WO2011103708A1 - 一种高比能量有机体系的电容电池 - Google Patents

一种高比能量有机体系的电容电池 Download PDF

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Publication number
WO2011103708A1
WO2011103708A1 PCT/CN2010/002248 CN2010002248W WO2011103708A1 WO 2011103708 A1 WO2011103708 A1 WO 2011103708A1 CN 2010002248 W CN2010002248 W CN 2010002248W WO 2011103708 A1 WO2011103708 A1 WO 2011103708A1
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Prior art keywords
carbon
negative electrode
positive electrode
electrode sheet
capacitor battery
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PCT/CN2010/002248
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English (en)
French (fr)
Inventor
杨恩东
安仲勋
吴明霞
曹小卫
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上海奥威科技开发有限公司
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Application filed by 上海奥威科技开发有限公司 filed Critical 上海奥威科技开发有限公司
Priority to US13/515,053 priority Critical patent/US20130155577A1/en
Priority to EP10846332.4A priority patent/EP2541671A4/en
Priority to JP2012554189A priority patent/JP2013520806A/ja
Publication of WO2011103708A1 publication Critical patent/WO2011103708A1/zh
Priority to IL221101A priority patent/IL221101A0/en

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    • 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
    • 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
    • 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
    • H01M4/13—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
    • 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
    • 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 present invention is in the field of capacitors and batteries, and relates to supercapacitors, particularly organic hybrid supercapacitors and lithium ion batteries. Background technique
  • 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 operating 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 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 and a high-conductivity organic solvent (such as acetonitrile) to form a mixed electrolyte, while polymer electrolytes are now only in the laboratory stage, still No commercial products emerged.
  • 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), this capacitor has a high power density of 5000-6000W/Kg, but its energy density is low, only 3-5Wh/Kg. Therefore, in order to further increase the energy density of organic supercapacitors, people A hybrid structural design is used, that is, different active materials are used for the positive and negative electrodes.
  • organic hybrid supercapacitors such as the use of activated carbon for the positive electrode, the use of lithium titanate for the negative electrode and the use of polythiophene for the positive electrode, and the use of an organic supercapacitor such as lithium titanate for the negative electrode.
  • LiMn 2 _xM x 0 4 is used for the positive electrode and activated carbon is used for the negative electrode, and the specific energy of the supercapacitor is up to 50 Wh/Kg (calculated based on the total mass of the positive and negative active materials).
  • organic hybrid supercapacitors are not ideal in terms of energy density and power density.
  • the positive electrode is a mixture of a lithium ion intercalation compound and a porous carbon material and a composite thereof
  • the negative electrode is a mixture of a porous carbon material and graphite and a composite thereof.
  • an object of the present invention is to use a hard carbon material having a high specific capacity and a good power performance on a negative electrode, and an activated carbon having an endless life can be infinitely used as a part of a mixed positive electrode material on a positive electrode, while maintaining a supercapacitor high.
  • a hard carbon material having a high specific capacity and a good power performance on a negative electrode and an activated carbon having an endless life can be infinitely used as a part of a mixed positive electrode material on a positive electrode, while maintaining a supercapacitor high.
  • An organic battery capacitor comprising a positive electrode, a negative electrode, a separator interposed therebetween, and an electrolyte, wherein the positive electrode is a mixture of a lithium ion intercalation compound and a porous carbon material.
  • the negative electrode is made of hard carbon, and the electrolyte is a non-aqueous organic solvent electrolyte containing lithium ions.
  • the hard carbon comprises at least one of a resin carbon and an organic polymer pyrolytic carbon, and a soft carbon solid phase carbonized material or a mixture thereof.
  • the lithium ion intercalation compound comprises: LiCo0 2 , LiMn 2 0 4 , LiNi0 2 , LiFeP0 4 , LiNio. 8 CoQ. 2 0 2 , LiNii/3 Coi/3 Mm /3 0 2 , LiMn0 2 One or a mixture.
  • the porous carbon should include one or a mixture of activated carbon, carbon cloth, carbon fiber, carbon felt, carbon aerogel, carbon nanotube
  • the lithium ion in the electrolyte is generated by at least one of LiC10 4 , LiBF 4 , LiPF 6 , LiCF 3 S0 3 , LiN(CF 3 S0 2 ) LiBOB, LiAsF 6 , and may be added to 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 , One or more of Pr 4 PBF 4 Bu 4 PBF 4 , the non-aqueous organic solvent in the electrolyte includes ethylene carbonate, propylene carbonate, Y-butyrolactone, dimethyl carbonate, and diethyl carbonate. One or more of ester, butylene carbonate, ethyl methyl carbonate, methyl propyl carbonate, vinyl sulfite, propylene sulf
  • the separator comprises a polyethylene microporous membrane, a polypropylene microporous membrane, a polyethylene polypropylene composite membrane, an inorganic ceramic membrane, a paper separator, and a non-woven membrane.
  • a method of preparing a capacitor battery of an organic system comprising:
  • Preparation steps of the positive electrode sheet First, the lithium ion intercalation compound, the porous carbon material, the conductive agent, and the binder are mixed, adjusted into a slurry, and then coated on the positive electrode current collector, dried, rolled, and cut. Cutting and vacuum drying to prepare a positive electrode sheet;
  • the conductive agent comprises one or a mixture of natural graphite powder, artificial graphite, carbon black, block black, mesocarbon microbeads, hard carbon, petroleum coke, carbon nanotubes, graphene, and
  • the binder includes one or more of polytetrafluoroethylene, polyvinylidene fluoride, hydroxypropylmethylcellulose, carboxymethylcellulose nano, and styrene-butadiene rubber.
  • the current collector of the positive electrode sheet comprises an aluminum foil, an aluminum mesh
  • the current collector of the negative electrode sheet comprises a copper foil and a copper mesh
  • the present invention makes the supercapacitor have high energy density and high power density by using a hard carbon material having a high specific capacity and good power performance on the negative electrode and using an infinite number of activated carbon as a part of the mixed positive electrode material on the positive electrode.
