CN104681311A - Novel lithium pre-embedding method of lithium ion capacitor - Google Patents

Novel lithium pre-embedding method of lithium ion capacitor Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
lithium
ion capacitor
embedding
new
charging
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410764686.1A
Other languages
Chinese (zh)
Other versions
CN104681311B (en
Inventor
阮殿波
曾福娣
傅冠生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NINGBO NANCHE NEW ENERGY TECHNOLOGY Co Ltd
Original Assignee
NINGBO NANCHE NEW ENERGY TECHNOLOGY Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NINGBO NANCHE NEW ENERGY TECHNOLOGY Co Ltd filed Critical NINGBO NANCHE NEW ENERGY TECHNOLOGY Co Ltd
Priority to CN201410764686.1A priority Critical patent/CN104681311B/en
Publication of CN104681311A publication Critical patent/CN104681311A/en
Application granted granted Critical
Publication of CN104681311B publication Critical patent/CN104681311B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/04Hybrid capacitors
    • H01G11/06Hybrid capacitors with one of the electrodes allowing ions or anions to be reversibly doped thereinto, e.g. lithium-ion capacitors [LICs]
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/14Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/32Carbon-based, e.g. activated carbon materials
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/50Electrodes characterised by their materials specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/54Electrolytes
    • H01G11/58Liquid electrolytes
    • H01G11/60Liquid electrolytes characterised by the solvent
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/54Electrolytes
    • H01G11/58Liquid electrolytes
    • H01G11/62Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
    • H01M50/429Natural polymers
    • H01M50/4295Natural cotton, cellulose or wood
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/44Fibrous material
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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

A kind of embedding lithium method of New Pre of lithium-ion capacitor
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.
CN201410764686.1A 2014-12-12 2014-12-12 A kind of new pre-embedding lithium method of lithium-ion capacitor Active CN104681311B (en)

Priority Applications (1)

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

Applications Claiming Priority (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.

Publications (2)

Publication Number Publication Date
CN104681311A true CN104681311A (en) 2015-06-03
CN104681311B CN104681311B (en) 2017-12-19

Family

ID=53316226

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410764686.1A Active CN104681311B (en) 2014-12-12 2014-12-12 A kind of new pre-embedding lithium method of lithium-ion capacitor

Country Status (4)

Country Link
CN (1) CN104681311B (en)
AU (1) AU2015100980A4 (en)
NL (1) NL2015824B1 (en)
WO (1) WO2016090977A1 (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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
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
WO2017214894A1 (en) * 2016-06-15 2017-12-21 Robert Bosch Gmbh Lithium-ion battery, and the method for producing the same
CN107731541A (en) * 2017-09-13 2018-02-23 东莞凯德新能源有限公司 A kind of cylindrical high-power lithium ion capacitor and preparation method thereof
CN108878974A (en) * 2017-05-16 2018-11-23 中信国安盟固利动力科技有限公司 A kind of lithium ion battery mends lithium electrolyte and mends lithium method
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
CN109786841A (en) * 2018-12-13 2019-05-21 中国科学院电工研究所 A kind of preparation method of lithium ion electrochemical energy storage device
CN109801796A (en) * 2019-01-11 2019-05-24 东莞凯德新能源有限公司 A kind of cathode pre-embedding lithium method and capacitor and production method
CN110061202A (en) * 2019-03-18 2019-07-26 合肥国轩高科动力能源有限公司 A kind of preparation method and ternary battery of ternary battery positive pole piece

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2014120718A1 (en) * 2013-01-30 2014-08-07 Nanoscale Components, Inc. Phased introduction of lithium into the pre-lithiated anode of a lithium ion electrochemical cell
CN104201320A (en) * 2014-09-16 2014-12-10 赵前永 Method for pre-lithiating electrode material of lithium ion battery

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101138058B (en) * 2005-03-31 2011-03-30 富士重工业株式会社 Lithium ion capacitor
CN101847513B (en) * 2010-02-26 2013-08-07 上海奥威科技开发有限公司 Preparation process of long-lived negative pole piece and capacitor battery using negative pole piece
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
US8735000B2 (en) * 2011-10-13 2014-05-27 Tokushu Tokai Paper Co., Ltd. Porous membrane and process for preparing the same
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
CN104037458B (en) * 2014-05-16 2017-02-22 中国科学院电工研究所 Manufacturing method of lithium ion energy storage device
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014120718A1 (en) * 2013-01-30 2014-08-07 Nanoscale Components, Inc. Phased introduction of lithium into the pre-lithiated anode of a lithium ion electrochemical cell
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

