CN105680119A - Hybrid energy-storing device and manufacturing method thereof - Google Patents
Hybrid energy-storing device and manufacturing method thereof Download PDFInfo
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- CN105680119A CN105680119A CN201610054215.0A CN201610054215A CN105680119A CN 105680119 A CN105680119 A CN 105680119A CN 201610054215 A CN201610054215 A CN 201610054215A CN 105680119 A CN105680119 A CN 105680119A
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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
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- 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
- H01M4/139—Processes of manufacture
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- 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
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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
- 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
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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
- 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
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- 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
Abstract
The invention discloses a hybrid energy-storing device. The hybrid energy-storing device comprises a porous carbon positive electrode, a titanium oxide negative electrode, a lithium-containing electrolyte solution, and a diaphragm consisting of a polyimide fiber membrane and filler attached to a single side of the polyimide fiber membrane. Double power supplies of a super capacitor and a battery can be combined outside, and internal fusion is realized through porous carbon, a titanium oxide and the high-temperature-resistant diagram, so that the hybrid energy-storing device has the characteristics of double electric layers of the super capacitor and lithium intercalation/de-intercalation hybrid energy-storing characteristic of a lithium ion battery.
Description
Technical field
The present invention relates to a kind of hybrid energy-storing device and its preparation method, belong to energy storage device field.
Background technology
Power cell energy density used at present is lower, and bulking value is big, it may also be useful to the life-span is short, and cost is higher, and operating temperature range is narrow, and the duration of charging is long. In order to improve these disadvantageous effects, people carry out the research and development of power cell from aspects such as positive electrode material, negative material, diaphragm electrolytes.
A series of social concerns that energy dilemma and environmental pollution bring, have impelled development that is energy-conservation and new-energy automobile. This wherein, electrical source of power becomes bottlenecks. Electrical source of power except to be met the power of automobile, energy, safety performance and easy for installation etc. require except, also require that charging is quick, it may also be useful to the life-span is long, and cost is low; But, electrical source of power energy density used at present is lower, and automobile continual mileage is short; Power density is less, and automobile starting, climbing and acceleration characteristics are poor; Bulking value is big, installs inconvenience; Work-ing life is short, can not be identical with whole car; Cost is higher, and whole car comprehensive cost remains high; Operating temperature range is narrow, and it is poor to adapt to; Duration of charging is long, and auxiliary facility has high input. These reasons hinder the large-scale application of electrical source of power on energy-conservation and new-energy automobile. Therefore, people start to find and meet power and method that energy is taken into account.
Two sources outer set syntype, namely battery and ultracapacitor are combined into composite power source, while meeting the service requirements of energy-conservation and new-energy automobile, it is possible to greatly improve the efficiency of battery, extend work-ing life. Such as, by lithium ion battery and ultracapacitor composition composite power source, as the electrical source of power of automobile, lithium ion battery provides the continual mileage required drive of automobile, ultracapacitor can in high-power output operating mode work such as startup, acceleration, climbings, the combination of the two improves the dynamic performance of automobile, extends the work-ing life of battery.
The inner fusion mode in two source, by a certain characteristic element of power cell and the characteristic element of ultracapacitor, by the optimization design of system, at same monomer endomixis, make the feature that it has two kinds of electrical source of power concurrently, trim point can be found between power density and energy density, meet particular automobile operating mode needs. Such as, for hybrid electric vehicle, it is possible to meet power requirement, take into account portion of energy demand, the pure motoring condition carrying out certain distance travels.
