CN104681311B - A kind of new pre-embedding lithium method of lithium-ion capacitor - Google Patents
A kind of new pre-embedding lithium method of lithium-ion capacitor Download PDFInfo
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- CN104681311B CN104681311B CN201410764686.1A CN201410764686A CN104681311B CN 104681311 B CN104681311 B CN 104681311B CN 201410764686 A CN201410764686 A CN 201410764686A CN 104681311 B CN104681311 B CN 104681311B
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- lithium
- negative pole
- ion capacitor
- embedding
- battery core
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 79
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000003990 capacitor Substances 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000007600 charging Methods 0.000 claims abstract description 17
- 230000004087 circulation Effects 0.000 claims abstract description 14
- 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 8
- 230000004888 barrier function Effects 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910010088 LiAlO4 Inorganic materials 0.000 claims description 2
- 229910013406 LiN(SO2CF3)2 Inorganic materials 0.000 claims description 2
- 229910013884 LiPF3 Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- 239000002390 adhesive tape Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 125000001292 4,6-dihydroxy-1,3-phenylene group Chemical group OC1=C(C=C(C(=C1)O)*)* 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 239000002002 slurry Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000011149 active material Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- 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
- 238000002360 preparation method Methods 0.000 description 6
- 230000008569 process Effects 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
- 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
- 230000000694 effects Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process 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
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 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
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process 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
-
- 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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- Engineering & Computer Science (AREA)
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Wood Science & Technology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of new pre-embedding lithium method of lithium-ion capacitor, and step is as follows：（1）Battery core is assembled, and is immersed in the organic solution containing lithium salts；（2）Positive pole and negative pole are connected into charge-discharge test instrument respectively, once to be discharged after once charging as a circulation, 1 100 circulations is carried out altogether, completes the pre- embedding lithium to negative pole；（3）Battery core after the completion of pre- embedding lithium is taken out, is put into pack case, injects electrolyte and is assembled into lithium-ion capacitor monomer.The too high problem of cost caused by can effectively solving lithium metal, porous current collector etc. using the present invention, can improve security, and simplification of flowsheet, suitable for industrialized production.
Description
Technical field
The present invention relates to lithium-ion capacitor field, more particularly to a kind of new pre- embedding lithium side of lithium-ion capacitor
Method.
Background technology
Lithium-ion capacitor is the new typical hybrid energy storage by lithium ion battery and double electric layers supercapacitor " inside simultaneously "
Device, have the advantages that high-energy-density of lithium-ion capacitor is with ultracapacitor high-specific-power, long-life concurrently, military project space flight,
The fields such as green energy resource are with a wide range of applications.The pre-embedding lithium method of lithium-ion capacitor typically uses Fuji Heavy at present
Method in industry patent of invention CN101138058B, i.e., the use of the metal foil with through hole is collector using lithium metal as lithium source,
Lithium metal is positioned over the relative position of negative pole, by short circuit lithium metal and negative pole, utilizes the potential between lithium metal and negative pole
Difference electric discharge is so as to by lithium insertion negative pole.This method can obtain energy density and the high Large Copacity large-scale electric power storage dress of output density
Put, and there is good charge-discharge characteristic, but problems be present：(1) lithium paper tinsel chemical property is extremely active so that lithium-ion electric
The production of container is high to environmental requirement；(2) used in amounts of lithium will be precisely controlled, and the very few improvement to voltage of lithium amount does not reach pre-
Phase effect, lithium amount is excessive to make monomer larger potential safety hazard be present again, therefore the uniformity of monomer is poor；(3) lithium-ion electric
Container fabrication process is complicated, and the key raw material such as lithium metal, porous current collector uses the cost for causing lithium-ion capacitor
It is high.
Existing process also have by short circuit negative pole and the short circuit dischange of lithium metal assign lithium mode be changed to negative pole and lithium metal it
Between connect charge-discharge test instrument, by electric discharge or charge and discharge cycles may be to lithium by Lithium-ion embeding carbon material used as anode, this method
The performance of ionistor monomer has been lifted, but can not solve the problems such as security, production cost.
