CN108428564A - A kind of preparation method of lithium-ion capacitor negative plate - Google Patents
A kind of preparation method of lithium-ion capacitor negative plate Download PDFInfo
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- CN108428564A CN108428564A CN201710077223.1A CN201710077223A CN108428564A CN 108428564 A CN108428564 A CN 108428564A CN 201710077223 A CN201710077223 A CN 201710077223A CN 108428564 A CN108428564 A CN 108428564A
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- lithium
- ion capacitor
- negative plate
- slmp
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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
- H01G11/84—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
-
- 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]
-
- 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
-
- 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
The invention discloses a kind of preparation methods of lithium-ion capacitor negative plate, including：1) negative electrode active material, SLMP, conductive agent, binder are fully mediated in a solvent, obtains ooze shape crude product；2) gained ooze shape crude product substep hot calender in step 1) is then dried in vacuo thick film and finish rolling, obtains the dry electrode film containing SLMP at the thick film of low solvent content；3) the dry electrode film heat in step 2) is compound in and is covered on carbon copper foil to get lithium-ion capacitor negative plate.Technical solution using the present invention can effectively solve the disadvantage that low existing lithium-ion capacitor negative plate bad adhesion, compacted density, the embedding lithium depth of product and lack of homogeneity.Lithium-ion capacitor monomer will be obtained after gained lithium-ion capacitor negative plate and EDLC positive plates, diaphragm, electrolyte and shell jointly assembling, monomer has the characteristics that volume specific volume is high, internal resistance is small and has extended cycle life after chemical conversion.
Description
Technical field
The present invention relates to a kind of energy storage electronic device more particularly to a kind of lithium-ion capacitor cathode piece preparation methods.
Technical background
With the development of science and technology, has many advantages, such as the lithium-ion electric that energy density is high, reliability is high and processability is good
Pond is more and more favored, and is widely used in all kinds of portable electronic devices.Traditional lithium ion battery due to internal resistance compared with
Greatly, the more low reason of power density so that its application is limited.Meanwhile electrochemical capacitor in double electrode layer (EDLC) is although there is length
Cycle life, wide temperature range, high power density, but that there is also such as capacity is low, operating voltage is low, energy density is low, puts certainly
Electric difference etc. also greatly limits the applicability of electrochemical capacitor in double electrode layer.It is different from ultracapacitor, lithium ion battery,
It is good etc. all that lithium-ion capacitor has had both long circulation life, high power density, high-energy density, high power capacity, high voltage, self discharge
More advantages are a kind of Asymmetric Supercapacitors that anode is different with cathode Mechanism of electrochemical behaviors of anhydrous, thus have wide development
Foreground.Lithium-ion capacitor is a kind of asymmetric capacitor that positive electrode and negative electrode charge-discharge principle is different, is adopted in structure design
With double layer capacitor positive electrode and the combined method of cathode material of lithium ion battery.Wherein, in negative material
In pre- embedded lithium ion can significantly reduce the current potential of lithium-ion capacitor cathode, improve the work electricity of lithium-ion capacitor monomer
Pressure, to make the energy density of lithium-ion capacitor greatly improve.
There are two types of the common methods of the pre- embedding lithium of lithium-ion capacitor negative material：Lithium foil pastes method and introduces " lithium electrode " method.
Wherein, it refers to that addition lithium piece or lithium foil are in direct contact with lithium-ion capacitor cathode at cathode that lithium foil, which pastes method, when product is noted
After entering electrolyte, the lithium ion in lithium piece or lithium foil dissolves rapidly into electrolyte, while the lithium ion in electrolyte enters
Pre- embedding lithium is realized in lithium-ion capacitor negative material.The technique that method carries out pre- embedding lithium to lithium-ion capacitor is pasted with lithium foil to have
There is following problem：First, since lithium piece or lithium foil to be in direct contact, embedding lithium rate and embedding lithium depth will after injecting electrolyte
Be unable to control so that the pre- embedding lithium of lithium-ion capacitor cathode is insufficient, embedding lithium it is insufficient will cause product cycle performance, times
Rate performance is poor；Second, due to introducing the extremely active lithium piece of chemical property or lithium foil as lithium source, so being put at cathode
It must be carried out in the anhydrous and oxygen-free environment for having inert gas shielding when setting lithium source, and positive and negative anodes collector is both needed to use to have and pass through
The copper foil or aluminium foil for wearing structure, cause industrial production cost higher.It refers to drawing in lithium-ion capacitor to be introduced into " lithium electrode " method
Enter the lithium piece or lithium alloy as third pole, is separated with diaphragm between third pole and cathode；After product injects electrolyte, pass through
Third pole exit is drawn into terminal shortcircuit with cathode or lithium-ion capacitor negative material is realized in a manner of constant-current discharge pre- embedding
Lithium.With introducing " lithium electrode " although method to lithium-ion capacitor carry out pre- embedding lithium can improve the pre- embedding lithium of negative material depth and
Even property, but this method takes longer, production cost higher, it is clear that be unfavorable for industrialized production.
