:45 : 10混合， 用 NMP调成浆料， 然后涂布厚度 16μηι的铜箔上 (涂 布增重为： 90g/m2) , 在 110 °C温度下烘干、 再经碾压、 裁片（尺寸为： 100* 154*0.09mm2)、 130°C温度下真空干燥 24h后， 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入 LiPF6浓度为 lmol/L , EC (碳 酸乙烯酯） /DEC (碳酸二乙酯） 物质的量浓度比为 1 : 1的电解液 80g, 组装成 方型超级聚酰亚胺电容电池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.2V, 静置 5min, 50A放电至 2.5V, 电容电池的比能量 为 56Wh/Kg, 比功率为 4600W/Kg, 经过 50A充放电循环 15000次后， 容量保持 率在 87%。
实施例 11
正极片的制作： 将总量为 500g的 LiFeP04、 多孔碳、 导电炭黑、 PVDF按质 量比为 20: 70： 5： 5混合， 用 NMP调成浆料， 然后涂布在厚度为 20μηι的铝箔 (涂布增重为： 140g/m2)上， 在 120°C温度下烘干、 再经碾压、 裁片（尺寸为： 100* 154*0.135mm), 130°C温度下真空干燥 24h后， 制作成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 多孔活性炭、 PVDF 按 质量比为 45:45: 10混合， 用 NMP调成浆料， 然后涂布厚度 16μηι的铜箔上 (涂 布增重为： 90g/m2) , 在 120 °C温度下烘干、 再经碾压、 裁片（尺寸为： 100*154*0.09mm2)、 130°C温度下真空干燥 24h后， 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入 LiPF6浓度为 lmol/L, EC (碳 酸乙烯酯） /DEC (碳酸二乙酯） 物质的量浓度比为 1 : 1的电解液 80g, 组装成 方型超级聚酰亚胺电容电池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.2V, 静置 5min, 50A放电至 2.5V, 电容电池的比能量 为 26Wh/Kg, 比功率为 5000W/Kg, 经过 50A充放电循环 15000次后， 容量保持 率在 95%。
实施例 12:
正极片的制作： 将总量为 500g的 LiFeP04、 多孔碳、 导电炭黑、 PVDF按质 量比为 85: 5: 5： 5混合，用 NMP调成浆料，然后涂布在 厚度为 20μηι的铝箔 (涂 布增重为： 140g/m2)上， 在 110°C温度下烘干、 再经碾压、 裁片（尺寸为： 100* 154*0.135mm), 130°C温度下真空干燥 24h后， 制作成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 多孔活性炭、 PVDF 按 质量比为 45:45: 10混合， 用 NMP调成浆料， 然后涂布厚度 16μηι的铜箔上 (涂 布增重为： 90g/m2) , 在 110 °C温度下烘干、 再经碾压、 裁片（尺寸为： 100*154*0.09mm2)、 130°C温度下真空干燥 24h后， 制作成负极片。 选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入 LiPF6浓度为 lmol/L, EC (碳 酸乙烯酯） /DEC (碳酸二乙酯） 物质的量浓度比为 1 : 1的电解液 80g, 组装成 方型超级聚酰亚胺电容电池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.2V, 静置 5min, 50A放电至 2.5V, 电容电池的比能量 为 65Wh/Kg, 比功率为 5000W/Kg, 经过 50A充放电循环 15000次后， 容量保持 率在 91%。
实施例 13:
正极片的制作： 将总量为 500g的 LiNi 8Co 202、 碳纤维、 导电炭黑、 PVDF 按质量比为 45 : 45： 5： 5混合， 用 NMP调成浆料， 然后涂布在 厚度为 20μηι 的铝箔（涂布增重为： 140g/m2)上， 在 110°C温度下烘干、 再经碾压、 裁片 (100* 154*0.135mm), 130°C温度下真空干燥 24h后， 制作成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 碳纳米管、 PVDF 按质 量比为 45:45: 10混合， 用 NMP调成浆料， 然后涂布厚度 16μηι的铜箔上 (涂布 增重为： 90g/m2) , 在 110 °C温度下烘干、 再经碾压、 裁片（尺寸为： 100*154*0.09mm2)、 130°C温度下真空干燥 24h后， 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入 LiC104浓度为 lmol/L, 碳酸丙 烯酉旨 /乙腈物质的量浓度比为 1 : 1的电解液 80g, 组装成方型超级聚酰亚胺电容 电池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.0V, 静置 5min, 50A放电至 2.3V, 电容电池的比能量 为 50Wh/Kg, 比功率为 4200W/Kg, 经过 50A充放电循环 15000次后， 容量保持 率在 82%。
