NL2015824B1 - Pre-embedment method for Li-ion capacitors. - Google Patents
Pre-embedment method for Li-ion capacitors. Download PDFInfo
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- NL2015824B1 NL2015824B1 NL2015824A NL2015824A NL2015824B1 NL 2015824 B1 NL2015824 B1 NL 2015824B1 NL 2015824 A NL2015824 A NL 2015824A NL 2015824 A NL2015824 A NL 2015824A NL 2015824 B1 NL2015824 B1 NL 2015824B1
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- 239000003990 capacitor Substances 0.000 title claims abstract description 146
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 61
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 13
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 13
- 238000007600 charging Methods 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000004743 Polypropylene Substances 0.000 claims description 27
- 238000007599 discharging Methods 0.000 claims description 24
- -1 LiAlO04 Chemical compound 0.000 claims description 20
- 229920001155 polypropylene Polymers 0.000 claims description 17
- 239000000835 fiber Substances 0.000 claims description 15
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 12
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 12
- 241001330002 Bambuseae Species 0.000 claims description 12
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 12
- 239000002390 adhesive tape Substances 0.000 claims description 12
- 239000011425 bamboo Substances 0.000 claims description 12
- 239000001913 cellulose Substances 0.000 claims description 12
- 229920002678 cellulose Polymers 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 229910013884 LiPF3 Inorganic materials 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 239000011230 binding agent Substances 0.000 claims 1
- 239000012141 concentrate Substances 0.000 claims 1
- 238000010280 constant potential charging Methods 0.000 claims 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 48
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 37
- 230000008569 process Effects 0.000 abstract description 13
- 238000004806 packaging method and process Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 208000028659 discharge Diseases 0.000 description 124
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 23
- 229910052782 aluminium Inorganic materials 0.000 description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 21
- 239000011888 foil Substances 0.000 description 21
- 239000011149 active material Substances 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- 239000011889 copper foil Substances 0.000 description 12
- 239000004417 polycarbonate Substances 0.000 description 9
- 238000003466 welding Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 6
- 229960004419 dimethyl fumarate Drugs 0.000 description 6
- 229910021385 hard carbon Inorganic materials 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000004804 winding Methods 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
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011325 microbead Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010277 constant-current charging Methods 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
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 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
- 230000003631 expected effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
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- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a novel pre-embedment method for a Li-ion capacitor, comprising the following steps of: (1) assembling a cell, and immersing the cell into an organic solution containing lithium salt; (2) connecting the anode and the cathode to a charge-discharge tester, respectively, to perform total 1 to 100 cycles each comprising one charge followed by one discharge, to finish the pre-embedment into the cathode; and (3) taking out the cell after the pre-embedment and putting the cell into a packaging shell, and injecting electrolyte into the packaging shell to form a single lithium ion capacitor. With the novel pre-embedment method of the preset invention, high cost resulted from the metal lithium and porous current collectors is effectively solved. The safety may be improved and the technological process may be simplified. The novel pre-embedment method of the preset invention is suitable for industrial production.
Description
PRE-EMBEDMENT METHOD FOR LI-ION CAPACITORS Technical Field of the Invention
The present invention relates to the field of Li-ion capacitors, and in particular to a novel pre-embedment method for a Li-ion capacitor.
Background of the Invention
Li-ion capacitors are novel classic hybrid energy storage devices incorporating Li-ion batteries into electric double-layer super capacitors. With both high specific energy of Li-ion capacitors and high specific power, long service life and the like of super capacitors together, such Li-ion capacitors have wide prospect of application in fields such as military aerospace and green energy. At present, the pre-embedment method for Li-ion capacitors is generally as that shown in Patent CN101138058B owned by Fuji Heavy Industries. That is, lithium metal is used as a lithium source and metal foil with through holes as a current collector; the lithium metal is placed in a position opposite to cathode; and by connecting the lithium metal to the cathode in short circuit, discharge is achieved due to a difference in potential between the lithium metal and the cathode, thus to embed the Li-ion into the cathode. By this method, it is possible to obtain a large-capacitance large-scale power storage device which has high energy density and output density and has an excellent charge-discharge characteristic. However, there are the following problems: first, since the chemical properties of lithium and foil are highly active, the production of Li-ion capacitors propose quite high requirements on the environment; second, it is required to precisely control the amount of lithium to be used because too less lithium will not achieve the expected effect while too much lithium will bring great safety risk to a single capacitor, resulting in poor consistency in single capacitors; and third, Li-ion capacitors are complex in manufacturing process, and the use of crucial raw materials such as lithium metal and porous current collector results in high cost of Li-ion capacitors.
