CN104681311A - Novel lithium pre-embedding method of lithium ion capacitor - Google Patents
Novel lithium pre-embedding method of lithium ion capacitor Download PDFInfo
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- CN104681311A CN104681311A CN201410764686.1A CN201410764686A CN104681311A CN 104681311 A CN104681311 A CN 104681311A CN 201410764686 A CN201410764686 A CN 201410764686A CN 104681311 A CN104681311 A CN 104681311A
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- lithium
- ion capacitor
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- negative pole
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 83
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003990 capacitor Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000007599 discharging Methods 0.000 claims abstract description 11
- 238000012360 testing method Methods 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 230000004888 barrier function Effects 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910010090 LiAlO 4 Inorganic materials 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims description 2
- 229910013553 LiNO Inorganic materials 0.000 claims description 2
- 229910013872 LiPF Inorganic materials 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- 101150058243 Lipf gene Proteins 0.000 claims description 2
- 239000002390 adhesive tape Substances 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 10
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000011149 active material Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- VOYADQIFGGIKAT-UHFFFAOYSA-N 1,3-dibutyl-4-hydroxy-2,6-dioxopyrimidine-5-carboximidamide Chemical compound CCCCn1c(O)c(C(N)=N)c(=O)n(CCCC)c1=O VOYADQIFGGIKAT-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000004308 accommodation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- -1 aluminium matter Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/60—Liquid electrolytes characterised by the solvent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/429—Natural polymers
- H01M50/4295—Natural cotton, cellulose or wood
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention provides a novel lithium pre-embedding method of a lithium ion capacitor. The method comprises the following steps that (1) a battery cell is assembled, and is soaked into an organic solution containing lithium salts; (2) a positive electrode and a negative electrode are respectively connected with a charging and discharging test instrument, and once discharging after once charging is used as a cycle, 1 to 1000 times of cycles are totally carried out, and the lithium pre-embedding on the negative electrode is completed; (3) the battery cell after the lithium pre-embedding completion is taken out and is put into a packaging case, the packaging case is filled with electrolyte and is assembled into a lithium ion capacitor single body. When the method is adopted, the problem of too high cost due to lithium metal, porous current collectors and the like can be effectively solved, the safety can be improved, the technical flow process can be simplified, and the method is applicable to industrial production.
Description
Technical field
The present invention relates to lithium-ion capacitor field, particularly relate to a kind of embedding lithium method of New Pre of lithium-ion capacitor.
Background technology
Lithium-ion capacitor is the novel typical hybrid energy storage device by lithium ion battery and double electric layers supercapacitor " inside also ", have the advantage such as high-energy-density and ultracapacitor high-specific-power, long-life of lithium-ion capacitor concurrently, be with a wide range of applications in fields such as military project space flight, green energy resources.The pre-embedding lithium method of current lithium-ion capacitor generally adopts the method in Fuji Heavy Industries patent of invention CN101138058B, namely with lithium metal for lithium source, use and there is the metal forming of through hole for collector, lithium metal is positioned over the relative position of negative pole, by short circuit lithium metal and negative pole, the electrical potential difference between lithium metal and negative pole is utilized to discharge thus embedded in negative pole by lithium.The method can obtain energy density and the high large-scale electrical storage device of Large Copacity of output density, and there is good charge-discharge characteristic, but there is following problem: (1) lithium paper tinsel chemical property is very active, makes the production of lithium-ion capacitor high to environmental requirement; (2) used in amounts of lithium will precisely control, and the very few improvement to voltage of lithium amount falls flat, and lithium amount too much can make again monomer there is larger potential safety hazard, and therefore the consistency of monomer is poor; (3) lithium-ion capacitor manufacturing process is complicated, and the use of the key raw material such as lithium metal, porous current collector makes the cost of lithium-ion capacitor remain high.
Existing technique also has to be composed lithium mode and changes into be connected charge-discharge test instrument between negative pole with lithium metal by short circuit negative pole and the short circuit dischange of lithium metal, by electric discharge or charge and discharge cycles by Lithium-ion embeding carbon material used as anode, the method may promote to some extent to the performance of lithium-ion capacitor monomer, but cannot solve the problem such as fail safe, production cost.
