CN109545566A - A kind of high specific energy lithium-ion capacitor - Google Patents
A kind of high specific energy lithium-ion capacitor Download PDFInfo
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- CN109545566A CN109545566A CN201811388465.3A CN201811388465A CN109545566A CN 109545566 A CN109545566 A CN 109545566A CN 201811388465 A CN201811388465 A CN 201811388465A CN 109545566 A CN109545566 A CN 109545566A
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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
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
- H01G11/30—Electrodes characterised by their material
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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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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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
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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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
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
Abstract
A kind of high specific energy lithium-ion capacitor, including battery core and shell, battery core encapsulate inside the shell, there is electrolyte between battery core and shell；The battery core is formed after combining lamination by anode pole piece, diaphragm and cathode pole piece；It is compounded with the heterogeneous composite material anode sizing agent layer that active carbon and conducting polymer and Gao Fu lithium material are mixed to form in the appearance of anode pole piece, makes full use of active carbon to cooperate with energy storage mechanism with conducting polymer, promotes the specific capacity of positive electrode.Invention passes through the selection of conducting polymer in optimization anode composite material, to obtain the lithium-ion capacitor of high-energy density.
Description
Technical field
The present invention relates to a kind of supercapacitors, refer in particular to a kind of utilization other materials change lithium-ion capacitor ratio
The lithium-ion capacitor of energy；Belong to lithium-ion capacitor technical field.
Background technique:
Lithium-ion capacitor (Lithium ion capacitor, LIC), anode use active carbon, are electric double layer energy storage machine
Reason, cathode use the processed lithium ion battery negative pole carbon material of prelithiation, are lithium ion battery energy storage mechnism, by electric double layer electricity
The advantages of container and secondary cell, organically combines the novel mixed type energy storage device with one.At the embedding lithium of negative electrode material
Reason greatly reduces cathode potential, therefore the operating voltage of device can reach 4.0V, compared to electric double layer super capacitor
Device, lithium-ion capacitor energy density are increased dramatically.Currently, 15 Wh/kg of commercial li-ion capacitor energy density is left
The right side, but still have biggish gap compared with secondary cell, mainly the mode of positive and negative anodes electrode storage energy is different, and anode is living
Property Carbon Materials by absorption/desorption ion physical energy storage, Carbon anode is insertion/deintercalation chemical energy storage of lithium ion, negative electrode material
Gram volume be much higher than positive electrode, the quality of positive plate active material is much higher than negative electrode tab, shadow during electrode structural designs
The promotion for ringing lithium-ion capacitor energy density, the specific capacity for promoting positive electrode are to promote having for ionistor energy density
Effect approach, therefore it is necessary to improve this.
On the other hand, height can be stored by the conducting polymer of representative of polypyrrole, polyaniline, polythiophene and its derivative
Charge density, generates big quasi- faraday's capacitor, and the energy density of conducting polymer is double layer capacitor absorbent charcoal material
10 ~ 100 times.But such mechanical property of materials is bad, long-term cycle stability can be poor.If both wanting to utilize conducting polymer
Exclusive advantage, at the same overcome again its there are the shortcomings that, conducting polymer and other electrode materials can be carried out it is compound, will be double
Electric layer capacitor is in conjunction with faraday's capacitor, by organic material in conjunction with inorganic material, is mentioned using the synergistic effect between each component
High whole synthesis performance.
Secondly it is a ring the most key in lithium-ion capacitor manufacturing technology that cathode assigns lithium technology in advance, is generallyd use active
Lithium metal as lithium source, and the porous current collector of higher operating costs, with realize it is pre- assign lithium when, lithium ion is worn in pole piece group
Shuttle causes production process technology condition is harsh, manufacturing cost is high, is difficult to scale to manufacture.