In the prior art, there is a case where the short-circuit discharge and lithium doping manner by connection of the cathode to lithium metal in short circuit is changed to connection of a charge-discharge tester between the cathode and the lithium metal, so that the Li-ion is embedded into the cathode carbon material by discharge or charge-discharge cycles. Although this method may allow for somewhat improvement to the performance of a single Li-ion capacitor, it fails to solve safety, production cost and other problems.
Chinese Patent Application CN102385991A disclosed a method for manufacturing a Li-ion capacitor and an application of the manufactured Li-ion capacitor, wherein the disclosed pre-embedment method was to form a lithium film on a surface of a diaphragm by vacuum vapor deposition, bring the lithium film to be opposite to the cathode, and pre-embed the Li+ in the lithium film into the cathode. Compared with the method disclosed by Fuji Heavy Industries, this method has the following advantages: first, since the lithium film is in direct contact with the cathode for pre-embedment in a subsequent process, there is no need to use any through-hole current collector and this may decrease the internal resistance of the products; second, by this method, it may be convenient to control the amount of lithium to be used so that the safety is improved to some extent; and third, since each layer of the cathode is in direct contact with the lithium film for lithium doping, the time required by lithium pre-doping may be greatly shortened. This method is feasible theoretically. However, its practical feasibility remains to be proven. J.P. Zheng team(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.) mixed nanoscale lithium metal powder having a passivation layer on its surface, as a lithium source, with hard carbon to prepare a cathode by a dry process, and then used activated carbon as an anode to form a single Li-ion capacitor. Compared with the structure proposed by Fuji Heavy Industries where lithium foil is used, a Li-ion capacitor of this structure may be manufactured in a dry room, without requiring a severe glovebox environment, thereby greatly increasing the operability.
Summary of the Invention
In order to solve problems of high pre-embedment and production cost, high safety risk, and complex process of a Li-ion capacitor, a novel pre-embedment method for a Li-ion capacitor is proposed. With the novel pre-embedment method of the preset invention, high cost resulted from the lithium metal and porous current collectors is effectively solved. The safety may be improved and the technological process may be simplified. The novel pre-embedment method of the preset invention is suitable for industrial production. The present invention is realized through the following technical solutions: in order to realize the objective, the present invention provides a novel pre-embedment method for a Li-ion capacitor, including the following steps of: (1) stacking or winding a cathode, a diaphragm, an anode and a diaphragm successively and then securing with an adhesive tape to form a cell, and immersing the cell into an organic solution containing lithium salt; (2) connecting the anode and the cathode to a charge-discharge tester, respectively, to perform a number of times, preferably a total 1 to 100 cycles, each including one charge followed by one discharge, to finish the pre-embedment into the cathode; and (3) taking out the cell after the pre-embedment and putting the cell into a packaging shell, and injecting electrolyte into the packaging shell to form a single Li-ion capacitor. Preferably, the anode current collector may be a foil or mesh of metals such as aluminous, stainless steel, iron and nickel, and the foil may be with or without pores.
Preferably, the cathode current collector may be foil or mesh of metals such as copper, stainless steel, iron and nickel, and the foil may be with or without pores.
Preferably, the lithium salt may be one of lithium salts, which are soluble in the organic solution, selected from LiPF6> LiBF4, UCIO4, L1AIO4, LiOH, U2CO3, CFhCOOLi, L1NO3, LiB(C204)2, LiP(C6H402)3, LiPF3(C2F5)3 and LiN(S02CF3)2. PC (polycarbonate), EC (ethylene carbonate), DEC (diethyl carbonate), DMC (dimethyl carbonate), DMF (dimethyl Fumarate), DME (1,2-dimethoxy-ethan) and THF (tetrahydrofuran).
Preferably, the way of connecting the anode to the cathode is connecting the anode to the cathode by charge-discharge equipment. In the whole loop, resistors may be added for connection in series, or direct connection may be realized without any resistors.
Preferably, the cell immersed into an organic solution containing lithium salt is subject to a cycle of charge — discharge or charge — self-discharge, and both the charge current and the discharge current are constant currents. Specifically, the constant current may be a current value corresponding to a rate of 0.01 C -10 C calculated based on the mass of the anode, the cathode or the cell.
Preferably, there is 1 to 100 charge-discharge cycles, the highest cut-off for the charge ranges from 3.6 V to 4.2 V, and the charge cut-off voltage in each of the cycles may be the same or different.
