CN105810452A - Method for lithium pre-embedment of negative electrode of lithium ion capacitor - Google Patents
Method for lithium pre-embedment of negative electrode of lithium ion capacitor Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 133
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 78
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000003990 capacitor Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000011889 copper foil Substances 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 15
- 239000006258 conductive agent Substances 0.000 claims description 13
- 239000011149 active material Substances 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 9
- 230000002269 spontaneous effect Effects 0.000 claims description 9
- 239000005486 organic electrolyte Substances 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000003610 charcoal Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000002388 carbon-based active material Substances 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 238000005253 cladding Methods 0.000 claims description 4
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 3
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 239000002931 mesocarbon microbead Substances 0.000 claims description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000011888 foil Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000007773 negative electrode material Substances 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- -1 for anode Chemical compound 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, 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
-
- 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)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to the field of a lithium ion capacitor, in particular to a method for lithium pre-embedment of a negative electrode of the lithium ion capacitor. The method comprises the following steps of preparing active paste of the negative electrode, and applying the paste onto a porous copper foil through which lithium ions can pass to prepare a negative pole plate; attaching a layer of low-cost lithium-containing material lithium sheet or a lithium foil on the back surface of the negative pole plate to prepare the negative pole plate capable of lithium embedment; preparing the lithium ion capacitor by the negative pole plate capable of lithium embedment; and enabling the lithium sheet attached onto the back surface of the negative electrode to be spontaneously embedded into a negative electrode material during the formation of the capacitor so as to complete the lithium pre-embedment of the negative electrode of the lithium ion capacitor. The method is simple and convenient, is low in cost and has very important significance to industrial production of the lithium ion capacitor.
Description
Technical field
The present invention relates to lithium-ion capacitor field, the method particularly relating to the pre-embedding lithium of a kind of lithium-ion capacitor negative pole.
Background technology
In recent years, along with the quick growth of energy demand, novel green energy storage device causes increasing concern as the core of national energy strategic development；Lithium-ion capacitor is a kind of emerging green energy storage device, its positive pole adopts the electric double layer energy storage material with carbon element similar with ultracapacitor, negative pole adopt similar with lithium ion battery can intercalation materials of li ions, thus possessed the advantages such as capacity is relatively big, voltage is high, big, the long service life of power, it is described as " ultracapacitor of future generation ".
In the process preparing lithium-ion capacitor, the pre-embedding lithium technology of negative pole is the step of most critical, and at present, pre-embedding lithium mainly has following several method:
1) use lithium ion cell positive or lithium sheet as lithium source, by the embedding lithium of method anticathode of external short circuit.Chinese invention patent if application number is CN201310001315.3 discloses the method for the pre-embedding lithium of a kind of lithium-ion capacitor negative pole, comprise the steps: lithium sheet, the first barrier film, negative pole, the second barrier film and positive pole are stacked gradually and be packaged in enclosure interior, after injecting the organic electrolyte containing lithium salts, be assembled into lithium-ion capacitor；When temperature is-30 DEG C ~ 60 DEG C, described negative pole and described lithium sheet being electrically connected, discharge 1h ~ 60h, it is achieved the pre-embedding lithium to described negative pole.The method of the pre-embedding lithium of above-mentioned lithium-ion capacitor negative pole, at a suitable temperature, by negative pole and lithium sheet are electrically connected, after electric discharge 1h ~ 60h, lithium sector-meeting in lithium-ion capacitor is slowly dissolve in electrolyte and forms lithium ion, thus being embedded in negative pole, it is achieved the pre-embedding lithium of anticathode, the lithium-ion capacitor capacity obtained is high.The method of the pre-embedding lithium of above-mentioned lithium-ion capacitor negative pole has only to the electric connection mode, reasonable time and the temperature that control between negative pole and lithium sheet, it becomes possible to obtains the lithium-ion capacitor of high power capacity, has the advantages such as operating procedure is simple.
But the method has the drawback that lithium ion cell positive or lithium sheet the 3rd pole are present in lithium-ion capacitor, causes capacitor gravimetric specific energy, energy density per unit volume to be greatly reduced.