By patent retrieval do not find have with the patent literature report of same technique of the present invention, have certain relationship with the present invention
Patent mainly have it is following:
1, number of patent application CN201810071152.9, a kind of entitled " hybrid super capacitor wet end furnish preparation side
Case ", applicant are as follows: the application for a patent for invention of Jiangsu Zun Dao Science and Technology Ltd., which disclose a kind of hybrid capacitors
Device wet end furnish preparation method, the preparation of the positive plate slurry including hybrid super capacitor and the cathode of hybrid super capacitor
The preparation of piece slurry；The raw material for preparing of the positive plate slurry of this kind of hybrid super capacitor includes active material spinel nickel mangaic acid
Lithium, adhesive PVDF and conductive agent SP；The raw material for preparing of the negative electrode tab slurry of this kind of hybrid super capacitor includes active material
AC, carboxyl methyl cellulose, adhesive LA132, adhesive PTFE (polytetrafluoroethylene (PTFE)) and conductive agent SP.
2, number of patent application CN201710770517.2, entitled " a kind of super capacitor combination electrode material and its system
Preparation Method ", applicant are as follows: the application for a patent for invention of University of Science & Technology, Beijing, which disclose a kind of supercapacitor compound electrics
Pole material and preparation method thereof, the method are former using the graphene of N doping as matrix in the preparation process of electrode material
Position polymerization Schiff base transition metal conducting polymer.N doping is carried out to graphene by addition urea, urea is in high temperature
Effect is lower to discharge ammonia, can nitrogenize to graphene, the high temperature heat radiation of microwave chemical reactor enhances the equal of reaction
One property has fake capacitance and excellent electrical conductance by the graphene of N doping, when the pure graphene of capacity ratio is as substrate
High 10%-20%, and nitrogen-doped graphene electrode material still keeps stablizing after multiple charge and discharge.But the patent is mixed with nitrogen
Miscellaneous graphene improves the circulation time of super capacitor as matrix in-situ polymerization Schiff base transition metal conducting polymer
Several and specific capacity, it is limited for the promotion of high energy ratio.
3, number of patent application CN201710729784.5, entitled " the fire-retardant organic electrolyte of supercapacitor,
Preparation method and supercapacitor ", applicant are as follows: the application for a patent for invention of good hundred million Electronic Science and Technology Co., Ltd. in Wujiang, this is specially
Benefit discloses the electrical property and the good organic electrolyte of anti-flammability, preparation method and super capacitor of a kind of supercapacitor
Device.The technical solution adopted by the present invention are as follows: a kind of fire-retardant organic electrolyte of supercapacitor, by electrolytic salt, non-aqueous
Organic solvent and function additive composition, above-mentioned electrolytic salt are tetraethylammonium tetrafluoroborate and double ethanedioic acid boric acid tetramethyls
Ammonium, the non-aqueous organic solvent are propene carbonate, dimethyl carbonate, methyl ethyl carbonate and gamma-butyrolacton, the function
Auxiliary agent is fluoro phosphonitrile compound.The patent proposes fire-retardant side primarily directed to organic electrolyte super capacitor fever problem on fire
Case, with increase high energy than unrelated.
By carefully analyzing to these above-mentioned patents, although these patents are directed to super capacitor and its production side
Method, it was also proposed that some improved technology schemes, but by carefully analyzing, these super capacitors proposed and preparation method thereof are all
Effectively solves the problems, such as lithium-ion capacitance high energy than manufacture in the presence of it is some, still need further to be studied.
Summary of the invention
Aiming at the problem that it is an object of the invention in the presence of existing lithium-ion capacitance high energy is than manufacture, one kind is proposed
The lithium can be substantially improved than manufacturing method than manufacturing method, this kind of lithium-ion capacitor high energy in new lithium-ion capacitor high energy
Ionistor high-energy density, and have the characteristics that preferable machinability and low cost.
In order to reach this purpose, the present invention provides a kind of high specific energy lithium-ion capacitor, including battery core and shell, electricity
Core encapsulates inside the shell, there is electrolyte between battery core and shell；The battery core is by anode pole piece, diaphragm and cathode pole piece
It is formed after combination lamination；It is characterized by: the appearance in anode pole piece is compounded with active carbon and conducting polymer and Gao Fu lithium material
Expect the heterogeneous composite material anode sizing agent layer being mixed to form, makes full use of active carbon to cooperate with energy storage mechanism with conducting polymer, mention
Rise the specific capacity of positive electrode.