Currently, being realized using stabilizing metallic lithium powder (SLMP) preparation prelithiation cathode and being melted into EDLC anodes
The pre- embedding lithium of negative material have embedding lithium uniformly, good product consistency, pre- embedding lithium time is short, lithium of predetermined amount carries control by cathode
The advantages that being formed with effect.In the patent of invention that Authorization Notice No. is 103021675 B of CN, inventor is successively by SLMP, binder
It is mixed into slurry with solvent and on spraying or sputter to the cathode coating containing active material, conductive agent and binder, passes through
Lithium-ion capacitor cathode is prepared after drying and roll-in；By activated carbon, conductive agent Super P, caking property polytetrafluoroethylene (PTFE)
(PTFE) it is configured to slurry and is coated on aluminium foil, lithium-ion capacitor anode is prepared after drying and roll-in；By this lithium
Ionistor anode is melted into the cathode containing prelithiation coating in 3.3V, preferably realizes the pre- embedding lithium of negative material.
But be coated with since negative electrode active material and SLMP are configured to slurry respectively, prepared electrode adhesion is poor, compacted density
Low, so that the negative electrode volume specific volume of lithium-ion capacitor is small, cyclical stability is poor, and when lithium-ion capacitor is fully melted into
Afterwards, the SLMP in prelithiation coating is fully dissolved into electrolyte, and can remain one layer in lithium-ion capacitor negative terminal surface glues
Agent is tied, causes the lithium-ion capacitor internal resistance after chemical conversion bigger than normal.
Invention content
The purpose of the present invention is for the low disadvantage of existing lithium-ion capacitor negative plate bad adhesion, compacted density, carry
For a kind of preparation method of lithium-ion capacitor negative plate, include the following steps：
1) negative electrode active material, SLMP, conductive agent, binder are fully mediated in a solvent, obtains crude product；
2) gained crude product substep hot calender in step 1) is then dried in vacuo thick film simultaneously at the thick film of low solvent content
Finish rolling obtains the dry electrode film containing SLMP；
3) the dry electrode film heat in step 2) is compound in and is covered on carbon copper foil to get lithium-ion capacitor negative plate.
In some embodiments, the preparation method of the lithium-ion capacitor negative plate more specifically includes：
1) by after lithium-ion capacitor negative electrode active material, SLMP and the dry-mixed 30min of conductive agent, solvent and bonding is added
Agent is fully mediated；
2) products obtained therefrom in step 1) is obtained solvent content 10~20 times with hot calender in 50~120 DEG C of hot calenders is
The thick film of 5~30wt%, after thick film is then dried in vacuo 12h at 150 DEG C finish rolling obtain the dry electrode containing SLMP to 30 μ m-thicks
Film；
3) by the dry electrode film of gained in step 2) by thermal composite machine heat be compound in 15 μ m-thicks cover on carbon copper foil to get to
Lithium-ion capacitor negative plate.
In some embodiments, the negative electrode active material, selected from natural flake graphite, artificial graphite, expanded graphite,
One kind or combinations thereof in hard carbon, carbonaceous mesophase spherules, polyacene and polyaniline.
In some embodiments, the SLMP is to coat one layer of inorganic material, the inorganic material choosing on lithium powder surface
From Li2CO3、LiF、Li3N and Li3PO4In one kind or combinations thereof.
In some embodiments, the conductive agent be selected from metal powder, acetylene black, Ketjen black, furnace black, conductive black,
One kind or combinations thereof in electrically conductive graphite, carbon nanotube, carbon nano-fiber and graphene.
In some embodiments, the binder is selected from fluorubber, polytetrafluoroethylene (PTFE), ultra-high molecular weight polyethylene, gathers
One kind in vinyl butyral and ethylene-tetrafluoroethylene copolymer or combinations thereof.
In some embodiments, described to be kneaded into negative electrode active material, SLMP, conductive agent, binder and solvent slightly
The equipment of product can be selected from planetary mixer, mixer, vacuum kneader or multiple roll pressure and mix machine.
In some embodiments, described that negative electrode active material, SLMP, conductive agent, binder are processed into crude product use
Solvent can be selected from propene carbonate, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, aliphatic hydrocarbon, cycloalkane, fragrance
One in hydrocarbon, crown ether, pyridine, tetrahydrofuran, acetone, methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, isopropanol, ethylene glycol, toluene
Kind or combinations thereof, preferably one kind or its group of propene carbonate, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate kind
It closes.
In some embodiments, the carbon copper foil that covers is the conductive coating and copper by being evenly applied to two surfaces of copper foil
Foil is constituted, and wherein copper thickness is 12 μm, and single-sided conductive coating layer thickness is 1.5 μm.
Another aspect of the present invention provides a kind of lithium-ion capacitor and preparation method thereof formed using negative plate as above.