  • the characteristics energy density and power density are calculated based on the weight of the actual supercapacitor), can be widely used in electric vehicles, power tools, solar energy storage, wind energy storage and other fields. detailed description
  • the invention relates to an organic hybrid supercapacitor battery, which comprises a positive electrode, a negative electrode, a separator interposed therebetween and an electrolyte.
  • the positive electrode is a mixture of a lithium ion intercalation compound and a porous activated carbon material
  • the negative electrode is a hard carbon
  • the electrolyte is used.
  • the hard carbon described in the present invention refers to a non-graphitizable carbon, generally having a high specific capacity (up to 300-700 mAh/g) and good rate performance, and the embedding of lithium ions in such materials does not cause a significant structure.
  • Expanded, having good charge and discharge cycle performance including carbonized carbon including a phenolic resin carbon, an epoxy resin carbon, a polynonanol resin carbon, a furfural resin carbon, and an organic polymer pyrocarbon
  • Organic polymer pyrolytic carbon includes benzene carbon, polydecyl alcohol pyrolytic carbon, polyvinyl chloride pyrolytic carbon, and phenolic pyrolytic carbon.
  • the lithium ion intercalation compound described in the present invention includes: LiCo0 2 , LiMn 2 0 4 , LiNi0 2 , LiFeP0 4 , LiNio. 8 Coo. 2 0 2 LiNii/3 Co 1/3 Mn 1/3 0 2 and the like.
  • the intercalation-deintercalation of lithium ions in such materials is good, the diffusion rate is fast, and the volume change accompanying the reaction is small, so that they all have good cycle characteristics and high current characteristics.
  • the lithium salt in the electrolytic solution described in the present invention includes at least one of LiC10 4 , LiBF 4 , LiPF 6 , LiCF 3 S0 3 , LiN(CF 3 S0 2 ) LiBOB, LiAsF 6 ;
  • the non-aqueous organic solvent includes carbonic acid Vinyl ester, propylene carbonate, ⁇ -butyrolactone, dimethyl carbonate, diethyl carbonate, butylene carbonate, ethyl methyl carbonate, methyl propyl carbonate, vinyl sulfite, propylene sulfite, acetic acid One or more of ester and acetonitrile.
  • organic electrolytes composed of lithium salts have high ionic conductivity, provide fast channels for lithium ion migration during charge and discharge, increase the rate of reaction, and have a wide range of electrochemically stable potentials (at 0-5V).
  • the characteristics are stable), good thermal stability, wide temperature range, etc., which greatly improves the stability of the charging and discharging reaction of the supercapacitor battery, which is beneficial to the improvement of the cycle life of the capacitor battery.
  • the separator described in the present invention comprises a polyethylene microporous membrane ( ⁇ ), a polypropylene microporous membrane ( ⁇ ), a composite membrane ( ⁇ + ⁇ + ⁇ ), an inorganic ceramic membrane, a paper separator, and the thickness thereof is generally 10-30.
  • ⁇ ⁇ with a pore size of 0.03 ⁇ m-0.05 m, has good ability to adsorb electrolyte and high temperature resistance.
  • the current collector of the positive electrode sheet is made of aluminum foil or aluminum mesh
  • the current collector of the negative electrode sheet is made of copper foil or copper mesh.
  • an appropriate amount of a conductive agent and a binder are added.
  • the conductive agent in the present invention is made of graphite powder having high conductivity, carbon black, black block or a mixture thereof.
  • the binder in the present invention is polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), hydroxypropylmethylcellulose (HPMC), carboxymethylcellulose (CMC) and styrene butadiene rubber (SBR). One or several of them.
  • the positive electrode sheet is prepared by: weighing a lithium ion intercalation compound, a porous carbon material, a conductive agent, and a binder according to a certain mass ratio, stirring it to a paste, and then applying it on a current collector, and baking it. Dry, crushed, cut, vacuum dried to prepare a positive electrode sheet.
  • the preparation steps of the negative electrode sheet are as follows: the hard carbon is mixed according to a certain mass ratio, the binder is mixed, stirred to a paste, and then coated on a current collector, dried, compacted, cut, vacuum dried to prepare a negative electrode. sheet.
  • the invention can be fabricated into a square-type super capacitor battery and a cylindrical super capacitor battery with a laminated or wound structure, and can maintain high power and high energy characteristics, and the outer casing can be made of aluminum plastic film and steel.
  • the main raw materials used in the examples are as follows:
  • LiMn 2 0 4 produced by Shijiazhuang Best Battery Materials Co., Ltd.;
  • LiCo0 2 - produced by Hunan Ruixiang New Materials Co., Ltd., model R747;
  • LiM0 2 produced by CITIC Guoan Mengli Company
  • LiFeP0 4 - produced by Tianjin Strand Energy Technology Co., Ltd., model SLFP-ES01;
  • LiNi Q . 8 C OQ . 2 0 2 Guangzhou Hongsen Materials Co., Ltd. production;
  • Porous carbon is produced by KURARAY, Japan, model YP-17D;
  • PVDF polyvinylidene fluoride
  • Conductive carbon black - produced by TIMCAL, model is Super-P;
  • 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 45:45:5:5, and a slurry was prepared by NMP, and then coated at 20 ⁇ m.
  • Aluminum foil (coating weight gain: 140g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried 24h (120 ⁇ 130°) C) Made into a positive electrode.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, slurried with NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) (1 : 1 )
  • the electrolyte is 10g, assembled into a square super capacitor battery.
  • 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 5A, left for 5 minutes, and discharged to 5A.
  • the specific energy of the 2.5V capacitor battery is 50 Wh/Kg, and the specific power is 5000 W/Kg.
  • the capacity retention rate is 80%.
  • 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 at 20 ⁇ m.
  • Aluminum foil (coating weight gain: 140g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried 24h (120 ⁇ 130°) C) Made into a positive electrode.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, and a slurry was prepared by NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ) ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) ( 1 : 1 )
  • the electrolyte is 10g, assembled into a square super capacitor battery.
  • the performance test is performed.
  • the test system is charged to 5V to 4.2V, left to stand for 5 minutes, 5A to 2.5V, and the specific energy of the capacitor battery is 21Wh/Kg. 5500 W/Kg, after 10,000 cycles of 5A charge and discharge, the capacity retention rate is 85%.
