CN109036871A - A kind of lithium-ion capacitor negative electrode material and preparation method thereof and a kind of lithium-ion capacitor - Google Patents
A kind of lithium-ion capacitor negative electrode material and preparation method thereof and a kind of lithium-ion capacitor Download PDFInfo
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- CN109036871A CN109036871A CN201811019978.7A CN201811019978A CN109036871A CN 109036871 A CN109036871 A CN 109036871A CN 201811019978 A CN201811019978 A CN 201811019978A CN 109036871 A CN109036871 A CN 109036871A
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- lithium
- active layer
- negative electrode
- ion capacitor
- electrode material
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- 239000003990 capacitor Substances 0.000 title claims abstract description 73
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 69
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 63
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 43
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000006229 carbon black Substances 0.000 claims abstract description 26
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 21
- 230000006641 stabilisation Effects 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 150000001721 carbon Chemical group 0.000 claims abstract description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000010008 shearing Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 230000000087 stabilizing effect Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 2
- 239000006181 electrochemical material Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 45
- 238000000034 method Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000013065 commercial product Substances 0.000 description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—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
- H01G11/04—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
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
-
- 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)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention belongs to electrochemical material technical field, in particular to a kind of lithium-ion capacitor negative electrode material and preparation method thereof and a kind of lithium-ion capacitor.Lithium-ion capacitor negative electrode material provided by the invention, including copper base and the active layer for being attached to the copper base single side, the active layer has porous structure, and the active layer load has stabilisation metallic lithium powder；The active layer includes fluorination multi-walled carbon nanotube, carbon black and binder；The fluorine atom of the fluorination multi-walled carbon nanotube and the molar ratio of carbon atom are 0.1~2.6:1.Embodiment the result shows that, the lithium-ion capacitor being prepared using above-mentioned negative electrode material, recycle 3000 times, energy density remains at 92% or more.
Description
Technical field
The invention belongs to electrochemical material technical field, in particular to a kind of lithium-ion capacitor negative electrode material and its preparation
Method and a kind of lithium-ion capacitor.
Background technique
In recent years, lithium ion super capacitor is by feat of its high-energy density, high power density and long circulation life etc.
Advantage has attracted the concern of extensive scholar.Lithium ion super capacitor includes anode, cathode, diaphragm and electrolyte, wherein cathode
Material therefor has a direct impact the performance of lithium-ion capacitor.
Currently, the type of lithium-ion capacitor negative electrode material is more, carbon material is exactly relatively conventional one kind, but at present with
After capacitor is made in negative electrode material based on carbon material, the cyclical stability of capacitor is poor.
Summary of the invention
The object of the present invention is to provide a kind of lithium-ion capacitor negative electrode materials, utilize cathode material provided by the invention
Expect that the lithium-ion capacitor being prepared has excellent cyclical stability.
To achieve the goals above, the invention provides the following technical scheme:
A kind of lithium-ion capacitor negative electrode material, including copper base and the active layer for being attached to the copper base single side, institute
Active layer is stated with porous structure, the active layer load has stabilisation metallic lithium powder；
The active layer includes fluorination multi-walled carbon nanotube, carbon black and binder；The fluorine of the fluorination multi-walled carbon nanotube
The molar ratio of atom and carbon atom is 0.1~2.6:1.
Preferably, in the active layer, the aperture in hole is 1~3mm；The stabilisation metallic lithium powder accounts for active layer quality
5~10%.
Preferably, the mass ratio that multi-walled carbon nanotube, carbon black and binder are fluorinated in the active layer is (15~20): 1:
(1.5~3).
The present invention provides the preparation methods of lithium-ion capacitor negative electrode material described in above-mentioned technical proposal, including walk as follows
It is rapid:
(1) fluorinated modified to multi-walled carbon nanotube progress using fluorization agent under protective atmosphere, it obtains fluorination multi wall carbon and receives
Mitron；
The fluorinated modified temperature is 130~180 DEG C, and the fluorinated modified time is 10~12h；
(2) mixture of the dispersion liquid of fluorination multi-walled carbon nanotube, carbon black and binder in the step (1) is cut
It cuts, obtains active slurry；
(3) active slurry of the step (2) is coated in the single side of copper base, forms active layer after dry；
(4) surface that will stabilize metallic lithium powder dispersion active layer in the step (3), obtains lithium after dry
Ionistor negative electrode material.
