CN106206063A - Water system hybrid super capacitor and preparation method thereof - Google Patents
Water system hybrid super capacitor and preparation method thereof Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000011230 binding agent Substances 0.000 claims abstract description 57
- 239000006258 conductive agent Substances 0.000 claims abstract description 53
- 239000000654 additive Substances 0.000 claims abstract description 51
- 230000000996 additive effect Effects 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 239000003792 electrolyte Substances 0.000 claims abstract description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 239000006260 foam Substances 0.000 claims abstract description 32
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 32
- 230000004888 barrier function Effects 0.000 claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 16
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010959 steel Substances 0.000 claims abstract description 13
- 239000011135 tin Substances 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000011889 copper foil Substances 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 10
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005030 aluminium foil Substances 0.000 claims abstract description 6
- 239000002905 metal composite material Substances 0.000 claims abstract description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 6
- 239000004744 fabric Substances 0.000 claims abstract description 3
- 230000004048 modification Effects 0.000 claims abstract description 3
- 238000012986 modification Methods 0.000 claims abstract description 3
- 238000007747 plating Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 28
- 239000002131 composite material Substances 0.000 claims description 19
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims description 18
- 150000004706 metal oxides Chemical class 0.000 claims description 18
- 238000003825 pressing Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 239000007767 bonding agent Substances 0.000 claims description 10
- 229910000464 lead oxide Inorganic materials 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical group [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000005538 encapsulation Methods 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- 238000007689 inspection Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- 101150096185 PAAS gene Proteins 0.000 claims description 4
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 4
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 3
- 229910013119 LiMxOy Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical class [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- AXTYOFUMVKNMLR-UHFFFAOYSA-N dioxobismuth Chemical compound O=[Bi]=O AXTYOFUMVKNMLR-UHFFFAOYSA-N 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920006184 cellulose methylcellulose Polymers 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 1
- 239000003610 charcoal Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- IRPDISVJRAYFBI-UHFFFAOYSA-N nitric acid;potassium Chemical group [K].O[N+]([O-])=O IRPDISVJRAYFBI-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- H01G11/32—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
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
- H01G11/46—Metal oxides
-
- 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 provides a kind of water system hybrid super capacitor and preparation method thereof, belong to the energy and power supply electronic components and parts technical field, it is intended to solve existing water system hybrid super capacitor structure complicated, the problem that preparation method is loaded down with trivial details.It is made up of positive plate, negative plate, barrier film between positive/negative plate and electrolyte；Positive plate is coated with the metal composite oxide LiM containing lithiumxOy, conductive agent, binding agent and press down the foam nickel sheet of mixture of oxygen additive, aluminium foil；Negative plate is coated with activated carbon, conductive agent, binding agent and presses down the foam nickel sheet of mixture, Copper Foil or the tin plating steel mesh of hydrogen additive；Barrier film is modification nonwoven cloth barrier film, and electrolyte is the neutral aqueous solution containing lithium and conduction supporting electrolyte, and conduction supporting electrolyte is the neutral aqueous solution containing potassium ion.Its structure and composition are simple and practical, and preparation method is simple, it is adaptable to preparation water system hybrid super capacitor.
Description
Technical field
The invention belongs to a kind of water system hybrid super capacitor in the energy and power supply electronic components and parts technical field.
Background technology
Along with the energy and the growing and technological progress of power technology, it is a series of that energy crisis and environmental pollution bring
Social problem, promotes people to continually develop at new energy field and explore.Among these: high power, high-energy-density, high safety
Property, low cost electrical source of power become study hotspot.The main direction of studying of electrical source of power has: secondary cell, ultracapacitor, combustion
Material battery etc..Ultracapacitor because its power density is high, have extended cycle life, the most also there is operating temperature range width, safety, nothing
The characteristics such as pollution, at development of renewable energies such as electric motor car, hybrid vehicle, elevator, accessory power supply, wind energy and solar energys
The fields such as electricity have important using value, it has also become have the green power supply of development prospect.In known technology, existing super
The energy density of capacitor is at about 10wh/kg, and it is compared with lithium ion battery, Ni-MH battery etc. or ratio is relatively low.But it is subject to
Its structure is limited, and its structure and composition are complicated, actually used are restricted, and both cost of manufacture is high, and preparation method is loaded down with trivial details again.
