CN104008893B - The preparation method of lithium ion hybrid capacitors and lithium ion hybrid capacitors thereof - Google Patents

The preparation method of lithium ion hybrid capacitors and lithium ion hybrid capacitors thereof Download PDF

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CN104008893B
CN104008893B CN201410146713.9A CN201410146713A CN104008893B CN 104008893 B CN104008893 B CN 104008893B CN 201410146713 A CN201410146713 A CN 201410146713A CN 104008893 B CN104008893 B CN 104008893B
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lithium
aluminum
electrode
composite membrane
plastic composite
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CN104008893A (en
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孙现众
马衍伟
张熊
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Institute of Electrical Engineering of CAS
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Institute of Electrical Engineering of CAS
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    • Y02E60/13Energy storage using capacitors

Abstract

The preparation method of a kind of lithium ion hybrid capacitors, comprises the following steps: a) according to order lamination or the winding of positive pole/barrier film/negative pole, electrode plates and barrier film are made battery core;B) battery core being put in aluminum-plastic composite membrane housing, by top margin and the first side hot-seal of aluminum-plastic composite membrane housing, the positive pole of battery core and the lug of negative pole stretch out aluminum-plastic composite membrane housing from top margin;C), during metal lithium electrode puts into aluminum-plastic composite membrane housing, metal lithium electrode and battery core placed adjacent also separate with barrier film, and the lug of metal lithium electrode stretches out aluminum-plastic composite membrane housing from second side;D) excessive electrolyte, the then second side of hot-seal aluminum-plastic composite membrane housing are injected to aluminum-plastic composite membrane housing;E) in constant current mode, with negative pole as working electrode, with metal lithium electrode for electrode, anticathode carries out pre-embedding lithium;F) take out metal lithium electrode, pour out unnecessary electrolyte, the second side of Vacuum Heat sealing aluminum-plastic composite membrane housing, obtain lithium ion hybrid capacitors.

Description

The preparation method of lithium ion hybrid capacitors and lithium ion hybrid capacitors thereof
Technical field
The present invention relates to the preparation method of a kind of lithium ion hybrid capacitors, and adopt the lithium ion mixing prepared in this way Type capacitor.
Background technology
Lithium ion hybrid capacitors is the storage of a kind of model electrochemical between lithium ion battery and double electric layers supercapacitor Energy device, the high power of its existing double electric layers supercapacitor and long-life feature, energy density is more super than electric double layer again simultaneously Capacitor is greatly improved.Being structurally characterized in that positive pole can use and comprising cell positive material and capacitance material of this device, negative The carbon back battery material of the most pre-embedding lithium, the core of preparation technology is the pre-embedding lithium technique of negative pole.Currently mainly have following several pre- Embedding lithium technique: (1) is first assembled into battery by negative pole and metal lithium sheet, carries out pre-embedding lithium, then by the way of outside discharge and recharge Battery is taken apart, takes out negative pole and be assembled into lithium ion mixing electric capacity again with positive pole secondary, see " Electrochimica Acta " 2014 Year volume 125 the 22-28 page.This method needs to disassemble in an inert atmosphere and assembled battery again, is not easy to large-scale production. (2) making negative pole the most directly contact with metal lithium sheet, under the driving of potential difference, lithium enters electrolyte from metal lithium sheet Being then embedded in negative pole, see that " Journal of Materials Chemistry A " deliver for 2014 is entitled: A Fast and The paper of Efficient Pre-doping Approach to High Energy Density Lithium-Ion Hybrid Capacitors.This Kind of method there is also with the same problem of method (1), it is simply that is assembled into by the mode of lamination or winding after needing pre-embedding lithium again Battery core and device.(3) pre-in positive pole mix the material rich in lithium as lithium source, make this part lithium be embedded into by charging process In negative pole.Chinese patent application 200710098687.7 " a kind of pre-embedding lithium method of lithium ion super capacitor negative pole " discloses By 3~cobalt acid lithium, nickle cobalt lithium manganate, LiMn2O4 or the Li of 50%2.6Co0.4N etc. mix in pole piece preparation process in positive pole and make For lithium source, " Advanced Energy Materials " 2011 volume 1 the 1002-1006 page also reports employing Li2MoO3 Mix positive pole as lithium source.This method there is problems of the lithium source material that this part mixes after first embedding lithium the most no longer to be had Electrochemistry capacitance or limited capacity, thus reduce the energy density of device.(4) with containing 30~50% the running through of percent opening The aluminium foil in hole and containing 30~50% the Copper Foil of through hole of percent opening respectively as positive pole and the collector of negative pole, prepare electrode slice Rear lamination or be wound into battery core, using metal lithium electrode for lithium source as the 3rd electrode by charge discharge to the pre-embedding lithium of negative pole (seeing Chinese patent application 201310374169.9).And the preparation of the aluminium foil of through hole and Copper Foil need use chemical attack or The method of machining, can significantly improve process costs.