Preferably, fluorization agent includes one of perfluorinated resin, Kynoar and polytetrafluoroethylene (PTFE) in the step (1)
Or it is several.
Preferably, the dispersion liquid of fluorination multi-walled carbon nanotube includes fluorination multi-walled carbon nanotube, surface in the step (2)
Activating agent and organic solvent.
Preferably, the surfactant includes polyvinylpyrrolidone (PVP), lauryl sodium sulfate (SDS) or ten
Dialkyl sulfonates (SDBS).
Preferably, the speed sheared in the step (2) is 8000~12000r/min, the time of shearing is 30~
60min。
Preferably, the stabilisation lithium metal dispersion liquid includes stabilizing metallic lithium powder and organic solvent, the stabilisation
The mass ratio of metallic lithium powder and organic solvent is 1:(50~200).
The present invention separately provides a kind of lithium-ion capacitor, including positive electrode, negative electrode material, electrolyte and diaphragm, institute
Stating negative electrode material is preparation method system described in lithium-ion capacitor negative electrode material described in above-mentioned technical proposal or above-mentioned technical proposal
Standby obtained lithium-ion capacitor negative electrode material.
Lithium-ion capacitor negative electrode material provided by the invention, including copper base and the work for being attached to the copper base single side
Property layer, the active layer has porous structure, and active layer load has stabilisation metallic lithium powder；The active layer includes fluorination
Multi-walled carbon nanotube, carbon black and binder；It is described fluorination multi-walled carbon nanotube fluorine atom and carbon atom molar ratio be 0.1~
2.6:1.The present invention is to be fluorinated multi-walled carbon nanotube as active component, wherein fluorination multi-walled carbon nanotube remains carbon nanotube
Original structure feature provides basis to improve reserves and the cyclical stability of lithium-ion capacitor；Meanwhile active layer is with more
Pore structure, the stabilisation lithium metal of load can react generation fluorination with the fluorine on fluorination multi-walled carbon nanotube in charge and discharge process
Lithium, protective condenser negative electrode material by the corrosion of electrolyte, do not further increase the stability of capacitor anode material.Embodiment
The result shows that the lithium-ion capacitor being prepared using above-mentioned negative electrode material, is recycled 3000 times, energy density remains at
92% or more.
Detailed description of the invention
Fig. 1 is embodiment 1 and 1 gained lithium-ion capacitor cycle-index of comparative example and energy density relationships figure.
Specific embodiment
The present invention provides a kind of lithium-ion capacitor negative electrode material, including copper base and it is attached to the copper base single side
Active layer, the active layer has porous structure, and active layer load has stabilisation metallic lithium powder；The active layer includes
It is fluorinated multi-walled carbon nanotube, carbon black and binder；The fluorine atom of the fluorination multi-walled carbon nanotube and the molar ratio of carbon atom are
0.1~2.6:1.
Lithium-ion capacitor negative electrode material of the present invention includes copper base, and the copper base is preferably copper foil.The present invention
There is no particular/special requirement to the size of the copper base, using well known to those skilled in the art.
Lithium-ion capacitor negative electrode material of the present invention further includes the active layer for being attached to the copper base single side, described
Active layer includes fluorination multi-walled carbon nanotube, carbon black and binder；The fluorine atom and carbon atom of the fluorination multi-walled carbon nanotube
Molar ratio be 0.1~2.6:1, preferably 0.5~2.5:1, more preferably 0.8~2.0:1.The binder preferably includes to gather
Vinylidene (PVDF).In the present invention, the mass ratio that multi-walled carbon nanotube, carbon black and binder are fluorinated in the active layer is excellent
It is selected as (15~20): 1:(1.5~3.0), more preferably (16~19): 1:(2~2.8).The present invention is to the carbon black and bonding
The source of agent does not have particular/special requirement, using root commercial product well known to those skilled in the art.