Preferably, the charge current in each of the cycles may be the same or different; and the discharge current in each of the cycles may be the same or different. There may be or may not be a constant voltage process followed by each charge process.
Preferably, the self-discharge in each of the cycles lasts 1 min to 10 h, and the self-discharge duration in each of the cycles may be the same or different.
Preferably, the cyclic charge-discharge processing is performed at a constant temperature ranging from 0°C to 60°C.
The Li-ion capacitor will produce a certain amount of heat during the charge-discharge process to rise the temperature of the cell of the capacitor. If the temperature of the cell of the capacitor is not controlled and when the temperature rises to a certain degree, electrolyte in the cell of the capacitor will decompose to generate a large amount of gas which will shock the cell of the well assembled Li-ion capacitor to damage the diaphragms and plates of the cell. Performing the charge-discharge process at a lower temperature may effectively inhibit the decomposition of the electrolyte in the cell of the capacitor, reduce or even eliminate the generation of gas, and thus protect the diaphragms and plates of the cell of the capacitor against damage.
Preferably, a charge regime in the cyclic discharge process is as follows: (1) at a pre-charge stage: charging with a low current of 0.01-0.05 C when the voltage of the capacitor is lower than 3 V; (2) at a constant-current high-rate charge stage: charging with a current having a charge rate of 0.1-0.5 C when the voltage of the capacitor is greater than 3 V and lower than 3.5 V; (3) at a constant-current low-rate charge stage: charging with a current having a charge rate of 0.05-0.1 C when the voltage of the capacitor is greater than 3.5 V and lower than the highest cut-off voltage; and (4) at a constant voltage charge stage: charging under a constant voltage when the voltage of the capacitor reaches the highest cut-off voltage, until the charge current is lower than 10-20 mA, and then stopping charging, the constant voltage being the highest cut-off voltage; a discharge regime is as follows: (1) at a first discharge stage: discharging with a discharge current having a discharge rate of 1-2 C when the voltage of the capacitor is greater than 3.5V and lower than or equal to the highest cut-off voltage; (2) at a second discharge stage: discharging with a discharge current having a discharge rate of 0.5-1 C when the voltage of the capacitor is greater than 3V and lower than or equal to 3.5 V; and (3) at a third discharge stage: discharging with a discharge current having a low discharge rate of 0.1-0.5 C when the voltage of the capacitor is lower than 3V.
Charging with a low current at the pre-charge stage may enable the capacitor to reach a high voltage in a stable state. The constant-current high-rate charging may enable the capacitor to reach a high voltage quickly. Since the cut-off voltage of the Li-ion capacitor ranges from 3.6 V to 4.2 V, after reaching 3.5 V by the high-rate constant-current charging, charging with a current having a low rate may prevent the voltage of the Li-ion capacitor from exceeding the cut-off voltage thus to prevent degradation of the performance of the capacitor. After the voltage of the capacitor reaches the cut-off voltage, charging under a constant voltage is required to continue to increase the capacity of the capacitor, while preventing over-voltage.
At an initial discharge stage of the capacitor, discharging in a high discharge rate may discharge as soon as possible if the performance of the capacitor permits; at a final discharge stage, discharging in a low rate may prevent, during the discharge process, the voltage of the capacitor from falling below the lowest acceptable voltage of the capacitor, thereby preventing the capacitor from being damaged by excessive discharge and too low voltage.
Preferably, the diaphragm is a composite diaphragm having polypropylene as a matrix, and the composite diaphragm having polypropylene as a matrix is prepared from the following substance by the following steps: uniformly mixing 80-85 wt% of polypropylene, 10-15 wt% of natural cellulose pulp, 3-5 wt% of kaolin powder and 0.5-1.5 wt% of silane coupling agent, and then processing by a dry process.
Preferably, the natural cellulose pulp in the polypropylene-based composite diaphragm is made by the following steps of: (1) adding bamboo fiber as raw material to a sodium hydroxide solution, and then steaming the sodium hydroxide solution in vacuum at 300°C for 2 h, wherein the mass ratio of the bamboo fiber to the sodium hydroxide solution is 1:4, and the concentration of the sodium hydroxide solution is 10 wt%; (2) taking out and washing the steamed bamboo fiber with water, then immersing the bamboo fiber into hot water at a temperature of 80-90°C for grinding followed by filtering, and then collecting the filtered solid; and (3) pulping the filtered solid by a pulping machine and concentrating to obtain the natural cellulose pulp having a solid content of 60-70 wt%.