  • 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 85:5:5:5, and the slurry was adjusted with NMP, and then coated at 20 ⁇ m.
  • Aluminum foil (coating weight gain: 140g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried 24h (120 ⁇ 130°) C) Made into a positive electrode.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, and a slurry was prepared by NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ) ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) ( 1 : 1 )
  • the electrolyte is 10g, assembled into a square super capacitor battery.
  • Capacitor battery After the activation, the performance test is carried out. The test system charges 5A to 4.2V, 5min for 5min, 5A for 2.5V, the specific energy of the capacitor battery is 50 Wh/Kg, and the specific power is 4300 W/Kg. After 5A. After 10,000 cycles of charge and discharge, the capacity retention rate was 65%.
  • 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 45:45:5:5, slurried with NMP, and then coated on an aluminum foil of 20 ⁇ m ( The coating weight gain is: 140g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130°C) Made into a positive electrode.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, slurried with NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) (1 : 1 )
  • the electrolyte is 10g, assembled into a square super capacitor battery.
  • the performance test is performed.
  • the test system is charged to 4.2V for 5A, left for 5min, 5A for 2.5V, and the specific energy of the capacitor battery is 61 Wh/Kg. It is 4800 W/Kg, and after 10,000 cycles of 5A charge and discharge, the capacity retention rate is 91%.
  • 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 on an aluminum foil of 20 ⁇ m ( The coating weight gain is: 140g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130°C) Made into a positive electrode.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, slurried with NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) Ester) (1: 1) 10g of electrolyte, assembled into a square supercapacitor battery.
  • the performance test is performed. The test system is charged to 5V to 4.2V, left to stand for 5 minutes, 5A to 2.5V, and the specific energy of the capacitor battery is 31Wh/Kg. 5200W/Kg, after 10000 cycles of 5A charge and discharge, the capacity retention rate is 94%.
  • 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 on an aluminum foil of 20 ⁇ m ( The coating weight gain is: 140g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130°C) Made into a positive electrode.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, slurried with NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) (1 : 1 )
  • the electrolyte is 10g, assembled into a square super capacitor battery.
  • the performance test is performed.
  • the test system is charged to 5V to 4.2V, left to stand for 5 minutes, 5A to 2.5V, and the specific energy of the capacitor battery is 70Wh/Kg. 5200W/Kg, after 10,000 cycles of 5A charge and discharge, the capacity retention rate is 85%.
  • Preparation of positive electrode sheet A total of 500 g of LiNi0 2 , porous carbon, conductive carbon black, and PVDF were mixed at a mass ratio of 45:45:5:5, slurried with NMP, and then coated on an aluminum foil of 20 ⁇ m ( The coating weight gain is: 140g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130°C) Made into a positive electrode.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, slurried with NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery cell, and then The positive pole group of the stacked battery core is welded on the aluminum ear, the negative pole group is welded on the nickel base ear, and the welded battery core is placed in the formed aluminum plastic film, and injected into the lmol/ L LiPF 6 — 10 g of EC (ethylene carbonate) / DEC (diethyl carbonate) (1 : 1 ) electrolyte, assembled into a square super capacitor battery. 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 5V to 4.2V, left to stand for 5 minutes, 5A to 2.5V, and the specific energy of the capacitor battery is 76 Wh/Kg. It is 4947 W/Kg, and after 10,000 cycles of 5A charge and discharge, the capacity retention rate is 85%.
  • Preparation of positive electrode sheet A total of 500 g of LiNi0 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 on an aluminum foil of 20 ⁇ m ( The coating weight gain is: 140g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130°C) Made into a positive electrode.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, slurried with NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) (1 : 1 )
  • the electrolyte is 10g, assembled into a square super capacitor battery.
  • the performance test is performed.
  • the test system is charged to 5V to 4.2V, left to stand for 5min, 5A to 2.5V, and the specific energy of the capacitor battery is 37Wh/Kg. 5452 W/Kg, after 10,000 cycles of 5A charge and discharge, the capacity retention rate is 92%.
  • Preparation of positive electrode sheet A total of 500 g of LiNi0 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 on an aluminum foil of 20 ⁇ m ( The coating weight gain is: 140g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130°C) Made into a positive electrode.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, slurried with NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) (1 : 1 )
  • the electrolyte is 10g, assembled into a square super capacitor battery.
  • the performance test is performed.
  • the test system is charged to 5V to 4.2V, left to stand for 5 minutes, 5A to 2.5V, and the specific energy of the capacitor battery is 81 Wh/Kg. It is 4232 W/Kg, and after 10,000 cycles of 5A charge and discharge, the capacity retention rate is 80%.
  • Example 10 Example 10:
  • 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 on an aluminum foil of 20 ⁇ m ( The coating weight gain is: 140g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130°C) Made into a positive electrode.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, slurried with NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) (1 : 1 )
  • the electrolyte is 10g, assembled into a square super capacitor battery.
  • the performance test is performed.
  • the test system is charged to 3.7V for 5A, left for 5min, 5A for discharge to 2.3V, and the specific energy of the capacitor battery is 55 Wh/Kg. It is 5452W/Kg, and after 10,000 cycles of 5A charge and discharge, the capacity retention rate is 94%.
  • 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 on an aluminum foil of 20 ⁇ m ( The coating weight gain is: 140g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130°C) Made into a positive electrode.
  • Preparation of negative electrode sheet Mix a total of 500g of hard carbon and PVDF at a mass ratio of 90:10, using NMP Adjusted into a slurry, then coated on a 16 ⁇ copper foil (coating weight gain: 90g / m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5 * 59.5mm 2 ), 24h vacuum drying (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) (1 : 1 )
  • the electrolyte is 10g, assembled into a square super capacitor battery.
  • the performance test is performed.
  • the test system is charged to 3.7V for 5A, left for 5min, 5A for discharge to 2.3V, and the specific energy of the capacitor battery is 20.3Wh/Kg. It is 6000W/Kg, and after 10,000 cycles of 5A charge and discharge, the capacity retention rate is 96%.