The present invention forms active layer to be fluorinated multi-walled carbon nanotube, carbon black and binder, wherein being fluorinated multi-walled carbon nanotube
The original structure feature of carbon nanotube is remained, enables the invention to utilize the fluorination rock-steady structure of multi-walled carbon nanotube and larger
Specific surface area embedding lithium is provided needed for space, avoid capacitor anode material volume caused by process of intercalation from excessively expanding and drop
The performance of low capacitor anode material.
In the present invention, the active layer has porous structure, and load has stabilisation metallic lithium powder.In the present invention,
The hole of the active layer is preferably micropore；The diameter in the hole is preferably 1~3nm, more preferably 1.5~2nm.In the present invention
In, the stabilisation metallic lithium powder accounts for the 5~10% of active layer quality, more preferably 6~8%.
The present invention (can load steady in the active layer load stabilization metallic lithium powder in active layer surface and aperture
Surely change metallic lithium powder), during capacitor charging/discharging, stabilizes in metallic lithium powder and active layer and be fluorinated on multi-walled carbon nanotube
Fluorine reaction generate lithium fluoride, can both reduce the loss of positive lithium ion, improve the first charge-discharge efficiency of capacitor, moreover it is possible to
Protective condenser negative electrode material by the corrosion of electrolyte, does not avoid the generation of Li dendrite, and finally improves lithium-ion capacitor
Cyclical stability.
The present invention also provides the preparation method of lithium-ion capacitor negative electrode material described in above-mentioned technical proposal, including it is as follows
Step:
(1) fluorinated modified to multi-walled carbon nanotube progress using fluorization agent under protective atmosphere, it obtains fluorination multi wall carbon and receives
Mitron；
The fluorinated modified temperature is 130~180 DEG C, and the fluorinated modified time is 10~12h；
(2) mixture of the dispersion liquid of fluorination multi-walled carbon nanotube, carbon black and binder in the step (1) is cut
It cuts, obtains active slurry；
(3) active slurry of the step (2) is coated in the single side of copper base, forms active layer after dry；
(4) surface that will stabilize metallic lithium powder dispersion active layer in the step (3), obtains lithium after dry
Ionistor negative electrode material.
The present invention is fluorinated modified to multi-walled carbon nanotube progress using fluorization agent under protective atmosphere, obtains fluorination multi wall
Carbon nanotube.In the present invention, the protective atmosphere preferably includes nitrogen or rare gas, and the rare gas is preferably argon gas
Shield or helium, more preferably argon gas.
In the present invention, the diameter of the multi-walled carbon nanotube is preferably 30~150nm, more preferably 40~120nm；It is more
The length of wall carbon nano tube is preferably 2~5 μm, and more preferably 3~4 μm；The number of plies of the wall of multi-walled carbon nanotube is preferably 20~
50 layers, more preferably 30~40 layers.The present invention does not have particular/special requirement to the source of the multi-walled carbon nanotube, using this field skill
Commercial product known to art personnel.
In the present invention, the fluorization agent preferably includes perfluorinated resin (CYTOP), Kynoar (PVDF) and polytetrafluoro
One or more of ethylene (PTFE), preferably perfluorinated resin (CYTOP), the structural formula of the perfluorinated resin are shown in formula I:
The present invention does not have particular/special requirement to the source of the multi-walled carbon nanotube and fluorization agent, using those skilled in the art
Well known commercial product.
In the present invention, the mass ratio of the multi-walled carbon nanotube and fluorization agent is preferably 1.8~2.5:1, more preferably
1.9~2.4:1 is further preferably 2.0~2.3:1.
In the present invention, the fluorinated modified temperature is preferably 130~180 DEG C, and more preferably 140~175 DEG C, then it is excellent
It is selected as 150~170 DEG C；The fluorinated modified time is preferably 10~12h, more preferably 11~12h, is further preferably 11h.
The present invention does not have particular/special requirement to the fluorinated modified specific embodiment, using known to those skilled in the art
Mode.In embodiments of the present invention, it is described it is fluorinated modified preferably two independences and connection tube furnace in carry out,
In the quartz boat for filling multi-walled carbon nanotube is placed in a tube furnace, place the quartz for filling fluorization agent in another tube furnace
Boat；It is passed through protective gas, after the air in tube furnace is discharged, the tube furnace for placing fluorization agent is warming up to fluorization agent and decomposes temperature
Degree；The tube furnace for placing multi-walled carbon nanotube is warming up to fluorinated modified temperature, is then kept the temperature, progress is fluorinated modified, after cooling
Obtain fluorination multi-walled carbon nanotube.