Further, the heterogeneous composite material anode sizing agent layer is by active carbon and conducting polymer and Gao Fu lithium material
Material is mixed to form heterogeneous composite material, is mixed together with conductive agent and binder, and add mixture into N-Methyl pyrrolidone
In, anode sizing agent is formed after vacuum high-speed stirred, then anode sizing agent is coated on the upper of positive pole aluminium foil piece, through drying, roll,
Anode pole piece is obtained after punching.
Further, the heterogeneous composite material anode sizing agent layer mixes system by the component of following mass percent meter
At: the active carbon of 42-72%, the conducting polymer of 20-50%, the conductive agent of 4-10%, the dispersing agent of 1-2% and the bonding of 3-10%
Agent.
Further, the active carbon specific surface area is greater than 1500 m2/g, and surface functional group content is in 0.5 meq/g
Hereinafter, tenor is less than 100 ppm, average pore size is in 1.7 nm or so, and partial size is at 8-10 μm.
Further, the conducting polymer is one of polypyrrole, polyaniline, polythiophene and its derivative or several
Kind, further preferred conducting polymer is polyaniline.
Further, the rich lithium material of the height is Li6CoO4、Li5FeO4、Li6MnO4One or more of, further
It is preferred that the high rich lithium material is Li6CoO4。
Further, the anode pole piece tow sides are coated with active charcoal and conducting polymer and Gao Fu lithium
Material is mixed to form heterogeneous composite material.
Further, the conductive agent is one in carbon black, graphite, carbon fiber, carbon nanotube, carbon fiber and graphene
Kind is a variety of.Preferably, the conductive agent is conductive carbon black, one-dimensional carbon nanotube, the two-dimensional graphene of zero dimension, structure
Build " point-line-face " three-phase composite conductive agent.
Further, the active carbon and conducting polymer and Gao Fu lithium material are mixed to form heterogeneous composite material use
Situ aggregation method preparation, can prepare finely dispersed active carbon and conducting polymer composite material in this way, sufficiently send out
Wave the characteristic of the two.
Further, it is logical that the active carbon, which is mixed to form heterogeneous composite material with conducting polymer and Gao Fu lithium material,
The active carbon suspension for preparing high dispersive first is crossed, aniline monomer is then added, while certain catalyst is added, in Gao Bibiao
Polymerization reaction occurs for the surface in situ of area activated carbon, realizes highly disperse active charcoal/conducting polymer composite material preparation side
Method is prepared；The active carbon and conducting polymer and Gao Fu lithium material heterogeneous composite material crushes skill using high-speed flow
Art preparation, realizes the uniform mixing of the composite material of different densities.
Further, the anode pole piece is with a thickness of 120-250 μm, and cathode pole piece is with a thickness of 50-90 μm.
Further, the high specific energy lithium-ion capacitor making step is as follows.
(1) N- crassitude is added in the rich lithium composite material of active carbon/conducting polymer/height, conductive agent and binder
Anode sizing agent is formed after vacuum high-speed stirred in ketone, anode sizing agent is uniformly coated on the tow sides of positive pole aluminium foil piece,
Through drying, roll, be punched after obtain anode pole piece；
(2) Carbon anode, conductive agent and binder are added in deionized water, form negative electrode slurry after vacuum high-speed stirred, will bears
Pole slurry is uniformly coated on the tow sides of cathode aluminium foil, through drying, roll, be punched after obtain cathode pole piece；
(3) battery core is obtained after anode pole piece, diaphragm and cathode pole piece combination lamination, battery core is placed in shell, electrolyte is injected,
Lithium-ion capacitor is obtained after encapsulation.