Summary of the invention
It is an object of the invention to provide a kind of more convenient, preparation method of lithium ion hybrid capacitors that process costs is lower.
In order to solve above-mentioned technical problem, the present invention by the following technical solutions:
The preparation method of a kind of lithium ion hybrid capacitors, comprises the following steps:
A) electrode plates and barrier film are made battery core according to order lamination or the winding of anode pole piece/barrier film/cathode pole piece;
B) battery core that step a) makes is put in aluminum-plastic composite membrane housing, top margin and the first side to aluminum-plastic composite membrane housing Hot-seal, stretches out the positive pole of battery core and the lug of negative pole from the top margin of aluminum-plastic composite membrane housing;
C) being put into by metal lithium electrode in aluminum-plastic composite membrane housing, metal lithium electrode and battery core placed adjacent also separate with barrier film; The lug of metal lithium electrode is stretched out from aluminum-plastic composite membrane housing second side;
D) excessive electrolyte is injected to aluminum-plastic composite membrane housing, then by the second side hot-seal of aluminum-plastic composite membrane housing;
E) with negative pole as working electrode, with metal lithium electrode for electrode, in the way of constant current discharge, anticathode is with constant current Discharge mode carries out pre-embedding lithium;
F) cut apart with a knife or scissors aluminum-plastic composite membrane housing, take out metal lithium electrode;Pour out unnecessary electrolyte, by aluminum-plastic composite membrane housing Second side Vacuum Heat sealing, obtains lithium ion hybrid capacitors.
Described anode pole piece includes positive electrode active materials and the aluminium foil without through hole, and positive electrode active materials is coated on aluminium foil;Institute The cathode pole piece stated includes negative active core-shell material and the Copper Foil without through hole, and negative active core-shell material is coated on Copper Foil.
Described positive electrode active materials is made up of the material with carbon element of a kind of anode material for lithium-ion batteries and a kind of high-specific surface area, presses 100 mass parts calculate, and described lithium ion anode material is 0~90 mass parts, and high-specific surface area material with carbon element is 10~100 matter Amount part, described anode material for lithium-ion batteries is nickle cobalt lithium manganate or nickel cobalt lithium aluminate or LiFePO4 or cobalt acid lithium, described High-specific surface area material with carbon element is activated carbon or the Carbon fibe of activity or porous, electrically conductive white carbon black or Graphene;Described negative active core-shell material For at least one in Delanium or carbonaceous mesophase spherules or hard carbon or soft carbon.For positive pole, active material is activated carbon Time show as electric double layer characteristic;Along with the ratio shared by the increase electric capacity of anode material for lithium-ion batteries content in positive electrode active materials Reducing, and the ratio shared by battery capacity inserting embedding lithium increases, even occupies an leading position, the present invention is referred to as lithium this kind of device Ar ion mixing type capacitor.
The electric current density of described pre-embedding lithium is 5~50mA/g, described electric current density quality based on negative active core-shell material.In advance After embedding lithium, the state-of-charge of negative pole is 50~80%.The present invention by add excess electrolyte and the pre-embedding lithium of low discharging current, from And in the case of using without the collector of through hole, it is also possible to reach to make the effect of the abundant embedding lithium of negative active core-shell material.Described The pre-embedding lithium that discharges refers to make lithium ion enter electrolyte from metal lithium electrode by the way of constant current discharge, then diffuses to negative pole And embed in negative active core-shell material, under the effect of electric field, lithium ion is in negative pole internal diffusion and redistribution.Metal lithium electrode conduct The lithium source of pre-embedding lithium, can play again the effect of lithium reference electrode simultaneously.