The lithium-ion capacitor preparation method includes：
1) by after lithium-ion capacitor negative electrode active material, SLMP and the dry-mixed 30min of conductive agent, solvent and bonding is added
Agent is fully mediated；
2) products obtained therefrom in step 1) is obtained solvent content 10~20 times with hot calender in 50~120 DEG C of hot calenders is
The thick film of 5~30wt%, after thick film is then dried in vacuo 12h at 150 DEG C finish rolling obtain the dry electrode containing SLMP to 30 μ m-thicks
Film；
3) by the dry electrode film of gained in step 2) by thermal composite machine heat be compound in 15 μ m-thicks cover on carbon copper foil to get to
Lithium-ion capacitor negative plate；
4) prepared by positive plate：By activated carbon, conductive black, polyacrylonitrile according to mass ratio be 90:3:7 autonomous preparation slurries
And be coated on 22 μ m-thick aluminium foils, successively through drying, roll process, obtain the EDLC positive plates of 250 μ m-thicks；
5) the lithium-ion capacitor negative plate prepared and the EDLC positive plates are cut into wide 35mm, positive length
660mm, cathode length 700mm；
6) be 25 μm by thickness, the PP diaphragms of width 41mm are wound into lithium-ion capacitor together with the positive/negative plate cut
Battery core；
7) after battery core being dried in vacuo 12h at 100 DEG C, lithium-ion capacitor electrolyte is placed under high-purity argon gas protection
Enter shell, riveting lid after middle vacuum impregnation to saturation imbibition state, sealing obtains Φ 22*45 welding needle type lithium-ion capacitor monomers.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) electrode film is prepared with wet pressing embrane method：Negative electrode active material, SLMP, conductive agent, binder are mediated in a solvent
At hot pressing film after soft sludge condition, the thick film of high self-supporting and low solvent content is obtained, SLMP is evenly distributed in thick film；
(2) the electrode film heat for being uniformly distributed SLMP is compound on the copper foil for covering carbon, obtains the lithium ion of high bond strength
Capacitor anode piece, this negative plate caking property is strong, compacted density is high, volume specific volume is high and good conductivity；
(3) the embedding lithium depth of lithium-ion capacitor and high uniformity that are made of this negative plate, internal resistance is small, has extended cycle life
It is low with production cost.
Term defines
The invention is intended to cover all replacement, modification and equivalent technical solutions, they are included in as claim is fixed
In the scope of the invention of justice.Those skilled in the art will appreciate that many and similar or equivalent method and material described herein
It can be used in the practice present invention.The present invention is not limited to method described herein and material.In document, patent and the class combined
One or more or contradict in the case of (include but not limited to defined in term, terms different from the application like material
Using, described technology etc.), it is subject to the application.
It will further be appreciated that certain features of the present invention, are clearly visible, are carried out in multiple independent embodiments
Description, but can also in combination be provided in single embodiment.Conversely, the various features of the present invention, for brevity,
It is described, but can also be provided individually or with any appropriate sub-portfolio in single embodiment.
Unless otherwise stated, all scientific and technical terminologies used in the present invention have with those skilled in the art of the invention's
It is generally understood identical meaning.All patents of the present invention and public publication are integrally incorporated this hair by reference
It is bright.
Term "comprising" or " comprising " are open language, that is, include the content specified by the present invention, but it is not precluded
Content in terms of him.
Unless explicitly stated otherwise in contrast, otherwise, pressure of the present invention, temperature are value range.For example,
" 0.2Mpa " indicates that pressure limit is 0.2Mpa ± 0.02Mpa；Ranging from 150 DEG C ± 5 DEG C of " 150 DEG C " expression temperature.
" SLMP " indicates to stabilize metallic lithium powder；" EDLC " indicates electrochemical capacitor in double electrode layer.
Specific implementation mode
As described below is the preferred embodiment of the present invention, and what the present invention was protected is not limited to following preferred implementation side
Formula.It should be pointed out that for those skilled in the art on the basis of this innovation and creation conceive, several deformations for making with
It improves, belongs to protection scope of the present invention.Raw material used in embodiment can be obtained by commercial sources.
Embodiment 1
1) 880 grams of natural flake graphites are weighed, 30 grams of SLMP and 30 gram of acetylene blacks are added in planetary mixer and stir
30min, is separately added into 1000 grams of propene carbonates and 60 grams of fluorubber mediate 120min, is evenly distributed the ooze shape of SLMP
Crude product；
2) with hot calender by ooze shape crude product obtained by step 1) in 80 DEG C of condition hot calenders 16 times, obtain propylene carbonate
Ester content is the thick film of 12.3wt%, and thick film is dried in vacuo to 12h and finish rolling at 150 DEG C, obtains the dry electrode film of 30 μ m-thicks；
3) dry electrode film heat obtained by step 2) is compound in the covering on carbon copper foil of 15 μ m-thicks with thermal composite machine, obtains 75 μm
Lithium-ion capacitor negative plate measures its compacted density by weight method；
4) it is 90 according to mass ratio by activated carbon, conductive black and polyacrylonitrile:3:7 autonomous preparation slurries are simultaneously coated on 22
On μ m-thick aluminium foil, successively through drying, roll process, 250 μ m-thick EDLC positive plates are obtained；
5) the lithium-ion capacitor negative plate prepared and the EDLC positive plates are cut into wide 35mm, positive length
660mm, cathode length 700mm；
6) be 25 μm by thickness, the PP diaphragms of width 41mm are wound into lithium-ion capacitor together with the positive/negative plate cut
Battery core；
7) after battery core being dried in vacuo 12h at 100 DEG C, lithium-ion capacitor Special electric is placed under high-purity argon gas protection
Enter shell, riveting lid in solution liquid after vacuum impregnation to saturation imbibition state, sealing obtains Φ 22*45 welding needle type lithium-ion capacitor lists
Body.