Chinese patent CN102385991A discloses a kind of method manufacturing lithium-ion capacitor and the lithium-ion capacitor utilizing it to manufacture, in this invention, the method for pre-embedding lithium is form lithium film by vacuum vapor deposition on one surface of the membrane, make lithium film relative with negative pole, embed negative pole in advance with the Li+ in lithium film.Compared to the method for Fuji Heavy, the method has the following advantages: (1) directly contacts in process subsequently, carry out pre-embedding lithium due to lithium film and negative pole, therefore without the need to using through hole collector, can reduce product internal resistance like this; (2) the method more conveniently can control the consumption of lithium, and fail safe increases; (3) every layer of negative pole all directly contacts tax lithium with lithium film, greatly can shorten the pre-tax lithium time.The method possible in theory, but its practical feasibility still needs to be investigated.
Flat seminar (the W.J.Cao of Zheng Jian, J.P.Zheng, Li-ion capacitors with carbon cathode and hard carbon/stabilized lithium metal powder anode electrodes, Journal of Power Sources, 213 (2012) 180-185.) use the surperficial nano level metal lithium powder with passivating film to be lithium source, make negative pole with dry process after mixing with hard carbon, active carbon is that positive pole is assembled into lithium-ion capacitor monomer.Compare Fuji Heavy and use the structure of lithium metal foil, the lithium-ion capacitor of this structure can manufacture in drying shed, and without the need to the severe rugged environment of glove box, considerably increases operability.
Summary of the invention
In order to the pre-embedding lithium production cost solving lithium-ion capacitor is high, potential safety hazard is large, the problem of complex process, we have proposed a kind of embedding lithium method of New Pre of lithium-ion capacitor, employing the present invention effectively can solve the high cost problem that lithium metal, porous current collector etc. cause, can fail safe be improved, and simplification of flowsheet, be applicable to suitability for industrialized production.
The present invention is achieved by the following technical solutions:
For achieving the above object, the invention provides a kind of embedding lithium method of New Pre of lithium-ion capacitor, step is as follows:
(1) negative pole, barrier film, positive pole, barrier film are stacked gradually or after reeling by adhesive tape fixing composition battery core, battery core is immersed in the organic solution containing lithium salts;
(2) positive pole is connected charge-discharge test instrument respectively with negative pole, after once charging, carries out single step of releasing electricity as a circulation, carry out 1-100 circulation altogether, complete the pre-embedding lithium of anticathode;
(3) battery core after being completed by pre-embedding lithium is taken out, and puts into pack case, injects electrolyte and is assembled into lithium-ion capacitor monomer.
Preferably, above-mentioned plus plate current-collecting body can be the paper tinsel or netted of the metals such as aluminium matter, stainless steel, iron, nickel, and paper tinsel used can porose or atresia.
Preferably, above-mentioned negative current collector can be the paper tinsel or netted of the metals such as copper, stainless steel, iron, nickel, and paper tinsel used can porose or atresia.
Preferably, above-mentioned lithium salts used can be LiPF
6, LiBF
4, LiClO
4, LiAlO
4, LiOH, Li
2cO
3, CH
3cOOLi, LiNO
3, LiB (C
2o
4)
2, LiP (C
6h
4o
2)
3, LiPF
3(C
2f
5)
3, LiN (SO
2cF
3)
2etc. dissolve in the lithium salts of organic solvent one or more.
Preferably, above-mentioned organic solution is at least containing the one in PC, EC, DEC, DMC, DMF, DME, THF, SL.
Preferably, the mode be connected with negative pole by positive pole is for be connected positive pole by charging/discharging apparatus with negative pole.Resistant series can be added connect in whole loop, also directly can connect without resistance.
Preferably, to charge → discharge or charge → self discharge cycling to the battery core immersing lithium salts organic solution, its charging current and discharging current are constant current.Concrete, constant current can be based on current value corresponding to 0.01C ~ 10C multiplying power of positive pole quality or negative pole quality or battery core Mass Calculation.
Preferably, the cycle-index of charge and discharge cycles operation is 1 ~ 100 time, and the highest cut-ff voltage of charging is between 3.6V ~ 4.2V, and the charge cutoff voltage in each circulation can be identical, also can be different.
Preferably, the charging current in each circulation can be identical, also can be different; Discharging current in each circulation can be identical, also can be different.One section of constant voltage process can be had after each charging process terminates, also can not carry out constant voltage process.
Preferably, in each circulation, the self discharge time is 1min ~ 10h.And the self discharge time in each circulation can be identical, also can be different.