The invention allows for a kind of lithium ion hybrid capacitors prepared by said method, described lithium ion mixed type electricity The running voltage of container is not higher than 4.0V, and the current potential of positive pole is not higher than the current potential phase of 4.2V, negative pole relative to lithium reference electrode 0.1V is not less than for lithium reference electrode.Because positive electrode active materials contains high-specific surface area material with carbon element, current potential is relative to lithium reference Electrode can cause the decomposition of electrolyte and the reduction of cycle life higher than 4.2V, and the current potential of negative pole is low relative to lithium reference electrode When 0.1V, the precipitation of lithium metal and the growth of Li dendrite can be caused during the embedding lithium of high power, cause potential safety hazard.
Accompanying drawing explanation
The structural representation of Fig. 1 lithium ion hybrid capacitors, in figure: 1 battery core, 11 positive pole ears, 12 negative lug, 2 Aluminum-plastic composite membrane housing, 21 finalization area, first side, 22 top margin finalization area, 23 finalization area, second side, 24 vacuum seal mouth regions, 3 metal lithium electrodes, 31 metal lithium electrode lugs;
The charging and discharging curve of initial 4 weeks of Fig. 2 embodiment 1 lithium ion hybrid capacitors;
Fig. 3 embodiment 1 and the curve of double curvature of comparative example.
Detailed description of the invention
The preparation method of positive pole and negative pole is: active material, binding agent and conductive agent are uniformly mixed into slurry according to a certain percentage After, with coater to without on the collector of through hole, after being dried through roll-in, cut and obtain the pole piece of electrode.
Described binding agent select Kynoar (PVDF), politef (PTFE), sodium carboxymethyl cellulose (CMC), The happy LA series aqueous binders etc. produced of butadiene-styrene rubber (SBR) and Chengdu mattress ground.Described conductive agent selected from conductive black, Electrically conductive graphite or CNT.The collector of positive pole is the aluminium foil without through hole, and the collector of negative pole is the Copper Foil without through hole. Positive electrode active materials is made up of the one of a kind of of anode material for lithium-ion batteries He the material with carbon element of high-specific surface area, by 100 mass Part calculates, and lithium ion anode material is 0~90 mass parts, and high-specific surface area material with carbon element is 10~100 mass parts, lithium-ion electric Pond positive electrode is nickle cobalt lithium manganate (LiNixCoyMnzO2) or nickel cobalt lithium aluminate (LiNixCoyAlzO2) or LiFePO4 (LiFePO4) or cobalt acid lithium (LiCoO2), high-specific surface area material with carbon element be activated carbon or the Carbon fibe of activity or porous, electrically conductive white carbon black or Graphene.Negative active core-shell material is at least one in Delanium or carbonaceous mesophase spherules or hard carbon or soft carbon.
As it is shown in figure 1, the preparation method of lithium ion hybrid capacitors is as follows:
1, according to the order of positive pole/barrier film/negative pole, the pole piece of electrode and barrier film lamination or winding are made battery core 1, by battery core 1 Put in aluminum-plastic composite membrane housing 2;
2, the hot-seal at 180 DEG C in the top margin finalization area 22 of aluminum-plastic composite membrane housing 2 and finalization area, first side 21, will just Pole lug 11 and negative lug 12 stretch out aluminum-plastic composite membrane housing 2 from top margin finalization area 22;
3, in the glove box of full argon or in hothouse, metal lithium electrode 3 is put in aluminum-plastic composite membrane housing 2, gold Belong to lithium electrode 3 and battery core 1 placed adjacent and separate with barrier film, by the lug 31 of metal lithium electrode from finalization area, second side 23 Stretch out aluminum-plastic composite membrane housing 2;
4, excessive electrolyte is injected, then in the finalization area, second side of aluminum-plastic composite membrane housing 2 toward aluminum-plastic composite membrane housing 2 23 hot-seals;
5, with negative pole as working electrode, with metal lithium electrode 3 for electrode, survey with the battery of Wuhan Lan electricity company CT2001A Examination instrument anticathode in the way of constant current discharge carries out the operation of pre-embedding lithium.The electric current density of pre-embedding lithium is 5~50mA/g, described Electric current density quality based on negative active core-shell material, after pre-embedding lithium, the state-of-charge of negative pole is 50~80%;
6, last, cut off aluminum-plastic composite membrane housing, take out metal lithium electrode 3 and lug 31, pour out unnecessary electrolyte, Vacuum seal mouth region 24 sealing of Vacuum Heat under vacuum of aluminum-plastic composite membrane housing 2, removes unnecessary aluminum-plastic composite membrane and obtains Lithium ion hybrid capacitors.