Chinese patent CN102385991A discloses a kind of method for manufacturing lithium-ion capacitor and utilizes its manufacture
Lithium-ion capacitor, the method for pre- embedding lithium is thin by vacuum vapor deposition formation lithium on one surface of the membrane in this invention
Film, make lithium film relative with negative pole, with the pre- embedded negative poles of the Li+ in lithium film.Compared to the method for Fuji Heavy, this method has
Following advantage：(1) because lithium film is directly contacted with negative pole to carry out pre- embedding lithium during then, therefore without using logical
Hole collector, it can so reduce product internal resistance；(2) the method can more conveniently control the dosage of lithium, and security increases；
(3) every layer of negative pole directly contacts tax lithium with lithium film, is substantially shorter the pre- tax lithium time.This method is possible in theory, but its
Practical feasibility still needs to be investigated.
The flat seminars of Zheng Jian (W.J.Cao, 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.) to have the nano level metal lithium powder of passivating film using surface be lithium source, it is and hard
Negative pole is made with dry process after carbon mixing, activated carbon is that positive pole is assembled into lithium-ion capacitor monomer.Make compared to Fuji Heavy
With the structure of lithium metal foil, the lithium-ion capacitor of the structure can be manufactured in drying shed, the harshness without glove box
Environment, considerably increase operability.
The content of the invention
High in order to solve the pre- embedding lithium production cost of lithium-ion capacitor, potential safety hazard is big, the problem of complex process, we
A kind of new pre-embedding lithium method of lithium-ion capacitor is proposed, can effectively solve lithium metal, porous afflux using the present invention
The too high problem of cost caused by body etc., security, and simplification of flowsheet can be improved, suitable for industrialized production.
The present invention is achieved by the following technical solutions：
To achieve the above object, the present invention provides a kind of new pre-embedding lithium method of lithium-ion capacitor, and step is as follows：
(1) composition battery core is fixed with adhesive tape after negative pole, barrier film, positive pole, barrier film being stacked gradually or wound, battery core is immersed
In organic solution containing lithium salts；
(2) positive pole and negative pole are connected into charge-discharge test instrument respectively, one is used as once to be discharged after once charging
Circulation, 1-100 circulation is carried out altogether, completes the pre- embedding lithium to negative pole；
(3) battery core after the completion of pre- embedding lithium is taken out, be put into pack case, inject electrolyte and be assembled into lithium-ion capacitance
Device monomer.
Preferably, above-mentioned plus plate current-collecting body can be the paper tinsels of metal or netted such as aluminum, stainless steel, iron, nickel, paper tinsel used
There can be hole or non-porous.
Preferably, above-mentioned negative current collector can be the paper tinsels of metal or netted such as copper, stainless steel, iron, nickel, and paper tinsel used can
To there is hole or non-porous.
Preferably, above-mentioned lithium salts used can be LiPF6、LiBF4、LiClO4、LiAlO4、LiOH、Li2CO3、
CH3COOLi、LiNO3、LiB(C2O4)2、LiP(C6H4O2)3、LiPF3(C2F5)3、LiN(SO2CF3)2Etc. dissolving in organic solvent
One or more in lithium salts.
Preferably, above-mentioned organic solution is at least containing one kind in PC, EC, DEC, DMC, DMF, DME, THF, SL.
Preferably, mode positive pole connected with negative pole is to be attached positive pole and negative pole by charging/discharging apparatus.
Resistant series connection can be added in whole loop, can also be directly connected to without resistance.
Preferably, the battery core for immersing lithium salts organic solution charge → discharge or charging → self discharge circulate operation,
Its charging current and discharge current are constant current.Specifically, constant current can be based on positive pole quality or negative pole quality or electricity
Current value corresponding to 0.01C~10C multiplying powers of core Mass Calculation.
Preferably, the cycle-index of charge and discharge cycles operation is 1~100 time, the highest blanking voltage of charging 3.6V~
Between 4.2V, the charge cutoff voltage in each circulation can be with identical, can also be different.