Compared with prior art, beneficial effect of the present invention is:
(1) by using the organic solvent containing lithium salts to come alternative lithium paper tinsel or nano level metal lithium, reducing costs, using atresia collector also to significantly reduce cost simultaneously;
(2) use the organic solvent containing lithium salts to substitute lithium paper tinsel, need not process in extreme circumstances, improve the fail safe of processing;
(3) connect positive pole and negative pole with charge-discharge test instrument, the time of pre-embedding lithium can be shortened, and improve the effect of pre-embedding lithium;
(4) simplification of flowsheet, can large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the specific capacity test schematic diagram of capacitor;
In figure: ordinate is the capacitor specific capacity that different discharging current records, and abscissa is discharging current.
Embodiment
Below in conjunction with embodiment, further illustrate content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation make the present invention or change all fall into scope; And the method in following embodiment, if no special instructions, be the conventional method of this area.
Embodiment 1
A manufacture method for lithium-ion capacitor, step is as follows:
(1) be that the slurry of active material is attached on non-porous aluminum foil as positive pole with active carbon, carbonaceous mesophase spherules is that the slurry of active material is attached on atresia Copper Foil as negative pole, PP/PE/PP tri-one polymer is barrier film, battery core is become according to the mode lamination of barrier film, negative pole, barrier film, positive pole, blend compounds band is fixed, and plus plate current-collecting body, negative current collector is welded with positive and negative electrode lug or leading-out terminal respectively;
(2) after drying, the immersion of this battery core is filled in the beaker of LiPF6-EC/PC/DEC solution;
(3) positive pole, negative pole is connected respectively with the both positive and negative polarity of charge-discharge test instrument, to be equivalent to the electric current constant current charge of 0.1C to 3.8V, at 3.8V constant voltage 1h, then open circuit leaves standstill 1h and allows monomer naturally discharge, circuit 0.1C constant current charge is again connected to 3.8V after 1h, and then open circuit discharges 1h naturally, so repeatedly through 3 charging/self discharge pulse periods process;
(4) battery core in step (3) is taken out, be put in plastic-aluminum shell, inject electrolyte, be assembled into flexible package monomer.
Embodiment 2
A manufacture method for lithium-ion capacitor, step is as follows:
(1) be that the slurry of active material is attached on non-porous aluminum foil as positive pole with active carbon, Delanium is that the slurry of active material is attached on atresia Copper Foil as negative pole, PP/PE/PP tri-one polymer is barrier film, battery core is become according to the mode lamination of barrier film, negative pole, barrier film, positive pole, blend compounds band is fixed, and plus plate current-collecting body, negative current collector is welded with positive and negative electrode lug or leading-out terminal respectively;
(2) after drying, battery core immersion is filled in the beaker of LiBF4-PC/DMF solution;
(3) positive pole, negative pole is connected respectively with the both positive and negative polarity of charge-discharge test instrument, to be equivalent to the electric current constant current charge of 0.1C to 3.8V, then open circuit leaves standstill 2h and allows monomer naturally discharge, circuit 0.1C constant current charge is again connected to 3.8V after 2h, and then open circuit discharges 2h naturally, so repeatedly through 10 charging/self discharge pulse periods process;
(4) battery core in step (3) is taken out, be put in square aluminum hull, inject electrolyte, be assembled into square individual.
Embodiment 3
A manufacture method for lithium-ion capacitor, step is as follows:
(1) be that the slurry of active material is attached on porous aluminium foil as positive pole with active carbon, hard charcoal is that the slurry of active material is attached on porous copper foil as negative pole, individual layer PP polymer film is barrier film, battery core is wound into according to the mode of barrier film, negative pole, barrier film, positive pole, blend compounds band is fixed, and plus plate current-collecting body, negative current collector is welded with positive and negative electrode lug or leading-out terminal respectively;
(2) after drying, battery core immersion is filled Li
2cO
3in the beaker of organic solution;
(3) positive pole is connected respectively with the both positive and negative polarity of charge-discharge test instrument, negative pole, to be equivalent to the electric current constant current charge of 0.2C to 3.8V, then open circuit leaves standstill the regular hour and allows monomer naturally discharge, and then connect circuit 0.2C constant current charge to 3.8V, and then open circuit discharges the regular hour naturally, through 50 charging/self discharge pulse period process, (wherein the self discharge time in 1st ~ 10 cycles is 0.5h so repeatedly, the self discharge time in 11st ~ 20 cycles is 1h, the self discharge time in 21st ~ 30 cycles is 1.5h, the self discharge time in 31st ~ 40 cycles is 2h, the self discharge time in 40th ~ 50 cycles is 3h),
(4) battery core in step (3) is taken out, be put in circular aluminum hull, inject electrolyte, be assembled into circular monomer.