The natural cellulose pulp manufactured by this method contains a large amount of natural cellulose which has advantages of good moisture absorption and excellent thermal stability. The moisture absorption and thermal stability of the polypropylene may be improved after mixing a small amount of the natural cellulose with polypropylene so that the absorption retention of the diaphragm to the electrolyte is enhanced, thereby improving the rate performance and cycle performance of products. Additionally, the natural cellulose generates cross-linking after being mixed with polypropylene and this enhances the tensile strength and puncture resistance strength of the diaphragm.
Compared with the prior art, the present invention has the following beneficial effects: (1) replacing the lithium foil or nanoscale lithium metal with the organic solution containing lithium salt reduces the cost, and meanwhile the use of non-porous current collectors also significantly reduces the cost; (2) replacing the lithium foil with the organic solution containing lithium salt requires no processing in an extreme environment, and as a result, the safety of processing is improved; (3) connecting the anode and the cathode with the charge-discharge tester may shorten the time required by the pre-embedment and improve the effect thereof; and (4) the simplification of the technological process may be suitable for mass industrial production.
Brief Description of the Drawings
Fig.1 is a schematic diagram of tests of the specific capacity of a capacitor; in which: the vertical axis represents specific capabilities of the capacitor tested at different discharge currents, and the horizontal axis represents discharge currents.
Detailed Description of the Invention
The content of the present invention will be described more specifically in conjunction with embodiments. It should be understood that the implementations of the present invention are not limited to the following embodiments, and instead, variations and changes in any form to the present invention will all fall into the protection scope of the present invention; and all methods in the following embodiments are conventional methods in the art, otherwise specifically stated.
Embodiment 1 A pre-embedment method for a lithium ion capacitor includes the following steps of: (1) adhering pulp containing activated carbon as active material to non-porous aluminum foil to serve as an anode, and adhering pulp containing mesophase carbon micro beads as active material to non-porous copper foil to serve as a cathode; by using a PP(Polypropylene)/PE(polyethylene)/PP tri-layer polymer as a diaphragm, stacking the diaphragm, the anode, the diaphragm and the cathode successively to form a cell, and then securing with an adhesive tape; and welding current collectors of both the anode and the cathode to tabs or leading-out terminals of both the anode and the cathode, respectively; (2) drying, and immersing the dried cell into a beaker containing a LiPFe-EC/PC/DEC solution; (3) connecting an anode and a cathode of a charge-discharge tester to the anode and the cathode, respectively, charging with a constant current of approximately 0.1 C until the voltage reaches 3.8 V and keeping at 3.8 V for 1 h, turning the circuit off and standing for 1 h so that a single capacitor discharges naturally, turning the circuit on again after 1 h later and charging with a constant current of 0.1 C until the voltage reaches 3.8 V, and then turning the circuit off again so that the single capacitor discharges naturally for 1 h, all of which steps are repeated for three charge/self-discharge pulse periods; and (4) taking the cell obtained in step (3) out and putting the cell into an aluminum-plastic shell, and injecting electrolyte into the aluminum-plastic shell to form a single flexibly packaged capacitor.
Embodiment 2 A pre-embedment method for a lithium ion capacitor includes the following steps of: (1) adhering pulp containing activated carbon as active material to non-porous aluminum foil to serve as an anode, and adhering pulp containing artificial graphite as active material to non-porous copper foil to serve as a cathode; by using a PP/PE/PP tri-layer polymer as a diaphragm, stacking the diaphragm, the cathode, the diaphragm and the anode successively to form a cell, and then securing with an adhesive tape; and welding current collectors of both the anode and the cathode to tabs or leading-out terminals of both the anode and the cathode, respectively; (2) drying, and immersing the dried cell into a beaker containing a LiBF4-PC/DMF solution; (3) connecting an anode and a cathode of a charge-discharge tester to the anode and the cathode, respectively, charging with a constant current of approximately 0.1 C until the voltage reaches 3.8 V, turning the circuit off and standing for 2 h so that a single capacitor discharges naturally, turning the circuit on again after 2 h later and charging with a constant current of 0.1 C until the voltage reaches 3.8 V, and then turning the circuit off again so that the single capacitor discharges naturally for 2 h, all of which steps are repeated for ten charge/self-discharge pulse periods; and (4) taking the cell obtained in step (3) out, putting the cell into a square aluminum shell, and injecting electrolyte into the square aluminum shell to form a single square capacitor.