2) in lithium-ion capacitor positive pole or negative material, rich lithium material is directly added as lithium source, in positive electrode, such as mix rich lithium compound, its shortcoming is in that the proportion of rich lithium compound differs with other positive electrodes and is more very much not easily formed uniform sizing material, and the rich lithium compound after embedding lithium becomes " dead volume ", and capacity contribution is little.
Therefore, study the pre-embedding lithium technology of succinct effective novel negative pole, be the key of lithium-ion capacitor industrialized development.
Summary of the invention
The method that it is an object of the invention to provide the pre-embedding lithium of a kind of lithium-ion capacitor negative pole, to solve the existing problem that lithium-ion capacitor energy density per unit volume is big and capacity characteristic is low.
To achieve these goals, the technical solution adopted in the present invention is:
The method of the pre-embedding lithium of a kind of lithium-ion capacitor negative pole, comprises the steps:
Preparation can embedding cathode of lithium active slurry, by described can embedding cathode of lithium active slurry cover or Electrostatic Absorption in can pass through lithium ion carrier on, repressed, prepare cathode pole piece.
Attaching one layer at the back side of described cathode pole piece for the lithium-containing materials as pre-embedding lithium lithium source, preparing can embedding cathode of lithium pole piece.
Embedding cathode of lithium pole piece, Carbon Materials anode pole piece and barrier film can combine and be packaged in enclosure interior by described, after injecting the organic electrolyte containing lithium ion, be assembled into lithium-ion capacitor.
When described lithium-ion capacitor is melted into, the lithium-containing materials being attached at the cathode pole piece back side is embedded in cathode pole piece material by electric potential difference is spontaneous, it is achieved the pre-embedding lithium to described lithium-ion capacitor negative pole.
As preferably, in the technical scheme of the application, described carrier is porous copper foil or copper mesh；The aperture of described Copper Foil or copper mesh is 10 ~ 100um.
As preferably, in the technical scheme of the application, described can the embedding cathode of lithium active slurry thickness that covers on carrier be 100 ~ 500um.
As preferably, in the technical scheme of the application, the thickness of the lithium-containing materials attached at the described cathode pole piece back side is 1 ~ 5um.
As preferably, in the technical scheme of the application, described lithium-containing materials is lithium sheet or lithium paper tinsel.
As preferably, in the technical scheme of the application, described can be made up of the component of following weight percentage by embedding cathode of lithium active slurry:
Can embedding lithium active material 70 ~ 85%, conductive agent 10 ~ 25% and binding agent 3 ~ 5%；
Described can embedding lithium active material be carbon active material or metal oxide active material；
Described conductive agent is Graphene or CNT or acetylene black or white carbon black；
Described binding agent is Kynoar or aqueous binders.
As preferably, in the technical scheme of the application, described can be preferably made up of the component of following weight percentage by embedding cathode of lithium active slurry:
Can embedding lithium active material 85%, conductive agent 10% and binding agent 5%.
As preferably, in the technical scheme of the application, described carbon active material is native graphite or Delanium or hard charcoal or MCMB.
As preferably, in the technical scheme of the application, described can be prepared by following methods by embedding cathode of lithium active slurry:
According to formula proportion, by described can embedding lithium active material, conductive agent and binding agent mixing, add water, carry out high-speed stirred, prepare.
As preferably, in the technical scheme of the application, the material of described Carbon Materials positive pole is that activated carbon, microcell graphitized carbon and cladding are containing at least one in lithium metal oxide charcoal.
The method of the pre-embedding lithium of lithium-ion capacitor negative pole of the present invention has the advantages that
1) present invention by attaching lithium sheet or the lithium source mode as pre-embedding lithium at the lithium-ion capacitor cathode pole piece back side, when capacitor is melted into, lithium sheet or lithium source are under the effect of electric potential difference, in spontaneous embedding negative material, the method does not increase capacitor weight and volume, substantially increases capacitor gravimetric specific energy and energy density per unit volume.
2) present invention passes through to adopt the lithium sheet sacrificing property or lithium paper tinsel as pre-embedding lithium lithium source, not only reduces cost, and has fully embedded into negative pole after lithium sheet or the chemical conversion of lithium paper tinsel, is absent from " dead volume ", and then substantially increases the capacity characteristic of lithium-ion capacitor.