The JMEnergy of Japan, Asahi Chemical Industry, NEC-TOKIN, ACT, Supreme Being visitor, FDK, TAIYO YUDAN, Hitachi's chemical conversion waits research and development lithium-ion capacitor, part has realized commercialization, Japanese fuji heavy industry Co., Ltd. (publication number US2009/0197171A1, US2010/0142121A1, US2010/0128415A1, US7, 733, 629B2, application number 200580004509.2, application number 200580001498.2, application number 200680032109.7, application number 200680038604.9, application number 200680042376.2, application number 200680046167.5, application number 200680049541.7, application number 200710145884.X) planned lithium-ion capacitor is applied to Si Balu automobile,Application number be 200410093962.2 Chinese patent report a kind of high tension super capacitor, negative material is made mashed prod apply on metal foil, after drying, roll-in make negative plate, embedding lithium is the de-lithiumation one-tenth of part again, form ultracapacitor with gac positive pole, there is the most high working voltage of about 4V. the Chinese patent of application number 200810046091.7 reports a kind of containing C, the high potential super capacitor electrode material of Fe and P element, the Chinese patent of application number 201010280801.X reports a kind of iron lithium phosphate load at gac as positive active material, the Chinese patent of application number 200710035051.8 reports and a kind of adopts the mixture of anode material for lithium-ion batteries and electrode material for super capacitor as positive active material, using the mixture of lithium ion battery negative material and electrode material for super capacitor as negative electrode active material, the Chinese patent of application number 200710035205.3 reports a kind of super capacitance cell, positive-active electrode materials adopts the mixture of Lithium-ion embeding compound and porous carbon material, negative electrode active electrode materials adopts the mixture of porous carbon material and graphite type material, application number be 200810031490.6 Chinese patent report a kind of the novel energy-storing device and the manufacture method thereof that have ultracapacitor and lithium ion battery characteristics concurrently, the Chinese patent that publication number is CN1866427A reports a kind of ultracapacitor based on the electroactive substance in liquid phase, the Chinese patent of application number 201010592947.8 reports a kind of novel water system/organic system mixed type lithium ion battery.
Comprehensive above analysis can be found out, in order to the energy advantage of the power advantage and lithium ion battery that play ultracapacitor, the inside combination that two power supply outside of ultracapacitor and battery can be combined through biomaterials realizes, thus obtains the hybrid energy-storing device having the two feature concurrently.
Summary of the invention
It is an object of the invention to provide a kind of hybrid energy-storing device and its preparation method, can by two power supply outside combination of ultracapacitor and battery, realize inner fusion by porous carbon, titanium oxide and high temperature resistant barrier film etc., there is the electrostatic double layer of super capacitor, the doff lithium hybrid energy-storing characteristic of lithium ion battery.
Technical solution of the present invention is achieved in that a kind of hybrid energy-storing device, comprise porous charcoal positive pole, titanium oxide negative pole, containing lithium electrolyte solution, the barrier film that is made up of the filler of polyimide fiber film and one side attachment thereof; It is characterized in that its preparation method is as follows: prepared by (1) porous charcoal positive pole: porous charcoal particle, specific surface area is 1500～2300m2The particle of/g accounts for the 10～30% of porous charcoal total mass; Take gac, conductive agent, Xylo-Mucine and SBR emulsion in mass ratio, add deionized water mixing 3～6h, obtain slurry, by slurry coating on aluminium foil, vacuum-drying, cut-parts obtain positive plate;
(2) barrier film preparation: take filler, binding agent made the solution that mass concentration is 20%, first by the 0.5～2% of cumulative volume binder solution mix 20～60min with filler, then by the 2% of cumulative volume binder solution mix 20～60min with filler; Binder solution by the 20% of cumulative volume mixes 20～60min with filler; With filler, remaining binder solution being mixed 20～60min, then under vacuum condition, continues mixing 1h, add solvent, forming solid content is the dispersion liquid of 4～30%.The dispersed liquid coating obtained is the one side of the polyimide fiber film of 20～80um at thickness, removes solvent, obtains barrier film;
(3) titanium negative pole preparation: take titanium oxide, conductive agent and polyvinylidene difluoride (PVDF) in mass ratio, adds N-Methyl pyrrolidone and stirs, obtain slurry, and the slurry coating obtained is on Copper Foil, and vacuum-drying, cut-parts obtain negative plate. According to positive plate, barrier film together with the sequential combination of negative plate, the barrier film face of attachment filler particle and titanium oxide electrode contact; Inject containing lithium electrolyte solution, encapsulation, aging, obtain hybrid energy-storing device.
