CN105551815B - A kind of lithium-ion capacitor and preparation method thereof - Google Patents
A kind of lithium-ion capacitor and preparation method thereof Download PDFInfo
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- CN105551815B CN105551815B CN201610072072.6A CN201610072072A CN105551815B CN 105551815 B CN105551815 B CN 105551815B CN 201610072072 A CN201610072072 A CN 201610072072A CN 105551815 B CN105551815 B CN 105551815B
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- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a kind of lithium-ion capacitor, including positive plate, negative plate, membrane and electrolyte between positive/negative plate.The cathode includes plus plate current-collecting body and the positive electrode being coated on plus plate current-collecting body, positive electrode is made of positive active material, binding agent, and wherein positive electrode active materials are made up of metal oxide and one or more in porous graphene, porous graphite alkynes or porous carbon fiber material blends In-situ reaction；The negative plate includes negative current collector and the negative material being coated on negative current collector, negative material is made of negative electrode active material, binding agent, and wherein negative active core-shell material is the one kind of surface after pore-creating, nitrogen treatment in the spherical natural graphite of in-situ growing carbon nano tube or nano metal nitride, graphitized intermediate-phase carbon microballoon, graphitization polyimides carbon microspheres；Above-mentioned lithium-ion capacitor has the advantages that operating voltage is high, power characteristic is good, energy density is high, safe to use.In addition, additionally provide a kind of lithium-ion capacitor preparation method.
Description
Technical field
The present invention relates to a kind of electrochemical energy storing device, more particularly to a kind of lithium-ion capacitor and preparation method thereof.
Background technology
The exacerbation increasingly of energy crisis and environmental problem, accelerates the fast development of New Energy Industry.Under existing situation
Green energy resource is performed to ultimate attainment environmentally friendly electrochemical energy storage technology for giving low-carbon energy-saving emission reduction to be paid more and more attention.
Recently, country proposes to establish nearly zero carbon emission engineering based on energy internet, and wherein core content just includes regenerative resource
Power generation, distributed energy storage technology etc., this proposes new and effective energy storage technology the requirement of higher, in addition, New energy electric vapour
Car, cold-starting power supply, high ferro/urban track traffic Brake energy recovery, marine ship platform, underwater hiding-machine power supply, UPS are not
The fields such as uninterruptible power are to high-energy-density, high power density electrochemical energy storing device it is also proposed that deep require.
At present, two kinds of most ripe electrochemical energy storage technologies are commercialized, one kind is lithium ion battery, and cathode is used containing lithium gold
Belong to oxide and be used as active material, anode using graphite as absorbent charcoal material, by positive and negative anodes Electrochemical lithiation storage energy,
Monomer energy density is up to 150 more than Wh/kg, but its power density is only 100 ~ 500 W/kg, and power-performance is poor, circulation
Service life only 1000 times, poor performance at low temperatures；Another is double electric layers supercapacitor, which uses active carbon with high specific surface area
For positive and negative anodes active material, energy is stored by physical absorption electric charge, therefore its power density is followed up to 5000 more than W/kg
The ring service life is up to more than 100000 times, it can be achieved that -50 DEG C of discharge and recharges of low temperature, but its energy density is only 2 ~ 5Wh/kg, energy of continuing a journey
Power is limited, it is impossible to is powered for a long time.Have the lithium-ion capacitor of both above-mentioned advantages, i.e. capacitor batteries concurrently, become people's research
Hot spot.