3) present invention is by preparing negative electrode active slurry, and slurry is overlying on and can prepare cathode pole piece through the mode on the porous-substrates of lithium ion, lithium sheet or the lithium source of specified quantitative is attached again at the back side of cathode pole piece, condition to realize pre-embedding lithium prepares, which is succinctly effective, applied widely, be conducive to industrialized production, there is huge potential using value.
Detailed description of the invention
For making the purpose of the application, technical scheme and advantage clearly, specific examples below, the application is described in further detail.
Embodiment 1
Prepare negative electrode active slurry: by weight percentage to be 85% negative active core-shell material native graphite, weight percentage be 10% conductive agent white carbon black and binding agent Kynoar mixing that weight percentage is 5%, after carrying out high-speed stirred, it is pressed into the thick negative electrode active pulp layer of 200um.
By the above-mentioned negative electrode active pulp layer Electrostatic Absorption prepared on the Copper Foil that aperture is 10um, repressed, make cathode pole piece, will cut, after welding electrode ear, attach the thick lithium paper tinsel of one layer of 1um in its back side, preparing can embedding cathode of lithium pole piece.
Above-mentioned can embedding cathode of lithium pole piece, activated carbon positive pole and barrier film combination winding shaping be packaged in enclosure interior, after injecting the organic electrolyte containing lithium ion, be assembled into lithium-ion capacitor.
Above-mentioned lithium-ion capacitor is melted under 0.1C electric current, and the current potential of lithium plate electrode is 0.2V by negative pole, and lithium paper tinsel is under the effect of above-mentioned electric potential difference in spontaneous embedding negative material, it is achieved the pre-embedding lithium to lithium-ion capacitor negative pole.
Embodiment 2
Prepare negative electrode active slurry: by weight percentage to be the 70% hard charcoal of negative active core-shell material, weight percentage be 25% conductive agent Graphene and binding agent Kynoar mixing that weight percentage is 5%, after carrying out high-speed stirred, it is pressed into the thick negative electrode active pulp layer of 100um.
By the above-mentioned negative electrode active pulp layer Electrostatic Absorption prepared on the copper mesh that aperture is 50um, repressed, make cathode pole piece, will cut, after welding electrode ear, attach the thick lithium paper tinsel of one layer of 5um in its back side, preparing can embedding cathode of lithium pole piece.
Above-mentioned can embedding cathode of lithium pole piece, microcell graphitized material positive pole and barrier film combination lamination shape and be packaged in enclosure interior, after injecting the organic electrolyte containing lithium ion, be assembled into lithium-ion capacitor.
Above-mentioned lithium-ion capacitor is melted under 0.2C electric current, and the current potential of lithium plate electrode is 0.18V by negative pole, and lithium paper tinsel is under the effect of above-mentioned electric potential difference in spontaneous embedding negative material, it is achieved the pre-embedding lithium to lithium-ion capacitor negative pole.
Embodiment 3
Prepare negative electrode active slurry: by weight percentage to be 80% negative active core-shell material MCMB, weight percentage be 17% conductive agent CNT and aqueous binders mixing that weight percentage is 3%, add water, after carrying out high-speed stirred, form the thick negative electrode active pulp layer of 500um.
By the above-mentioned negative electrode active pulp layer Electrostatic Absorption prepared on the Copper Foil that aperture is 100um, repressed, make cathode pole piece, will cut, after welding electrode ear, attach the thick lithium paper tinsel of one layer of 3um in its back side, preparing can embedding cathode of lithium pole piece.
Above-mentioned embedding cathode of lithium pole piece, cladding can combine winding shaping containing lithium metal oxide charcoal positive pole and barrier film and are packaged in enclosure interior, after injecting the organic electrolyte containing lithium ion, being assembled into lithium-ion capacitor.
Above-mentioned lithium-ion capacitor is melted under 0.1C electric current, and the current potential of lithium plate electrode is 0.2V by negative pole, and lithium paper tinsel is under the effect of above-mentioned electric potential difference in spontaneous embedding negative material, it is achieved the pre-embedding lithium to lithium-ion capacitor negative pole.
Embodiment 4
Prepare negative electrode active slurry: by weight percentage to be 75% negative active core-shell material Delanium, weight percentage be 21% conductive agent acetylene black and aqueous binders mixing that weight percentage is 4%, add water, after carrying out high-speed stirred, form the thick negative electrode active pulp layer of 300um.