In the present invention, the fluorization agent decomposition temperature is preferably 320~380 DEG C, and more preferably 330~360 DEG C.This hair
The bright mode to the cooling does not have particular/special requirement, using well known to those skilled in the art.
The present invention preferably prepares fluorination multi-walled carbon nanotube under the above conditions, can protect the structure of multi-walled carbon nanotube not
It is destroyed, moreover it is possible to pass through the number of the adjustment control fluorination multi-wall carbon nano-tube pipe surface fluorine atom in reaction time.
After obtaining fluorination multi-walled carbon nanotube, the present invention is by the dispersion liquid of the fluorination multi-walled carbon nanotube, carbon black and glues
The mixture of knot agent is sheared, and active slurry is obtained.
In the present invention, the dispersion liquid of the fluorination multi-walled carbon nanotube preferably includes fluorination multi-walled carbon nanotube, surface
Activating agent and organic solvent, the surfactant preferably include polyvinylpyrrolidone (PVP), lauryl sodium sulfate
(SDS) or dodecyl sodium sulfate (SDBS), the organic solvent preferably include N-Methyl pyrrolidone (NMP) or ethyl alcohol.
In the present invention, it is described fluorination multi-walled carbon nanotube and surfactant mass ratio be preferably 1:0.05~
0.12, more preferably 1:0.07~0.11 are further preferably 1:0.8~0.1.The present invention is to the dosage of the organic solvent without spy
It is different to require, fluorination multi-walled carbon nanotube can be made evenly dispersed.In embodiments of the present invention, the volume of the organic solvent with
The mass ratio for being fluorinated multi-walled carbon nanotube is preferably (8~12) mL:1g, more preferably (9~11) mL:1g.
In the present invention, the dispersion liquid of the fluorination multi-walled carbon nanotube is preferably formed by ultrasonic disperse, the ultrasound
Frequency be preferably 50~150KHz, more preferably 80~130KHz；The time of ultrasound is preferably 1~2h, more preferably 1.2~
1.5h。
In the present invention, in the active slurry, fluorination multi-walled carbon nanotube, carbon black and binder mass ratio with it is above-mentioned
It is consistent with the mass ratio of binder that it is fluorinated multi-walled carbon nanotube, carbon black in active layer described in technical solution, is not repeated herein.
The present invention does not have special want to the order by merging of fluorination the multi-walled carbon nanotube dispersion liquid, carbon black and binder
It asks.After mixing, the present invention shears gained mixture, to obtain finely dispersed active slurry.In the present invention, described
The speed of shearing is preferably 8000~12000r/min, more preferably 9000~11000r/min；The time of shearing is preferably 30
~60min, more preferably 35~55min.
After obtaining active slurry, the active slurry is coated in the single side of copper base by the present invention, forms activity after dry
Layer.In the present invention, the coated weight of the active slurry is preferably 0.003~0.008g/cm2, more preferably 0.004~
0.006g/cm2.The present invention does not have particular/special requirement to the coating method of the active slurry, and preferably scraper method coats.
In the present invention, the drying is preferably dried in vacuo, and the vacuum drying temperature is preferably 60~80 DEG C, more
Preferably 65~75 DEG C；The vacuum drying time is preferably 12~15h, more preferably 13~14h；The present invention is to described true
The dry pressure of sky does not have particular/special requirement, using well known to those skilled in the art.
After forming active layer, the present invention will stabilize metallic lithium powder dispersion in the surface of the active layer, drying
After obtain lithium-ion capacitor negative electrode material.In the present invention, the lithium solution preferably includes to stabilize lithium metal and organic molten
Agent, it is described to stabilize the commercial product that lithium metal is preferably Shanghai 4 wheel driven new energy Co., Ltd.The organic solvent preferably wraps
Include toluene and/or dimethylbenzene.In the present invention, the mass ratio for stabilizing lithium metal and organic solvent be preferably 1:(50~
200), more preferably 1:(100~150).The present invention is not special to the generation type for stabilizing metallic lithium powder dispersion liquid
It is required that using mode well known to those skilled in the art.