Assembled monomer is transferred in air dry oven with 65 DEG C of forced air drying 12h, the electrolyte in battery core is made to fill
Sub-dip stain；Monomer is cooled to room temperature, first with 50mA constant-current charges to 4V, then with 50mA constant-current discharges to 2V, cycle 10 times is complete
At chemical conversion, the capacity and internal resistance value of monomer after test chemical conversion.To the monomer after chemical conversion with 10C constant current charge and discharges within the scope of 2~4V
Electricity cycle 100000 times, the capacity and internal resistance value of monomer after test loop.Test result is as shown in table 1.
Embodiment 2
1) it weighs in 880 grams of artificial graphites, 30 grams of mixed machines of SLMP and 30 gram of copper powder addition multiple roll pressure and mixes 30min,
It is separately added into 1000 grams of ethylene carbonates and 60 grams of polytetrafluoroethylene (PTFE) mediates 120min, the ooze shape for being evenly distributed SLMP is thick
Product；
2) with hot calender by ooze shape crude product obtained by step 1) in 120 DEG C of condition hot calenders 11 times, obtain carbonic acid second
Enester content is the thick film of 8.9wt%, and thick film is dried in vacuo to 12h and finish rolling at 150 DEG C, obtains the dry electrode film of 30 μ m-thicks；
3) dry electrode film heat obtained by step 2) is compound in the covering on carbon copper foil of 15 μ m-thicks with thermal composite machine, obtains 75 μm
Lithium-ion capacitor negative plate measures its compacted density by weight method；
4) it is 90 according to mass ratio by activated carbon, conductive black and polyacrylonitrile:3:7 autonomous preparation slurries are simultaneously coated on 22
On μ m-thick aluminium foil, successively through drying, roll process, 250 μ m-thick EDLC positive plates are obtained；
5) the lithium-ion capacitor negative plate prepared and the EDLC positive plates are cut into wide 35mm, positive length
660mm, cathode length 700mm；
6) be 25 μm by thickness, the PP diaphragms of width 41mm are wound into lithium-ion capacitor together with the positive/negative plate cut
Battery core；
7) after battery core being dried in vacuo 12h at 100 DEG C, lithium-ion capacitor Special electric is placed under high-purity argon gas protection
Enter shell, riveting lid in solution liquid after vacuum impregnation to saturation imbibition state, sealing obtains Φ 22*45 welding needle type lithium-ion capacitor lists
Body.
Assembled monomer is transferred in air dry oven with 65 DEG C of forced air drying 12h, the electrolyte in battery core is made to fill
Sub-dip stain；Monomer is cooled to room temperature, first with 50mA constant-current charges to 4V, then with 50mA constant-current discharges to 2V, cycle 10 times is complete
At chemical conversion, the capacity and internal resistance value of monomer after test chemical conversion.To the monomer after chemical conversion with 10C constant current charge and discharges within the scope of 2~4V
Electricity cycle 100000 times, the capacity and internal resistance value of monomer after test loop.Test result is as shown in table 1.
Embodiment 3
1) it weighs in 880 grams of expanded graphites, 30 grams of SLMP and 30 gram of Ketjen black addition mixers and stirs 30min, add respectively
Enter 1000 grams of dimethyl carbonates and 60 grams of ultra-high molecular weight polyethylenes mediate 120min, the ooze shape for being evenly distributed SLMP is thick
Product；
2) with hot calender by ooze shape crude product obtained by step 1) in 60 DEG C of condition hot calenders 20 times, obtain carbonic acid diformazan
Ester content is the thick film of 19.6wt%, and thick film is dried in vacuo to 12h and finish rolling at 150 DEG C, obtains the dry electrode film of 30 μ m-thicks；
3) dry electrode film heat obtained by step 2) is compound in the covering on carbon copper foil of 15 μ m-thicks with thermal composite machine, obtains 75 μm
Lithium-ion capacitor negative plate measures its compacted density by weight method；
4) it is 90 according to mass ratio by activated carbon, conductive black and polyacrylonitrile:3:7 autonomous preparation slurries are simultaneously coated on 22
On μ m-thick aluminium foil, successively through drying, roll process, 250 μ m-thick EDLC positive plates are obtained；
5) the lithium-ion capacitor negative plate prepared and the EDLC positive plates are cut into wide 35mm, positive length
660mm, cathode length 700mm；
6) be 25 μm by thickness, the PP diaphragms of width 41mm are wound into lithium-ion capacitor together with the positive/negative plate cut
Battery core；
7) after battery core being dried in vacuo 12h at 100 DEG C, lithium-ion capacitor Special electric is placed under high-purity argon gas protection
Enter shell, riveting lid in solution liquid after vacuum impregnation to saturation imbibition state, sealing obtains Φ 22*45 welding needle type lithium-ion capacitor lists
Body.