  • 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 on an aluminum foil of 20 ⁇ m ( The coating weight gain is: 140g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130°C) Made into a positive electrode.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, slurried with NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) (1 : 1 )
  • the electrolyte is 10g, assembled into a square super capacitor battery.
  • the performance test is performed.
  • the test system is charged to 3.7V for 5A, left for 5min, 5A for discharge to 2.3V, and the specific energy of the capacitor battery is 65Wh/Kg. 4900W/Kg, after 10000 cycles of 5A charge and discharge, the capacity retention rate is 90%.
  • Preparation of positive electrode sheet A total of 500 g of LiNi Q . 8 C OQ . 2 2 2 , porous carbon, conductive carbon black, and PVDF were mixed at a mass ratio of 45:45:5:5, and the slurry was adjusted with NMP. Then coated on a 20 ⁇ aluminum foil (coating weight: 140g / m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5 * 59.5mm 2 ), 24h vacuum Dry (120 ⁇ 130 °C) to make a positive electrode.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, slurried with NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) (1 : 1 )
  • the electrolyte is 10g, assembled into a square super capacitor battery.
  • the performance test is performed.
  • the test system is charged to 5V to 4.2V, left to stand for 5 minutes, 5A to 2.5V, and the specific energy of the capacitor battery is 71 Wh/Kg. It is 5088 W/Kg, and after 10,000 cycles of 5A charge and discharge, the capacity retention rate is 78%.
  • Preparation of positive electrode sheet A total of 500 g of LiNi Q . 8 C OQ . 2 2 2 , porous carbon, conductive carbon black, and PVDF were mixed at a mass ratio of 20:70:5:5, and the slurry was adjusted with NMP. Then coated on a 20 ⁇ aluminum foil (coating weight: 140g / m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5 * 59.5mm 2 ), 24h vacuum Dry (120 ⁇ 130 ° C) to make a positive electrode sheet.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, and the slurry was adjusted with NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ) ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) ( 1 : 1 )
  • the electrolyte is 10g, assembled into a square super capacitor battery.
  • the performance test is performed.
  • the test system is charged to 5V to 4.2V, left to stand for 5 minutes, 5A to 2.5V, and the specific energy of the capacitor battery is 25Wh/Kg. 5570 W/Kg, after 10,000 cycles of 5A charge and discharge, the capacity retention rate is 83%.
  • Preparation of positive electrode sheet A total of 500 g of LiNi Q . 8 C OQ . 2 0 2 , porous carbon, conductive carbon black, and PVDF were mixed at a mass ratio of 85:5:5:5, and the slurry was adjusted with NMP. Then coated in 20 ⁇ of aluminum foil (coating weight gain is: On the 140 g/m 2 ), it was dried (110 to 120 ° C), rolled, cut into pieces (size: 37.5*59.5 mm 2 ), and vacuum dried (120 to 130 ° C) for 24 hours to prepare a positive electrode sheet.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, slurried with NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) (1 : 1 )
  • the electrolyte is 10g, assembled into a square super capacitor battery.
  • the performance test is performed.
  • the test system is charged to 4.2V for 5A, left for 5min, 5A for 2.5V, and the specific energy of the capacitor battery is 82Wh/Kg.
  • the specific power is 4621 W/Kg, after 10,000 cycles of 5A charge and discharge, the capacity retention rate is 70%.
  • Example 16 Example 16:
  • Preparation of positive electrode sheet A total of 500 g of LiNi 1/3 Co 1/3 Mn 1/3 0 2 , porous carbon, conductive carbon black, and PVDF are mixed at a mass ratio of 45:45:5:5, and adjusted by NMP. Slurry, then coated on 20 ⁇ aluminum foil (coating weight: 140g/m 2 ), dried (110 ⁇ 120 ° C), laminated, cut pieces (size: 37.5*59.5mm 2 ), 24h vacuum drying (120 ⁇ 130 ° C) to make a positive electrode sheet.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, slurried with NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) (1 : 1 )
  • the electrolyte is 10g, assembled into a square super capacitor battery.
  • the performance test is performed.
  • the test system is charged to 5V to 4.2V, left to stand for 5min, 5A to 2.5V, and the specific energy of the capacitor battery is 66 Wh/Kg. It is 5225W/Kg, and after 10,000 cycles of 5A charge and discharge, the capacity retention rate is 90%.
  • Example 17 Preparation of positive electrode sheet: A total of 500 g of LiNi 1/3 Co 1/3 Mn 1/3 0 2 , porous carbon, conductive carbon black, and PVDF are mixed at a mass ratio of 20:70:5:5, and adjusted by NMP. Slurry, then coated on 20 ⁇ aluminum foil (coating weight: 140g/m 2 ), dried (110 ⁇ 120 ° C), laminated, cut pieces (size: 37.5*59.5mm 2 ), 24h vacuum drying (120 ⁇ 130 ° C) to make a positive electrode sheet.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, slurried with NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) (1 : 1 )
  • the electrolyte is 10g, assembled into a square super capacitor battery.
  • the performance test is performed.
  • the test system is charged to 5V to 4.2V, left to stand for 5 minutes, and 5A is discharged to 2.5V.
  • the specific energy of the capacitor battery is 23Wh/Kg, and the specific power is 6005W/Kg, after 10000 cycles of 5A charge and discharge, the capacity retention rate is 94%.
  • Preparation of positive electrode sheet A total of 500 g of LiNi 1/3 Co 1/3 Mn 1/3 0 2 , porous carbon, conductive carbon black, and PVDF are mixed at a mass ratio of 85:5:5:5, and adjusted by NMP. Slurry, then coated on 20 ⁇ aluminum foil (coating weight: 140g/m 2 ), dried (110 ⁇ 120 ° C), laminated, cut pieces (size: 37.5*59.5mm 2 ), vacuum drying (120 ⁇ 130 ° C) at 24 h to prepare a positive electrode sheet.