The present invention has the advantages that
The present invention passes through the selection of conducting polymer in optimization anode composite material, to obtain the lithium-ion electric of high-energy density
Container, do so have the advantages that it is following some:
1, ion storage energy being adsorbed/is desorbed using high-specific surface area, conducting polymer and Li+ occur doping and generate fake capacitance,
High richness lithium material carries out pre- embedding lithium to cathode carbon as lithium source, using initial charge, makes lithium-ion electric using common collector
Container, the specific capacity of the positive electrode of Lai Tigao lithium-ion capacitor；
2, active carbon is adsorption/desorption ion physical energy storage by high-specific surface area, and specific surface area is low to be unfavorable for energy
The promotion of density；Secondly, the aperture of active carbon is too small, and ion is difficult into organic electrolyte, the surface of active carbon is caused
Utilization rate is low, causes capacity relatively low, and it is relatively low that aperture will cause greatly very much active carbon specific surface area；Again, the surface function of active carbon
Group and tenor influence leakage current, the cycle life etc. of lithium-ion capacitor.Comprehensively consider, the active carbon physical parameter control
System is in above range；
3, increase lithium-ion capacitor system lithium ion content using richness lithium material high in positive combination electrode, supplement Carbon anode is first
The irreversible embedding lithium of secondary charge and discharge electrical loss realizes the preparation of inexpensive lithium-ion capacitor.
Detailed description of the invention
Fig. 1 is the structural diagram of the present invention.
Specific embodiment
It is next combined with specific embodiments below that the present invention is further explained.
Embodiment one
A kind of high specific energy lithium-ion capacitor, including positive pole aluminium foil piece 1, cathode aluminium foil 2, electrolyte 4 and diaphragm 3, positive aluminium
Paillon 1, cathode aluminium foil 2 combine to form battery core with diaphragm 3, are encapsulated in shell 5；The positive pole aluminium foil piece tow sides apply
It is furnished with positive electrode 6, the cathode aluminium foil tow sides have been coated with negative electrode material, and the positive electrode 6 is by following quality
The component of percentages is mixed: the active carbon of 42-72%, the conducting polymer of 20-50%, the conductive agent of 4-10%, 1-2%
The binder of dispersing agent and 3-10%；The negative electrode material is mixed by the component of following mass percent meter: the stone of 42-72%
Black alkene, the conducting polymer of 20-50%, the conductive agent of 4-10% and 4-10% binder.
Preferably, active carbon (AC-1) 69kg, polyaniline 20kg, conductive agent (Super P) 5kg, binder (SBR) are chosen
5kg and dispersing agent (CMC) 1kg.
When production, using deionized water as solvent, the true of 10L successively is added in dispersing agent, conductive agent, active carbon and binder
In outage speed grout mixer, mixture is carried out by vacuum high-speed stirred 4-6h with the speed of 3500rpm, is gone during this period by addition
Ionized water adjusts the viscosity of slurry, and the solid content for controlling slurry obtains anode sizing agent between 20-40%.Anode sizing agent is used
The mode of continuous coating machine is uniformly coated on the tow sides of positive pole aluminium foil piece (etched foil), coating process pole piece thickness control
260 μm are made as, drying temperature is 110 DEG C, application rate 5m/min, by the electrode after drying using continuous roller in 40t
Pressure, 5m/min compaction speed under the conditions of rolled, roll the control of rear thickness of electrode at 240 μm, and by above-mentioned electrode
It is punched into the anode pole piece of (50-60) mm* (70-80) mm.
Graphene 70kg, polyaniline 20kg are weighed again, and conductive agent (Super P) 5kg, binder (PVDF) 5kg are successively pressed
Sequence is added in N-Methyl pyrrolidone solution, and the additional amount by controlling solvent maintains the viscosity of slurry and solid content respectively
In 5000cps and 60%, 4-6h is stirred under conditions of vacuum, 3500rpm by vacuum high-speed mixer, obtains negative electrode slurry.
By negative electrode slurry using it is two-sided be continuously coated with by the way of be coated on cathode aluminium foil (etched foil), coating thickness, application rate
And drying temperature is respectively maintained at 90 μm, 5m/min and 130 DEG C.Cathode can be obtained after above-mentioned electrode is rolled, is punched
Pole piece, wherein rolling and punching condition prepares identical with anode, cathode pole piece thickness control is at 65 μm or so.
Above-mentioned positive and negative electrode pole piece, PP/PE/PP type laminated diaphragm (production of Celgard company, the U.S.) is folded using " arcuate "
Sheet mode builds up the battery core of 75*55*6.2mm, wherein the tab of 10 positive plates pools together aluminium pole ears in ultrasonic welding, 10
The tab of a cathode pole piece pools together aluminium pole ears in ultrasonic welding, and tab spacing is 15mm.