In the present invention, the coated weight for stabilizing metallic lithium powder dispersion liquid is preferably 0.005~0.012g/cm2, more
Preferably 0.075~0.01g/cm2.The present invention does not have particular/special requirement to the coating method of the lithium powder solution, using this field
Known to technical staff.In embodiments of the present invention, the stabilisation metallic lithium powder dispersion liquid is preferably applied by scraper method
Overlay on the surface of active layer.
After coating, the copper sheet that the present invention is coated with stabilizing metallic lithium powder dispersion liquid is dried, and is had in drying process
Solvent removal is supported on stabilisation lithium metal on active layer.In the present invention, the drying is preferably dried in vacuo, institute
Stating vacuum drying temperature is preferably 140~170 DEG C, and more preferably 145~160 DEG C, be further preferably 145~155 DEG C；Vacuum is dry
The dry time is preferably 22~26h, more preferably 22~25h, is further preferably 23~25h.The present invention is to described vacuum drying
Pressure does not have particular/special requirement, using well known to those skilled in the art.
After vacuum drying, the material after the vacuum drying is preferably carried out roll-in by the present invention, to improve the intensity of material
And tap density.The present invention does not have particular/special requirement to the specific embodiment of the roll-in.After roll-in, the present invention is preferably to roll-in
Material afterwards is cut, to obtain the electrode slice for being suitable for capacitor anode.In the present invention, the capacitor anode piece
Diameter be preferably 14mm.
The present invention also provides a kind of lithium-ion capacitor, including positive electrode, negative electrode material, electrolyte and diaphragm, institutes
Stating negative electrode material is preparation method system described in lithium-ion capacitor negative electrode material described in above-mentioned technical proposal or above-mentioned technical proposal
Standby obtained lithium-ion capacitor negative electrode material.
In the present invention, the positive electrode preferably includes aluminum substrate and the positive-active layer for being attached to aluminum substrate surface；
The positive-active layer includes active carbon, carbon black and binder.The present invention does not have particular/special requirement to the aluminum substrate, using ability
Known to field technique personnel.In the present invention, the thickness of the positive-active layer is preferably 0.01~0.05mm, more preferably
For 0.02~0.03mm.The mass ratio of active carbon, carbon black and binder is preferably (15~20) in the active layer: 1:(1.5~
3.0), more preferably (16~19): 1:(2~2.8).
In the present invention, the binder preferably includes Kynoar.The present invention is to the active carbon, carbon black and bonding
The source of agent does not have particular/special requirement, using commercial product well known to those skilled in the art.
In the present invention, the preparation method of the positive electrode preferably includes:
Active carbon dispersion liquid, carbon black and binder are mixed, obtain positive-active slurry after shearing dispersion；
The positive-active slurry is coated on aluminum substrate, obtains positive electrode after dry.
The present invention mixes active carbon dispersion liquid, carbon black and binder, obtains positive-active slurry after shearing dispersion.At this
In invention, the active carbon dispersion liquid preferably includes active carbon and N-Methyl pyrrolidone (NMP).The present invention is to the N- methyl
The quality of pyrrolidones does not have particular/special requirement, and the active carbon can be made evenly dispersed.The present invention to the active carbon and
The source of N-Methyl pyrrolidone does not have particular/special requirement, using commercial product well known to those skilled in the art.
In the present invention, the active carbon dispersion liquid is preferably formed under ultrasound condition, and the frequency of the ultrasound is preferably
50~150KHz, more preferably 80~130KHz；The time of ultrasound is preferably 1~2h, more preferably 1.2~1.5h.
In the present invention, the speed of the shearing dispersion is preferably 8000~12000r/min, more preferably 9000~
11000r/min；The time of shearing dispersion is preferably 40~60min, more preferably 50~55min.The present invention divides active carbon
The mixture of dispersion liquid, carbon black and binder carries out shearing dispersion, each component can be made to be sufficiently mixed, it is evenly dispersed to obtain active carbon
Positive-active slurry.
After obtaining positive electrode active materials, the positive-active slurry is coated on aluminum substrate by the present invention, is obtained after dry
Positive electrode.In the present invention, the coated weight of the positive-active slurry is preferably 0.003~0.008g/cm2, more preferably
0.005~0.006g/cm2.The present invention does not have particular/special requirement, preferably scraper method to the coating method of the positive-active slurry
Coating.