Summary of the invention
In order to overcome the deficiencies in the prior art, solve existing water system hybrid super capacitor structure complicated, preparation method
Loaded down with trivial details problem.The purpose of the present invention is to provide a kind of structure and composition is simple and practical, and preparation method is simple, and cost of manufacture is low,
The new-type water system hybrid super capacitor having wide range of applications and preparation method.
Electrochemical mixed capacitor (EHSC) is a kind of novel energy storage unit between ultracapacitor and battery, it
There is specific capacity more higher than ultracapacitor or specific energy and more higher power density than battery, be hybrid electric vehicle, power
One of optimum selection of power supply.Constructing of its material and system is the emphasis of research.Mixed capacitor has double electricity in mechanism
Layer capacitor and the double characteristic of secondary cell, can make full use of different materials capacitance characteristic under different potentials interval
Improve operating voltage range and the energy value of ultracapacitor.
According to super capacitor energy density computing formula E=1/2CV2Understanding, the energy of ultracapacitor to be improved is close
Degree can be set about in terms of two: one is the electrode active material of exploitation high power capacity, how to increase the specific surface area of material and obtains
Obtain effective pore sife distribution and become the emphasis of research；Two is the electrolyte of exploitation high potential window.Organic electrolyte can be by capacitor
Running voltage bring up to 2.7V, capacitor working pressure can be brought up to 4V by ionic liquid, but uses organic or ion-conductance
Solve liquid, be susceptible to combustion explosion accident, have potential safety hazard；On the other hand, organic system is used to require the most strictly to control
Production environment processed, covert adds manufacturing cost.Therefore exploitation water system high voltage super capacitor is imperative.
Being limited by the electrochemical window 1.23V of water decomposition, the running voltage of existing aqueous super capacitor is 1.2V.Voltage
Though higher aqueous super capacitor has been reported that, but for ultracapacitor core zwitterion in the course of the work simultaneously at electricity
Pole react cause electrolyte dry-out problem, liberation of hydrogen analysis oxygen problem etc. does not propose actual property solution under high voltage.
The present invention proposes the high voltage water system hybrid super capacitor of a kind of fast charging and discharging, and solves on formula system
Liberation of hydrogen and the method for analysis oxygen is suppressed under high voltage；This hybrid capacitor can keep preferably holding under high current charge-discharge
Amount, more preferable cyclical stability and longer service life；And the preparation method of this hybrid capacitor a kind of is proposed simultaneously.
Aquo-lithium ion battery open source literature shows, be correlated with positive electrode and activated carbon of lithium ion matches, at aqueous liquid
System is expected to obtain high voltage super capacitor；The present invention is that the metal composite oxide that can embed and deviate from lithium ion is for just
Pole, height compares the mesoporous carbon in face and activated carbon is negative pole, and neutral is electrolyte containing lithium aqueous solution, is assembled into hybrid capacitor
Device.
The present invention solves the problems referred to above and be the technical scheme is that
A kind of water system hybrid super capacitor, it be by positive plate, negative plate, barrier film between positive/negative plate and
Electrolyte forms；Positive plate is coated with the metal composite oxide LiMxOy containing lithium, conductive agent, binding agent and presses down oxygen additive
The foam nickel sheet of mixture, aluminium foil；Negative plate is coated with activated carbon, conductive agent, binding agent and presses down the mixing of hydrogen additive
The foam nickel sheet of thing, Copper Foil；Barrier film is modification nonwoven cloth barrier film, and described electrolyte is the neutral aqueous solution containing lithium and conduction
Holding electrolyte, the lithium salts in electrolyte is lithium sulfate, lithium nitrate, lithium chloride, and conduction supporting electrolyte is the neutrality containing potassium ion
Aqueous solution.