Embodiment 3 A pre-embedment method for a lithium ion capacitor includes the following steps of: (1) adhering pulp containing activated carbon as active material to porous aluminum foil to serve as an anode, and adhering pulp containing hard carbon as active material to porous copper foil to serve as a cathode; by using a single-PP polymer as a diaphragm, winding the diaphragm, the cathode, the diaphragm and the anode successively to form a cell, and then securing with an adhesive tape; and welding current collectors of both the anode and the cathode to tabs or leading-out terminals of both the anode and the cathode, respectively; (2) drying, and immersing the dried cell into a beaker containing a U2CO3 organic solution; (3) connecting an anode and a cathode of a charge-discharge tester to the anode and the cathode, respectively, charging with a constant current of approximately 0.2 C until the voltage reaches 3.8 V, turning the circuit off and standing for a certain period of time so that a single capacitor discharges naturally, turning the circuit on again and charging with a constant current of 0.2 C until the voltage reaches 3.8 V, and then turning the circuit off again so that the single capacitor discharges naturally for a certain period of time, all of which steps are repeated for fifty charge/self-discharge pulse periods (wherein the self-discharge lasts for 0.5 h in the first to tenth periods, the self-discharge lasts for 1 h in the eleventh to twentieth periods, the self-discharge lasts for 1.5 h in the twenty first to thirtieth periods, the self-discharge lasts for 2 h in the thirty first to fortieth periods, and the self-discharge lasts for 3 h in the fortieth to fiftieth periods); and (4) taking the cell obtained in step (3) out and putting the cell into a round aluminum shell, and injecting electrolyte into the round aluminum shell to form a single round capacitor.
Embodiment 4 A pre-embedment method for a lithium ion capacitor includes the following steps of: (1) adhering pulp containing activated carbon as active material to non-porous aluminum foil to serve as an anode, and adhering pulp containing mesophase carbon micro beads as active material to non-porous copper foil to serve as a cathode; by using polypropylene-based natural fiber composite material as a diaphragm, stacking the diaphragm, the cathode, the diaphragm and the anode successively to form a cell, and then securing with an adhesive tape; and welding current collectors of both the anode and the cathode to tabs or leading-out terminals of both the anode and the cathode, respectively; (2) drying, and immersing the dried cell into a beaker containing a LiPFe-EC/PC/DEC solution; (3) connecting an anode and a cathode of a charge-discharge tester to the anode and the cathode, respectively, performing three charge/discharge periods at a constant temperature of 0°C according to the following regimes: a charge regime: a) at a pre-charge stage: charging with a low current of 0.01 C when the voltage of the capacitor is lower than 3 V; b) at a constant-current high-rate charge stage: charging with a current having a charge rate of 0.1 C when the voltage of the capacitor is greater than 3 V and lower than 3.5 V; c) at a constant-current low-rate charge stage: charging with a current having a charge rate of 0.05 C when the voltage of the capacitor is greater than 3.5 V and lower than 4.2 V; and d) at a constant voltage charge stage: charging under a constant voltage of 4.2 V when the voltage of the capacitor reaches 4.2 V, until the charge current is lower than 10 mA, and then stopping charging; and a discharge regime: a) at a first discharge stage: discharging with a discharge current having a discharge rate of 1 C when the voltage of the capacitor is greater than 3.5V and lower than or equal to 4.2 V; b) at a second discharge stage: discharging with a discharge current having a discharge rate of 0.5 C when the voltage of the capacitor is greater than 3V and lower than or equal to 3.5V; and c) at a third discharge stage: discharging with a discharge current having a low discharge rate of 0.1 C when the voltage of the capacitor is lower than 3V; and (4) taking the cell obtained in step (3) out, putting the cell into an aluminum-plastic shell, and injecting electrolyte into the aluminum-plastic shell to form a single flexibly packaged capacitor.