Assembled monomer is transferred in air dry oven with 65 DEG C of forced air drying 12h, the electrolyte in battery core is made to fill
Sub-dip stain；Monomer is cooled to room temperature, first with 50mA constant-current charges to 4V, then with 50mA constant-current discharges to 2V, cycle 10 times is complete
At chemical conversion, the capacity and internal resistance value of monomer after test chemical conversion.To the monomer after chemical conversion with 10C constant current charge and discharges within the scope of 2~4V
Electricity cycle 100000 times, the capacity and internal resistance value of monomer after test loop.Test result is as shown in table 1.
Embodiment 4
1) 880 grams of hard carbons are weighed, 30 grams of SLMP and 30 gram of conductive blacks are added in vacuum kneader and stir 30min, difference
1000 grams of ethyl alcohol are added and 60 grams of polyvinyl butyrals mediate 120min, are evenly distributed the ooze shape crude product of SLMP；
2) with hot calender by ooze shape crude product obtained by step 1) in 110 DEG C of condition hot calenders 16 times, obtain toluene and contain
Amount is the thick film of 8.8wt%, and thick film is dried in vacuo to 12h and finish rolling at 150 DEG C, obtains the dry electrode film of 30 μ m-thicks；
3) dry electrode film heat obtained by step 2) is compound in the covering on carbon copper foil of 15 μ m-thicks with thermal composite machine, obtains 75 μm
Lithium-ion capacitor negative plate measures its compacted density by weight method；
4) it is 90 according to mass ratio by activated carbon, conductive black and polyacrylonitrile:3:7 autonomous preparation slurries are simultaneously coated on 22
On μ m-thick aluminium foil, successively through drying, roll process, 250 μ m-thick EDLC positive plates are obtained；
5) the lithium-ion capacitor negative plate prepared and the EDLC positive plates are cut into wide 35mm, positive length
660mm, cathode length 700mm；
6) be 25 μm by thickness, the PP diaphragms of width 41mm are wound into lithium-ion capacitor together with the positive/negative plate cut
Battery core；
7) after battery core being dried in vacuo 12h at 100 DEG C, lithium-ion capacitor Special electric is placed under high-purity argon gas protection
Enter shell, riveting lid in solution liquid after vacuum impregnation to saturation imbibition state, sealing obtains Φ 22*45 welding needle type lithium-ion capacitor lists
Body.
Assembled monomer is transferred in air dry oven with 65 DEG C of forced air drying 12h, the electrolyte in battery core is made to fill
Sub-dip stain；Monomer is cooled to room temperature, first with 50mA constant-current charges to 4V, then with 50mA constant-current discharges to 2V, cycle 10 times is complete
At chemical conversion, the capacity and internal resistance value of monomer after test chemical conversion.To the monomer after chemical conversion with 10C constant current charge and discharges within the scope of 2~4V
Electricity cycle 100000 times, the capacity and internal resistance value of monomer after test loop.Test result is as shown in table 1.
Embodiment 5
1) 880 grams of carbonaceous mesophase spherules are weighed, 30 grams of SLMP and 30 gram of graphenes are added in planetary mixer and stir
30min, is separately added into 1000 grams of acetone and 60 grams of ethylene-tetrafluoroethylene copolymers mediate 120min, is evenly distributed SLMP
Ooze shape crude product；
2) with hot calender by ooze shape crude product obtained by step 1) in 120 DEG C of condition hot calenders 10 times, obtain hexamethylene
Content is the thick film of 7.1wt%, and thick film is dried in vacuo to 12h and finish rolling at 150 DEG C, obtains the dry electrode film of 30 μ m-thicks；
3) dry electrode film heat obtained by step 2) is compound in the covering on carbon copper foil of 15 μ m-thicks with thermal composite machine, obtains 75 μm
Lithium-ion capacitor negative plate measures its compacted density by weight method；
4) it is 90 according to mass ratio by activated carbon, conductive black and polyacrylonitrile:3:7 autonomous preparation slurries are simultaneously coated on 22
On μ m-thick aluminium foil, successively through drying, roll process, 250 μ m-thick EDLC positive plates are obtained；
5) the lithium-ion capacitor negative plate prepared and the EDLC positive plates are cut into wide 35mm, positive length
660mm, cathode length 700mm；
6) be 25 μm by thickness, the PP diaphragms of width 41mm are wound into lithium-ion capacitor together with the positive/negative plate cut
Battery core；
7) after battery core being dried in vacuo 12h at 100 DEG C, lithium-ion capacitor Special electric is placed under high-purity argon gas protection
Enter shell, riveting lid in solution liquid after vacuum impregnation to saturation imbibition state, sealing obtains Φ 22*45 welding needle type lithium-ion capacitor lists
Body.