Above-mentioned water system hybrid super capacitor, described positive plate or be coated with the metal composite oxide containing lithium
LiMxOy, conductive agent, binding agent and press down the tin plating steel mesh of oxygen additive agent mixture.
Above-mentioned water system hybrid super capacitor, lithium-contained composite metal oxide, conductive agent in described positive plate, presses down oxygen and adds
Add the mixture of agent, binding agent, the composition of mixture by weight ratio for lithium-contained composite metal oxide 88～95 parts, press down oxygen and add
Add agent 0.5～1.5 parts, conductive agent 3～5 parts, binding agent 1.5～5.5 parts, lithium-contained composite metal oxide be modified lithium manganate,
Cobalt acid lithium, nickle cobalt lithium manganate, the embedding de-material of a kind of～several lithium ion of LiFePO4, conductive agent is nikel powder, cobalt protoxide, charcoal
Black a kind of～several conductive agent, pressing down oxygen additive is yittrium oxide, any one flat rare earth oxide zirconic, and binding agent is for having
Machine binding agent CMC, HPMC type bonding agent, hydroxyethyl cellulose HEC bonding agent, PTFE type bonding agent, bonding agent SBR, polypropylene
Any one～several binding agent in acid sodium PAAS, PVA type bonding agent.
Above-mentioned water system hybrid super capacitor, activated carbon in described negative plate, hydrogen inhibitor, conductive agent, binding agent mixed
Compound forms, and is by weight ratio: activated carbon 88～95 parts, press down hydrogen additive 1.0～1.5 parts, conductive agent 3～5 parts, binding agent
1.5～5.0 parts；Activated carbon is any one activity of modified activated carbon, CNT, vapor-grown carbon fibers VGCF, Graphene
Charcoal, conductive agent is any one conductive agent of nikel powder, white carbon black, graphite, and pressing down hydrogen additive is lead oxide, Indium sesquioxide., bismuth oxide oxidation
In thing any one～several press down hydrogen additive, binding agent be in CMC, HPMC, HEC, PTFE, SBR, PAAS, PVA any one～
Several binding agents.
Above-mentioned water system hybrid super capacitor, described in press down oxygen additive be yittrium oxide, any one rare earth oxygen zirconic
Compound, press down hydrogen additive be lead oxide, Indium sesquioxide., bismuth oxide oxide any one press down hydrogen additive.
Above-mentioned water system hybrid super capacitor, described barrier film be thickness be 100 μm～180 μm non-woven fabrics grafting every
Film.
Above-mentioned water system hybrid super capacitor, described electrolyte is to be sulfur containing the active electrolyte in lithium neutral aqueous solution
Acid lithium, lithium nitrate, lithium chloride, lithium phosphate any one～several, the concentration of electrolyte is 1-3mol/L.
Above-mentioned water system hybrid super capacitor, described conduction supporting electrolyte is containing the electricity in potassium ion neutral aqueous solution
Solution matter be potassium sulfate, potassium nitrate any one, conduction supporting electrolyte concentration be
0.5-1mol/L。
Above-mentioned water system hybrid super capacitor, it is characterised in that described capacitor be shaped as column type, square, knob
In button-type any one, its shell is any one composite of organic plastics, metal material and metallo organic material.