实施例 14
正极片的制作： 将总量为 500g的 LiNi 8Co 202、 碳纤维、 导电炭黑、 PVDF 按质量比为 20: 70： 5： 5混合， 用 NMP调成浆料， 然后涂布在厚度为 20μηι的 铝箔 (涂布增重为： 140g/m2)上， 在 120°C温度下烘干、再经碾压、 裁片 （尺寸为： 100* 154*0.135mm), 120°C温度下真空干燥 24h后， 制作成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 碳纳米管、 PVDF 按质 量比为 20: 70 ： 10混合， 用 NMP调成浆料， 然后涂布厚度为 16μηι的铜箔上 (涂布增重为： 90g/m2) , 在 120°C温度下烘干、 再经碾压、 裁片（尺寸为： 100*154*0.09mm2)、 120°C温度下真空干燥 24h后， 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入 LiPF6浓度为 lmol/L,碳酸丙烯 酉旨 /乙腈物质的量浓度比为 1 : 1的电解液 80g, 组装成方型超级聚酰亚胺电容电 池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.0V, 静置 5min, 50A放电至 2.3V, 电容电池的比能量 为 38Wh/Kg, 比功率为 5800W/Kg, 经过 50A充放电循环 15000次后， 容量保持 率在 89%。
实施例 15 正极片的制作： 将总量为 500g的 LiNi 8Co 202、 碳纤维、 导电炭黑、 PVDF 按质量比为 85: 5 : 5 : 5混合， 用 NMP调成浆料， 然后涂布在厚度为 20μηι的 铝箔 (涂布增重为： 140g/m2)上， 在 120°C温度下烘干、再经碾压、 裁片 （尺寸为： 100* 154*0.135mm), 120°C温度下真空干燥 24h后， 制作成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 碳纳米管、 PVDF 按质 量比为 45: 45 ： 10混合， 用 NMP调成浆料， 然后涂布厚度为 16μηι的铜箔上 (涂布增重为： 90g/m2) , 在 120°C温度下烘干、 再经碾压、 裁片（尺寸为： 100*154*0.09mm2)、 120°C温度下真空干燥 24h后， 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入 LiPF6浓度为 lmol/L,碳酸丙烯 酉旨 /乙腈物质的量浓度比为 1 : 1的电解液 80g, 组装成方型超级聚酰亚胺电容电 池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.0V, 静置 5min, 50A放电至 2.3V, 电容电池的比能量 为 65Wh/Kg, 比功率为 4700W/Kg, 经过 50A充放电循环 20000次后， 容量保持 率在 89%。
实施例 16:
正极片的制作： 将总量为 500g的 LiNii/3 Coi/3 Μη1/302、 碳纳米管、 导电炭 黑、 PVDF按质量比为 45: 45 : 5 : 5混合， 用 NMP调成浆料， 然后涂布在 厚 度为 20μηι的铝箔（涂布增重为： MOg/m2)上， 在 110°C温度下烘干、 再经碾压、 裁片（100*154*0.135mm)、 130°C温度下真空干燥 24h后， 制作成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 碳气凝胶、 PVDF 按质 量比为 45:45: 10混合， 用 NMP调成浆料， 然后涂布厚度 16μηι的铜箔上 (涂布 增重为： 90g/m2) , 在 110 °C温度下烘干、 再经碾压、 裁片（尺寸为：
100*154*0.09mm2)、 130°C温度下真空干燥 24h后， 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入锂离子总浓度为 lmol/L的等量 LiAsFe/ LiBOB , γ _丁内酯 /碳酸曱丙酯的物质的量浓度比为 1 : 1的电解液 80g, 组装成方型超级聚酰亚胺电容电池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.1V, 静置 5min, 50A放电至 2.2V, 电容电池的比能量 为 50Wh/Kg, 比功率为 4200W/Kg, 经过 50A充放电循环 15000次后， 容量保持 率在 82%。