The running voltage of lithium ion hybrid capacitors using preparation method of the present invention to prepare is not higher than 4.0V, and the current potential of positive pole Current potential relative to lithium reference electrode not higher than 4.2V, negative pole is not less than 0.1V relative to lithium reference electrode.
Embodiment 1
The active material of negative pole is artificial graphite C AG-3MT, and binding agent is sodium carboxymethyl cellulose and butadiene-styrene rubber, conductive agent For conductive black Super C45, by Delanium: conductive black: sodium carboxymethyl cellulose: the matter of butadiene-styrene rubber=90:5:2:3 Amount makes slurry than mix homogeneously, is applied to without on 12 microns of thick Copper Foils of through hole, dry after through roll-in, cut and obtain The pole piece of negative pole.The surface density of pole coating layer one side is 39.3g/m2
The active material of positive pole is nickle cobalt lithium manganate LiNi0.5Co0.2Mn0.3O2, high-specific surface area material with carbon element is activated carbon YP50F, Binding agent is Kynoar, and conductive agent is conductive black Super C45 and electrically conductive graphite KS-6, by activated carbon: nickel cobalt mangaic acid Lithium: conductive black: electrically conductive graphite: the quality of Kynoar=60:20:10:2:8 makes slurry than mix homogeneously, is coated with Cloth on the thick aluminium foil of 20 microns without through hole, after being dried through roll-in, cut and obtain the pole piece of positive pole.Pole coating layer list The surface density in face is 33.1g/m2
It is prepared as battery core with the pole piece of above-mentioned positive pole and negative pole, battery core is put in aluminum-plastic composite membrane housing, seal plastic-aluminum combined The top margin of putamina body and first side.Metal lithium electrode is put into again, between metal lithium electrode and battery core in aluminum-plastic composite membrane housing Having barrier film to separate, inject excessive electrolyte in glove box, electrolyte is the LiPF of 1mol/L6Electrolyte, solvent is carbonic acid The mixed solvent of vinyl acetate, dimethyl carbonate and diethyl carbonate 1:1:1 in mass ratio.Then aluminum-plastic composite membrane housing is sealed Second side.The electric current density of pre-embedding lithium is 5mA/g, described electric current density quality based on negative active core-shell material.Pre-embedding lithium The state-of-charge of rear negative pole is 50%.Finally, cut off aluminum-plastic composite membrane housing, take out metal lithium electrode, pour out unnecessary electrolysis Liquid, then vacuum seal, obtain lithium ion hybrid capacitors.With the cell tester of Wuhan Lan electricity company CT2001A with Lithium ion hybrid capacitors is tested by the mode of constant current charge-discharge, the most all uses identical means of testing.This enforcement The operating voltage range of example is 2.5~4.0V.The potential change scope of positive pole and negative pole is using metal lithium electrode as reference electrode Record, the most identical.
Comparative example:
Use positive pole same as in Example 1 and negative electricity pole piece to prepare battery core, then battery core put in aluminum-plastic composite membrane housing, The top margin of heat-sealing aluminum-plastic composite membrane housing and first side, inject appropriate electrolyte in glove box, and electrolyte is 1mol/L's LiPF6Electrolyte, solvent is the mixed solvent of ethylene carbonate, dimethyl carbonate and diethyl carbonate 1:1:1 in mass ratio.It After, the second side of vacuum seal aluminum-plastic composite membrane housing, obtain lithium ion hybrid capacitors.To lithium ion mixed type electric capacity Device is tested in 2.5~4.0V voltage ranges.
Fig. 2 show the charging and discharging curve of embodiment 1 lithium ion hybrid capacitors, and wherein curve 1 is that positive pole is joined relative to lithium The ratio potential change curve of electrode, potential change scope is 2.89~4.19V, and curve 2 is the electricity of lithium ion hybrid capacitors Buckling line, voltage range is 2.5~4.0V.Curve 3 is the negative pole potential change curve relative to lithium reference electrode, and current potential becomes Change scope is 0.18~0.39V.