Above-mentioned water system hybrid super capacitor, the preparation method of described water system hybrid super capacitor, for following steps:
1) preparation of positive plate:
By lithium-contained composite metal oxide, press down oxygen additive, conductive agent, binding agent are weighed by above-mentioned weight proportion, mixed
After closing uniformly, it is coated in nickel foam, metal aluminum foil, tin-coated steel online, by appointing of the nickel foam after electrode coated material and aluminium foil
It is standby that a kind of drier roll is pressed into sheet；
2) preparation of negative plate:
By activated carbon, press down hydrogen additive, conductive agent, binding agent are weighed by above-mentioned weight proportion, remix uniformly after, be coated with
Overlay on nickel foam, Copper Foil, tin-coated steel on the net, any one drier roll of the nickel foam after electrode coated material and Copper Foil is pressed into sheet
Standby；
3) capacitor product is assembled:
By the way of lamination or winding, cylinder or rectangular cell it is fabricated to after positive plate, barrier film and negative plate being cut,
Inject electrolyte, draw positive wire and negative wire, after shell encapsulation assembles, qualified through inspection, become the water of the present invention
It it is hybrid super capacitor product.
The present invention be the metal composite oxide that can embed and deviate from lithium ion as positive pole, height compares the mesoporous carbon in face
And activated carbon is negative pole, neutral is electrolyte containing lithium aqueous solution, realizes single lithium ion " rocking chair " in charge and discharge process, the most anti-
Only electrolyte decomposition；Containing potassium ion supporting electrolyte in electrolyte, improve electrolyte speed, thus reduce super capacitor
Equivalent resistance；Positive pole interpolation presses down oxygen additive, improves overpotential for oxygen evolution, and negative pole interpolation presses down hydrogen additive, improves overpotential of hydrogen evolution,
Thus the decomposition voltage of water is brought up to more than 2.0V.
Owing to the present invention has been designed with technique scheme, efficiently solve existing water system hybrid super capacitor
Structure is complicated, the problem that preparation method is loaded down with trivial details.Also showing through testing result on trial for several times, it has structure and composition is the most real
Simple by, preparation method, cost of manufacture is low, and the advantage such as have wide range of applications, it is adaptable to preparation water system hybrid super capacitor.
Accompanying drawing explanation
With embodiment, the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is embodiment of the present invention LiMn2O4/C hybrid capacitor CV curve chart in different voltage ranges, and contrast is not
With CV curve ratio electric capacity, this system optimum operating voltage is 1.8V.
Fig. 2 be embodiment of the present invention LiMn2O4/C hybrid capacitor a certain week CV curve chart, curve has a pair obvious
Oxidoreduction peak, illustrate that this system has Faraday pseudo-capacitance behavior.
Fig. 3 is embodiment of the present invention hybrid capacitor cycle charge-discharge curve chart.
Fig. 4 is embodiment of the present invention hybrid capacitor single charging and discharging curve figure.
Fig. 5 is embodiment of the present invention hybrid capacitor capacity and cycle-index graph of a relation.
Detailed description of the invention
Embodiment 1
Lithium-contained composite metal oxide, conductive agent in the water system hybrid super capacitor positive plate of the present embodiment, press down oxygen and add
Adding the mixture of agent, binding agent, the composition of mixture is lithium-contained composite metal oxide 91.8g by weight ratio, presses down oxygen interpolation
Agent 1.2g, conductive agent 4g, binding agent 3g, lithium-contained composite metal oxide is the embedding de-material of lithium ion of LiFePO4, conductive agent
For nikel powder conductive agent, pressing down oxygen additive is yittrium oxide rare earth oxide, and binding agent is CMC and PTFE hybrid adhesive；
The mixture of activated carbon, hydrogen inhibitor, conductive agent, binding agent in described negative plate, the composition of mixture is joined by weight
Compare for activated carbon 91.8g, press down hydrogen additive 1.2g, conductive agent 4g, binding agent 3g；Activated carbon is modified activated carbon, and conductive agent is
Nikel powder, pressing down hydrogen additive is lead oxide, and binding agent is CMC binding agent；
Described pressing down the rare earth oxide that oxygen additive is yittrium oxide, pressing down hydrogen additive is lead oxide；
Described barrier film be thickness be 140 μm non-woven fabrics grafting barrier film；
In described electrolyte, active electrolyte is lithium sulfate, and the concentration of electrolyte is 2.0mol/L, conduction supporting electrolyte
Conduction supporting electrolyte be potassium nitrate, conduction supporting electrolyte concentration be 0.8mol/L；
Described capacitor be shaped as column type, its shell is stainless steel material.