Described anode activated charcoal, conductive agent, Xylo-Mucine and SBR emulsion mass ratio are 86～90:5～10:1～3:1～3; Described metatitanic acid lithium, conductive agent and polyvinylidene difluoride (PVDF) mass ratio are 80～85:10～15:5～8.
Described filler comprises aluminium sesquioxide, polynite, titanium dioxide, graphene oxide, barium titanate, and quality is the 2～40% of polyimide fiber film quality.
Described binding agent comprises polyvinylidene difluoride (PVDF), R 1216-polyvinylidene fluoride copolymer, tetrafluoroethylene, Xylo-Mucine, polyoxyethylene, polyvinyl alcohol, and quality is the 5～20% of packing quality.
Described porous charcoal comprises one or more in gac, active Graphene, charcoal-aero gel, Carbon foam, activated carbon fiber, carbon nanotube.
Described titanium oxide comprises metatitanic acid lithium, titanium dioxide and material modified.
The positively effect of the present invention by two power supply outside combination of ultracapacitor and battery, can realize inner fusion by porous carbon, titanium oxide and high temperature resistant barrier film etc., have the electrostatic double layer of super capacitor, the doff lithium hybrid energy-storing characteristic of lithium ion battery. The hybrid energy-storing device preparation technology of the present invention is simple, security height, is easy to realize.
Accompanying drawing explanation
Fig. 1 is the structural representation of the hybrid energy-storing device of the present invention.
Fig. 2 is the SEM photograph of the gac positive plate of the embodiment of the present invention 1.
Fig. 3 is the SEM photograph of the barrier film attachment additive granules one side of the embodiment of the present invention 1.
The barrier film that Fig. 4 is the embodiment of the present invention 1 does not adhere to additive granules SEM photograph simultaneously.
Fig. 5 is the SEM photograph of the lithium titanate anode sheet of the embodiment of the present invention 1.
Fig. 6 is the charging and discharging curve figure of the embodiment of the present invention 1.
Embodiment
Described embodiment is the specific descriptions of the claim to the present invention, and claim includes but not limited to described embodiment content.
Embodiment 1
(1) gac positive plate preparation: 90:5:5 takes gac (specific surface area is 1480m in mass ratio2The gac of/g and specific surface area are 2300m2The mixture of the gac of/g 9:1 in mass ratio), conductive agent, 1% Xylo-Mucine and 50% SBR emulsion, add deionized water mixing 3h, obtain the slurry that solid content is 28%, by slurry coating on aluminium foil, vacuum-drying, cut-parts obtain positive plate.
(2) barrier film preparation: take aluminium sesquioxide (the 10% of polyimide quality), R 1216-vinylidene fluoride copolymers is made the binder solution that mass concentration is 20%, first by the 0.5% of cumulative volume binder solution and aluminium sesquioxide mixing 20min, then by the 2% of cumulative volume binder solution and aluminium sesquioxide mixing 20min; Binder solution by the 20% of cumulative volume and aluminium sesquioxide mixing 1h; By remaining binder solution and aluminium sesquioxide mixing 1h, then under vacuum condition, continuing mixing 1h, add acetone, forming solid content is the dispersion liquid of 4%.The dispersed liquid coating obtained is the one side of the polyimide fiber film of 40um at thickness, removes solvent, obtains barrier film.
(3) lithium titanate anode sheet preparation: 85:10:5 takes metatitanic acid lithium, conductive agent and polyvinylidene difluoride (PVDF) in mass ratio, adding N-Methyl pyrrolidone to stir, obtain the slurry that solid content is 35%, the slurry coating obtained is on Copper Foil, vacuum-drying, cut-parts obtain negative plate.