Assembled monomer is transferred in air dry oven with 65 DEG C of forced air drying 12h, the electrolyte in battery core is made to fill
Sub-dip stain；Monomer is cooled to room temperature, first with 50mA constant-current charges to 4V, then with 50mA constant-current discharges to 2V, cycle 10 times is complete
At chemical conversion, the capacity and internal resistance value of monomer after test chemical conversion.To the monomer after chemical conversion with 10C constant current charge and discharges within the scope of 2~4V
Electricity cycle 100000 times, the capacity and internal resistance value of monomer after test loop.Test result is as shown in table 1.
Comparative example 1
1) it is 91 according to mass ratio by artificial graphite, electrically conductive graphite and polytetrafluoroethylene (PTFE):3:6 are configured to viscosity with water is
The slurry of 2500cP and be spread evenly across 15 μ m-thicks on the copper foil, successively through drying, roll process, obtain 75 μm of lithium from
Sub-capacitor negative plate measures its compacted density by weight method；
2) it is 90 in mass ratio by activated carbon, conductive black and polyacrylonitrile:3:7 autonomous preparation slurries are simultaneously coated on 22 μm
Thickness, successively through drying, roll process, obtains 250 μ m-thick EDLC positive plates on aluminium foil；
3) the lithium-ion capacitor negative plate prepared and the EDLC positive plates are cut into wide 35mm, positive length
660mm, cathode length 700mm；
4) it is 25 μm by thickness, the PP diaphragms of width 41mm and the positive/negative plate cut are wound into lithium-ion capacitor together
Battery core；
5) it after battery core being dried in vacuo 12h at 100 DEG C, is transferred in vacuum glove box and dismantles, put to negative plate tail portion
It sets wide 30mm, long 80mm, thick 45 μm of lithium metal foil and wraps battery core again；
6) after the battery core of cathode tail portion placement lithium metal foil being entered shell, 9 grams of lithium ions are injected into shell under vacuum
Capacitor special electrolysis liquid, riveting lid, sealing obtain Φ 22*45 welding needle type lithium-ion capacitor monomers.
Monomer post-processes and test method is with embodiment 1, and test result is shown in Table 1.
Comparative example 2
1) taking band, there are three the Φ 22*45 welding needle type lithium-ion capacitor cover boards of exit, wherein three exit difference
For the positive pole ear with Φ 22*45 welding needle type lithium-ion capacitor battery cores, negative lug and as " lithium electrode " pole of third pole
Ear is connected；
2) lithium-ion capacitor negative plate and EDLC positive plates are prepared respectively by 1 identical method of comparative example and divide
With thickness it is 25 μm after cutting, is wound into Φ 22*45 welding needle type lithium-ion capacitor battery cores together with the PP diaphragms of width 41mm；
3) after battery core being dried in vacuo 12h at 100 DEG C, lithium-ion capacitor Special electric is placed under high-purity argon gas protection
Solve vacuum impregnation extremely saturation imbibition state in liquid；
4) it takes " lithium electrode " that 60mg length is 30mm and welds upper nickel matter lug, " lithium electrode " is fitted into PP diaphragms, is placed
In saturation dipping electrolyte Φ 22*45 welding needle type lithium-ion capacitor battery cores core space in, respectively by battery core anode pole
Ear, battery core negative lug and " lithium electrode " lug are riveted on three exits on cover board, sealing, are obtained tool and are drawn there are three electrode
The Φ 22*45 welding needle type lithium-ion capacitor monomers of outlet.
Assembled monomer is transferred in air dry oven with 65 DEG C of forced air drying 12h, the electrolyte in battery core is made to fill
Sub-dip stain.Good monomer to be dried is cooled to room temperature, and the cathode exit on cover board is coupled with " lithium electrode " exit and is filled
On the anode and cathode of discharge tester, with 10mA constant-current discharges to 0.05V hereinafter, realizing the pre- embedding of lithium-ion capacitor cathode
Lithium.For the initial capacity and internal resistance value of test unit, first the positive pole exit on cover board is coupled with cathode exit
On the anode and cathode of charge-discharge test instrument, with 50mA constant-current charges to 4V, then with 50mA constant-current discharges to 2V, cycle 10 times is complete
At chemical conversion, the capacity and internal resistance value of monomer after test chemical conversion.Finally monomer is followed within the scope of 2~4V with 10C constant current charge-discharges
Ring 100000 times, the capacity and internal resistance value of monomer after test loop.Test result is as shown in table 1.