The water system hybrid super capacitor of above-described embodiment, the preparation method of described water system hybrid super capacitor, for such as
Lower step:
1) preparation of positive plate:
By weight ratio for lithium-contained composite metal oxide 91.8g, press down oxygen additive 1.2g, conductive agent 4g, binding agent 3g
Weigh, after mix homogeneously, be coated in nickel foam, metal aluminum foil, tin-coated steel on the net, by the aluminium foil drier roll after electrode coated material
It is pressed into sheet standby；
2) preparation of negative plate:
By weight ratio for activated carbon 91.8g, press down hydrogen additive 1.2g, conductive agent 4g, binding agent 3g weighing, mix homogeneously
After, it is coated in nickel foam, Copper Foil, tin-coated steel on the net, the nickel foam drier roll after electrode coated material is pressed into sheet standby；
3) capacitor product is assembled:
By the way of winding, it is fabricated to cylindrical battery after positive plate, barrier film and negative plate being cut, injects electrolyte,
Draw positive wire and negative wire, after shell encapsulation assembles, qualified through inspection, become the water system hybrid super electricity of the present invention
Container products (I).
Embodiment 2
Lithium-contained composite metal oxide, conductive agent in the water system hybrid super capacitor positive plate of the present embodiment, press down oxygen and add
Adding the mixture of agent, binding agent, the composition of mixture is lithium-contained composite metal oxide 93.8g by weight ratio, presses down oxygen interpolation
Agent 1.2g, conductive agent 2g, binding agent 3g, lithium-contained composite metal oxide is the embedding de-material of lithium ion of cobalt acid lithium, and conductive agent is
Nikel powder conductive agent, pressing down oxygen additive is yittrium oxide rare earth oxide, and binding agent is the hybrid adhesive of HEC and PTFE；
The mixture of activated carbon, hydrogen inhibitor, conductive agent, binding agent in described negative plate, the composition of mixture is joined by weight
Compare for activated carbon 92g, press down hydrogen additive 1.2g, conductive agent 4g, binding agent 3g；Activated carbon is CNT, and conductive agent is nikel powder,
Pressing down hydrogen additive is lead oxide, Indium sesquioxide. mixture, and binding agent is CMC binding agent；
Described pressing down the rare earth oxide that oxygen additive is yittrium oxide, pressing down hydrogen additive is lead oxide and Indium sesquioxide.；
Described barrier film be thickness be 150 μm non-woven fabrics grafting barrier film；
In described electrolyte active electrolyte be the concentration of lithium nitrate be 2.5mol/L, conduction supporting electrolyte is nitric acid
Potassium, concentration is 0.5mol/L；
Being shaped as of described capacitor is square, and its shell is ABS material.
The water system hybrid super capacitor of above-described embodiment, the preparation method of described water system hybrid super capacitor, for such as
Lower step:
1) preparation of positive plate:
By weight ratio for lithium-contained composite metal oxide 93.8g, press down oxygen additive 1.2g, conductive agent 2g, binding agent 3g,
After mix homogeneously, it is coated in nickel foam, metal aluminum foil, tin-coated steel on the net, the nickel foam after electrode coated material is dried roll-in
The most standby；
2) preparation of negative plate:
By weight ratio for activated carbon 92g, press down hydrogen additive 1.2g, conductive agent 4g, binding agent 3g weighing, mix homogeneously
After, it is coated in nickel foam, Copper Foil, tin-coated steel on the net, the nickel foam drier roll after electrode coated material is pressed into sheet standby；
3) capacitor product is assembled:
It is fabricated to rectangular cell by lamination process after positive plate, barrier film and negative plate being cut, injects electrolyte, draw
Positive wire and negative wire, after shell encapsulation assembles, qualified through inspection, become the water system hybrid super capacitor of the present invention
Product (II).