Fig. 3 show the high rate performance curve of embodiment 1 and comparative example, and abscissa is multiplying power (unit is C), and vertical coordinate is Specific capacity based on positive electrode active materials quality (unit is mAh/g), curve 1 is the high rate performance curve of embodiment 1, bent Line 2 is the high rate performance curve of comparative example.It can be seen that both there is good high rate performance.But after pre-embedding lithium technique, Discharge and recharge under the electric current density of 25mA/g, specific capacity is brought up to 34.8mAh/g by 25.4mAh/g, improves 37%.
Embodiment 2~6
The active material of the negative pole of embodiment 2~6 is hard carbon LN-0010, and binding agent is sodium carboxymethyl cellulose and butadiene-styrene rubber, Conductive agent is conductive black Super C45, by hard carbon: conductive black: sodium carboxymethyl cellulose: butadiene-styrene rubber=90:5:2:3's Quality makes slurry than mix homogeneously, is applied to without on 12 microns of thick Copper Foils of through hole, after being dried through roll-in, cut Pole piece to negative pole.The surface density of pole coating layer one side is 47.0g/m2
The active material of positive pole is nickle cobalt lithium manganate LiNi0.5Co0.2Mn0.3O2, high-specific surface area material with carbon element is activated carbon YP50F, Binding agent is Kynoar, and conductive agent is conductive black Super C45 and electrically conductive graphite KS-6, by positive electrode active materials: lead Electricity white carbon black: electrically conductive graphite: the quality of Kynoar=80:10:2:8 makes slurry than mix homogeneously, is applied to without running through On 20 microns of thick aluminium foils in hole, after being dried through roll-in, cut and obtain the pole piece of positive pole.The matter of the component of positive electrode active materials Amount is shown in Table 1 than the surface density with coating one side.
After preparing battery core with the pole piece of above-mentioned positive pole and negative pole, battery core is put in aluminum-plastic composite membrane housing, seal plastic-aluminum combined The top margin of putamina body and first side, and in aluminum-plastic composite membrane housing, put into metal lithium electrode, between metal lithium electrode and battery core Barrier film is had to separate.Injecting excessive electrolyte in glove box, electrolyte is the LiPF of 1mol/L6Electrolyte, solvent is carbonic acid The mixed solvent of vinyl acetate, dimethyl carbonate and diethyl carbonate 1:1:1 in mass ratio.Then aluminum-plastic composite membrane housing is sealed Second side.The electric current density of pre-embedding lithium is 6mA/g, and described electric current density is quality based on negative active core-shell material.Pre-embedding After lithium, the state-of-charge of negative pole is 60%.Take out metal lithium electrode, pour out unnecessary electrolyte after, vacuum seal, obtain lithium from Sub-hybrid capacitors.Lithium ion hybrid capacitors carries out charge-discharge test, based on positive pole in 2.0~4.0V voltage ranges The specific capacity of active material and positive pole are shown in Table 1 with negative pole relative to the current potential of lithium reference electrode.
Table 1
As can be seen from Table 1, along with in positive electrode active materials, the content increase specific capacity of nickle cobalt lithium manganate dramatically increases, but by Capacity in the negative pole of this group capacitor is fixing, so the current potential lower limit of negative pole significantly reduces, and the current potential of embodiment 4~6 Be down to below 0.1V in interval, and cycle life significantly reduces.Embodiment 2 and 10000 weeks capacity of embodiment 3 charge and discharge cycles are protected Holdup is more than 90%, and embodiment 4~6 1000 weeks capacity of charge and discharge cycles have been decayed more than 50%.