It is dried in vacuo by battery core at 65 DEG C, under conditions of -0.1MPa for 24 hours, puts it into aluminium after battery core is cooled to room temperature
In plastic film outer packaging bag, three sides including tab one side are subjected to hot-seal, are and then electrolysed on one side from remaining
The injection of liquid (LiPF6 solution, solvent are the mixture of EC, DEC and DMC that volume ratio is 1:1:1), the injection rate of electrolyte are
Inlet is finally carried out a heat-seal by 40g.
By capacitor, (Wuhan morning China produces, model BT2013C) carries out 2.7V/50mA on Land charge-discharge test instrument
(CC/CC) chemical conversion test, obtains entire super capacitor after the capacitor is then carried out secondary encapsulation, cutting edge Shape correction
Device.Subsequent high rate performance test current density is respectively 100,200,500,1000,2000,5000mA/g.The capacitor exists
With the energy density of 38.6Wh/kg under the conditions of 100mA/g.2000 capacity retention ratios are recycled under 5000mA/g current density is
95%。
Embodiment 2
This embodiment differs from embodiment 1 in that:
Positive electrode formula: active carbon 65kg, polypyrrole 20kg, conductive agent (Super P) 4kg, binder (PVDF+PTFE
According to the quality of 1:1 than mixture) 10kg and dispersing agent (CMC, viscosity are less than 300cps) 1kg.
Negative electrode material formula: graphene 60kg, polypyrrole 20kg, conductive agent (Super P) 10kg, binder (PVDF+
PTFE is according to the quality of 1:1 than mixture) 10kg.
The other the same as in Example 1.
The capacitor has the energy density of 44.6Wh/kg under the conditions of 100mA/g, recycles under 5000mA/g current density
2000 capacity retention ratios are 86%.
Embodiment 3
This embodiment differs from embodiment 1 in that:
Positive electrode formula: active carbon 45kg, polythiophene 20kg, polyaniline 27kg, conductive agent (Super P) 4kg, binder
(SBR) 3kg and dispersing agent (CMC) 1kg.
Negative electrode material formula: graphene 45kg, polythiophene 20kg, polyaniline 27kg, conductive agent (Super P) 4kg, bonding
Agent (PVDF) 4kg.
The other the same as in Example 1.
The capacitor is under the conditions of 100mA/g with the energy density of 55.3Wh/kg.It is recycled under 5000mA/g current density
2000 capacity retention ratios are 81%.
Embodiment 4
This embodiment differs from embodiment 1 in that:
Positive electrode formula: active carbon 55kg, polyaniline 20kg, polypyrrole 10kg, conductive agent (Super P) 4kg, binder
(PVDF+PTFE is according to the quality of 1:1 than mixture) 10kg and dispersing agent (CMC, viscosity are less than 300cps) 1kg.
Negative electrode material formula: graphene 50kg, polyaniline 20kg, polypyrrole 10kg, conductive agent (Super P) 10kg glue
Tie agent (PVDF+PTFE is according to the quality of 1:1 than mixture) 10kg.
The other the same as in Example 1.
The capacitor has the energy density of 51.5Wh/kg under the conditions of 100mA/g, recycles under 5000mA/g current density
2000 capacity retention ratios are 95%.
One aspect of the present invention is by verifying the compound of different carbon material and conducting polymer；On the other hand, pass through comparison
The mixing ratio of different carbon materials and conducting polymer obtains the super electricity with highest energy density and optimum cycle stability
Container positive and negative anodes composite material and its optimum proportioning.
Through the foregoing embodiment it can be seen that the present invention relates to a kind of high specific energy lithium-ion capacitor, including battery core and outer
Shell, battery core encapsulate inside the shell, there is electrolyte between battery core and shell；The battery core is by anode pole piece, diaphragm and to bear
It is formed after pole pole piece combination lamination；It is characterized by: the appearance in anode pole piece is compounded with active carbon and conducting polymer and height
The heterogeneous composite material anode sizing agent layer that rich lithium material is mixed to form, makes full use of active carbon to cooperate with energy storage machine with conducting polymer
System, promotes the specific capacity of positive electrode.