  • Preparation of negative electrode sheet A total of 500 g of hard carbon and PVDF were mixed at a mass ratio of 90:10, slurried with NMP, and then coated on a copper foil of 16 ⁇ m (coating weight gain: 90 g/m 2 ), dried (110 ⁇ 120 ° C), crushed, cut pieces (size: 37.5*59.5mm 2 ), vacuum dried at 24h (120 ⁇ 130 ° C) to make a negative electrode sheet.
  • a three-layer composite separator is used as a separator, and a positive electrode sheet (8 sheets), a separator, and a negative electrode sheet (9 sheets) are laminated into a battery core, and then the positive electrode group of the stacked battery core is welded to 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 injected with 1 mol/L LiPF 6 — EC (ethylene carbonate) / DEC (diethyl carbonate) (1 : 1 )
  • the electrolyte is 10g, assembled into a square super capacitor battery.
  • the performance test is performed.
  • the test system is charged to 4.2V for 5A, left for 5min, 5A for 2.5V, and the specific energy of the capacitor battery is 78 Wh/Kg. It is 5000W/Kg, and after 10,000 cycles of 5A charge and discharge, the capacity retention rate is 83%.
  • the positive electrode uses a mixture of a lithium ion intercalation compound and a porous carbon
  • the negative electrode using a hard carbon supercapacitor battery exhibits good energy density, power density, and cycle life; it can also be seen that when the same is used
  • the performance of the capacitor battery varies with the lithium ion intercalation compound; it can also be seen that the ratio of intercalating lithium ion compound to porous carbon in the positive electrode also has a great influence on the performance of the supercapacitor battery.
  • the proportion of porous carbon increases, the specific power of the capacitor battery increases, the cycle life increases, but the specific energy decreases.
  • the ratio of intercalated lithium ion compound to porous carbon is practical between 17: 1-2: 7, depending on the Working conditions can take different ratios to meet the needs of users.

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Description

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， 特别是有机混合型超级电 容器和锂离子电池。 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采用电池的非极化电极（如氢氧化镍）， 另一极采用 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； 有机电解质则一般采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。
超级电容器采用有机电解质， 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采用 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， 人们采 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， 出现了如正极采用活性炭、负极采用钛酸锂和正极采用聚噻吩， 负极采用钛酸锂等有机超级电容器。 在申请号为 200510110461.5的专利中， 正极采用 LiMn2_xMx04, 负极采用活性炭， 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。 在申请号为 200710035205.3的专利中， 正极采用锂离子嵌入化合物与多 孔炭材料的混合物及它们的复合物， 负极采用多孔炭材料与石墨的混合物及它们的复 合物。 此类超级电容器由于负极引入了多孔碳， 虽然在常温会提高器件的比功率， 但 在高温下负极的多孔碳会使电解液分解， 很难实用化。 发明内容
针对上述问题，本发明的目的是在负极上使用比容量高、功率性能好的硬碳材料， 并且在正极上使用循环寿命能达到无限次的活性炭作为混合正极材料的一部分， 在保 持超级电容器高功率、 循环寿命长、 无污染、 高安全性、 免维护等特性的前提下， 大 幅度提高超级电容器的能量密度和循环寿命， 进一步拓宽超级电容器的应用领域。
本发明的目的是这样实现的： 一种有机体系的电容电池， 由正极、 负极、 介于两 者之间的隔膜及电解液组成， 其中， 正极采用锂离子嵌入化合物和多孔碳材料的混合 物， 负极采用硬碳， 电解液采用含有锂离子的非水有机溶剂电解液。
其中， 所述的硬碳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 至少一种或者其混合物。
其中， 所述的锂离子嵌入化合物包括： LiCo02、 LiMn204、 LiNi02、 LiFeP04、 LiNio.8CoQ.202、 LiNii/3 Coi/3 Mm/302 、 LiMn02中的一种或者混合物。
其中， 所述的多孔碳应包括活性炭、 碳布、 碳纤维、 碳毡、 碳气凝胶、 碳纳米管 中的一种或者混合物
其中，所述的电解液中的锂离子由 LiC104、 LiBF4、 LiPF6、 LiCF3S03、 LiN(CF3S02) LiBOB、 LiAsF6中的至少一种产生， 并且可能加入 Me3EtNBF4、 Me2Et2NBF4、 MeEt3NBF4、 Et4NBF4、 Pr4NBF4、 MeBu3NBF4、 Bu4NBF4、 Hex4NBF4、 Me4PBF4、 Et4PBF4、 Pr4PBF4 Bu4PBF4中的一种或者几种， 所述的电解液中的非水有机溶剂包括碳酸乙烯 酯、 碳酸丙烯酯、 Y -丁内酯、 碳酸二甲酯、 碳酸二乙酯、 碳酸丁烯酯、 碳酸甲乙酯、 碳酸甲丙酯、 亚硫酸乙烯酯、 亚硫酸丙烯酯、 乙酸乙酯、 乙腈中的一种或几种。
其中， 所述的隔膜包括聚乙烯微孔膜、 聚丙烯微孔膜、 聚乙烯聚丙烯复合膜、 无 机陶瓷膜、 纸隔膜、 无纺布隔膜。
一种制备有机体系的电容电池的方法， 包括：
( 1 )正极片的制备步骤： 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)负极片的制备步骤： 首先将硬碳、 导电剂、 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 )组装步骤： 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。
其中， 所述的导电剂包括天然石墨粉、 人造石墨、 炭黑、 乙块黑、 中间相炭微球、 硬炭、 石油焦、 碳纳米管、 石墨烯、 中的一种或混合物， 并且所述的粘结剂包括聚四 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苯橡胶中的一种或几 种。
其中， 所述的正极片的集流体包括铝箔、 铝网， 并且所述的负极片的集流体包括 铜箔、 铜网。
本发明通过在负极上使用比容量高、 功率性能好的硬碳材料， 并且在正极上使用 循环寿命能达到无限次的活性炭作为混合正极材料的一部分， 使得超级电容器具有高 能量密度、 高功率密度的特性 （能量密度和功率密度都是根据实际超级电容器的重量 计算出来的）， 可广泛应用于电动汽车、 电动工具、 太阳能储能、 风能储能等领域。 具体实施方式
下面通过具体实施例对本发明作进一步的说明。