After coating, the material after coating is dried in the present invention, and the drying is preferably dried in vacuo, and the vacuum is dry
Dry temperature is preferably 60~80 DEG C, and more preferably 65~75 DEG C；The vacuum drying time is preferably 12~15h, more excellent
It is selected as 13~14h；The present invention does not have particular/special requirement to the vacuum drying pressure, is using well known to those skilled in the art
It can.
After drying, the material after drying is preferably carried out roll-in by the present invention, to improve the intensity and vibration density of positive electrode
Degree.The present invention does not have particular/special requirement to the specific embodiment of the roll-in.After roll-in, the present invention is preferably to the material after roll-in
It is cut, to obtain the electrode slice for being suitable for capacitor anode.In the present invention, the diameter of the capacitor anode material
It is preferred that consistent with the size of negative electrode material described in above-mentioned technical proposal.
Lithium-ion capacitor provided by the invention includes diaphragm, and the diaphragm is preferably microporous polypropylene membrane.In the present invention
In embodiment, the diaphragm is preferably U.S. CeLgard, the commercial product of LLC company.
Lithium-ion capacitor provided by the invention includes electrolyte, and the electrolyte preferably includes lithium hexafluoro phosphate
(LiPF6), ethylene carbonate (EC) and dimethyl carbonate (DMC)；The concentration of the lithium hexafluoro phosphate is preferably 0.8~
1.5mol/L, more preferably 1~1.2mol/L；The weight ratio of the ethylene carbonate and dimethyl carbonate be preferably 1:0.8~
1.2, more preferably 1:0.8~1.
The present invention does not have particular/special requirement to the source of the diaphragm and electrolyte, using city well known to those skilled in the art
Sell product.
The present invention does not have particular/special requirement to the preparation method of the lithium-ion capacitor, preferably in vacuum glove box according to
Anode cover, positive plate, diaphragm, negative electrode tab, steel disc, elastic slice, negative electrode casing, be added dropwise electrolyte sequence be assembled into lithium ion super electricity
Container.In above-mentioned assembling sequence, the assemble method of each step is method well known to those skilled in the art.
In the present invention, the lithium ion super capacitor has excellent cyclical stability, recycles 1000 times, energy is close
Degree is close to 100%, and after recycling 3000 times, energy density remains to be maintained at 92% or more.
In embodiment of above, unless otherwise specified, agents useful for same is commercial product well known to those skilled in the art；
Do not refer to that place is all made of mode well known to those skilled in the art.
In order to further illustrate the present invention, with reference to the accompanying drawings and examples to a kind of lithium-ion capacitance provided by the invention
Device negative electrode material and preparation method thereof and a kind of lithium-ion capacitor are described in detail, but cannot be interpreted as them to this
The restriction of invention protection scope.
Embodiment 1
Prepare two tube furnaces, number is No. 1 tube furnace and No. 2 tube furnaces respectively, and two tube furnaces are passed through soft air pipe
It is end-to-end, weighs the solid-state like CYTOP of 30g in quartz curette, being placed on No. 1 tube furnace, weigh the multi-walled carbon nanotube of 15g
In in quartz curette, being placed in No. 2 tube furnaces, two-pipe furnace, which is passed through argon gas, to be ensured mutually to connect, and closes air valve after air is discharged.
No. 1 tube furnace is warming up to 380 DEG C with the rate of 2 DEG C/min, with same heating rate by No. 2 diamond heatings to 150 DEG C,
It is continually fed into argon gas, when two tube furnace soaking times are 10h, obtains fluorination multi-walled carbon nanotube.Fluorine through detection preparation
The fluorine atom of multi-walled carbon nano-tube and the molar ratio of carbon atom are 1.5:1.
The fluorination multi-walled carbon nanotube of 1.7g and the polyvinylpyrrolidone surfactant of 0.14g are weighed in beaker,
15mLN- methyl pyrrolidone solvent is added, after ultrasonic disperse 2h, the binder of super carbon black (SP), 0.2g that 0.1g is added is poly-
Vinylidene (PVDF) obtains active slurry with 10000r/min high speed shear 1h in high-shearing dispersion emulsifying machine；Using scraping
Obtained active slurry is uniformly coated on copper foil by the skill in using a kitchen knife in cookery, is then placed in 75 DEG C of drying 10h in vacuum oven, is obtained attached
The copper sheet of active layer.