实施例 17
正极片的制作： 将总量为 500g的 LiNii/3 Coi/3 Mm/302、 碳纳米管、 导电炭 黑、 PVDF按质量比为 20: 70 : 5 : 5混合， 用 NMP调成浆料， 然后涂布在厚度 为 20μηι的铝箔 (涂布增重为： 140g/m2)上， 在 120°C温度下烘干、 再经碾压、裁 片 （尺寸为： 100*154*0.135mm)、 120°C温度下真空干燥 24h后， 制作成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 碳气凝胶、 PVDF 按质 量比为 20: 70 ： 10混合， 用 NMP调成浆料， 然后涂布厚度为 16μηι的铜箔上 (涂布增重为： 90g/m2) , 在 120°C温度下烘干、 再经碾压、 裁片（尺寸为： 100*154*0.09mm2)、 120°C温度下真空干燥 24h后， 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入锂离子总浓度为 lmol/L的等量 LiAsFe/ LiBOB , 碳酸丙烯酯 /乙腈物质的量浓度比为 1 : 1的电解液 80g, 组装成 方型超级聚酰亚胺电容电池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.1V, 静置 5min, 50A放电至 2.2V, 电容电池的比能量 为 38Wh/Kg, 比功率为 5800W/Kg, 经过 50A充放电循环 15000次后， 容量保持 率在 89%。
实施例 18
正极片的制作： 将总量为 500g的 LiNii/3 Coi/3 Mm/302、 碳纳米管、 导电炭 黑、 PVDF按质量比为 85: 5 : 5 : 5混合， 用 ΝΜΡ调成浆料， 然后涂布在厚度 为 20μηι的铝箔 (涂布增重为： 140g/m2)上， 在 120°C温度下烘干、 再经碾压、裁 片 （尺寸为： 100*154*0.135mm)、 120°C温度下真空干燥 24h后， 制作成正极片。
负极片的制作： 将总量为 500g的高密度改性石墨、 碳气凝胶、 PVDF 按质 量比为 45: 45 ： 10混合， 用 NMP调成浆料， 然后涂布厚度为 16μηι的铜箔上 (涂布增重为： 90g/m2) , 在 120°C温度下烘干、 再经碾压、 裁片（尺寸为： 100*154*0.09mm2)、 120°C温度下真空干燥 24h后， 制作成负极片。
选用聚酰亚胺为隔膜， 将正极片 （22片）、 隔膜、 负极片 （23片）层叠成电 芯， 然后将叠好的电芯的正极极群焊在铝制极耳上、 负极极群焊在镍制极耳上， 将焊好后的电芯放入成型好的铝塑膜中， 并注入锂离子总浓度为 lmol/L的等量 LiAsFe/ LiBOB , 碳酸丙烯酯 /乙腈物质的量浓度比为 1 : 1的电解液 80g, 组装成 方型超级聚酰亚胺电容电池。
性能测试： 电容电池经化成（即电容电池性能的激活）后， 进行性能测试， 测试制度为 30A充电至 4.1V, 静置 5min, 50A放电至 2.2V, 电容电池的比能量 为 65Wh/Kg, 比功率为 4700W/Kg, 经过 50A充放电循环 20000次后， 容量保持 率在 89%。 本发明的聚酰亚胺电容电池在一个电解池中实现了锂离子电池和超级电容 器的原理和技术的结合， 釆用聚酰亚胺隔膜作为绝缘体， 通过电化学计算和电化 学设计，使裡离子嵌入脱嵌反应和快速可逆的二维准二维法拉第反应有机的结合 在一起，使高能量电容电池在保持超级电容器高比功率、长寿命和快速充电特性 的同时， 大幅度提高了比能量， 同时兼具超级电容器和锂离子电池的性能特点。
上述实施例仅为本发明的优选实施例， 不能看作是对本发明保护范围的限 制，本领域的技术人员在本发明的基础上所作的任何非实质性的变形及替换均属 于本发明的保护范围。

Claims

权 利 要 求 书
1. 一种聚酰亚胺电容电池， 由正极、 负极、 介于两者之间的聚合物 膜及 电解液组成，其特征在于： 其中正极材料为锂离子嵌入化合物和多孔碳材 |Η·的潞 合物， 负极材料为改性石墨和多孔活性碳材料的混合物， 所述聚合物隔膜) ¾聚酰 亚胺隔膜， 所述电解液为含有锂离子化合物和有机溶剂的电解液。
2. 根据权利要求 1所述的聚酰亚胺电容电池， 其特征在于： 所述锂 ^子嵌 入化合物为 LiCo02、 LiMn204. LiFeP〇4、 LiFeMnP04、 LiNio.sCoo.2O2、 LiNi /3 Co 1/3 Mni/302 中的一种或者两种以上混合。
3. 根据权利要求 1所述的聚酰亚胺电容电池， 其特征在于： 所述改 't生石墨 的密度 > 2.2g/cm3, 为树脂碳和有机聚合物热解碳， 以及软碳固相碳材料 fl1的至 少一种或者两种以上混合。