By the above-mentioned negative electrode active pulp layer Electrostatic Absorption prepared on the Copper Foil that aperture is 80um, repressed, make cathode pole piece, will cut, after welding electrode ear, attach the thick lithium paper tinsel of one layer of 4um in its back side, preparing can embedding cathode of lithium pole piece.
Above-mentioned embedding cathode of lithium pole piece, cladding can combine winding shaping containing lithium metal oxide charcoal positive pole and barrier film and are packaged in enclosure interior, after injecting the organic electrolyte containing lithium ion, being assembled into lithium-ion capacitor.
Above-mentioned lithium-ion capacitor is melted under 0.2C electric current, and the current potential of lithium plate electrode is 0.21V by negative pole, and lithium paper tinsel is under the effect of above-mentioned electric potential difference in spontaneous embedding negative material, it is achieved the pre-embedding lithium to lithium-ion capacitor negative pole.
Embodiment 5
Prepare negative electrode active slurry: by weight percentage to be 83% negative active core-shell material native graphite, weight percentage be 21% conductive agent white carbon black and aqueous binders mixing that weight percentage is 4%, add water, after carrying out high-speed stirred, form the thick negative electrode active pulp layer of 400um.
By the above-mentioned negative electrode active pulp layer Electrostatic Absorption prepared on the copper mesh that aperture is 30um, repressed, make cathode pole piece, will cut, after welding electrode ear, attach the thick lithium paper tinsel of one layer of 2um in its back side, preparing can embedding cathode of lithium pole piece.
Above-mentioned can embedding cathode of lithium pole piece, material with carbon element and barrier film combination lamination shape and be packaged in enclosure interior, after injecting the organic electrolyte containing lithium ion, be assembled into lithium-ion capacitor.
Above-mentioned lithium-ion capacitor is melted under 0.2C electric current, and the current potential of lithium plate electrode is 0.21V by negative pole, and lithium paper tinsel is under the effect of above-mentioned electric potential difference in spontaneous embedding negative material, it is achieved the pre-embedding lithium to lithium-ion capacitor negative pole.
Slurry, by preparing negative electrode active slurry, is overlying on the multiple aperture Copper Foil of permeable lithium ion by the present invention, prepares cathode pole piece, then attaches the lithium-containing materials lithium sheet of one layer of low cost or the mode of lithium paper tinsel at the cathode pole piece back side, and preparing can embedding cathode of lithium pole piece；By can embedding cathode of lithium pole piece, then prepare lithium-ion capacitor；When capacitor is melted into, it is attached to the lithium sheet at the negative pole back side by, in the spontaneous embedding negative material of electric potential difference, completing the pre-embedding lithium of lithium-ion capacitor negative pole；The method succinctly facilitates, and cost is low, and lithium-ion capacitor industrialization is had extremely important value.
Porous copper foil used in above example, it is possible to for commercial products, it is possible to for self-control, Homemade method is as follows:
With commercially available thickness be 30um the LITHIUM BATTERY collector Copper Foil of dual light for raw material, described Copper Foil is coiled material, adopts DC electrolysis oxidizing process, and step is as follows:
A) it is negative electrode with inertia graphite, for anode, Copper Foil is carried out pretreatment hair engaging aperture with described Copper Foil.In pretreatment hair engaging aperture process, being provided with the hydrochloric acid that concentration is 5mol/L that temperature is 50 DEG C in electrolysis bath, DC electrolysis electric current density is 0.7A/cm2, time 10s.
B) Copper Foil after above-mentioned process adopt industry deionized water be carried out.
C) after cleaning, it is negative electrode with inertia graphite, for anode, Copper Foil is carried out electrolysis reaming with described Copper Foil.In electrolysis reaming procedure, the mixed liquor of hydrochloric acid, potassium chloride and oxalic acid that temperature is 50 DEG C it is provided with in electrolysis bath, wherein said concentration of hydrochloric acid is 2.5mol/L, described potassium chloride concentration is 2mol/L, and described oxalic acid is concentration is 0.5mol/L, and DC electrolysis electric current density is 0.3A/cm2, the time is 10min.