The stabilisation lithium metal of 0.5g is dissolved in the dimethylbenzene of 50mL, lithium powder solution is obtained；Using scraper method by lithium
Powder solution is coated uniformly on the copper sheet of attachment activity layer, is continued to be put into vacuum oven after 150 DEG C of drying for 24 hours, taking-up roller
Pressure, is finally punched into the negative electricity pole piece of φ 14mm.
Positive plate: weighing the active carbon (AC) of 1.7g and in beaker, the N-Methyl pyrrolidone of solvent 15mL is added
(NMP), after ultrasonic shear 2h, the super carbon black of 0.1g (SP), 0.2g binder Kynoar (PVDF) is added, in high shear point
It dissipates in mulser with 10000r/min high speed shear 1h, obtains positive-active slurry；Using scraper method by positive-active obtained
Slurry is uniformly coated on aluminium foil, is then placed in vacuum oven after 150 DEG C of drying for 24 hours, is taken out roll-in, be finally punched into
The anode electrode piece of φ 14mm.
Using LiPF6For electrolyte, porous polypropylene film is diaphragm, according to anode cover, anode in vacuum glove box
Piece, diaphragm, negative electrode tab, steel disc, elastic slice, negative electrode casing, be added dropwise electrolyte sequence be assembled into lithium ion super capacitor.
Embodiment 2~3
Lithium-ion capacitor negative electrode material, positive electrode and lithium-ion capacitor are prepared according to the method for embodiment 1, it is different
Place is the difference of raw material dosage and step parameter, is specifically listed in Tables 1 and 2.
Comparative example 1
Lithium-ion capacitor negative electrode material is prepared according to the method for embodiment 1, the difference is that without fluorinated modified.
The preparation parameter of 1 Examples 1 to 3 of table fluorination multi-wall carbon nano-tube
2 Examples 1 to 3 negative electrode material characteristic parameter of table
Performance test and result
Utilize micrometer, the test of specific surface area analysis instrument and battery testing cabinet testing example 1~3 and 1 gained of comparative example
The structure and its chemical property of lithium-ion capacitor.Test result is as shown in table 3~4 and Fig. 1.Fig. 1 is embodiment 1 and right
1 gained lithium-ion capacitor cycle-index of ratio and energy density relationships figure.As shown in Figure 1, the lithium-ion capacitor of comparative example 1
Energy density sharply decline, when recycling 500 times, energy density conservation rate be lower than 80%, and utilize cathode provided by the invention
Lithium-ion capacitor that material is prepared recycles 1000 times, and energy density conservation rate is close to 100%, after circulation 3000 times, energy
Metric density remains to be maintained at 92% or more, illustrates that lithium-ion capacitor provided by the invention has excellent cyclical stability.
1 lithium-ion capacitor negative electrode material structure feature of 3 Examples 1 to 3 of table and comparative example
By 3 test result of table it is found that negative electrode material provided by the invention has porous structure, aperture is approached in 1~3nm
Micropore provides sufficient lithium ion accommodation space for battery charging and discharging, and lithium ion is avoided to be embedded in the influence to negative electrode material structure；
In addition, the lithium fluoride energy guard electrode of load is not influenced by electrolyte, further extend the service life of capacitor.
The electrical performance testing result of 1 lithium-ion capacitor of 4 Examples 1 to 3 of table and comparative example
From the data in table 4, it can be seen that the energy density of lithium-ion capacitor provided by the invention is maintained at higher level, and compare
The energy density of the lithium-ion capacitor of example 1, with regard to rapid decrease, illustrates lithium-ion capacitance provided by the invention after circulation 500 times
Device has excellent cyclical stability.
By above embodiments and comparative example it is found that lithium-ion capacitor negative electrode material provided by the invention have it is excellent steady
It is qualitative, it is suitble to the negative electrode material as lithium-ion capacitor.