4. 根据权利要求 1所述的聚酰亚胺电容电池， 其特征在于： 所述多 ^碳材 料为活性炭、 碳布、 碳纤维、 碳毡、 碳气凝胶、 碳纳米管中的一种或者两杆以上 混合。
5. 才艮据权利要求 1所述的聚酰亚胺电容电池， 其特征在于： 所述聚 ^亚胺 隔膜为曲孔膜，其厚度为 10-30μηι,孔径为 0.03μιη-0.05μηι,孔隙率为 90% 495%。
6. 根据权利要求 1所述的聚酰亚胺电容电池， 其特征在于： 所述电)^液中 包括锂离子化合物， 所述锂离子化合物为 LiC104、 LiBF4、 LiPF6、 LiCF|S03、 LiN(CF3S02)、 LiBOB、 LiAsF6中的一种或两种以上混合； 相转移催化剂 | 所述 相转移催化剂为 Me3EtNBF4、 Me2Et2NBF4 MeEt3 BF4, Et4 BF4 Pr4^BF4, MeBu3NBF4、 Bu4NBF4, Hex4NBF4、 Me4PBF4、 Et4PBF4、 Pr4PBF4. Bu4PB 4中的 一种或两种以上混合； 有机溶剂， 所述有机溶剂为碳酸乙烯酯、 碳酸丙 酯、 γ -丁内酯、 碳酸二曱酯、 碳酸二乙酯、 碳酸丁烯酯、 碳酸曱乙酯、 碳酸曱 酯、 亚石克酸乙烯酯、 亚石克酸丙烯酯、 乙酸乙酯、 乙腈中的一种或两种以上混^。
7. 如权利要求 1所述的聚酰亚胺电容电池的制作方法， 包括以下步砵：
( 1 )正极片的制备： 首先将锂离子嵌入化合物、 多孔炭材料、 导电剂、 粘 结剂混合， 调成装料， 然后涂布在正极集流体上， 经烘干、 碾压、 裁切、 善空干 燥制备成正极片；
( 2 ) 负极片的制备： 首先将改性石墨、 多孔碳材料、 粘结剂混合， 成浆 料， 然后涂布在负极集流体上， 经烘干、 碾压、 裁切、 真空干燥制备成负 I极片； 权 利 要 求书
( 3 )组装： 将制备好的正、 负极片经叠片或卷绕成电芯， ^铝塑膜 铝壳、 塑料壳或钢壳中， 然后进行封口、 注入在非水有机溶剂中含有锂离子的 解液
8. 根据权利要求 7所述的聚酰亚胺电容电池的制作方法， 其特征在 j : 所 述正极在制备步骤中锂离子嵌入化合物、 多孔炭材料、 导电剂、 粘结剂按 下重 量百分比混合：
锂离子嵌入化合物 20 - 85 %
多孔炭材料 5 - 70 %
导电剂 5 %
粘结剂 5%;
所述负极制作步驟中高密度改性石墨、 多孔活性炭、粘结剂按以下重 )f百分 比混合：
高密度改性石墨 45 %
多孔活性炭 45 %
粘结剂 5 %。
9. 根据权利要求 7所述的聚酰亚胺电容电池的制作方法， 其特征在+: 所 述的导电剂包括天然石墨粉、 人造石墨、 炭黑、 乙炔黑、 中间相炭微球、 密度 改性石墨、 石油焦、 碳纳米管、 石墨烯、 中的一种或两种以上混合； 所述的粘结 剂为聚四氟乙烯、 聚偏氟乙烯、 羟丙基甲基纤维素、羧甲基纤维素纳和丁 ^^胶 中的一种或两种以上混合。
10. 根据权利要求 7所述的聚酰亚胺电容电池的制作方法， 其特征 ^于：所 述的正极片的集流体为铝箔或者铝网， 所述的负极片的集流体为铜箔或者铜网。
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Cited By (3)

* Cited by examiner, † Cited by third party
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CN116554827A (zh) * 2023-06-16 2023-08-08 华东理工大学 一种聚合物粘结剂的制备方法与在硅负极锂电池中的应用

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102290245B (zh) * 2011-04-29 2012-11-21 深圳市惠程电气股份有限公司 一种聚酰亚胺电容电池及其制作方法
JP5892420B2 (ja) * 2012-01-18 2016-03-23 日産自動車株式会社 電気デバイス用電極、電気デバイス用電極の製造方法、電気デバイス用電極構造体及び電気デバイス
US10396365B2 (en) 2012-07-18 2019-08-27 Printed Energy Pty Ltd Diatomaceous energy storage devices
US9136065B2 (en) 2012-07-18 2015-09-15 Nthdegree Technologies Worldwide Inc. Diatomaceous energy storage devices
US9548511B2 (en) 2012-07-18 2017-01-17 Nthdegree Technologies Worldwide Inc. Diatomaceous energy storage devices
EP2698346A1 (en) * 2012-08-14 2014-02-19 Clariant International Ltd. Mixed sulphate containing lithium-manganese-metal phosphate