The heterogeneous composite material anode sizing agent layer is that active carbon is mixed shape with conducting polymer and Gao Fu lithium material
It at heterogeneous composite material, is mixed together, and is added mixture into N-Methyl pyrrolidone with conductive agent and binder, through vacuum
Form anode sizing agent after high-speed stirred, then anode sizing agent be coated on the upper of positive pole aluminium foil piece, through drying, roll, be punched after obtain
Obtain anode pole piece.
The heterogeneous composite material anode sizing agent layer is mixed by the component of following mass percent meter: 42-72%'s
Active carbon, the conducting polymer of 20-50%, the conductive agent of 4-10%, the dispersing agent of 1-2% and 3-10% binder.
The active carbon specific surface area is greater than 1500 m2/ g(preferably, 1500-1800 m2/ g), surface functional group contains
Amount in 0.5 meq/g (preferably, 0.2-0.5 meq/g) hereinafter, tenor preferably less than 100 ppm(, 60-80
Ppm), average pore size is in 1.5-1.8 nm or so, and partial size is at 8-10 μm.
The conducting polymer is one or more of polypyrrole, polyaniline, polythiophene and its derivative, further
It is preferred that conducting polymer is polyaniline.
The rich lithium material of the height is Li6CoO4、Li5FeO4、Li6MnO4One or more of, it is further preferably described
High richness lithium material is Li6CoO4。
The anode pole piece tow sides are coated with active charcoal and mix with conducting polymer and Gao Fu lithium material
Form heterogeneous composite material.
The conductive agent is one of carbon black, graphite, carbon fiber, carbon nanotube, carbon fiber and graphene or more
Kind.Preferably, the conductive agent is conductive carbon black, one-dimensional carbon nanotube, the two-dimensional graphene of zero dimension, " point-is constructed
Line-face " three-phase composite conductive agent.
The active carbon and conducting polymer and Gao Fu lithium material are mixed to form heterogeneous composite material using in-situ polymerization
Both method preparation, can prepare finely dispersed active carbon and conducting polymer composite material in this way, give full play to
Characteristic.
It is by making first that the active carbon, which is mixed to form heterogeneous composite material with conducting polymer and Gao Fu lithium material,
The active carbon suspension of standby high dispersive, is then added aniline monomer, while certain catalyst is added, in high-specific surface area activity
Polymerization reaction occurs for the surface in situ of charcoal, realize the preparation of highly disperse active charcoal/conducting polymer composite material preparation method and
At；The active carbon and conducting polymer and Gao Fu lithium material heterogeneous composite material is prepared using high-speed flow crushing technology,
Realize the uniform mixing of the composite material of different densities.
The anode pole piece is with a thickness of 120-250 μm, and cathode pole piece is with a thickness of 50-90 μm.
The present invention has the advantages that
The present invention passes through the selection of conducting polymer in optimization anode composite material, to obtain the lithium-ion electric of high-energy density
Container, do so have the advantages that it is following some:
1, ion storage energy being adsorbed/is desorbed using high-specific surface area, conducting polymer and Li+ occur doping and generate fake capacitance,
High richness lithium material carries out pre- embedding lithium to cathode carbon as lithium source, using initial charge, makes lithium-ion electric using common collector
Container, the specific capacity of the positive electrode of Lai Tigao lithium-ion capacitor；
2, active carbon is adsorption/desorption ion physical energy storage by high-specific surface area, and specific surface area is low to be unfavorable for energy
The promotion of density；Secondly, the aperture of active carbon is too small, and ion is difficult into organic electrolyte, the surface of active carbon is caused
Utilization rate is low, causes capacity relatively low, and it is relatively low that aperture will cause greatly very much active carbon specific surface area；Again, the surface function of active carbon
Group and tenor influence leakage current, the cycle life etc. of lithium-ion capacitor.Comprehensively consider, the active carbon physical parameter control
System is in above range；
3, increase lithium-ion capacitor system lithium ion content using richness lithium material high in positive combination electrode, supplement Carbon anode is first
The irreversible embedding lithium of secondary charge and discharge electrical loss realizes the preparation of inexpensive lithium-ion capacitor.