本发明一种有机混合型超级电容电池， 由正极、 负极、 介于两者之间的隔膜及电 解液组成， 正极采用锂离子嵌入化合物与多孔活性炭材料的混合物， 负极为硬碳， 电 解液采用含有锂离子的非水有机溶剂。 本发明中所述的硬碳是指难石墨化碳， 一般具有比容量高 （达 300-700mAh/g)、 倍率性能好的特点， 同时锂离子在这类材料中的嵌入不会引起结构显著膨胀， 具有很 好的充放电循环性能， 它包括包括树脂碳和有机聚合物热解碳， 所述树脂碳包括酚醛 树脂碳、 环氧树脂碳、 聚糠醇树脂碳、 糠醛树脂碳， 并且所述有机聚合物热解碳包括 苯碳、 聚糠醇热解碳、 聚氯乙烯热解碳、 酚醛热解碳。
本发明中所述的锂离子嵌入化合物包括： LiCo02、 LiMn204、 LiNi02、 LiFeP04、 LiNio.8Coo.202 LiNii/3 Co1/3 Mn1/302等。 锂离子在这类材料中嵌入-脱嵌可逆性好、 扩 散速度快， 伴随反应的体积变化小， 这样它们都具有良好的循环特性和大电流特性。
本发明中所述的电解液中的锂盐包括 LiC104、 LiBF4、 LiPF6、 LiCF3S03、 LiN(CF3S02) LiBOB、 LiAsF6中的至少一种； 非水有机溶剂包括碳酸乙烯酯、 碳酸丙 烯酯、 γ-丁内酯、 碳酸二甲酯、 碳酸二乙酯、 碳酸丁烯酯、 碳酸甲乙酯、 碳酸甲丙酯、 亚硫酸乙烯酯、 亚硫酸丙烯酯、 乙酸乙酯、 乙腈中的一种或几种。 这些由锂盐组成的 有机电解液具有高的离子电导率， 能为充放电过程中锂离子的迁移提供快速的通道， 增加反应的速率； 同时具有电化学稳定的电位范围宽 （在 0-5V之间是稳定的）、 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。
本发明中所述的隔膜包括聚乙烯微孔膜 （ΡΕ )、 聚丙烯微孔膜 （ΡΡ )、 复合膜 (ΡΡ+ΡΕ+ΡΡ)、 无机陶瓷膜、 纸隔膜， 其厚度一般在 10-30 μ ηι， 孔径在 0.03 μ m-0.05 m， 具有良好的吸附电解液的能力和耐高温特性。
本发明中正极片的集流体采用铝箔、 铝网， 负极片的集流体采用铜箔、 铜网。 在 极片的制作中， 加入适量的导电剂和粘结剂。 本发明中导电剂采用具有高导电性的石 墨粉、 炭黑、 乙块黑或它们的混合物。 本发明中的粘结剂采用聚四氟乙烯 （PTFE)、 聚偏氟乙烯 （PVDF)、 羟丙基甲基纤维素 （HPMC)、 羧甲基纤维素纳 （CMC) 和丁 苯橡胶 （SBR) 中的一种或几种。
本发明中， 正极片的制作步骤为： 按照一定的质量比称取锂离子嵌入化合物、 多 孔炭材料、 导电剂、 粘结剂混合后， 搅拌至膏状， 然后涂在集流体上， 经烘干、 碾压、 裁切、 真空干燥制备成正极片。 负极片的制作步骤为： 按照一定的质量比称取硬碳、 粘结剂混合后， 搅拌至膏状， 然后涂在集流体上， 经烘干、 碾压、 裁切、 真空干燥制 备成负极片。 本发明根据实际应用情况， 可以制作成叠片或卷绕结构的方型超级电容电池和圆 柱型超级电容电池， 并都能保持高功率、 高能量的特性， 其外壳可以采用铝塑膜、 钢 壳、 吕壳
实施例中使用的主要原材料如下：
LiMn204—石家庄百思特电池材料有限公司生产；
LiCo02—湖南瑞翔新材料有限公司生产， 型号为 R747;
LiM02—中信国安盟固利公司生产；
LiFeP04—天津斯特兰能源科技有限公司生产， 型号为 SLFP-ES01 ;
LiNiQ.8COQ.202—广州鸿森材料有限公司生产；
LiNii/3 Coi/3 Mn1/302—河南新乡华鑫能源材料股份有限公司；
多孔炭一日本 KURARAY公司生产， 型号为 YP-17D;
PVDF (聚偏氟乙烯）一上海三爱富新材料股份有限公司生产， 型号为 FR921; NMP ( 1-甲基 -2-吡咯烷酮）一上海实验试剂有限公司；
导电炭黑一 TIMCAL公司生产， 型号为 Super-P;
三层复合隔膜 （PP/PE/PP)—日本宇部生产；
实施例 1 :
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 45： 45 : 5 : 5混合，用 NMP调成浆料，然后涂布在 20μηι的铝箔 (涂布增重为： 140g/m2) 上， 经烘干（110〜120°C )、碾压、裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥（120〜 130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP 调成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选 用三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙 酯） （1 : 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 4.2V, 静置 5min， 5A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 5A充放循环 10000 次后， 容量保持率在 80%。
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 20μηι的铝箔 (涂布增重为： 140g/m2) 上， 经烘干（110〜120°C )、碾压、裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥（120〜 130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP调 成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾 压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选用 三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙酯） ( 1： 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 4.2V,静置 5min， 5A放电至 2.5V, 电容电池的比能量为 21Wh/Kg， 比功率为 5500 W/Kg, 经过 5A充放循环 10000次后， 容量保持率在 85%。
实施例 3
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 85： 5 : 5 : 5混合，用 NMP调成浆料，然后涂布在 20μηι的铝箔 (涂布增重为： 140g/m2) 上， 经烘干（110〜120°C )、碾压、裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥（120〜 130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP调 成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾 压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选用 三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙酯） ( 1： 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 4.2V,静置 5min， 5A放电至 2.5V, 电容电池的比能量为 50 Wh/Kg, 比功率为 4300 W/Kg, 经过 5A充放循环 10000次后， 容量保持率在 65%。
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按质量比为 45： 45 : 5 : 5混合，用 NMP调成浆料，然后涂布在 20μηι的铝箔 (涂布增重为： 140g/m2) 上， 经烘干（110〜120°C )、碾压、裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥（120〜 130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP 调成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选 用三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙 酯） （1 : 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 4.2V, 静置 5min， 5A放电至 2.5V, 电容电池的比能量为 61 Wh/Kg， 比功率为 4800 W/Kg， 经过 5A充放循环 10000 次后， 容量保持率在 91%。
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 20μηι的铝箔 (涂布增重为： 140g/m2) 上， 经烘干（110〜120°C )、碾压、裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥（120〜 130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP 调成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选 用三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙 酯） （1 : 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 4.2V, 静置 5min， 5A放电至 2.5V, 电容电池的比能量为 31Wh/Kg， 比功率为 5200W/Kg， 经过 5A充放循环 10000 次后， 容量保持率在 94%。