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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
CN109314269A (en) * 2016-06-15 2019-02-05 罗伯特·博世有限公司 Lithium ion battery and preparation method thereof
WO2017214894A1 (en) * 2016-06-15 2017-12-21 Robert Bosch Gmbh Lithium-ion battery, and the method for producing the same
CN109314269B (en) * 2016-06-15 2021-10-29 罗伯特·博世有限公司 Lithium ion battery and preparation method thereof
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
CN108878974A (en) * 2017-05-16 2018-11-23 中信国安盟固利动力科技有限公司 A kind of lithium ion battery mends lithium electrolyte and mends lithium 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
CN107731541A (en) * 2017-09-13 2018-02-23 东莞凯德新能源有限公司 A kind of cylindrical high-power lithium ion capacitor and preparation method thereof
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
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
CN109786841A (en) * 2018-12-13 2019-05-21 中国科学院电工研究所 A kind of preparation method of lithium ion electrochemical energy storage device
CN109801796A (en) * 2019-01-11 2019-05-24 东莞凯德新能源有限公司 A kind of cathode pre-embedding lithium method and capacitor and production method
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
CN110061202A (en) * 2019-03-18 2019-07-26 合肥国轩高科动力能源有限公司 A kind of preparation method and ternary battery of ternary battery positive pole piece

Also Published As

Publication number Publication date
WO2016090977A1 (en) 2016-06-16
AU2015100980A4 (en) 2015-09-17
NL2015824B1 (en) 2017-02-15
CN104681311B (en) 2017-12-19
NL2015824A (en) 2016-09-20

Similar Documents

Publication Publication Date Title
CN104681311A (en) Novel lithium pre-embedding method of lithium ion capacitor
CN104701031A (en) Lithium ion capacitor manufacturing method and lithium ion capacitor
CN103413904B (en) A kind of manufacture method of diaphragm for polymer lithium ion battery
CN101699590B (en) Hybrid supercapacitor
CN201682023U (en) Lithium ion battery
US20120321913A1 (en) Manufacturing method for long-lived negative electrode and capacitor battery adopting the same
CN108427077A (en) A kind of experimental method for analysing lithium using reference electrode monitoring cathode
CN105355457B (en) Lithium-ion capacitor and its chemical synthesizing method
CN109817473B (en) Lithium pre-embedding method of lithium ion electrochemical energy storage device
CN105449166B (en) A kind of preparation method of sodium-ion battery cathode pole piece
Ping et al. Electrochemical performance of MCMB/(AC+ LiFePO 4) lithium-ion capacitors
CN105655147A (en) Lithium-ion capacitor negative electrode unit and preparation method thereof, and lithium-ion capacitor
CN103050732B (en) Lithium titanate-based chemical power supply
CN105761944B (en) A kind of hybrid super capacitor anode composite piece and preparation method thereof, hybrid super capacitor
CN108155027B (en) A kind of method of the pre- embedding lithium of lithium ion super capacitor cathode
WO2020118880A1 (en) Graphite positive electrode and zinc negative electrode-based hybrid super capacitor
CN106449126A (en) Method of embedding lithium for lithium ion capacitor by using third electrodes
CN102299375B (en) Lithium ion power battery and preparation method thereof
CN208352138U (en) A kind of electrochemical energy storage device
CN103367700B (en) Lithium ion secondary battery cathode and lithium rechargeable battery
CN107591249B (en) Electrochemical energy storage device
CN106409529B (en) A kind of embedding lithium method of lithium-ion capacitor
CN202585619U (en) Novel lithium ion battery cathode and lithium ion battery employing cathode
KR101863441B1 (en) Lithium secondary cell including a cathode active material structure
CN109346335A (en) Lithium source active material, anode pole piece, lithium-ion capacitor and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information
CB02 Change of applicant information

Address after: 315112 Zhejiang city of Ningbo province Yinzhou District five Township Wuxiang No. 552 West Road

Applicant after: Ningbo CRRC New Energy Technology Co.,Ltd.

Address before: 315112 Zhejiang city of Ningbo province Yinzhou District five Township Wuxiang No. 552 West Road

Applicant before: Ningbo Nanche New Energy Technology Co., Ltd.

GR01 Patent grant
GR01 Patent grant