D), after the Copper Foil after above-mentioned process is sequentially carried out secondary cleaning, post processing electrolysis, three cleanings, porous copper foil is namely prepared.Processing in electrowinning process in the rear, be provided with the mixed liquor of phosphoric acid that temperature is 50 DEG C and sulphuric acid in electrolysis bath, wherein phosphoric acid concentration is 2.5mol/L, and sulfuric acid concentration is 2.5mol/L, and DC electrolysis electric current density is 0.5A/cm2, time 2min.
Wherein, in pretreatment hair engaging aperture and electrolysis reaming procedure, Copper Foil sequentially passes through electrolysis bath by running roller dragging and carries out DC electrolysis.
The porous copper foil prepared has through hole in a thickness direction, and aperture is between 90-110um, and porosity 27%, copper foil surface pattern, hot strength, thickness etc. meet LITHIUM BATTERY copper foil of affluxion body index, meet electrode material coating needs.
Raw materials used, equipment in the present invention, unless otherwise noted, is the conventional raw material of this area, equipment；Method therefor in the present invention, unless otherwise noted, is the conventional method of this area.
The above, be only presently preferred embodiments of the present invention, not the present invention is imposed any restrictions, every any simple modification, change and equivalent transformation above example made according to the technology of the present invention essence, all still falls within the protection domain of technical solution of the present invention.
Claims (10)
1. a method for the pre-embedding lithium of lithium-ion capacitor negative pole, is characterized in that, comprise the steps:
Preparation can embedding cathode of lithium active slurry, by described can embedding cathode of lithium active slurry cover or Electrostatic Absorption in can pass through lithium ion carrier on, repressed, prepare cathode pole piece；
Attaching one layer at the back side of described cathode pole piece for the lithium-containing materials as pre-embedding lithium lithium source, preparing can embedding cathode of lithium pole piece；
Embedding cathode of lithium pole piece, Carbon Materials positive pole and barrier film can combine and be packaged in enclosure interior by described, after injecting the organic electrolyte containing lithium ion, be assembled into lithium-ion capacitor；
When described lithium-ion capacitor is melted into, the lithium-containing materials being attached at the cathode pole piece back side is embedded in cathode pole piece material by electric potential difference is spontaneous, it is achieved the pre-embedding lithium to described lithium-ion capacitor negative pole.
2. the method for the pre-embedding lithium of lithium-ion capacitor negative pole according to claim 1, is characterized in that, described carrier is porous copper foil or copper mesh；The aperture of described Copper Foil or copper mesh is 10-100um.
3. the method for the pre-embedding lithium of lithium-ion capacitor negative pole according to claim 1, is characterized in that, described can the embedding cathode of lithium active slurry thickness that covers on carrier be 100-500um.
4. the method for the pre-embedding lithium of lithium-ion capacitor negative pole according to claim 1, is characterized in that, the thickness of the lithium-containing materials attached at the described cathode pole piece back side is 1-5um.
5. the method for the pre-embedding lithium of lithium-ion capacitor negative pole according to claim 1 or 4, is characterized in that, described lithium-containing materials is lithium sheet or lithium paper tinsel.
6. the method for the pre-embedding lithium of lithium-ion capacitor negative pole according to claim 1, is characterized in that, described can be made up of the component of following weight percentage by embedding cathode of lithium active slurry:
Can embedding lithium active material 70-85%, conductive agent 10-25% and binding agent 3-5%；
Described can embedding lithium active material be carbon active material or metal oxide active material；
Described conductive agent is Graphene or CNT or acetylene black or white carbon black；
Described binding agent is Kynoar or aqueous binders.
7. the method for the pre-embedding lithium of lithium-ion capacitor negative pole according to claim 6, is characterized in that, described can be made up of the component of following weight percentage by embedding cathode of lithium active slurry:
Can embedding lithium active material 85%, conductive agent 10% and binding agent 5%.
8. the method for the pre-embedding lithium of lithium-ion capacitor negative pole according to claim 6 or 7, is characterized in that, described carbon active material is native graphite or Delanium or hard charcoal or MCMB.