Embodiment 5 A pre-embedment method for a lithium ion capacitor includes the following steps of: (1) adhering pulp containing activated carbon as active material to non-porous aluminum foil to serve as an anode, and adhering pulp containing artificial graphite as active material to non-porous copper foil to serve as a cathode; by using polypropylene-based natural fiber composite material as a diaphragm, stacking the diaphragm, the cathode, the diaphragm and the anode successively to form a cell, and then securing with an adhesive tape; and welding current collectors of both the anode and the cathode to tabs or leading-out terminals of both the anode and the cathode, respectively; (2) drying, and immersing the dried cell into a beaker containing a LiBF4-PC/DMF solution; (3) connecting an anode and a cathode of a charge-discharge tester to the anode and the cathode, respectively, performing ten charge/discharge periods at a constant temperature of 30°C according to the following regimes: a charge regime: a) at a pre-charge stage: charging with a low current of 0.03 C when the voltage of the capacitor is lower than 3 V; b) at a constant-current high-rate charge stage: charging with a current having a charge rate of 0.3 C when the voltage of the capacitor is greater than 3 V and lower than 3.5 V;c) at a constant-current low-rate charge stage: charging with a current having a charge rate of 0.075 C when the voltage of the capacitor is greater than 3.5 V and lower than 4.2 V; and d) at a constant voltage charge stage: charging under a constant voltage of 4.2 V when the voltage of the capacitor reaches 4.2 V, until the charge current is lower than 15 mA, and then stopping charging; and a discharge regime: a) at a first discharge stage: discharging with a discharge current having a discharge rate of 1.5 C when the voltage of the capacitor is greater than 3.5V and lower than or equal to 4.2 V; b) at a second discharge stage: discharging with a discharge current having a discharge rate of 0.75 C when the voltage of the capacitor is greater than 3V and lower than or equal to 3.5V; and c) at a third discharge stage: discharging with a discharge current having a low discharge rate of 0.3 C when the voltage of the capacitor is lower than 3V; and (4) taking the cell obtained in step (3) out, putting the cell into a square aluminum shell, and injecting electrolyte into the square aluminum shell to form a single square capacitor.
Embodiment 6 A pre-embedment method for a lithium ion capacitor includes the following steps of: (1) adhering pulp containing activated carbon as active material to porous aluminum foil to serve as an anode, and adhering pulp containing hard carbon as active material to porous copper foil to serve as a cathode; by using polypropylene-based natural fiber composite material as a diaphragm, winding the diaphragm, the cathode, the diaphragm and the anode successively to form a cell, and then securing with an adhesive tape; and welding current collectors of both the anode and the cathode to tabs or leading-out terminals of both the anode and the cathode, respectively; (2) drying, and immersing the dried cell into a beaker containing a U2CO3 organic solution; and (3) connecting an anode and a cathode of a charge-discharge tester to the anode and the cathode, respectively, performing fifty charge/discharge periods at a constant temperature of 60°C according to the following regimes: a charge regime: a) at a pre-charge stage: charging with a low current of 0.05 C when the voltage of the capacitor is lower than 3 V; b) at a constant-current high-rate charge stage: charging with a current having a charge rate of 0.5 C when the voltage of the capacitor is greater than 3 V and lower than 3.5 V; c) at a constant-current low-rate charge stage: charging with a current having a charge rate of 0.1 C when the voltage of the capacitor is greater than 3.5 V and lower than 4.2 V; and d) at a constant voltage charge stage: charging under a constant voltage of 4.2 V when the voltage of the capacitor reaches 4.2 V, until the charge current is lower than 20mA, and then stopping charging; and a discharge regime: a) at a first discharge stage: discharging with a discharge current having a discharge rate of 2 C when the voltage of the capacitor is greater than 3.5V and lower than or equal to 4.2 V; b) at a second discharge stage: discharging with a discharge current having a discharge rate of 1 C when the voltage of the capacitor is greater than 3V and lower than or equal to 3.5V; and c) at a third discharge stage: discharging with a discharge current having a low discharge rate of 0.5 C when the voltage of the capacitor is lower than 3V; and (4) taking the cell obtained in step (3) out, putting the cell into a round aluminum shell, and injecting electrolyte into the round aluminum shell to form a single round capacitor.
Comparative Example 1 A method for manufacturing a Li-ion capacitor includes the following steps of: (1) adhering pulp containing activated carbon as active material to porous aluminum foil to serve as an anode, and adhering pulp containing hard carbon as active material to porous copper foil to serve as a cathode; by using a PP/PE/PP tri-layer polymer as a diaphragm and by closely compressing the lithium foil onto the copper foil as a lithium electrode, stacking the diaphragm, the anode, the diaphragm, the cathode, the diaphragm, the lithium electrode and the diaphragm successively to form a cell, and then securing with an adhesive tape; and welding current collectors of all the anode, the cathode and the lithium electrode to tabs or leading-out terminals of both the anode and the cathode, respectively; (2) putting the cell into an aluminum-plastic shell, and injecting electrolyte of a LiPF6-EC/PC/DEC solution into the aluminum-plastic shell to form a single flexibly packaged capacitor; and (3) short-circuit embedding: directly connecting the cathode to the lithium electrode in short circuit by leads for discharge pre-embedment.