Patent 201110320933.5 discloses a kind of super capacitance cell, and the capacitor batteries positive active material is using work
The mixture of property charcoal, carbon aerogels, carbon nanotubes or pyrolytic carbon and anode material for lithium-ion batteries, and activated carbon, carbon aerogels
Although specific surface area is high, electric conductivity is still unsatisfactory, and carbon nanotubes belongs to one-dimensional electric material, and specific surface area is relatively
It is low, and pyrolytic carbon is all poor from specific surface area or electric conductivity, cannot improve power-performance by a relatively large margin, anode
Active material uses the mixture of silicon nanowires, carbon nanotube and graphene, and there are huge when for intercalation materials of li ions for silicon materials
Volumetric expansion blockage effect, be unfavorable for long-term cycle performance, the specific surface area of the graphene disclosed out is also only 200 ~ 600
m2/g.Patent 201010114612.5 discloses a kind of super capacitance cell, which is hard charcoal material
Material, but hard carbon material discharge voltage is big with volume change, and first charge-discharge efficiency is low, discharge voltage hysteresis is obvious, just
Pole active material uses Lithium-ion embeding compound and porous carbon material（Activated carbon, carbon cloth, carbon fiber, charcoal felt, carbon aerogels,
Carbon nanotubes）Mixture, there are the problem of with patent 201110320933.5 be the same.Patent 201510130056.3 is draped over one's shoulders
A kind of lithium super capacitance cell negative electrode is revealed, method is by lithium powder spreading to anode graphite or hard carbon material surface, then through roll-in
Obtain anode, the drawbacks of this method is that lithium powder spreading amount technique is harsh, the serious is the use of metallic state lithium, long-term
It is careless slightly to be easy to cause Li dendrite there is security risk in charge and discharge process, so as to wear out membrane, cause short circuit.In addition,
Two common issues existing for three patents of above-mentioned disclosure, one are constrained to negative active core-shell material structure, power-performance
It cannot obtain maximizing and play, the second is the extra additive that all employ non-material body carries out additional conductive, add
Anode and cathode slurry stirring technique difficulty.
The content of the invention
An object of the present invention seeks to provide a kind of lithium-ion capacitor.
Another object of the present invention seeks to provide a kind of preparation method of lithium-ion capacitor.
To achieve these goals, technical scheme is as follows：
A kind of lithium-ion capacitor, including positive plate, negative plate, membrane and electrolyte between positive/negative plate, its
It is characterized in that the cathode includes plus plate current-collecting body and the positive electrode being coated on plus plate current-collecting body, positive electrode is lived by cathode
Property material, binding agent form, wherein positive electrode active materials are by metal oxide and porous graphene, porous graphite alkynes or porous charcoal
One or more are made up of In-situ reaction in fibrous material mixture；The negative plate includes negative current collector and is coated on negative
Negative material on the collector of pole, negative material are made of negative electrode active material, binding agent, and wherein negative active core-shell material is surface
The spherical natural graphite of growth in situ carbon nanotube or nano metal nitride, graphitized intermediate-phase after pore-creating, nitrogen treatment
One kind in carbon microspheres, graphitization polyimides carbon microspheres.
A kind of lithium-ion capacitor, the one or more in metal oxide MxOy, M=Mn, Co, Ni, x are
1st, 2,3,4 or 5, y 1,2,3,4 or 5.
A kind of lithium-ion capacitor, metal oxide and porous graphene, porous graphite alkynes or porous carbon fiber
The mass ratio of material is 1 ~ 30: 70~99.
A kind of lithium-ion capacitor, the ratio surface of porous graphene, porous graphite alkynes or porous carbon fiber material
Product is 500 ~ 3000 m2/g。
A kind of lithium-ion capacitor, surface is after pore-creating, nitrogen treatment, among spherical natural graphite, graphitization
Nitrogen mass content is 1 ~ 9% in phase carbon microspheres, graphitization polyimides carbon microspheres.
A kind of lithium-ion capacitor, surface after pore-creating, nitrogen treatment, surface in situ growth carbon nanotube or
Nano metal nitride is with spherical natural graphite, graphitized intermediate-phase carbon microballoon, graphitization polyimides carbon microspheres mass ratio
0.5~5 : 95~99.5。
A kind of lithium-ion capacitor, diaphragm material is polyimides, polysulfonamides, polysulfones ether, melamine, poly-
One kind in fragrant acid amides, polyphenylene sulfide, thickness are 5 ~ 30 μm.
A kind of lithium-ion capacitor, electrolyte is lithium hexafluoro phosphate in electrolyte（LiPF6）, lithium perchlorate
（LiClO4）, hexafluoroarsenate lithium（LiAsF6）, LiBF4 (LiBF4), di-oxalate lithium borate（LiBOB）, difluoro oxalate boron
Sour lithium（LiDFOB）, two（Trimethyl fluoride sulfonyl）Imine lithium（LiTFSI）, double fluorine sulfimide lithiums（LiFSI）, trifluoromethanesulfonic acid
Lithium（LiCF3SO3）, hexafluoro-antimonic acid lithium（LiSbF6）, three（Pentafluoroethyl group）Three lithium fluophosphates（LiFAP）In one or more.