9. the method for the pre-embedding lithium of lithium-ion capacitor negative pole according to claim 6 or 7, is characterized in that, described can be prepared by following methods by embedding cathode of lithium active slurry:
According to formula proportion, by described can embedding lithium active material, conductive agent and binding agent mixing, add water, carry out high-speed stirred, prepare.
10. the method for the pre-embedding lithium of lithium-ion capacitor negative pole according to claim 1, is characterized in that, the material of described Carbon Materials positive pole is that activated carbon, microcell graphitized carbon and cladding are containing at least one in lithium metal oxide charcoal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610155521.3A CN105810452A (en) | 2016-03-18 | 2016-03-18 | Method for lithium pre-embedment of negative electrode of lithium ion capacitor |
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| CN107958788A (en) * | 2017-12-06 | 2018-04-24 | 中国科学院上海技术物理研究所 | One kind contacts embedding lithium type lithium ion super capacitor |
| CN108183197A (en) * | 2017-12-19 | 2018-06-19 | 国联汽车动力电池研究院有限责任公司 | A kind of composite metal lithium negative pole structure and preparation method thereof |
| CN110416522A (en) * | 2019-08-02 | 2019-11-05 | 上海汽车集团股份有限公司 | A kind of composite negative pole material containing lithium, preparation method and its application in the lithium secondary battery |
| CN110517902A (en) * | 2019-08-26 | 2019-11-29 | 福建翔丰华新能源材料有限公司 | Lithium-ion capacitor negative electrode material and preparation method thereof |
| WO2021023010A1 (en) * | 2019-08-02 | 2021-02-11 | 宁德时代新能源科技股份有限公司 | Splicedly formed lithium strip, preparation method therefor, and negative pole, cell, lithium ion battery, battery module, battery pack and apparatus related thereto |
| CN113593920A (en) * | 2021-08-09 | 2021-11-02 | 中国科学院青岛生物能源与过程研究所 | Lithium ion capacitor negative pole piece and preparation method thereof |
| CN113889344A (en) * | 2020-07-02 | 2022-01-04 | 中车青岛四方车辆研究所有限公司 | Formation method of lithium ion capacitor |
| CN114823162A (en) * | 2022-05-18 | 2022-07-29 | 中国第一汽车股份有限公司 | Method for widening voltage range of lithium ion capacitor |
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| CN107958788A (en) * | 2017-12-06 | 2018-04-24 | 中国科学院上海技术物理研究所 | One kind contacts embedding lithium type lithium ion super capacitor |
| CN108183197A (en) * | 2017-12-19 | 2018-06-19 | 国联汽车动力电池研究院有限责任公司 | A kind of composite metal lithium negative pole structure and preparation method thereof |
| CN110416522A (en) * | 2019-08-02 | 2019-11-05 | 上海汽车集团股份有限公司 | A kind of composite negative pole material containing lithium, preparation method and its application in the lithium secondary battery |
| WO2021023010A1 (en) * | 2019-08-02 | 2021-02-11 | 宁德时代新能源科技股份有限公司 | Splicedly formed lithium strip, preparation method therefor, and negative pole, cell, lithium ion battery, battery module, battery pack and apparatus related thereto |
| US11223050B2 (en) | 2019-08-02 | 2022-01-11 | Contemporary Amperex Technology Co., Limited | Spliced lithium strip, preparation method thereof, and related negative electrode plate, battery core, lithium ion battery, battery module, battery pack and apparatus |
| CN110517902A (en) * | 2019-08-26 | 2019-11-29 | 福建翔丰华新能源材料有限公司 | Lithium-ion capacitor negative electrode material and preparation method thereof |
| CN113889344A (en) * | 2020-07-02 | 2022-01-04 | 中车青岛四方车辆研究所有限公司 | Formation method of lithium ion capacitor |
| CN113889344B (en) * | 2020-07-02 | 2023-05-16 | 中车青岛四方车辆研究所有限公司 | Lithium ion capacitor formation method |
| CN113593920A (en) * | 2021-08-09 | 2021-11-02 | 中国科学院青岛生物能源与过程研究所 | Lithium ion capacitor negative pole piece and preparation method thereof |
| CN114823162A (en) * | 2022-05-18 | 2022-07-29 | 中国第一汽车股份有限公司 | Method for widening voltage range of lithium ion capacitor |
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