Preferably, the charging current in circulation can be with identical every time, can also be different；The discharge current in circulation can every time
, can also be different with identical.There can be one section of constant voltage process after each charging process terminates, also can be without constant voltage process.
Preferably, the self discharge time is 1min~10h in each circulation.And the self discharge time in each circulation can phase
Together, can also be different.
Compared with prior art, the beneficial effects of the present invention are：
(1) lithium paper tinsel or nano level metal lithium are substituted by using the organic solvent containing lithium salts, reduces cost, simultaneously
Cost is also significantly reduced using non-porous collector；
(2) lithium paper tinsel is substituted using the organic solvent containing lithium salts, without processing in extreme circumstances, improves the safety of processing
Property；
(3) positive pole and negative pole are connected with charge-discharge test instrument, the time of pre- embedding lithium can be shortened, and improve the effect of pre- embedding lithium
Fruit；
(4) simplification of flowsheet, can large-scale industrial production.
Brief description of the drawings
Fig. 1 is the specific capacity test schematic diagram of capacitor；
In figure：Ordinate is the capacitor specific capacity that different discharge currents measure, and abscissa is discharge current.
Embodiment
With reference to embodiment, present disclosure is further illustrated.It should be appreciated that the implementation of the present invention is not limited to
In the following examples, any formal accommodation or change made to the present invention both fall within the scope of the present invention；Under and
The method in embodiment is stated, is the conventional method of this area unless otherwise instructed.
Embodiment 1
A kind of preparation method of lithium-ion capacitor, step are as follows：
(1) slurry using activated carbon as active material is attached on non-porous aluminum foil as positive pole, and carbonaceous mesophase spherules are work
The slurry of property material, which is attached on non-porous copper foil, is used as negative pole, and the one polymer of PP/PE/PP tri- is barrier film, according to barrier film, negative pole,
Barrier film, the mode lamination of positive pole are fixed into battery core, blend compounds band, by plus plate current-collecting body, negative current collector respectively with positive and negative electrode pole
Ear or leading-out terminal are welded；
(2) battery core is immersed in the beaker for filling LiPF6-EC/PC/DEC solution after drying；
(3) positive pole, negative pole are connected respectively with the both positive and negative polarity of charge-discharge test instrument, with the electric current constant-current charge equivalent to 0.1C
To 3.8V, in 3.8V constant pressure 1h, it is then turned off circuit standing 1h and allows monomer to discharge naturally, circuit 0.1C constant currents are again switched on after 1h
3.8V is charged to, then disconnecting circuit discharges 1h naturally again, so repeatedly by 3 chargings/self discharge pulse period processing；
(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 kind of preparation method of lithium-ion capacitor, step are as follows：
(1) slurry using activated carbon as active material is attached to as positive pole on non-porous aluminum foil, and Delanium is active matter
The slurry of matter, which is attached on non-porous copper foil, is used as negative pole, and the one polymer of PP/PE/PP tri- is barrier film, according to barrier film, negative pole, barrier film,
The mode lamination of positive pole is fixed into battery core, blend compounds band, by plus plate current-collecting body, negative current collector respectively with positive and negative electrode lug or
Leading-out terminal is welded；
(2) battery core is immersed in the beaker for filling LiBF4-PC/DMF solution after drying；
(3) positive pole, negative pole are connected respectively with the both positive and negative polarity of charge-discharge test instrument, with the electric current constant-current charge equivalent to 0.1C
To 3.8V, it is then turned off circuit and stands 2h allowing monomer to discharge naturally, circuit 0.1C constant-current charges is again switched on after 2h to 3.8V, so
Disconnecting circuit discharges 2h naturally again afterwards, so repeatedly by 10 chargings/self discharge pulse period processing；
(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 kind of preparation method of lithium-ion capacitor, step are as follows：
(1) slurry using activated carbon as active material is attached on porous aluminium foil as positive pole, and hard charcoal is active material
Slurry, which is attached on porous copper foil, is used as negative pole, and individual layer PP polymer films are barrier film, according to barrier film, negative pole, barrier film, positive pole side