A kind of lithium-ion capacitor, solvent is dimethyl carbonate in electrolyte（DMC）, diethyl carbonate（DEC）、
Methyl ethyl carbonate（EMC）, propene carbonate（PC）, ethylene carbonate（EC）, methyl propyl carbonate（MPC）, gamma-butyrolacton（GBL）、
Fluorinated ethylene carbonate（FEC）, ethyl acetate（EA）, tri-methyl ethyl acetate（TMEA）, methyl butyrate（MB）, methyl propionate
（MP）, ethyl propionate（EP）, propyl propionate（PP）, propyl acetate（PA）, methyl acetate（MA）, ethyl acetoacetate（EAA）, three
One or more in methyl acetic acid methyl esters.
In the present invention, cathode power-performance is improved using porous graphene, porous graphite alkynes or porous carbon fiber material, than
Surface area is up to 1000 ~ 3000 m2/ g, and excellent conductivity, are not required to additional conductive agent addition；Negative electrode active material is with spherical day
Right graphite, graphitized intermediate-phase carbon microballoon, graphitization polyimides carbon microspheres are base material, after the pore-creating of surface, improve ion
After diffusion velocity, then via nitride processing so that nitrogen element content increase in material, so as to improve material Reversible lithium insertion capacity, more
Further using surface in situ growth carbon nanotube or nano metal nitride technology, improve material conductivity, from without
Additional conductive agent addition beyond material body, reduces the complexity of cathode size mixed process, and technique simplifies.The present invention
In also using polyimides, polysulfonamides material be used as diaphragm material, be greatly improved lithium-ion capacitor device use pacify
Quan Xing；This, which is gone back in electrolyte, with the addition of high pressure resistant electrolyte, so as to improve voltage use scope, equally play improve lithium from
Sub-capacitor security and service life.
A kind of preparation scheme of lithium-ion capacitor provided by the invention is as follows：
A kind of lithium-ion capacitor preparation method, includes the following steps：
（1）Positive active material is mixed with binding agent in blender, 60 ~ 300min is stirred, during which by adding N-
Methyl pyrrolidone adjusts slurry viscosity to suitable.Negative electrode active material is added in binding agent, stirs 60 ~ 300min, phase
Between by adding water adjust slurry viscosity to suitable；
（2）Conductive black is uniformly mixed with binding agent, is respectively coated in the porous aluminum foil current collector of cathode, anode Porous Cu
Paper tinsel collector, after coating, 5 ~ 15 μm of thickness, the porous aluminum foil current collector of cathode and anode porous copper foil collector after conductive agent drying
Percent opening is 20 ~ 60%, and thickness is 10 ~ 30 μm；
（3）By step（1）The anode sizing agent, cathode size are respectively coated on step（2）Described is filled with conductive agent
Porous aluminum foil current collector, on porous copper foil collector, dry, compacting, cut-parts, spot welding lug；
（4）Lithium auxiliary electrode is by being compacted lithium and being filled in copper mesh, titanium net or stainless (steel) wire collector, pass through lug
Extraction obtains, and lithium is sheet or powdered.
（5）According to lithium auxiliary electrode/membrane/anode/membrane/cathode/membrane/anode/membrane/cathode/membrane/negative
Pole ... order, is assembled according to order to obtain battery core using lamination or winding process, battery core is placed in laminated aluminum film, noted
Liquid, dipping, after discharge and recharge chemical conversion, secondary fluid injection, vacuum-pumping and sealing, obtains lithium-ion capacitor device.
A kind of lithium-ion capacitor preparation method, negative or positive electrode active material are with binding agent mass ratio：
80~95 : 5~10。
A kind of lithium-ion capacitor preparation method, binding agent is polytetrafluoroethylene (PTFE)（PTFE）, Kynoar
（PVDF）, hydroxypropyl methyl cellulose（HPMC）, sodium carboxymethylcellulose（CMC）And butadiene-styrene rubber（SBR）In one kind or more
Kind.