Embodiment 3
The positive electrode of the present embodiment uses business-like LiMn2O4, spinel lithium manganate, yittrium oxide, nikel powder, CMC and
PTFE by weight ratio for 93g, 1g, 4g, 0.24g, 1.76g be mixed into slurry, uniformly after be coated in foam nickel sheet, will coating
The foam nickel sheet of electrode material is dried rolling backlash and makes positive plate；Negative pole uses business-like activated carbon (Kuraray chemistry business
Industry charcoal), by activated carbon, Indium sesquioxide., bismuth oxide, nikel powder, CMC, ptfe emulsion by by weight ratio be 92g, 0.2g,
After 1.0g, 5.0g, 1.8g are mixed into slurry, uniformly after be coated in foam nickel sheet, the foam nickel sheet of electrode coated material is done
Negative plate is made in dry roll-in backlash；Positive plate, barrier film and negative plate are stacked successively, injects electrolyte, composition R2032 button electricity
Container.In this case study on implementation, the coating density of positive pole is 6mg/cm2, negative pole coated face density is 12mg/cm2, barrier film uses Coudé
Precious ni-mh grafting barrier film, thickness is 0.16mm, and concentration of electrolyte is 1.5mol/LLi2SO4+0.5mol/LK2SO4。
In the present embodiment, the running voltage of capacitor is 1.8V, and recording than electric capacity is 85.5F/g, and energy density reaches 38wh/
Kg is suitable with plumbic acid energy-storage battery.
Embodiment 4
The positive electrode of the present embodiment uses business-like 523NCM ternary material, by 523NCM ternary material, yittrium oxide,
Nikel powder, CMC and PTFE by weight ratio for 93kg, 1kg, 4kg, 0.24kg, 1.76kg be mixed into slurry, uniformly after be coated in bubble
In foam nickel sheet, the foam nickel sheet of electrode coated material is dried rolling backlash and makes positive plate；Negative pole uses business-like activity
Charcoal (Kuraray chemistry business charcoal)；By activated carbon, Indium sesquioxide., bismuth oxide, nikel powder, CMC, ptfe emulsion by weight ratio
For 92kg, 0.2kg, 1.0kg, 5.0 parts, after 0.25kg, 1.55kg be mixed into slurry, uniformly after be coated in foam nickel sheet, will
Negative plate is made in the foam nickel sheet dryer roll pressure backlash of electrode coated material；Positive plate, barrier film and negative plate are stacked successively, note
Enter electrolyte, form R2032 button capacitor.In this case study on implementation, the coating density of positive pole is 4.5mg/cm2, negative pole coated face
Density is 12mg/cm2, barrier film uses Coudé treasured ni-mh grafting barrier film, and thickness is 0.16mm, and concentration of electrolyte is 1.5mol/
LLi2SO4+0.5mol/LK2SO4。
In the present embodiment, the running voltage of capacitor is 1.9V, and recording than electric capacity is 90F/g, and energy density reaches 45wh/kg.
Embodiment 5
Lithium-contained composite metal oxide, conductive agent in the water system hybrid super capacitor positive plate of the present embodiment, press down oxygen and add
Adding the mixture of agent, binding agent, the composition of mixture is lithium-contained composite metal oxide 90g by weight ratio, presses down oxygen additive
1.2g, conductive agent 4g, binding agent 3g, lithium-contained composite metal oxide is the embedding de-material of lithium ion of lithium nickelate, and conductive agent is nickel
Powder conductive agent, pressing down oxygen additive is zirconium oxide rare earth oxide, and binding agent is the binding agent of organic binder bond CMC；
The composition of mixture in described negative plate, is activated carbon 92g by weight ratio, presses down hydrogen additive 1.2g, conductive agent
4g, binding agent 3g；Activated carbon is modified activated carbon, and conductive agent is nikel powder, and pressing down hydrogen additive is lead oxide and Indium sesquioxide., binding agent
For CMC binding agent；
The described oxygen additive that presses down is zirconic rare earth oxide, and pressing down hydrogen additive is lead oxide and Indium sesquioxide.；
Described barrier film be thickness be 180 μm non-woven fabrics grafting barrier film；
In described electrolyte, active electrolyte is lithium nitrate, and the concentration of electrolyte is 1.8mol/L, conduction supporting electrolyte
For potassium nitrate, the concentration of conduction supporting electrolyte is 0.8mol/L；
Described capacitor be shaped as square, its shell is stainless steel material.