Embodiment 7
The active material of the negative pole of the present embodiment is made up of by 1:1 mass ratio soft carbon and MCMB, and binding agent is carboxymethyl Sodium cellulosate and butadiene-styrene rubber, conductive agent is conductive black Super P Li, by active material: sodium carboxymethyl cellulose: butylbenzene Rubber: the quality of conductive black=90:5:2:3 makes slurry than mix homogeneously, is applied to 12 microns of thick Copper Foils without through hole On, after being dried through roll-in, cut and obtain the pole piece of negative pole.The surface density of pole coating layer one side is 30.0g/m2
The active material of positive pole is pressed by the Graphene of the Carbon fibe after nickel cobalt lithium aluminate, activation, porous, electrically conductive white carbon black and few layer The mass ratio composition of 1:1:1:1, binding agent is Kynoar, by active material: the mass ratio of Kynoar=90:10 mixes Close and uniformly make slurry, be applied to without on 20 microns of thick aluminium foils of through hole, dry after through roll-in, cut and obtain positive pole Pole piece.The surface density of pole coating layer one side is 25g/m2
After preparing battery core with the pole piece of above-mentioned positive pole and negative pole, put in aluminum-plastic composite membrane housing, seal aluminum-plastic composite membrane housing Top margin and first side, and put into metal lithium electrode, between metal lithium electrode and battery core, have barrier film to separate.Glove box is noted Entering excessive electrolyte, electrolyte is the LiPF of 1mol/L6Electrolyte, solvent is ethylene carbonate, dimethyl carbonate and carbonic acid The mixed solvent of diethylester 1:1:1 in mass ratio.Then the second side of aluminum-plastic composite membrane housing is sealed.The electric current of pre-embedding lithium is close Degree is 50mA/g, described electric current density quality based on negative active core-shell material.After pre-embedding lithium, the state-of-charge of negative pole is 80%. After cutting off aluminum-plastic composite membrane housing, taking out metal lithium electrode, pour out unnecessary electrolyte, vacuum seal, obtain lithium ion mixing Type capacitor.
Embodiment 8
The active material of the negative pole of the present embodiment is hard carbon LN-0010, and binding agent is sodium carboxymethyl cellulose and butadiene-styrene rubber, leads Electricity agent is conductive black Super P Li, by hard carbon: sodium carboxymethyl cellulose: butadiene-styrene rubber: the matter of conductive black=90:5:2:3 Amount makes slurry than mix homogeneously, is applied to without on 12 microns of thick Copper Foils of through hole, dry after through roll-in, cut and obtain The pole piece of negative pole.
The active material of positive pole is cobalt acid lithium, and high-specific surface area material with carbon element is activated carbon YP80F, and binding agent is Kynoar, Conductive agent is conductive black Super P Li and electrically conductive graphite KS-15, by activated carbon: cobalt acid lithium: conductive black: electrically conductive graphite: The quality of Kynoar=60:20:10:2:8 makes slurry than mix homogeneously, is applied to 20 microns of thickness without through hole Aluminium foil on, after being dried through roll-in, cut and obtain the pole piece of positive pole.
It is prepared as battery core with the pole piece of above-mentioned positive pole and negative pole, battery core is put in aluminum-plastic composite membrane housing, seal plastic-aluminum combined The top margin of putamina body and first side.Metal lithium electrode is put into again, between metal lithium electrode and battery core in aluminum-plastic composite membrane housing Having barrier film to separate, inject excessive electrolyte in glove box, electrolyte is the LiPF of 1mol/L6Electrolyte, solvent is carbonic acid The mixed solvent of vinyl acetate, Allyl carbonate 1:1 in mass ratio.Then the second side of aluminum-plastic composite membrane housing is sealed.Pre-embedding The electric current density of lithium is 10mA/g, described electric current density quality based on negative active core-shell material.After pre-embedding lithium, negative pole is charged State is 60%.Cut off aluminum-plastic composite membrane housing, take out metal lithium electrode, pour out unnecessary electrolyte, then vacuum seal, Obtain lithium ion hybrid capacitors.
Embodiment 9
The active material of the negative pole of the present embodiment is hard carbon LN-0001, and binding agent is sodium carboxymethyl cellulose and butadiene-styrene rubber, leads Electricity agent is conductive black Super P Li, by hard carbon: sodium carboxymethyl cellulose: butadiene-styrene rubber: the matter of conductive black=90:5:2:3 Amount makes slurry than mix homogeneously, is applied to without on 12 microns of thick Copper Foils of through hole, dry after through roll-in, cut and obtain The pole piece of negative pole.
The active material of positive pole is LiFePO4, and high-specific surface area material with carbon element is activated carbon YP80F, and binding agent is Kynoar, Conductive agent is conductive black Super P Li and electrically conductive graphite KS-15, by activated carbon: LiFePO4: conductive black: conduction stone Ink: the quality of Kynoar=60:20:10:2:8 makes slurry than mix homogeneously, is applied to without through hole 20 micro- On the aluminium foil that rice is thick, after being dried through roll-in, cut and obtain the pole piece of positive pole.