According to positive plate 1, barrier film 2 together with the sequential combination of negative plate 3, the barrier film face of attachment filler particle and titanium oxide electrode contact; Inject containing lithium electrolyte solution, encapsulation, aging, obtain hybrid energy-storing device.
Embodiment 2
(1) gac positive plate preparation: 88:7:5 takes gac (specific surface area is 1420m in mass ratio2The gac of/g and specific surface area are 1800m2The mixture of the gac of/g 7:3 in mass ratio), conductive agent, 1% Xylo-Mucine and 50% SBR emulsion, add deionized water mixing 3h, obtain the slurry that solid content is 29%, by slurry coating on aluminium foil, vacuum-drying, cut-parts obtain positive plate.
(2) barrier film preparation: take polynite (the 2% of polyimide quality), polyoxyethylene is made the binder solution that mass concentration is 40%, first by the 1% of cumulative volume binder solution and polynite mixing 20min, then by the 2% of cumulative volume binder solution and polynite mixing 20min; Binder solution by the 30% of cumulative volume and polynite mixing 1h; By remaining binder solution and polynite mixing 1h, then under vacuum condition, continuing mixing 1h, add deionized water, forming solid content is the dispersion liquid of 10%. The dispersed liquid coating obtained is the one side of the polyimide fiber film of 40um at thickness, removes solvent, obtains barrier film.
(3) lithium titanate anode sheet preparation: 80:12:8 takes metatitanic acid lithium, conductive agent and polyvinylidene difluoride (PVDF) in mass ratio, adding N-Methyl pyrrolidone to stir, obtain the slurry that solid content is 35%, the slurry coating obtained is on Copper Foil, vacuum-drying, cut-parts obtain negative plate.
According to positive plate 1, barrier film 2 together with the sequential combination of negative plate 3, the barrier film face of attachment filler particle and titanium oxide electrode contact; Inject containing lithium electrolyte solution, encapsulation, aging, obtain hybrid energy-storing device.
Embodiment 3
(1) gac positive plate preparation: 86:6:8 takes gac (specific surface area is 1480m in mass ratio2The gac of/g and specific surface area are 1680m2The mixture of the gac of/g 8:2 in mass ratio), conductive agent, 1% Xylo-Mucine and 50% SBR emulsion, add deionized water mixing 3h, obtain the slurry that solid content is 27%, by slurry coating on aluminium foil, vacuum-drying, cut-parts obtain positive plate.
(2) barrier film preparation: take barium titanate (the 40% of polyimide quality), polyvinyl alcohol is made the binder solution that mass concentration is 40%, first by the 5% of cumulative volume binder solution and barium titanate mixing 20min, then by the 5% of cumulative volume binder solution and barium titanate mixing 20min; Binder solution by the 20% of cumulative volume and barium titanate mixing 1h; By remaining binder solution and aluminium sesquioxide mixing 1h, then under vacuum condition, continuing mixing 1h, add deionized water, forming solid content is the dispersion liquid of 30%. The dispersed liquid coating obtained is the one side of the polyimide fiber film of 40um at thickness, removes solvent, obtains barrier film.
(3) lithium titanate anode sheet preparation: 85:10:5 takes metatitanic acid lithium, conductive agent and polyvinylidene difluoride (PVDF) in mass ratio, adding N-Methyl pyrrolidone to stir, obtain the slurry that solid content is 37%, the slurry coating obtained is on Copper Foil, vacuum-drying, cut-parts obtain negative plate.
According to positive plate 1, barrier film 2 together with the sequential combination of negative plate 3, the barrier film face of attachment filler particle and titanium oxide electrode contact; Inject containing lithium electrolyte solution, encapsulation, aging, obtain hybrid energy-storing device.