In above-mentioned preparation method, positive and negative anodes are not required to plus any additional conductive agent, reduce anode and cathode slurry stirring technique and answer
Miscellaneous degree, and positive and negative anodes porous current collector is used, be conducive to ion and quickly transmit, and in collector applying conductive agent, have
Beneficial to internal resistance is reduced, the power-performance of lithium-ion capacitor is improved.
The present invention passes through above-mentioned optimization positive and negative pole material structure, electrode material component, bath composition, further optimization
Lithium-ion capacitor preparation process, is conducive to the performance of lithium-ion capacitor power-performance, while improves energy density, security
And charge discharge life, it can be widely applied to renewable energy power generation, distributed energy storage technology, New-energy electric vehicle, low-temperature starting
Dynamic power supply, high ferro/urban track traffic Brake energy recovery, marine ship platform, underwater hiding-machine power supply, UPS uninterrupted power sources
Deng field.
Embodiment
Lithium-ion capacitor and preparation method are described further below by specific embodiment.
Embodiment 1
Cathode：（1）Graphene is placed in potassium hydroxide solution, by chemical activation method, preparing specific surface area is
2500m2The porous graphene material of/g；（2）Obtained porous graphene is dissolved in n,N-Dimethylformamide, then by certain
Ratio adds manganese acetylacetonate and nickel acetylacetonate, and above-mentioned mixed liquor is placed in polytetrafluoroethyllining lining stainless steel high pressure after stirring
In kettle, 200 DEG C of insulation 20h, manganese oxide nickel/porous graphene compound is obtained after cooling washing, wherein manganese oxide nickel with it is porous
The mass ratio of graphene is 20:80；（3）It is 90 in mass ratio by this mixture and binding agent PVDF:10 ratios are stirred, and are added
Enter NMP and adjust slurry viscosity；（4）Slurry is coated on the porous aluminium foil containing 6 μ m-thick conductive agents, porous aluminum foil thickness is 20 μ
M, percent opening is 30%；（5）Above-mentioned pole piece, in 120 DEG C of vacuum drying 24h, obtains positive plate through drying, roll-in, cut-parts.
Anode：（1）Using Hummer methods, by graphitized intermediate-phase carbon microballoon（Particle diameter ~ 10 μm）After aoxidizing pore-creating, ammonia is placed in
High-temperature ammonolysis processing is carried out in the atmosphere furnace of gas shielded, nitrogen mass content is 2%, grows charcoal on surface using CVD method afterwards
Nanotube, is 3 by controlling growth time to control the mass ratio of carbon nanotube and graphitized intermediate-phase carbon microballoon:97；（2）Will
（1）Obtained material is with binding agent CMC, SBR according to mass ratio 93:2.5:4.5 are stirred, and add suitable quantity of water adjusting slurry and glue
Degree；（3）Slurry is coated on the porous copper foil containing 6 μ m-thick conductive agents, porous copper foil thickness is 10 μm, percent opening 35%；
（4）Above-mentioned pole piece, in 120 DEG C of vacuum drying 24h, obtains negative plate through drying, roll-in, cut-parts.
Lithium auxiliary electrode：The metal lithium sheet that thickness is 100 μm is compacted on stainless (steel) wire, and welds upper nickel strap lug.
According to the order of lithium auxiliary electrode/membrane/anode/membrane/cathode/membrane/anode, form and roll up according to lamination process
Core, is placed in plastic-aluminum housing and is placed in laminated aluminum film, and membrane uses polyimide film, and thickness is 15 μm.
By LiPF6It is dissolved in LiBOB electrolyte according to certain mass ratio in EC and DMC solvents, film for additive is carbonic acid
Vinylene（VC）With high pressure additives for overcharge protection agent biphenyl（BP）, this electrolyte is injected in core, first will just after dipping
Pole, by external circuits, carries out embedding lithium so that cathode metal oxide is converted into containing lithium metal oxide with lithium piece；Afterwards will be negative
Pole, by external circuits, carries out embedding lithium, lithium-inserting amount can accommodate the 80% of peak capacity for anode with lithium piece；Secondary fluid injection, vacuumizes
Sealing, obtains lithium-ion capacitor device.