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 20μηι的铝箔 (涂布增重为： 140g/m2) 上， 经烘干（110〜120°C )、碾压、裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥（120〜 130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP 调成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选 用三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙 酯） （1 : 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 4.2V, 静置 5min， 5A放电至 2.5V, 电容电池的比能量为 70Wh/Kg， 比功率为 5200W/Kg， 经过 5A充放循环 10000 次后， 容量保持率在 85%。 实施例 7:
正极片的制作： 将总量为 500g的 LiNi02、 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 20μηι的铝箔 (涂布增重为： 140g/m2) 上， 经烘干（110〜120°C )、碾压、裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥（120〜 130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP 调成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选 用三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙 酯） （1 : 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 4.2V, 静置 5min， 5A放电至 2.5V, 电容电池的比能量为 76 Wh/Kg， 比功率为 4947 W/Kg， 经过 5A充放循环 10000 次后， 容量保持率在 85%。
实施例 8
正极片的制作： 将总量为 500g的 LiNi02、 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 20μηι的铝箔 (涂布增重为： 140g/m2) 上， 经烘干（110〜120°C )、碾压、裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥（120〜 130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP 调成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选 用三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙 酯） （1 : 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 4.2V, 静置 5min， 5A放电至 2.5V, 电容电池的比能量为 37Wh/Kg， 比功率为 5452 W/Kg， 经过 5A充放循环 10000 次后， 容量保持率在 92%。
实施例 9
正极片的制作： 将总量为 500g的 LiNi02、 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 20μηι的铝箔 (涂布增重为： 140g/m2) 上， 经烘干（110〜120°C )、碾压、裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥（120〜 130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP 调成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选 用三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙 酯） （1 : 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 4.2V, 静置 5min， 5A放电至 2.5V, 电容电池的比能量为 81 Wh/Kg， 比功率为 4232 W/Kg， 经过 5A充放循环 10000 次后， 容量保持率在 80%。 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 20μηι的铝箔 (涂布增重为： 140g/m2) 上， 经烘干（110〜120°C )、碾压、裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥（120〜 130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP 调成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选 用三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙 酯） （1 : 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 3.7V, 静置 5min， 5A放电至 2.3 V, 电容电池的比能量为 55 Wh/Kg， 比功率为 5452W/Kg， 经过 5A充放循环 10000 次后， 容量保持率在 94%。
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 20μηι的铝箔 (涂布增重为： 140g/m2) 上， 经烘干（110〜120°C )、碾压、裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥（120〜 130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP 调成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选 用三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙 酯） （1 : 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 3.7V, 静置 5min， 5A放电至 2.3 V，电容电池的比能量为 20.3Wh/Kg，比功率为 6000W/Kg，经过 5A充放循环 10000 次后， 容量保持率在 96%。
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 20μηι的铝箔 (涂布增重为： 140g/m2) 上， 经烘干（110〜120°C )、碾压、裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥（120〜 130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP 调成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选 用三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙 酯） （1 : 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 3.7V, 静置 5min， 5A放电至 2.3 V, 电容电池的比能量为 65Wh/Kg， 比功率为 4900W/Kg， 经过 5A充放循环 10000 次后， 容量保持率在 90%。 实施例 13:
正极片的制作： 将总量为 500g的 LiNiQ.8COQ.202、 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 20μηι的铝箔 (涂布增重为： 140g/m2)上， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干 燥 （120〜130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP 调成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选 用三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙 酯） （1 : 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 4.2V, 静置 5min， 5A放电至 2.5V, 电容电池的比能量为 71 Wh/Kg， 比功率为 5088 W/Kg， 经过 5A充放循环 10000 次后， 容量保持率在 78%。
实施例 14:
正极片的制作： 将总量为 500g的 LiNiQ.8COQ.202、 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 20μηι的铝箔 (涂布增重为： 140g/m2)上， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干 燥 （120〜130°C ) 制作成正极片。
负极片的制作：将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合，用 NMP调 成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾 压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选用 三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙酯） ( 1： 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 4.2V,静置 5min， 5A放电至 2.5V, 电容电池的比能量为 25Wh/Kg， 比功率为 5570 W/Kg, 经过 5A充放循环 10000次后， 容量保持率在 83%。