Comparative Example 2 A pre-embedment method for a lithium ion capacitorincludes the following steps of: (1) adhering pulp containing activated carbon as active material to porous aluminum foil to serve as an anode, and adhering pulp containing artificial graphite as active material to porous copper foil to serve as a cathode; by using a PP/PE/PP tri-layer polymer as a diaphragm and by closely compressing the lithium foil onto the copper foil as a lithium electrode, stacking the diaphragm, the anode, the diaphragm, the cathode, the diaphragm, the lithium electrode and the diaphragm successively to form a cell, and then securing with an adhesive tape; and welding current collectors of all the anode, the cathode and the lithium electrode to tabs or leading-out terminals of both the anode and the cathode, respectively; (2) putting the cell into a square aluminum shell, and injecting electrolyte of a UBF4-PC/DMF solution into the square aluminum shell to form a single square capacitor; and (3) short-circuit embedding: directly connecting the cathode to the lithium electrode in short circuit by leads for discharge pre-embedment.
Comparative Example 3 A method for manufacturing a Li-ion capacitor includes the following steps of: (1) adhering pulp containing activated carbon as active material to porous aluminum foil to serve as an anode, and adhering pulp containing hard carbon as active material to porous copper foil to serve as a cathode; by using a Single-PP polymer as a diaphragm and by closely compressing the lithium foil onto the copper foil as a lithium electrode, winding the diaphragm, the anode, the diaphragm, the cathode, the diaphragm, the lithium electrode and the diaphragm successively to form a cell, and then securing with an adhesive tape; and welding current collectors of all the anode, the cathode and the lithium electrode to tabs or leading-out terminals of both the anode and the cathode, respectively; (2) putting the cell into a round aluminum shell, and injecting a U2CO3 organic solution into the round aluminum shell to form a single flexibly packaged round capacitor; and (3) short-circuit embedding: directly connecting the cathode to the lithium electrode in short circuit by leads for discharge pre-embedment.
Comparative Example 4
Super capacitor FB series are commercially available from NEC-tokin.
Detection methods and results 1. Specific capacity of capacitors A comprehensive battery performance detector LRBT-02 is utilized to test the specific discharge capacities of Embodiments 1,2 and 3 and Comparative Examples at currents of 1 C, 5 C and 10 C, respectively. The results are as shown in Fig. 1. 2. Capacity retention ratio
As for Embodiments 1, 2 and 3 and Comparative Examples, charge and discharge are performed at currents of 1 C, 5 C and 10 C, and as for the correspondingly embodiments, charge and discharge are performed in a same manner as that described in Embodiments 4, 5 and 6. The capacity retention ratios are recorded, and the results are as shown in Table 1. 3. The initial amount of lithium to be embedded is detected by an externally connected charge-discharge tester which may monitor the embedment amount of lithium in real time. The results are as shown in Table 2.
As can be known from Fig. 1, a Li-ion capacitor manufactured by this pre-embedment method of the present invention has a significantly high specific capacity and a low drop in the specific capacity of the capacitor while discharging at a high current when compared with a Li-ion capacitor manufactured by a conventional process.
Table 1
As can be known from Table 1, both a Li-ion capacitor manufactured by this method of the present invention and a Li-ion capacitor manufactured by connecting the cathode to the lithium electrode in short circuit as a pre-embedment method may ensure, at various charge-discharge currents, a high capacity by a few cycles, and however, after many charge-discharge cycles, the Li-ion capacitor manufactured by this method of the present invention exhibits a higher capacity retention ratio, and stable results at various different currents. The service life and use effect of a capacitor are limited by the degree of embedment. It is indicated by Table 1 that the pre-embedment way used in the present invention benefits a capacitor to allow the capacitor to show more stable long-term use performance while ensuring the fundamental functions of the capacitor, and prolongs the service life of the capacitor.
Table 2
As can be known from Table 2, different durations and different currents for charge-discharge cycles have little influence on the initial embedment amount of a capacitor. Temperature, at which the embedment is performed, has certain influence on the initial embedment amount. Too low temperature will hinder the process of embedment, and lower current will require longer charge-discharge duration. The embedment amount of the capacitor may be increased slightly, so that the service life and the charge-discharge efficiency of the capacitor may be improved. Charging/discharging with a low current is more effective to the increase in the embedment amount of the capacitor.