The water system hybrid super capacitor of above-described embodiment, the preparation method of described water system hybrid super capacitor, for such as
Lower step:
1) preparation of positive plate:
By above-mentioned lithium-contained composite metal oxide, press down oxygen additive, conductive agent, binding agent weight proportion weigh, mixing
After Jun Yun, it is coated in nickel foam, metal aluminum foil, tin-coated steel on the net, the nickel foam drier roll after electrode coated material is pressed into sheet
Standby；
2) preparation of negative plate:
By above-mentioned activated carbon, press down hydrogen additive, conductive agent, binding agent weight proportion weigh, after mix homogeneously, be coated in
Nickel foam, Copper Foil, tin-coated steel are online, the drier roll of the Copper Foil after electrode coated material are pressed into sheet standby；
3) capacitor product is assembled:
By lamination rectangular cell after positive plate, barrier film and negative plate being cut, inject electrolyte, draw positive wire and
Negative wire, after shell encapsulation assembles, qualified through inspection, become water system hybrid super capacitor product (III) of the present invention.
Claims (10)
1. a water system hybrid super capacitor, it is characterised in that this capacitor be by positive plate, negative plate, between both positive and negative polarity
Barrier film between sheet and electrolyte composition；Positive plate is coated with the metal composite oxide LiM containing lithiumxOy, conductive agent, viscous
Tie agent and press down the foam nickel sheet of oxygen additive agent mixture, aluminium foil；Negative plate be coated with activated carbon, conductive agent, binding agent and
Press down the foam nickel sheet of the mixture of hydrogen additive, Copper Foil；Barrier film is modification nonwoven cloth barrier film, and described electrolyte is containing in lithium
Property aqueous solution and conduction supporting electrolyte, conduction supporting electrolyte be the neutral aqueous solution containing potassium ion.
Water system hybrid super capacitor the most according to claim 1, it is characterised in that positive plate is coated with answering containing lithium
Close metal-oxide LiMxOy, conductive agent, binding agent and press down the tin plating steel mesh of oxygen additive agent mixture.
Water system hybrid super capacitor the most according to claim 1, it is characterised in that containing the compound gold of lithium in described positive plate
Belonging to oxide, conductive agent, press down the mixture of oxygen additive, binding agent, the composition of mixture be compound golden containing lithium by weight ratio
Belong to oxide 88～95 parts, press down oxygen additive 0.5～1.5 parts, conductive agent 3～5 parts, binding agent 1.5～5.5 parts, be combined containing lithium
Metal-oxide is the embedding de-material of a kind of～several lithium ion of modified lithium manganate, cobalt acid lithium, nickle cobalt lithium manganate, LiFePO4,
Conductive agent is a kind of～several conductive agent of nikel powder, cobalt protoxide, white carbon black, and pressing down oxygen additive is yittrium oxide, zirconic arbitrary
Planting rare earth oxide, binding agent is organic binder bond CMC, HPMC type bonding agent, hydroxyethyl cellulose HEC bonding agent, PTFE type
Any one～several binding agent in bonding agent, bonding agent SBR, sodium polyacrylate PAAS, PVA type bonding agent.