Through charge-discharge test, gained lithium-ion capacitor energy density is 75 Wh/kg, maximum power density 7000W/
Kg, continuous 20000 discharge and recharges, capacity retention ratio 95%.
Embodiment 2
Cathode：（1）Graphite alkene is placed in potassium hydroxide solution, by chemical activation method, preparing specific surface area is
2000m2The porous graphite alkynes material of/g；（2）Obtained porous graphite alkynes is dissolved in n,N-Dimethylformamide, adds second
Above-mentioned mixed liquor, is placed in polytetrafluoroethyllining lining stainless steel autoclave by acyl acetone manganese and acetylacetone cobalt after stirring, 220 DEG C
24h is kept the temperature, the matter of manganese oxide cobalt/porous graphite alkynes compound, wherein manganese oxide cobalt and porous graphite alkynes is obtained after cooling washing
Amount is than being 15:85；（3）It is 90 in mass ratio by this compound and binding agent PVDF:10 ratios are stirred, and are added NMP and are adjusted
Slurry viscosity；（4）Slurry is coated on the porous aluminium foil containing 6 μ m-thick conductive agents, porous aluminum foil thickness is 20 μm, percent opening is
30%；（5）Above-mentioned pole piece, in 120 DEG C of vacuum drying 24h, obtains positive plate through drying, roll-in, cut-parts.
Anode：（1）Using Hummer methods, by spherical natural graphite（Particle diameter ~ 15 μm）After aoxidizing pore-creating, with tetrabutyl titanate
Mix in ethanol, add distilled water and be hydrolyzed, nitric acid is added dropwise and adjusts suitable pH as 2.0 to control hydrolysis rate, after dry,
Progress high-temperature ammonolysis processing in the atmosphere furnace of protection of ammonia is placed in, obtains to surface and is coated with the spherical natural of nano metal titanium nitride
Graphite composite material, nitrogen mass content are 3%；（2）Will（1）Obtained material is with binding agent CMC, SBR according to mass ratio
93:2.5:4.5 are stirred, and add suitable quantity of water and adjust slurry viscosity；（3）Slurry is coated on containing the porous of 6 μ m-thick conductive agents
On copper foil, porous copper foil thickness is 10 μm, percent opening 35%；（4）Above-mentioned pole piece is through drying, roll-in, cut-parts, in 120 DEG C of vacuum
24h is dried, obtains negative plate.
Lithium auxiliary electrode：The metal lithium sheet that thickness is 100 μm is compacted on stainless (steel) wire, and welds upper nickel strap lug.
According to the order of lithium auxiliary electrode/membrane/anode/membrane/cathode/membrane/anode, form and roll up according to lamination process
Core, is placed in plastic-aluminum housing, and every using film Polysulfonamide, thickness is 15 μm.
By LiPF6It is dissolved in LiDFOB electrolyte according to certain mass ratio in EC and DMC solvents, additive is fluoro carbonic acid
Vinyl acetate（FEC）With high pressure additives for overcharge protection agent biphenyl（BP）, this electrolyte is injected in core, first will just after dipping
Pole, by external circuits, carries out embedding lithium so that cathode metal oxide is converted into containing lithium metal oxide with lithium piece；Afterwards will be negative
Pole, by external circuits, carries out embedding lithium, lithium-inserting amount can accommodate the 80% of peak capacity for anode with lithium piece；After discharge and recharge chemical conversion, two
Secondary fluid injection, vacuum-pumping and sealing, obtains lithium-ion capacitor device.
Through charge-discharge test, gained lithium-ion capacitor energy density is 70 Wh/kg, maximum power density 6500W/
Kg, continuous 20000 discharge and recharges, capacity retention ratio 93%.