Comparative example 1:
A manufacture method for lithium-ion capacitor, step is as follows:
(1) be that the slurry of active material is attached on porous aluminium foil as positive pole with active carbon, hard charcoal is that the slurry of active material is attached on porous copper foil as negative pole, PP/PE/PP tri-one polymer is barrier film, lithium paper tinsel is closely crimped on Copper Foil as lithium electrode, battery core is become according to the mode lamination of barrier film, positive pole, barrier film, negative pole, barrier film, lithium electrode, barrier film, blend compounds band is fixed, and plus plate current-collecting body, negative current collector, lithium electrode collector is welded with positive and negative electrode lug or leading-out terminal respectively;
(2) this battery core is put in plastic-aluminum shell, injects LiPF6-EC/PC/DEC electrolysis of solutions liquid, be assembled into flexible package monomer;
(3) the embedding lithium of short circuit: negative pole and lithium electrode are carried out by wire direct short-circuit the embedding lithium that discharges;
Comparative example 2:
A manufacture method for lithium-ion capacitor, step is as follows:
(1) be that the slurry of active material is attached on porous aluminium foil as positive pole with active carbon, Delanium is that the slurry of active material is attached on porous copper foil as negative pole, PP/PE/PP tri-one polymer is barrier film, lithium paper tinsel is closely crimped on Copper Foil as lithium electrode, battery core is become according to the mode lamination of barrier film, positive pole, barrier film, negative pole, barrier film, lithium electrode, barrier film, blend compounds band is fixed, and plus plate current-collecting body, negative current collector, lithium electrode collector is welded with positive and negative electrode lug or leading-out terminal respectively;
(2) this battery core is put in square aluminum hull, injects LiBF4-PC/DMF electrolysis of solutions liquid, be assembled into square individual;
(3) the embedding lithium of short circuit: negative pole and lithium electrode are carried out by wire direct short-circuit the embedding lithium that discharges;
Comparative example 3:
A manufacture method for lithium-ion capacitor, step is as follows:
(1) be that the slurry of active material is attached on porous aluminium foil as positive pole with active carbon, hard charcoal is that the slurry of active material is attached on porous copper foil as negative pole, individual layer PP polymer film is barrier film, lithium paper tinsel is closely crimped on Copper Foil as lithium electrode, battery core is wound into according to the mode of barrier film, positive pole, barrier film, negative pole, barrier film, lithium electrode, barrier film, blend compounds band is fixed, and plus plate current-collecting body, negative current collector, lithium electrode collector is welded with positive and negative electrode lug or leading-out terminal respectively;
(2) this battery core is put in circular aluminum hull, injects Li
2cO
3organic solution, be assembled into circular monomer flexible package monomer;
(3) the embedding lithium of short circuit: negative pole and lithium electrode are carried out by wire direct short-circuit the embedding lithium that discharges;
Comparative example 4:
The Super capacitor FB series that commercial NEC-tokin produces.
Detection method and result:
1, the specific capacity of capacitor
Use LRBT-02 battery performance comprehensive detector, embodiment and comparative example are carried out specific discharge capacity test at 1C, 5C and 10C respectively, and result as shown in Figure 1.
2, capability retention
Use 1C respectively, 5C and 10C carries out discharge and recharge to embodiment and comparative example, and record its capability retention, result is as shown in table 1.
3, lithium-inserting amount first
Charge-discharge test instrument is connected by outside, can the lithium-inserting amount of Real-Time Monitoring capacitor, result is as shown in table 2.
As shown in Figure 1, the lithium-ion capacitor using pre-embedding lithium method of the present invention to make, has significantly higher specific capacity, and in high current discharge situation, the fall of capacitor specific capacity is less than to the lithium-ion capacitor of traditional handicraft making.
Table 1:
As shown in Table 1, adopt the lithium-ion capacitor that method of the present invention makes, with the lithium-ion capacitor by negative pole and lithium electrode short circuit are made as pre-embedding lithium method, under each charging and discharging currents, the circulation of a small amount of number of times all can ensure higher capacity, and after repeatedly cycle charge-discharge, the capacitor that method of the present invention makes has higher capability retention, and stable result is had under different electric current, the height of embedding lithium degree have impact on couple capacitors life-span and result of use, table 1 result describes the pre-embedding lithium mode that the present invention uses, better effect can be played to capacitor, ensure that the groundwork of capacitor makes capacitor have more stable Long-Term Properties simultaneously, improve the life-span of capacitor.