The invention can be described as follows: A pre-embedment method for a lithium ion capacitor, comprising the following steps of: stacking or winding a cathode, a diaphragm, an anode and a diaphragm successively and then securing with an adhesive tape to form a cell, and immersing the cell into an organic solution containing lithium salt; (2) connecting the anode and the cathode to a charge-discharge tester, respectively, to perform a number of cycles each comprising one charge followed by one discharge, to finish the pre-embedment into the cathode; and (3) taking out the cell after the pre-embedment and putting the cell into a packaging shell, and injecting electrolyte into the packaging shell to form a single lithium ion capacitor.
One or more of the following additional preferred features can be part of preferred embodiments of the invention, alone or in any combination of features: - current collectors in the anode and the cathode are current collectors with or without pores; - the lithium salt is at least one of lithium salts, which are soluble in the organic solution, selected from LiPF6> LiBF4, UCIO4, L1AIO4, LiOH, U2CO3, CFI3COOU, UNO3, LiB(C204)2, LiP(CeFl402)3, LiPF3(C2F5)3 and LiN(S02CF3)2, and the organic solution is at least one of PC, EC, DEC, DMC, DMF, DME, THF and SL; - the discharge in the cycle is discharge of the tester or self-discharge of the cell; - the charge and the discharge are of constant current, and the charge-discharge rate ranges from 0.01 C to10 C; - the highest cut-off voltage for the charge ranges from 3.6 V to 4.2 V; - currents and voltages separately for the charge and discharge in each of the cycles may be the same or different wherein preferably the discharge in each of the cycles lasts for 1 min to 10 h; - the number of cycles totals 1 to 100; - the charge and discharge in each of the cycles are performed at a constant temperature ranging from 0°C to 60°C; - the charge regime is as follows: at a pre-charge stage: charging with a low current of 0.01-0.05 C when the voltage of the capacitor is lower than 3 V; (2) at a constant-current high-rate charge stage: charging with a current having a charge rate of 0.1-0.5 C when the voltage of the capacitor is greater than 3 V and lower than 3.5 V; (3) at a constant-current low-rate charge stage: charging with a current having a charge rate of 0.05-0.1 C when the voltage of the capacitor is greater than 3V and lower than the highest cut-off voltage; and (4) at a constant-voltage charge stage: charging under a constant voltage when the voltage of the capacitor reaches the highest cut-off voltage, until the charge current is lower than 10-20 mA, and then stopping charging, the constant voltage being the highest cut-off voltage; a discharge regime is as follows: at a first discharge stage: discharging with a discharge current having a discharge rate of 1 -2 C when the voltage of the capacitor is greater than 3.5V and lower than or equal to the highest cut-off voltage; (2) at a second discharge stage: discharging with a discharge current having a discharge rate of 0.5-1 C when the voltage of the capacitor is greater than 3V and lower than or equal to 3.5V; and (3) at a third discharge stage: discharging with a discharge current having a low discharge rate of 0.1 -0.5 C when the voltage of the capacitor is lower than 3V; - the diaphragm is a composite diaphragm having polypropylene as a matrix, and the composite diaphragm having polypropylene as a matrix is prepared from the following substance by the following steps: uniformly mixing 80-85 wt% of polypropylene, 10-15 wt% of natural cellulose pulp, 3-5 wt% of kaolin powder and 0.5-1.5 wt% of silane coupling agent, and then processing by a dry process, wherein preferably the natural cellulose pulp is made by the following steps of: (1) adding bamboo fiber as raw material to a sodium hydroxide solution, and then steaming the sodium hydroxide solution in vacuum at 300°C for 2 h, wherein the mass ratio of the bamboo fiber to the sodium hydroxide solution is 1:4, and the concentration of the sodium hydroxide solution is 10 wt%; (2) taking out and washing the steamed bamboo fiber with water, then soaking the bamboo fiber in hot water at a temperature of 80-90 °C for grinding followed by filtering, and then collecting the filtered solid; and (3) pulping the filtered solid by a pulping machine and concentrating to obtain the natural cellulose pulp having a solid content of 60-70 wt%.
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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 |
WO2017214894A1 (en) * | 2016-06-15 | 2017-12-21 | 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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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 |
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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 |
US9748599B2 (en) * | 2013-01-30 | 2017-08-29 | 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 |
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 |
CN104201320A (en) * | 2014-09-16 | 2014-12-10 | 赵前永 | Method for pre-lithiating electrode material of lithium ion battery |
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 |
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