It is prepared as battery core with the pole piece of above-mentioned positive pole and negative pole, battery core is put in aluminum-plastic composite membrane housing, seal plastic-aluminum combined The top margin of putamina body and first side.Metal lithium electrode is put into again, between metal lithium electrode and battery core in aluminum-plastic composite membrane housing Having barrier film to separate, inject excessive electrolyte in glove box, electrolyte is the LiPF of 1mol/L6Electrolyte, solvent is carbonic acid The mixed solvent of vinyl acetate, dimethyl carbonate and diethyl carbonate 1:1:1 in mass ratio.Then aluminum-plastic composite membrane housing is sealed Second side.The electric current density of pre-embedding lithium is 10mA/g, and described electric current density is quality based on negative active core-shell material.In advance After embedding lithium, the state-of-charge of negative pole is 60%.Cut off aluminum-plastic composite membrane housing, take out metal lithium electrode, pour out unnecessary electrolyte, Then vacuum seal, obtains lithium ion hybrid capacitors.

Claims (4)

1. the preparation method of a lithium ion hybrid capacitors, it is characterised in that described preparation method comprises the following steps:
A) electrode plates and barrier film are made battery core (1) according to order lamination or the winding of anode pole piece/barrier film/cathode pole piece;
B) battery core (1) made by step a) is put in aluminum-plastic composite membrane housing (2), by aluminum-plastic composite membrane housing (2) Top margin and first side hot-seal, by the positive pole ear (11) of battery core (1) and negative lug (12) from plastic-aluminum combined putamina The top margin of body (2) stretches out;
C) metal lithium electrode (3) is put in aluminum-plastic composite membrane housing (2), metal lithium electrode (3) and battery core (1) phase Adjacent placement also separates with barrier film;The lug of metal lithium electrode (1) is stretched out from the second side of aluminum-plastic composite membrane housing (2);
D) excessive electrolyte is injected to aluminum-plastic composite membrane housing (2), then by the second side of aluminum-plastic composite membrane housing (2) Hot-seal;
E) with negative pole as working electrode, with metal lithium electrode for electrode, in the way of constant current discharge, anticathode carries out pre-embedding Lithium;
F) cut apart with a knife or scissors aluminum-plastic composite membrane housing (2), take out metal lithium electrode (3), pour out unnecessary electrolyte, by plastic-aluminum combined The second side Vacuum Heat sealing of putamina body (2), obtains lithium ion hybrid capacitors;
Described anode pole piece includes positive electrode active materials and the aluminium foil without through hole, and positive electrode active materials is coated on described aluminium foil On;Described cathode pole piece includes negative active core-shell material and the Copper Foil without through hole, and negative active core-shell material is coated on described Copper Foil On.
The preparation method of lithium ion hybrid capacitors the most according to claim 1, it is characterised in that described positive pole is lived Property material be made up of the material with carbon element of a kind of anode material for lithium-ion batteries and a kind of high-specific surface area, by 100 mass parts calculate, Described lithium ion anode material is 0~90 mass parts, and high-specific surface area material with carbon element is 10~100 mass parts;Described lithium from Sub-cell positive material is nickle cobalt lithium manganate or nickel cobalt lithium aluminate or LiFePO4 or cobalt acid lithium, described high-specific surface area material with carbon element For activated carbon or the Carbon fibe of activity or porous, electrically conductive white carbon black or Graphene;Described negative active core-shell material is Delanium or centre At least one in phase carbosphere or hard carbon or soft carbon.
The preparation method of lithium ion hybrid capacitors the most according to claim 1, it is characterised in that described pre-embedding lithium Electric current density be 5~50mA/g, described electric current density quality based on negative active core-shell material;After pre-embedding lithium, negative pole is charged State is 50~80%.
4. the lithium ion hybrid capacitors prepared according to the preparation method described in claim 1 or 2 or 3, it is characterised in that The running voltage of described lithium ion hybrid capacitors is not higher than 4.0V, and the current potential of positive pole is relative to lithium reference electrode not higher than 4.2V, the current potential of negative pole are not less than 0.1V relative to lithium reference electrode.
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