实施例 15:
正极片的制作： 将总量为 500g的 LiNiQ.8COQ.202、 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 20μηι的铝箔 (涂布增重为： 140g/m2)上， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干 燥 （120〜130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP 调成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选 用三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙 酯） （1 : 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 4.2V, 静置 5min， 5A放电至 2.5V, 电容电池的比能量为 82Wh/Kg， 比功率为 4621 W/Kg， 经过 5A充放循环 10000 次后， 容量保持率在 70%。 实施例 16:
正极片的制作： 将总量为 500g的 LiNi1/3 Co1/3 Mn1/302、 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 20μηι的铝箔 (涂布增 重为： 140g/m2)上， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h 真空干燥 （120〜130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP 调成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选 用三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙 酯） （1 : 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 4.2V, 静置 5min， 5A放电至 2.5V, 电容电池的比能量为 66 Wh/Kg， 比功率为 5225W/Kg， 经过 5A充放循环 10000 次后， 容量保持率在 90%。
实施例 17: 正极片的制作： 将总量为 500g的 LiNi1/3 Co1/3 Mn1/302、 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 20μηι的铝箔 (涂布增 重为： 140g/m2)上， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h 真空干燥 （120〜130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP 调成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选 用三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙 酯） （1 : 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 4.2V, 静置 5min， 5A放电至 2.5V, 电容电池的比能量为 23Wh/Kg， 比功率为 6005W/Kg， 经过 5A充放循环 10000 次后， 容量保持率在 94%。
实施例 18:
正极片的制作： 将总量为 500g的 LiNi1/3 Co1/3 Mn1/302、 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 20μηι的铝箔 (涂布增重 为： 140g/m2)上， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真 空干燥 （120〜130°C ) 制作成正极片。
负极片的制作： 将总量为 500g的硬碳、 PVDF 按质量比为 90: 10混合， 用 NMP 调成浆料， 然后涂布 16μηι的铜箔上 (涂布增重为： 90g/m2)， 经烘干 （110〜120°C )、 碾压、 裁片 (尺寸为： 37.5*59.5mm2)、 24h真空干燥 （120〜130°C ) 制作成负极片。 选 用三层复合隔膜为隔膜， 将正极片 （8片）、 隔膜、 负极片 （9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 lmol/L LiPF6— EC (碳酸乙烯酯） /DEC (碳酸二乙 酯） （1 : 1 ) 的电解液 10g， 组装成方型超级电容电池。 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 5A充电至 4.2V, 静置 5min， 5A放电至 2.5V, 电容电池的比能量为 78 Wh/Kg， 比功率为 5000W/Kg， 经过 5A充放循环 10000 次后， 容量保持率在 83%。 从以上实施例可以看出， 正极使用锂离子嵌入化合物与多孔碳的混合物， 负极使 用硬碳的超级电容电池表现出良好的能量密度、 功率密度和循环寿命； 从中也可以看 出， 当使用相同的负极时， 电容电池的性能随着锂离子嵌入化合物的变化而有一定的 差别； 从中还可以看出正极中嵌入锂离子化合物和多孔碳的比例也对超级电容电池性 能有很大的影响， 当多孔碳比例增加， 电容电池的比功率增加， 循环寿命增加， 但比 能量减少， 当嵌入锂离子化合物和多孔碳的比在 17: 1-2： 7之间都有实用价值， 根据 不同的工况可以采取不同的配比达到用户的需求。
本说明书中所述的只是本发明的几种较佳具体实施例， 以上实施例仅用以说明本 发明的技术方案而非对本发明的限制。 凡本领域技术人员依本发明的构思通过逻辑分 析、 推理或者有限的实验可以得到的技术方案， 皆应在本发明的范围之内。

Claims

权 利 要 求 书
1. 一种高比能量有机体系的电容电池， 由正极、 负极、 介于两者之间的隔膜及电 解液组成， 其特征在于正极采用锂离子嵌入化合物和多孔碳材料的混合物， 负极采用 硬碳， 电解液采用含有锂离子的非水有机溶剂电解液。
2. 根据权利要求 1所述的有机体系的电容电池， 其特征在于所述的硬碳包括树脂 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其混合物。
3.根据权利要求 1所述的有机体系的电容电池，其特征在于所述的锂离子嵌入化 合物包括： LiCo02、 LiMn204、 LiNi02、 LiFeP04、 LiNio.8CoQ.202、 LiNi1/3 Co1/3 Mn1/302 、 LiMn02中的一种或者混合物。
4. 根据权利要求 1所述的有机体系的电容电池， 其特征在于所述的多孔碳应包括 活性炭、 碳布、 碳纤维、 碳毡、 碳气凝胶、 碳纳米管中的一种或者混合物
5.根据权利要求 1所述的有机体系的电容电池，其特征在于所述的电解液中的锂 离子由 LiC104、 LiBF4、 LiPF6、 LiCF3S03、 LiN(CF3S02)、 LiBOB、 LiAsF6中的至少一 种产生， 并且可能加入 Me3EtNBF4、 Me2Et2NBF4、 MeEt3NBF4、 Et4NBF4、 Pr4NBF4、 MeBu3NBF4、 Bu4NBF4、 Hex4NBF4、 Me4PBF4、 Et4PBF4、 Pr4PBF4、 Bu4PBF4中的一种 或者几种，所述的电解液中的非水有机溶剂包括碳酸乙烯酯、碳酸丙烯酯、 Y -丁内酯、 碳酸二甲酯、 碳酸二乙酯、 碳酸丁烯酯、 碳酸甲乙酯、 碳酸甲丙酯、 亚硫酸乙烯酯、 亚硫酸丙烯酯、 乙酸乙酯、 乙腈中的一种或几种。
6.根据权利要求 1所述的有机体系的电容电池，其特征在于所述的隔膜包括聚乙 烯微孔膜、 聚丙烯微孔膜、 聚乙烯聚丙烯复合膜、 无机陶瓷膜、 纸隔膜、 无纺布隔膜。
7. 一种制备根据权利要求 1所述的有机体系的电容电池的方法， 包括：
( 1 )正极片的制备步骤： 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)负极片的制备步骤： 首先将硬碳、 导电剂、 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 )组装步骤： 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。
8. 根据权利要求 7所述的方法， 其中所述的导电剂包括天然石墨粉、 人造石墨、 炭黑、 乙块黑、 中间相炭微球、 硬炭、 石油焦、 碳纳米管、 石墨烯、 中的一种或混合 物， 并且所述的粘结剂包括聚四氟乙烯、 聚偏氟乙烯、 羟丙基甲基纤维素、 羧甲基纤 维素纳和丁苯橡胶中的一种或几种。
9. 根据权利要求 7所述的方法， 其中所述的正极片的集流体包括铝箔、 铝网， 并 且所述的负极片的集流体包括铜箔、 铜网。
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IL221101A0 (en) 2012-09-24
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JP2013520806A (ja) 2013-06-06
US20130155577A1 (en) 2013-06-20
CN101847516A (zh) 2010-09-29

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