Comparative example 3
1) it is 91 in mass ratio by expanded graphite, electrically conductive graphite and polytetrafluoroethylene (PTFE):3:6 are configured to viscosity with water is
The slurry of 2500cP and be spread evenly across 15 μ m-thicks on the copper foil, successively through drying, roll process, obtain the lithium of 65 μ m-thicks
Ionistor negative plate；
2) it is 85 in mass ratio by the SLMP of LiF claddings and fluorubber:15 are scattered in propylene carbonate solvent and are glued
Degree is the slurry of 2350cP and is spread evenly across on negative plate obtained by step 1), successively through drying, roll process, obtains 75 μm
Lithium-ion capacitor composite negative plate measures its compacted density by weight method；
3) it is 90 according to mass ratio by activated carbon, conductive black and polyacrylonitrile:3:7 autonomous preparation slurries are simultaneously coated on 22
On μ m-thick aluminium foil, successively through drying, roll process, 250 μ m-thick EDLC positive plates are obtained；
4) the lithium-ion capacitor negative plate prepared and the EDLC positive plates are cut into wide 35mm, positive length
660mm, cathode length 700mm；
5) be 25 μm by thickness, the PP diaphragms of width 41mm are wound into lithium-ion capacitor together with the positive/negative plate cut
Battery core；
6) after battery core being dried in vacuo 12h at 100 DEG C, lithium-ion capacitor Special electric is placed under high-purity argon gas protection
Enter shell, riveting lid in solution liquid after vacuum impregnation to saturation imbibition state, sealing obtains Φ 22*45 welding needle type lithium-ion capacitor lists
Body.
Assembled monomer is transferred in air dry oven with 65 DEG C of forced air drying 12h, the electrolyte in battery core is made to fill
Sub-dip stain；Monomer is cooled to room temperature, first with 50mA constant-current charges to 4V, then with 50mA constant-current discharges to 2V, cycle 10 times is complete
At chemical conversion, the capacity and internal resistance value of monomer after test chemical conversion.To the monomer after chemical conversion with 10C constant current charge and discharges within the scope of 2~4V
Electricity cycle 100000 times, the capacity and internal resistance value of monomer after test loop.Test result is as shown in table 1.
The performance test results
1 the performance test results of table
According to the test result of embodiment 1-5, using first by lithium-ion capacitor negative electrode active material, SLMP, conduction
Agent, binder are fully mediated in low boiling point solvent, then are prepared successively through hot pressing film, vacuum drying, hot composition process flow
Lithium-ion capacitor negative plate compacted density be more than 1.04g/cm3, the Φ 22*45 welding needle type lithiums that are assembled into this negative plate
Ionistor monomer initial capacity after 50mA is melted into is more than 280F, and internal resistance is less than 40m Ω, and monomer is through 10C constant current charge-discharges
Cycle 100000 times, capacity attenuation rate are less than 5%, and internal resistance increase rate is less than 13%；According to the test of comparative example 1 and comparative example 2
As a result, using lithium-ion capacitor negative electrode active material, conductive agent and binder and water are first configured to low viscosity slurry, then
The lithium-ion capacitor negative plate compacted density that coated, dry successively, roll process is prepared is 0.9307g/cm3, use this
Kind negative plate pastes or introduces the Φ 22*45 welding needle type lithium-ion capacitor lists being assembled into as " lithium electrode " of third pole with lithium foil
Body initial capacity after 50mA is melted into is less than 240F, and internal resistance is more than 70m Ω, and monomer recycles 100000 times through 10C constant current charge-discharges,
Capacity attenuation rate is all higher than 10%, and internal resistance increase rate is also above 18%；According to the test result of comparative example 3, using first by SLMP,
Binder and solvent are mixed into slurry, be coated on the cathode coating containing active material, conductive agent and binder according to
The secondary lithium-ion capacitor composite negative plate compacted density prepared through drying, roll process and comparative example 1 are essentially identical, initially
Electrical property and cycle 100000 times after electrical property also be not so good as embodiment 1-5.Show compound with the electrode film heat for being uniformly distributed SLMP
At electrode have higher compacted density, the Φ 22*45 welding needle types lithium-ion capacitor monomer initial electrical performances being assembled into and
Cyclical stability is superior to prior art level.
Claims (10)
1. a kind of preparation method of lithium-ion capacitor negative plate, including：
1) negative electrode active material, SLMP, conductive agent, binder are fully mediated in a solvent, obtains crude product；
2) gained crude product substep hot calender in step 1) is then dried in vacuo thick film and essence at the thick film of low solvent content
It rolls, obtains the dry electrode film containing SLMP；
3) the dry electrode film heat in step 2) is compound in and is covered on carbon copper foil to get lithium-ion capacitor negative plate.
2. the preparation method of lithium-ion capacitor negative plate according to claim 1, it is characterised in that：
1) after lithium-ion capacitor negative electrode active material, SLMP and the dry-mixed 30min of conductive agent, solvent will be added and binder fills
Divide and mediates；
2) by products obtained therefrom hot calender in step 1) 50~120 DEG C of hot calenders obtain for 10~20 times solvent content be 5~
The thick film of 30wt%, after thick film is then dried in vacuo 12h at 150 DEG C finish rolling obtain the dry electrode film containing SLMP to 30 μ m-thicks；
3) by the dry electrode film of gained in step 2) by thermal composite machine heat be compound in 15 μ m-thicks cover on carbon copper foil to get to lithium from
Sub-capacitor negative plate.