Embodiment 3
Cathode：（1）Carbon fibe is placed in potassium hydroxide solution, by chemical activation method, preparing specific surface area is
2200m2The porous carbon fiber material of/g；（2）Obtained porous carbon fiber is dissolved in n,N-Dimethylformamide, adds second
Above-mentioned mixed liquor, is placed in polytetrafluoroethyllining lining stainless steel autoclave by acyl acetone cobalt after stirring, 200 DEG C of insulation 24h, cooling
Cobalt oxide/porous graphite alkynes compound is obtained after washing, the wherein mass ratio of cobalt oxide and porous graphene is 20:80；（3）Will
This compound is 90 in mass ratio with binding agent PVDF:10 ratios are stirred, and are added NMP and are adjusted slurry viscosity；（3）By slurry
It is coated on the porous aluminium foil containing 6 μ m-thick conductive agents, porous aluminum foil thickness is 20 μm, percent opening 30%；（4）Above-mentioned pole piece warp
Drying, roll-in, cut-parts, in 120 DEG C of vacuum drying 24h, obtain positive plate.
Anode：（1）Using Hummer methods, by graphitization polyimides carbon microspheres（Particle diameter ~ 5 μm）After aoxidizing pore-creating, it is placed in
High-temperature ammonolysis processing is carried out in the atmosphere furnace of protection of ammonia, nitrogen mass content is 2%, is grown afterwards using CVD method on surface
Carbon nanotube, is 5 by controlling growth time to control the mass ratio of carbon nanotube and graphitized intermediate-phase carbon microballoon:95；（2）
Will（1）Obtained material is with binding agent CMC, SBR according to mass ratio 93:2.5:4.5 are stirred, and add suitable quantity of water and adjust slurry
Viscosity；（3）Slurry is coated on the porous copper foil containing 6 μ m-thick conductive agents, porous copper foil thickness is 10 μm, percent opening 35%；
（4）Above-mentioned pole piece, in 120 DEG C of vacuum drying 24h, obtains negative plate through drying, roll-in, cut-parts.
Using lamination process, cathode, membrane, anode lamination assembling are placed in laminated aluminum film, membrane into core successively
Using polyimide film, thickness is 15 μm；
By LiPF6It is dissolved in LiBOB electrolyte according to certain mass ratio in EC and DMC solvents, film for additive is carbonic acid
Vinylene（VC）With high pressure additives for overcharge protection agent biphenyl（BP）, this electrolyte is injected in core, after dipping, first will
Cathode, by external circuits, carries out embedding lithium so that cathode metal oxide is converted into containing lithium metal oxide with lithium piece；Afterwards will
Anode, by external circuits, carries out embedding lithium, lithium-inserting amount can accommodate the 80% of peak capacity for anode with lithium piece；After discharge and recharge chemical conversion,
Secondary fluid injection, vacuum-pumping and sealing, obtains lithium-ion capacitor device.
Through charge-discharge test, gained lithium-ion capacitor energy density is 68 Wh/kg, maximum power density 7200W/
Kg, continuous 20000 discharge and recharges, capacity retention ratio 93%.
Embodiment 4
Change the raw material of positive electrode active materials in embodiment 1 into nickel acetylacetonate, finally obtain nickel oxide/porous graphene
Combination electrode material, the oxide after embedding lithium in cathode are changed into nickel oxide containing lithium metal, and membrane is changed to polysulfones ether, remaining and reality
It is identical to apply example 1, through charge-discharge test, gained lithium-ion capacitor energy density is 50 Wh/kg, and maximum power density is
7500W/kg, continuous 20000 discharge and recharges, capacity retention ratio 95%.
Embodiment 5
Change the raw material of positive electrode active materials in embodiment 2 into manganese acetylacetonate, finally obtain manganese oxide/porous graphite alkynes
Combination electrode material, the oxide after embedding lithium in cathode are changed into manganese oxide containing lithium metal, and membrane is changed to melamine, remaining with
Embodiment 2 is identical, and through charge-discharge test, gained lithium-ion capacitor energy density is 55 Wh/kg, and maximum power density is
6000W/kg, continuous 20000 discharge and recharges, capacity retention ratio are more than 92%.