Formula is wound into battery core, and blend compounds band is fixed, by plus plate current-collecting body, negative current collector respectively with positive and negative electrode lug or leading-out terminal
Welded；
(2) battery core is immersed after drying and fills Li2CO3In the beaker of organic solution；
(3) positive pole, negative pole are connected respectively with the both positive and negative polarity of charge-discharge test instrument, with the electric current constant-current charge equivalent to 0.2C
To 3.8V, it is then turned off circuit and stands the regular hour allowing monomer to discharge naturally, is then again switched on circuit 0.2C constant-current charges
To 3.8V, then disconnecting circuit discharges the regular hour naturally again, so repeatedly by 50 chargings/at the self discharge pulse period
Reason (the self discharge time in wherein the 1st~10 cycle is 0.5h, and self discharge time in the 11st~20 cycle is 1h, the 21st~
The self discharge time in 30 cycles is 1.5h, and self discharge time in the 31st~40 cycle is 2h, the 40th~50 cycle from
Discharge time 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 kind of preparation method of lithium-ion capacitor, step are as follows：
(1) slurry using activated carbon as active material is attached on porous aluminium foil as positive pole, and hard charcoal is active material
Slurry, which is attached on porous copper foil, is used as negative pole, and the one polymer of PP/PE/PP tri- is barrier film, and lithium paper tinsel, which is closely crimped on copper foil, to be made
For lithium electrode, lamination is fixed into battery core, blend compounds band in the way of barrier film, positive pole, barrier film, negative pole, barrier film, lithium electrode, barrier film, will
Plus plate current-collecting body, negative current collector, lithium electrode collector are welded with positive and negative electrode lug or leading-out terminal respectively；
(2) battery core is put in plastic-aluminum shell, injects LiPF6-EC/PC/DEC solution electrolyte, be assembled into flexible package list
Body；
(3) the embedding lithium of short circuit：Negative pole and lithium electrode are subjected to the embedding lithium that discharges by wire direct short-circuit；
Comparative example 2：
A kind of preparation method of lithium-ion capacitor, step are as follows：
(1) slurry using activated carbon as active material is attached to as positive pole on porous aluminium foil, and Delanium is active matter
The slurry of matter, which is attached on porous copper foil, is used as negative pole, and the one polymer of PP/PE/PP tri- is barrier film, and lithium paper tinsel is closely crimped on copper foil
Upper to be used as lithium electrode, lamination is consolidated into battery core, blend compounds band in the way of barrier film, positive pole, barrier film, negative pole, barrier film, lithium electrode, barrier film
It is fixed, plus plate current-collecting body, negative current collector, lithium electrode collector are welded with positive and negative electrode lug or leading-out terminal respectively；
(2) battery core is put in square aluminum hull, injects LiBF4-PC/DMF solution electrolyte, be assembled into square individual；
(3) the embedding lithium of short circuit：Negative pole and lithium electrode are subjected to the embedding lithium that discharges by wire direct short-circuit；
Comparative example 3：
A kind of preparation method of lithium-ion capacitor, step are as follows：
(1) slurry using activated carbon as active material is attached on porous aluminium foil as positive pole, and hard charcoal is active material
Slurry, which is attached on porous copper foil, is used as negative pole, and individual layer PP polymer films are barrier film, and lithium paper tinsel, which is closely crimped on copper foil, is used as lithium
Pole, battery core is wound into the way of barrier film, positive pole, barrier film, negative pole, barrier film, lithium electrode, barrier film, blend compounds band is fixed, by positive pole
Collector, negative current collector, lithium electrode collector are welded with positive and negative electrode lug or leading-out terminal respectively；
(2) battery core is put in circular aluminum hull, injects Li2CO3Organic solution, be assembled into circular monomer flexible package list
Body；
(3) the embedding lithium of short circuit：Negative pole and lithium electrode are subjected to the embedding lithium that discharges by wire direct short-circuit；
Comparative example 4：
The Super capacitor FB series of NEC-tokin productions purchased in market.
Detection method and result：
1st, the specific capacity of capacitor
Using LRBT-02 battery performance comprehensive detectors, embodiment and comparative example are put in 1C, 5C and 10C respectively
Electric specific capacity test, as a result as shown in Figure 1.