US9397341B2 (en) 2012-10-10 2016-07-19 Nthdegree Technologies Worldwide Inc. Printed energy storage device
US9520598B2 (en) 2012-10-10 2016-12-13 Nthdegree Technologies Worldwide Inc. Printed energy storage device
KR102071269B1 (ko) 2013-07-17 2020-01-30 엔티에이치 디그리 테크놀로지스 월드와이드 인코포레이티드 프린트된 산화은 배터리들
EP3496192A1 (en) * 2014-01-22 2019-06-12 Printed Energy Pty Ltd Diatomaceous energy storage devices
WO2015156167A1 (ja) * 2014-04-11 2015-10-15 日産自動車株式会社 扁平型二次電池
EP2952518A1 (en) * 2014-06-05 2015-12-09 Cytec Canada Inc. Organic Phosphonium Salts, a Method for their Preparation, and their Use in Electrochemical Systems
CN104616901A (zh) * 2015-01-27 2015-05-13 上海奥威科技开发有限公司 一种钠离子超级电容器及其制备方法
JP6470616B2 (ja) * 2015-03-31 2019-02-13 旭化成株式会社 リチウム空気電池
DE102015218436A1 (de) 2015-09-25 2017-03-30 Robert Bosch Gmbh Symmetrischer Hybridsuperkondensator
JP6657829B2 (ja) * 2015-11-17 2020-03-04 株式会社リコー 非水電解液蓄電素子
DE112016006819T5 (de) * 2016-06-01 2019-01-10 Gm Global Technology Operations, Llc Lithium-ionen-batterie und kondensator-hybridisierung auf material- und elektrodenniveau
EP3324479B1 (de) * 2016-11-21 2019-05-08 VARTA Microbattery GmbH Asymmetrische, sekundäre elektrochemische zelle
CN106654208B (zh) * 2016-12-21 2018-07-24 深圳市沃特玛电池有限公司 一种磷酸铁锂电池负极材料的制备方法
TWI887813B (zh) * 2017-04-18 2025-06-21 英商立可行有限公司 能量儲存裝置
CN108281610B (zh) * 2018-01-17 2020-05-05 广东石油化工学院 一种复合正极极片的锂离子电池
CN110474052B (zh) * 2019-07-29 2022-09-02 湖南文理学院 一种锂离子电池电极材料及制备方法
CN113948757A (zh) * 2020-07-16 2022-01-18 深圳格林德能源集团有限公司 一种聚合物锂离子电池及其制作方法
CN113363584A (zh) * 2021-07-19 2021-09-07 河源市联懋新材料有限公司 一种锂离子电池及其电解液、电极的制造方法
CN113675008A (zh) * 2021-08-12 2021-11-19 上海奥威科技开发有限公司 一种聚合物基固态超级电容器及其制备方法和应用
CN114566393B (zh) * 2022-03-23 2025-01-14 上海奥威科技开发有限公司 一种用于锂离子电容器的复合正极材料及其应用
JP7835430B2 (ja) * 2022-03-30 2026-03-25 株式会社クオルテック 電池の製造方法
EP4478387A3 (en) * 2023-06-13 2025-04-02 Skeleton Technologies GmbH Electrolyte compositions for energy storage cells with fast charge and dis-charge capabilites

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6280873B1 (en) * 1999-04-08 2001-08-28 Quallion, Llc Wound battery and method for making it