Claims (5)
1. a hybrid energy-storing device, comprise porous charcoal positive pole, titanium oxide negative pole, containing lithium electrolyte solution, by the barrier film that forms of filler of polyimide fiber film and one side attachment thereof, it is characterised in that, preparation method comprises the steps:
(1) porous charcoal positive pole preparation: porous charcoal particle, specific surface area is 1500～2300m2The particle of/g accounts for the 10～30% of porous charcoal total mass; Take gac, conductive agent, Xylo-Mucine and SBR emulsion in mass ratio, add deionized water mixing 3～6h, obtain slurry, by slurry coating on aluminium foil, vacuum-drying, cut-parts obtain positive plate;
(2) barrier film preparation: take filler, binding agent made the solution that mass concentration is 20%, first by the 0.5～2% of cumulative volume binder solution mix 20～60min with filler, then by the 2% of cumulative volume binder solution mix 20～60min with filler; Binder solution by the 20% of cumulative volume mixes 20～60min with filler; With filler, remaining binder solution being mixed 20～60min, then under vacuum condition, continues mixing 1h, add solvent, forming solid content is the dispersion liquid of 4～30%; The dispersed liquid coating obtained is the one side of the polyimide fiber film of 20～80um at thickness, removes solvent, obtains barrier film;
(3) titanium negative pole preparation: take titanium oxide, conductive agent and polyvinylidene difluoride (PVDF) in mass ratio, add N-Methyl pyrrolidone stir, obtain slurry, the slurry coating obtained on Copper Foil, vacuum-drying, cut-parts obtain negative plate; According to positive plate, barrier film together with the sequential combination of negative plate, the barrier film face of attachment filler particle and titanium oxide electrode contact; Inject containing lithium electrolyte solution, encapsulation, aging, obtain hybrid energy-storing device.
2. a kind of hybrid energy-storing device according to claim 1 and its preparation method, it is characterised in that, described anode activated charcoal, conductive agent, Xylo-Mucine and SBR emulsion mass ratio are 86～90:5～10:1～3:1～3.
3. a kind of hybrid energy-storing device according to claim 1 and its preparation method, it is characterised in that, described metatitanic acid lithium, conductive agent and polyvinylidene difluoride (PVDF) mass ratio are 80～85:10～15:5～8.
4. a kind of hybrid energy-storing device according to claim 1 and its preparation method, it is characterised in that, described filler comprises aluminium sesquioxide, polynite, titanium dioxide, graphene oxide, barium titanate, and quality is the 2～40% of polyimide fiber film quality.
5. a kind of hybrid energy-storing device according to claim 1 and its preparation method, it is characterized in that, described binding agent comprises polyvinylidene difluoride (PVDF), R 1216-polyvinylidene fluoride copolymer, tetrafluoroethylene, Xylo-Mucine, polyoxyethylene, polyvinyl alcohol, and quality is the 5～20% of packing quality.
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| CN107565082A (en) * | 2017-07-11 | 2018-01-09 | 中国第汽车股份有限公司 | A kind of composite diaphragm |
| CN111213260A (en) * | 2017-08-17 | 2020-05-29 | 微宏动力系统（湖州）有限公司 | Anode, anode preparation method and lithium ion battery |
| WO2020207362A1 (en) * | 2019-04-08 | 2020-10-15 | 青岛九环新越新能源科技股份有限公司 | Energy storage device having bipolar conductive film connecting structure |
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| CN202601423U (en) * | 2012-06-15 | 2012-12-12 | 渤海大学 | Super-capacitance lithium-air battery |
| CN103545120A (en) * | 2013-10-30 | 2014-01-29 | 中国第一汽车股份有限公司 | Organic system hybrid capacitor with rice-hull-based activated carbon serving as electrode material |
| CN104022247A (en) * | 2014-06-24 | 2014-09-03 | 中国第一汽车股份有限公司 | Multi-element composite lithium ion battery diaphragm and preparation method thereof |
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