2nd, capability retention
Use 1C, 5C and 10C to carry out discharge and recharge to embodiment and comparative example respectively, record its capability retention, as a result such as
Shown in table 1.
3rd, lithium-inserting amount first
By external connection charge-discharge test instrument, can monitoring capacitor in real time lithium-inserting amount, as a result as shown in table 2.
As shown in Figure 1, the lithium-ion capacitor made using the pre-embedding lithium method of the present invention, there is significantly higher specific volume
Amount, and under high current discharge scenario, the lithium-ion capacitance of traditional handicraft making is less than to the fall of capacitor specific capacity
Device.
Table 1：
As shown in Table 1, using the present invention method make lithium-ion capacitor, with by by negative pole and lithium electrode short circuit make
The lithium-ion capacitor made for pre-embedding lithium method, under each charging and discharging currents, the circulation of a small amount of number can all ensure higher
Capacity, and after multiple cycle charge-discharge, the capacitor that method of the invention makes has higher capability retention, Yi Ji
There is stable result under different electric currents, the height of embedding lithium degree have impact on capacitor and life-span and using effect, the result of table 1 are said
The pre- embedding lithium mode that the clear present invention uses, more preferable effect can be played to capacitor, ensures the groundwork of capacitor simultaneously
So that capacitor there are more stable Long-Term Properties, the life-span of capacitor is improved.
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 charge and discharge cycles of different time and electric current influence little on the lithium-inserting amount first of capacitor, smaller
Electric current needed for the discharge and recharge time it is longer, the lithium-inserting amount of capacitor can slightly be lifted, can improve capacitor service life and
Efficiency for charge-discharge.
Claims (3)
1. the new pre-embedding lithium method of a kind of lithium-ion capacitor, it is characterised in that step is as follows：
（1）Composition battery core is fixed with adhesive tape after negative pole, barrier film, positive pole, barrier film are stacked gradually or wound, battery core is immersed and contained
In the organic solution of lithium salts；
（2）Positive pole and negative pole are connected into charge-discharge test instrument respectively, once to be discharged after once charging as a circulation,
1-100 circulation is carried out altogether, completes the pre- embedding lithium to negative pole；
（3）Battery core after the completion of pre- embedding lithium is taken out, is put into pack case, injects electrolyte and is assembled into lithium-ion capacitor list
Body；The lithium salts is LiPF6、LiBF4、LiClO4、LiAlO4、LiOH、Li2CO3、CH3COOLi、LiNO3、LiB(C2O4)2、LiP
(C6H4O2)3、LiPF3(C2F5)3、LiN(SO2CF3)2Dissolve at least one of lithium salts of organic solvent, organic solution PC,
At least one of EC, DEC, DMC, DMF, DME, THF, SL；Electric discharge is tester electric discharge or battery core self discharge in the circulation；
The charging and discharging are constant current, and electric current is 0.01C-10C；The charging highest blanking voltage is 3.6V-4.2V；It is described
Discharge time is 1min-10h in each circulation.
A kind of 2. new pre-embedding lithium method of lithium-ion capacitor as claimed in claim 1, it is characterised in that the positive pole and
Collector is non-porous or have a hole collector in negative pole.