CN101079510A (zh) * 2007-06-25 2007-11-28 中南大学 一种超级电容电池
CN101752539A (zh) * 2008-12-01 2010-06-23 比亚迪股份有限公司 一种锂离子二次电池用聚酰亚胺隔膜以及锂离子电池
CN102290245A (zh) * 2011-04-29 2011-12-21 深圳市惠程电气股份有限公司 一种聚酰亚胺电容电池及其制作方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000138074A (ja) * 1998-10-30 2000-05-16 Asahi Glass Co Ltd 二次電源
JP2000228222A (ja) * 1999-02-05 2000-08-15 Asahi Glass Co Ltd 二次電源
JP4284934B2 (ja) * 2001-09-20 2009-06-24 旭硝子株式会社 二次電源
JP2004079370A (ja) * 2002-08-20 2004-03-11 Sony Corp 電池
US20040253520A1 (en) * 2003-05-13 2004-12-16 Wensley C. Glen Polyimide matrix electrolyte and improved batteries therefrom
US8405957B2 (en) * 2005-12-08 2013-03-26 Hitachi Maxell, Ltd. Separator for electrochemical device and method for producing the same, and electrochemical device and method for producing the same
JPWO2008029502A1 (ja) * 2006-08-29 2010-01-21 ユニチカ株式会社 電極形成用バインダー、そのバインダーを用いた電極形成用スラリー、そのスラリーを用いた電極、その電極を用いた二次電池、その電極を用いたキャパシタ
JP5262266B2 (ja) * 2008-04-22 2013-08-14 株式会社Ｇｓユアサ 非水電解質電池
CN100590761C (zh) * 2008-06-16 2010-02-17 中南大学 一种超级电容电池的制造方法
US8283074B2 (en) * 2008-08-15 2012-10-09 Uchicago Argonne, Llc Electrolyte salts for nonaqueous electrolytes
JP5636960B2 (ja) * 2008-10-02 2014-12-10 宇部興産株式会社 多孔質ポリイミド膜及びその製造方法
JP5001977B2 (ja) * 2009-05-15 2012-08-15 Ｊｆｅケミカル株式会社 黒鉛質粒子、リチウムイオン二次電池およびその負極材料
CN101974828B (zh) * 2010-09-30 2012-12-19 江西先材纳米纤维科技有限公司 一种共聚聚酰亚胺纳米纤维非织造布及其制备方法和应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6280873B1 (en) * 1999-04-08 2001-08-28 Quallion, Llc Wound battery and method for making it
CN101079510A (zh) * 2007-06-25 2007-11-28 中南大学 一种超级电容电池
CN101752539A (zh) * 2008-12-01 2010-06-23 比亚迪股份有限公司 一种锂离子二次电池用聚酰亚胺隔膜以及锂离子电池
CN102290245A (zh) * 2011-04-29 2011-12-21 深圳市惠程电气股份有限公司 一种聚酰亚胺电容电池及其制作方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2704248A4 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113422060A (zh) * 2021-06-21 2021-09-21 北京宇程科技有限公司 一种锂离子电池用耐高温一体化电极及其制备方法
CN115472896A (zh) * 2022-09-26 2022-12-13 欣旺达电动汽车电池有限公司 二次电池及用电装置
CN115472896B (zh) * 2022-09-26 2023-07-14 欣旺达电动汽车电池有限公司 二次电池及用电装置
CN116554827A (zh) * 2023-06-16 2023-08-08 华东理工大学 一种聚合物粘结剂的制备方法与在硅负极锂电池中的应用

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