Table 2:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Lithium-inserting amount (mAh/g) first | 112.3±5.7 | 114.2±6.1 | 114.5±9.4 |
As shown in Table 2, the first lithium-inserting amount impact of charge and discharge cycles on capacitor of different time and electric current is little, and needed for less electric current, the discharge and recharge time is longer, slightly can promote the lithium-inserting amount of capacitor, can improve useful life and the efficiency for charge-discharge of capacitor.
Claims (8)
1. the embedding lithium method of the New Pre of lithium-ion capacitor, it is characterized in that, step is as follows:
(1) negative pole, barrier film, positive pole, barrier film are stacked gradually or after reeling by adhesive tape fixing composition battery core, battery core is immersed in the organic solution containing lithium salts;
(2) positive pole is connected charge-discharge test instrument respectively with negative pole, after once charging, carries out single step of releasing electricity as a circulation, carry out 1-100 circulation altogether, complete the pre-embedding lithium of anticathode;
(3) battery core after being completed by pre-embedding lithium is taken out, and puts into pack case, injects electrolyte and is assembled into lithium-ion capacitor monomer.
2. the embedding lithium method of the New Pre of a kind of lithium-ion capacitor as claimed in claim 1, is characterized in that, in described positive pole and negative pole, collector is atresia or porose collector.
3. the embedding lithium method of the New Pre of a kind of lithium-ion capacitor as claimed in claim 1, is characterized in that, described lithium salts is LiPF
6, LiBF
4, LiClO
4, LiAlO
4, LiOH, Li
2cO
3, CH
3cOOLi, LiNO
3, LiB (C
2o
4)
2, LiP (C
6h
4o
2)
3, LiPF
3(C
2f
5)
3, LiN (SO
2cF
3)
2etc. at least one dissolved in the lithium salts of organic solvent, organic solution is at least one in PC, EC, DEC, DMC, DMF, DME, THF, SL.
4. the embedding lithium method of the New Pre of a kind of lithium-ion capacitor as claimed in claim 1, is characterized in that, in described circulation, electric discharge is tester electric discharge or battery core self discharge.
5. the embedding lithium method of the New Pre of a kind of lithium-ion capacitor as claimed in claim 1, is characterized in that, described charging and discharging is constant current, and electric current is 0.01C-10C.
6. the embedding lithium method of the New Pre of a kind of lithium-ion capacitor as claimed in claim 1, is characterized in that, the highest cut-ff voltage of described charging is 3.6V-4.2V.
7. the embedding lithium method of New Pre of a kind of lithium-ion capacitor as described in claim 1,4,5 and 6, it is characterized in that, the charging and discharging currents in described each circulation, charging/discharging voltage can be identical, also can be different.
8. the embedding lithium method of New Pre of a kind of lithium-ion capacitor as described in claim 1,4,5 and 7, is characterized in that, in described each circulation, discharge time is 1min-10h.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410764686.1A CN104681311B (en) | 2014-12-12 | 2014-12-12 | A kind of new pre-embedding lithium method of lithium-ion capacitor |
| AU2015100980A AU2015100980A4 (en) | 2014-12-12 | 2015-07-23 | A new lithium pre-insertion method for lithium ion capacitors |
| PCT/CN2015/088970 WO2016090977A1 (en) | 2014-12-12 | 2015-09-06 | Novel lithium pre-embedding method for lithium ion capacitor |
| NL2015824A NL2015824B1 (en) | 2014-12-12 | 2015-11-20 | Pre-embedment method for Li-ion capacitors. |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410764686.1A CN104681311B (en) | 2014-12-12 | 2014-12-12 | A kind of new pre-embedding lithium method of lithium-ion capacitor |
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| CN104681311B CN104681311B (en) | 2017-12-19 |
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|---|---|
| CN (1) | CN104681311B (en) |
| AU (1) | AU2015100980A4 (en) |
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| WO (1) | WO2016090977A1 (en) |
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| CN105355457A (en) * | 2015-12-16 | 2016-02-24 | 上海奥威科技开发有限公司 | Lithium ion capacitor and formation method thereof |
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| WO2016090977A1 (en) * | 2014-12-12 | 2016-06-16 | 宁波南车新能源科技有限公司 | Novel lithium pre-embedding method for lithium ion capacitor |
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Also Published As
| Publication number | Publication date |
|---|---|
| AU2015100980A4 (en) | 2015-09-17 |
| WO2016090977A1 (en) | 2016-06-16 |
| CN104681311B (en) | 2017-12-19 |
| NL2015824A (en) | 2016-09-20 |
| NL2015824B1 (en) | 2017-02-15 |
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