3. the new pre-embedding lithium method of a kind of lithium-ion capacitor as claimed in claim 1, it is characterised in that described each to follow
Charging and discharging currents, charging/discharging voltage in ring can be with identical, can also be different.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
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| 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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| CN104681311B (en) * | 2014-12-12 | 2017-12-19 | 宁波中车新能源科技有限公司 | A kind of new pre-embedding lithium method of lithium-ion capacitor |
| CN104701031B (en) * | 2014-12-12 | 2018-01-09 | 宁波中车新能源科技有限公司 | The preparation method and lithium-ion capacitor of a kind of lithium-ion capacitor |
| CN105355457B (en) * | 2015-12-16 | 2018-01-19 | 上海奥威科技开发有限公司 | Lithium-ion capacitor and its chemical synthesizing method |
| CN105679547A (en) * | 2016-03-10 | 2016-06-15 | 南京理工大学 | Nickel ferrite based lithium ion hybrid capacitor and preparation method thereof |
| US20190181430A1 (en) * | 2016-06-15 | 2019-06-13 | Robert Bosch Gmbh | Lithium-ion battery, and the method for producing the same |
| CN106206075A (en) * | 2016-06-22 | 2016-12-07 | 凌容新能源科技（上海）有限公司 | Electrode preparation method and super lithium capacitor fabrication method |
| CN108878974B (en) * | 2017-05-16 | 2021-06-29 | 荣盛盟固利新能源科技有限公司 | Lithium ion battery lithium supplement electrolyte and lithium supplement method |
| CN107731541B (en) * | 2017-09-13 | 2019-04-19 | 东莞凯德新能源有限公司 | A kind of cylinder high-power lithium ion capacitor and preparation method thereof |
| CN109659140A (en) * | 2017-10-11 | 2019-04-19 | 中国科学院大连化学物理研究所 | Lithium ion super capacitor cathode pre-embedding lithium method |
| CN107910186A (en) * | 2017-10-23 | 2018-04-13 | 安徽铜峰电子股份有限公司 | The pre-embedding lithium method of chargeable coin shape lithium-ion capacitor |
| CN109300698B (en) * | 2018-09-28 | 2022-02-18 | 桑顿新能源科技(长沙)有限公司 | Lithium ion capacitor and preparation method thereof |
| CN109786841B (en) * | 2018-12-13 | 2020-12-15 | 中国科学院电工研究所 | Preparation method of lithium ion electrochemical energy storage device |
| CN109801796B (en) * | 2019-01-11 | 2021-01-22 | 东莞凯德新能源有限公司 | Negative electrode lithium pre-embedding method, capacitor and manufacturing method |
| CN110061202B (en) * | 2019-03-18 | 2021-07-06 | 合肥国轩高科动力能源有限公司 | Preparation method of ternary battery positive pole piece and ternary battery |
| CN112635930B (en) * | 2020-12-22 | 2023-02-07 | 东莞东阳光科研发有限公司 | Liquid injection method of lithium-sulfur soft package battery |
| CN113097567B (en) * | 2021-03-29 | 2022-04-12 | 湖南高远电池有限公司 | Manufacturing method of high-energy-density soft package battery |
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| CN203552954U (en) * | 2013-10-30 | 2014-04-16 | 中国第一汽车股份有限公司 | Lithium pre-embedding device for lithium ion capacitor |
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| KR101128654B1 (en) * | 2010-08-19 | 2012-03-26 | 삼성전기주식회사 | Method of pre-doping Lithium ion into electrode and method of manufacturing electrochemical capacitor using the same |
| KR101138502B1 (en) * | 2010-08-27 | 2012-04-25 | 삼성전기주식회사 | Method of manufacturing lithium ion capacitor |
| MX2013007712A (en) * | 2011-10-13 | 2013-09-26 | Tokushu Tokai Paper Co Ltd | Microporous membrane and manufacturing method therefor. |
| CN103050295B (en) * | 2012-12-20 | 2016-03-23 | 上海奥威科技开发有限公司 | A kind of lithium-ion capacitor |
| ES2763631T3 (en) * | 2013-01-30 | 2020-05-29 | Nanoscale Components Inc | Gradual introduction of lithium into the lithium pretreated anode of a lithium ion electrochemical cell |
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| CN104681311B (en) * | 2014-12-12 | 2017-12-19 | 宁波中车新能源科技有限公司 | A kind of new pre-embedding lithium method of lithium-ion capacitor |
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| CN203552954U (en) * | 2013-10-30 | 2014-04-16 | 中国第一汽车股份有限公司 | Lithium pre-embedding device for lithium ion capacitor |
| CN104201320A (en) * | 2014-09-16 | 2014-12-10 | 赵前永 | Method for pre-lithiating electrode material of lithium ion battery |
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| CN104681311A (en) | 2015-06-03 |
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