Embodiment described above only represents the several embodiments in the present invention, its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (9)
1. a kind of lithium-ion capacitor, including positive plate, negative plate, membrane and electrolyte between positive/negative plate, it is special
Sign is that the positive plate includes plus plate current-collecting body and the positive electrode being coated on plus plate current-collecting body, and positive electrode is lived by cathode
Property material, binding agent form, wherein positive electrode active materials are by metal oxide and porous graphene, porous graphite alkynes or porous charcoal
One or more are made up of In-situ reaction in fibrous material mixture；The negative plate includes negative current collector and is coated on negative
Negative material on the collector of pole, negative material are made of negative electrode active material, binding agent, and wherein negative active core-shell material is spherical
Native graphite, graphitized intermediate-phase carbon microballoon or graphitization polyimides carbon microspheres surface are after pore-creating is handled, then nitrogen treatment,
The last composite material that growth in situ carbon nanotube or nano metal nitride obtain again.
2. a kind of lithium-ion capacitor according to claim 1, it is characterised in that the metal oxide is MxOy, M
One or more in=Mn, Co, Ni, x 1,2,3,4 or 5, y 1,2,3,4 or 5.
A kind of 3. lithium-ion capacitor according to claim 1, it is characterised in that the metal oxide and porous stone
The mass ratio of black alkene, porous graphite alkynes or porous carbon fiber material is 1 ~ 30: 70~99.
4. a kind of lithium-ion capacitor according to claim 1, it is characterised in that the porous graphene, porous graphite
The specific surface area of alkynes or porous carbon fiber material is 500 ~ 3000 m2/g。
5. a kind of lithium-ion capacitor according to claim 1, it is characterised in that surface is after pore-creating and nitrogen treatment, ball
Nitrogen mass content is 1 ~ 9% in shape native graphite, graphitized intermediate-phase carbon microballoon, graphitization polyimides carbon microspheres.
6. a kind of lithium-ion capacitor according to claim 1, it is characterised in that spherical natural graphite, graphitized intermediate-phase
Carbon microspheres or graphitization polyimides carbon microspheres surface after pore-creating, then the quality of the obtained material of nitrogen treatment with spherical
The carbon nanotubes or nanometer of native graphite, graphitized intermediate-phase carbon microballoon or the growth of graphitization polyimides carbon microspheres surface in situ
The mass ratio of metal nitride is：95~99.5:0.5~5.
A kind of 7. lithium-ion capacitor according to claim 1, it is characterised in that the diaphragm material for polyimides,
Polysulfonamides, one kind in polysulfones ether, melamine, Nomex, polyphenylene sulfide, thickness are 5 ~ 30 μm.
8. a kind of lithium-ion capacitor according to claim 1, it is characterised in that electrolyte is six in the electrolyte
Lithium fluophosphate（LiPF6）, lithium perchlorate（LiClO4）, hexafluoroarsenate lithium（LiAsF6）, LiBF4 (LiBF4), double oxalic acid
Lithium borate（LiBOB）, difluorine oxalic acid boracic acid lithium（LiDFOB）, two（Trimethyl fluoride sulfonyl）Imine lithium（LiTFSI）, double fluorine sulphonyl
Imine lithium（LiFSI）, trifluoromethanesulfonic acid lithium（LiCF3SO3）, hexafluoro-antimonic acid lithium（LiSbF6）, three（Pentafluoroethyl group）Three fluorophosphoric acid
Lithium（LiFAP）In one or more.
9. a kind of lithium-ion capacitor according to claim 1, it is characterised in that solvent is carbonic acid in the electrolyte
Dimethyl ester（DMC）, diethyl carbonate（DEC）, methyl ethyl carbonate（EMC）, propene carbonate（PC）, ethylene carbonate（EC）, carbon
Sour first propyl ester（MPC）, gamma-butyrolacton（GBL）, fluorinated ethylene carbonate（FEC）, ethyl acetate（EA）, tri-methyl ethyl acetate
（TMEA）, methyl butyrate（MB）, methyl propionate（MP）, ethyl propionate（EP）, propyl propionate（PP）, propyl acetate（PA）, acetic acid
Methyl esters（MA）, ethyl acetoacetate（EAA）, one or more in methyl trimethylacetate.
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| JP6587579B2 (en) * | 2016-05-30 | 2019-10-09 | 太陽誘電株式会社 | Lithium ion capacitor |
| CN108305992B (en) * | 2017-01-12 | 2020-05-12 | 中国科学院化学研究所 | Carbon-coated lithium ion battery electrode material and preparation method thereof |
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