Negative electrode material provided by the invention improves multi-wall carbon nano-tube using multi-walled carbon nanotube as raw material, by fluorinated modified
The conductivity and capacity of pipe, and prelithiation is carried out to the active layer of cell negative electrode material using metallic lithium powder is stabilized, electricity can be made
Pond negative electrode material forms lithium fluoride protective layer in charge and discharge process, further protects cell negative electrode material from organic electrolyte
Corrosion, make cell negative electrode material performance stablize play；And the generation of lithium fluoride is also avoided that the generation of Li dendrite, keeps
The uniformity of cell negative electrode material, the promotion for lithium ion battery cyclical stability provide basis.
Preparation method provided by the invention is simple and easy to control, is suitble to large-scale promotion application.
Although above-described embodiment is made that detailed description to the present invention, it is only a part of the embodiment of the present invention,
Rather than whole embodiments, people can also obtain other embodiments under the premise of without creativeness according to the present embodiment, these
Embodiment belongs to the scope of the present invention.
Claims (10)
1. a kind of lithium-ion capacitor negative electrode material, described including copper base and the active layer for being attached to the copper base single side
Active layer has porous structure, and the active layer load has stabilisation metallic lithium powder；
The active layer includes fluorination multi-walled carbon nanotube, carbon black and binder；The fluorine atom of the fluorination multi-walled carbon nanotube
Molar ratio with carbon atom is 0.1~2.6:1.
2. lithium-ion capacitor negative electrode material as described in claim 1, which is characterized in that in the active layer, the aperture in hole
For 1~3mm；The stabilisation metallic lithium powder accounts for the 5~10% of active layer quality.
3. lithium-ion capacitor negative electrode material as claimed in claim 1 or 2, which is characterized in that be fluorinated in the active layer more
The mass ratio of wall carbon nano tube, carbon black and binder is (15~20): 1:(1.5~3).
4. the preparation method of any one of claims 1 to 3 lithium-ion capacitor negative electrode material, includes the following steps:
(1) fluorinated modified to multi-walled carbon nanotube progress using fluorization agent under protective atmosphere, obtain fluorination multi-wall carbon nano-tube
Pipe；
The fluorinated modified temperature is 130~180 DEG C, and the fluorinated modified time is 10~12h；
(2) mixture of the dispersion liquid of fluorination multi-walled carbon nanotube, carbon black and binder in the step (1) is sheared,
Obtain active slurry；
(3) active slurry of the step (2) is coated in the single side of copper base, forms active layer after dry；
(4) surface that will stabilize metallic lithium powder dispersion active layer in the step (3), obtains lithium ion after dry
Capacitor anode material.
5. preparation method as claimed in claim 4, which is characterized in that fluorization agent includes perfluorinated resin, gathers in the step (1)
One or more of vinylidene and polytetrafluoroethylene (PTFE).
6. preparation method as claimed in claim 4, which is characterized in that point of fluorination multi-walled carbon nanotube in the step (2)
Dispersion liquid includes fluorination multi-walled carbon nanotube, surfactant and organic solvent.
7. preparation method as claimed in claim 6, which is characterized in that the surfactant include polyvinylpyrrolidone,
Lauryl sodium sulfate or dodecyl sodium sulfate.
8. such as the described in any item preparation methods of claim 5~7, which is characterized in that the speed of shearing is in the step (2)
8000~12000r/min, the time of shearing are 30~60min.
9. preparation method as claimed in claim 4, which is characterized in that the stabilisation metallic lithium powder dispersion liquid includes stabilizing
Metallic lithium powder and organic solvent, the metallic lithium powder and the mass ratio of organic solvent of stabilizing is 1:(50~200).
10. a kind of lithium-ion capacitor, including positive electrode, negative electrode material, electrolyte and diaphragm, which is characterized in that described negative
Pole material is any one of any one of the claims 1 to 3 lithium-ion capacitor negative electrode material or claim 4~9 system
The lithium-ion capacitor negative electrode material that Preparation Method is prepared.
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| CN112928381A (en) * | 2019-12-06 | 2021-06-08 | 北京航空航天大学 | Lithium-supplementing electrode plate and lithium-supplementing diaphragm of lithium ion battery and preparation method of lithium-supplementing electrode plate and lithium-supplementing diaphragm |
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