3. the preparation method of lithium-ion capacitor negative plate according to claim 1 or 2, which is characterized in that described negative
Pole active material is selected from natural flake graphite, artificial graphite, expanded graphite, hard carbon, carbonaceous mesophase spherules, polyacene and polyphenyl
One kind in amine or combinations thereof.
4. the preparation method of lithium-ion capacitor negative plate according to claim 1 or 2, which is characterized in that described
SLMP is to coat one layer of inorganic material on lithium powder surface, and the inorganic material is selected from Li2CO3、LiF、Li3N and Li3PO4In one
Kind or combinations thereof.
5. the preparation method of lithium-ion capacitor negative plate according to claim 1 or 2, which is characterized in that described to lead
Electric agent is selected from metal powder, acetylene black, Ketjen black, furnace black, conductive black, electrically conductive graphite, carbon nanotube, carbon nano-fiber and stone
One kind or combinations thereof in black alkene.
6. the preparation method of lithium-ion capacitor negative plate according to claim 1 or 2, which is characterized in that described viscous
It ties agent and is selected from fluorubber, polytetrafluoroethylene (PTFE), ultra-high molecular weight polyethylene, polyvinyl butyral and ethylene-tetrafluoroethylene copolymerization
One kind in object or combinations thereof.
7. the preparation method of lithium-ion capacitor negative plate according to claim 1 or 2, which is characterized in that described to incite somebody to action
Negative electrode active material, SLMP, conductive agent, binder and solvent are kneaded into the solvent of crude product, propene carbonate, ethylene carbonate
Ester, dimethyl carbonate, methyl ethyl carbonate, aliphatic hydrocarbon, cycloalkane, aromatic hydrocarbon, crown ether, pyridine, tetrahydrofuran, acetone, methanol, second
One kind or combinations thereof in alcohol, propyl alcohol, butanol, amylalcohol, isopropanol, ethylene glycol, toluene；It is described by negative electrode active material, SLMP,
The equipment that conductive agent, binder and solvent are kneaded into crude product is selected from planetary mixer, mixer, vacuum kneader or multiple roll
Pressure mixes machine.
8. the preparation method of lithium-ion capacitor negative plate according to claim 1 or 2, which is characterized in that described to cover
Carbon copper foil is that conductive coating by being evenly applied to two surfaces of copper foil and copper foil are constituted, and wherein copper thickness is 12 μm, single side
Conductive coating thickness is 1.5 μm.
9. a kind of lithium-ion capacitor, which is characterized in that used including claim 1~8 any one of them lithium-ion capacitor
The negative plate that the preparation method of negative plate obtains.
10. a kind of preparation method of lithium-ion capacitor as claimed in claim 9, includes the following steps：
1) after lithium-ion capacitor negative electrode active material, SLMP and the dry-mixed 30min of conductive agent, solvent will be added and binder fills
Divide and mediates；
2) by products obtained therefrom hot calender in step 1) 50~120 DEG C of hot calenders obtain for 10~20 times solvent content be 5~
The thick film of 30wt%, after thick film is then dried in vacuo 12h at 150 DEG C finish rolling obtain the dry electrode film containing SLMP to 30 μ m-thicks；
3) by the dry electrode film of gained in step 2) by thermal composite machine heat be compound in 15 μ m-thicks cover on carbon copper foil to get to lithium from
Sub-capacitor negative plate；
4) prepared by positive plate：By activated carbon, conductive black, polyacrylonitrile according to mass ratio be 90:3:7 autonomous preparation slurries simultaneously apply
It is distributed on 22 μ m-thick aluminium foils, successively through drying, roll process, obtains the EDLC positive plates of 250 μ m-thicks；
5) the lithium-ion capacitor negative plate prepared and the EDLC positive plates are cut into wide 35mm, positive length 660mm,
Cathode length 700mm；
6) be 25 μm by thickness, the PP diaphragms of width 41mm are wound into lithium-ion capacitor electricity together with the positive/negative plate cut
Core；
7) it after battery core being dried in vacuo 12h at 100 DEG C, is placed in lithium-ion capacitor electrolyte under high-purity argon gas protection true
Enter shell, riveting lid after sky dipping to saturation imbibition state, sealing obtains Φ 22*45 welding needle type lithium-ion capacitor monomers.
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| CN110931718A (en) * | 2018-09-20 | 2020-03-27 | 中能中科（天津）新能源科技有限公司 | Lithium paste and preparation method and application thereof |
| CN111326717A (en) * | 2018-12-13 | 2020-06-23 | 深圳先进技术研究院 | Aluminum negative electrode material, preparation method and secondary battery |
| CN112490399A (en) * | 2021-01-27 | 2021-03-12 | 郑州中科新兴产业技术研究院 | Method for pre-lithium of lithium ion battery cathode |
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Application publication date: 20180821 |