Claims (10)
1. a kind of high specific energy lithium-ion capacitor, including battery core and shell, battery core is encapsulated inside the shell, between battery core and shell
There is electrolyte；The battery core is formed after combining lamination by anode pole piece, diaphragm and cathode pole piece；It is characterized by: just
The appearance of pole pole piece is compounded with the heterogeneous composite material anode that active carbon and conducting polymer and Gao Fu lithium material are mixed to form and starches
The bed of material makes full use of active carbon to cooperate with energy storage mechanism with conducting polymer, promotes the specific capacity of positive electrode.
2. high specific energy lithium-ion capacitor as described in claim 1, it is characterised in that: the heterogeneous composite material anode slurry
The bed of material is that active carbon and conducting polymer and Gao Fu lithium material are mixed to form heterogeneous composite material, with conductive agent and binder one
Mixing is played, and is added mixture into N-Methyl pyrrolidone, forms anode sizing agent after vacuum high-speed stirred, then anode is starched
Material be coated on the upper of positive pole aluminium foil piece, through drying, roll, be punched after obtain anode pole piece.
3. high specific energy lithium-ion capacitor as claimed in claim 2, it is characterised in that: the heterogeneous composite material anode slurry
The bed of material is mixed by the component of following mass percent meter: the active carbon of 42-72%, the conducting polymer of 20-50%, 4-10%
Conductive agent, the dispersing agent of 1-2% and the binder of 3-10%.
4. high specific energy lithium-ion capacitor as claimed in claim 3, it is characterised in that: the active carbon specific surface area is greater than
1500 m2/g, surface functional group content is in 0.5 meq/g hereinafter, tenor is less than 100 ppm, and average pore size is in 1.7 nm
Left and right, partial size is at 8-10 μm.
5. high specific energy lithium-ion capacitor as claimed in claim 3, is characterized in that: the conducting polymer be polypyrrole,
One or more of polyaniline, polythiophene and its derivative, further preferred conducting polymer are polyaniline.
6. high specific energy lithium-ion capacitor as claimed in claim 3, it is characterised in that: the described rich lithium material of height is
Li6CoO4、Li5FeO4、Li6MnO4One or more of, the further preferably described high rich lithium material is Li6CoO4。
7. high specific energy lithium-ion capacitor as claimed in claim 2, it is characterised in that: the anode pole piece positive and negative two
Face is coated with active charcoal and conducting polymer and Gao Fu lithium material is mixed to form heterogeneous composite material.
8. high specific energy lithium-ion capacitor as claimed in claim 2, it is characterised in that: the conductive agent be carbon black, graphite,
One or more of carbon fiber, carbon nanotube, carbon fiber and graphene.Preferably, the conductive agent is leading for zero dimension
Black, the one-dimensional carbon nanotube of electrical carbon, two-dimensional graphene construct " point-line-face " three-phase composite conductive agent.
9. high specific energy lithium-ion capacitor as claimed in claim 2, it is characterised in that: the active carbon and conducting polymer
Heterogeneous composite material is mixed to form with high rich lithium material to prepare using situ aggregation method, can prepare be uniformly dispersed in this way
Active carbon and conducting polymer composite material, the characteristic both given full play to.
10. high specific energy lithium-ion capacitor as claimed in claim 7, it is characterised in that: the active carbon and conducting polymer
It is the active carbon suspension by preparing high dispersive first that object and Gao Fu lithium material, which are mixed to form heterogeneous composite material, is then added
Aniline monomer, while certain catalyst is added, polymerization reaction occurs in the surface in situ of active carbon with high specific surface area, realizes high
Dispersion active carbon/conducting polymer composite material preparation method is prepared；The active carbon and conducting polymer and height
Rich lithium material heterogeneous composite material is prepared using high-speed flow crushing technology, realizes the uniform mixed of the composite material of different densities
It closes.
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