Water system hybrid super capacitor the most according to claim 1, it is characterised in that activated carbon in described negative plate, press down
Hydrogen agent, conductive agent, the mixture of binding agent, by weight ratio for activated carbon 88～95 parts, press down hydrogen additive 1.0～1.5 parts, lead
Electricity agent 3～5 parts, binding agent 1.5～5.0 parts；Activated carbon is modified activated carbon, CNT, vapor-grown carbon fibers VGCF, stone
Any one activated carbon of ink alkene, conductive agent is any one conductive agent of nikel powder, white carbon black, graphite, and pressing down hydrogen additive is lead oxide, oxygen
Change any one in indium, bismuth oxide oxide～several additive, binding agent is CMC, HPMC, HEC, PTFE, SBR, PAAS,
Any one～several binding agent in PVA.
Water system hybrid super capacitor the most according to claim 1, it is characterised in that described in press down oxygen additive for oxidation
Yttrium, any one rare earth oxide zirconic, press down hydrogen additive be lead oxide, Indium sesquioxide., bismuth oxide oxide any one add
Add agent.
Water system hybrid super capacitor the most according to claim 1, it is characterised in that described barrier film be thickness be 100 μm
～180 μm non-woven fabrics grafting barrier film.
Water system hybrid super capacitor the most according to claim 1, it is characterised in that described electrolyte is containing lithium neutral water
Active electrolyte in solution be lithium sulfate, lithium nitrate, lithium chloride, lithium phosphate any one～several, the concentration of electrolyte is
1-3mol/L。
Water system hybrid super capacitor the most according to claim 1, it is characterised in that described conduction supporting electrolyte is for containing
Electrolyte in potassium ion neutral aqueous solution be potassium sulfate, potassium nitrate any one, conduction supporting electrolyte concentration be 0.5-
1mol/L。
Water system hybrid super capacitor the most according to claim 1, it is characterised in that described capacitor be shaped as cylinder
In type, square, coin shape any one, its shell is any one composite wood of organic plastics, metal material and metallo organic material
Material.
Water system hybrid super capacitor the most according to claim 1, it is characterised in that described water system hybrid capacitor
The preparation method of device, for following steps:
1) preparation of positive plate:
By lithium-contained composite metal oxide, press down oxygen additive, conductive agent, binding agent are weighed by above-mentioned weight proportion, mixing is all
After even, it is coated in nickel foam, metal aluminum foil, tin-coated steel online, by any one of the nickel foam after electrode coated material and aluminium foil
It is standby that drier roll is pressed into sheet；
2) preparation of negative plate:
By activated carbon, press down hydrogen additive, conductive agent, binding agent are weighed by above-mentioned weight proportion, remix uniformly after, be coated in
Nickel foam, Copper Foil, tin-coated steel are online, the nickel foam after electrode coated material or Copper Foil drier roll are pressed into sheet standby；
3) capacitor product is assembled:
By the way of lamination or winding, it is fabricated to cylinder or rectangular cell after positive plate, barrier film and negative plate being cut, injects
Electrolyte, draws positive wire and negative wire, and after shell encapsulation assembles, qualified through inspection, the water system becoming the present invention is mixed
Close ultracapacitor product.
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| CN201610666559.7A CN106206063A (en) | 2016-08-13 | 2016-08-13 | Water system hybrid super capacitor and preparation method thereof |
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| CN107393727A (en) * | 2017-07-17 | 2017-11-24 | 深圳中科瑞能实业有限公司 | Deintercalation material can be embedded in and be used as potassium ion hybrid super capacitor negative material and potassium ion hybrid super capacitor and preparation method thereof |
| CN108335914A (en) * | 2018-01-23 | 2018-07-27 | 江苏尊道科技有限公司 | A kind of hybrid super capacitor wet end furnish preparation method |
| CN108962622A (en) * | 2018-07-16 | 2018-12-07 | 晋江瑞碧科技有限公司 | A kind of preparation method of Carbon anode electrode plate |
| CN109473290A (en) * | 2017-09-08 | 2019-03-15 | 中国科学院物理研究所 | A kind of aqueous solution kalium ion battery capacitor and application |
| CN114975893A (en) * | 2022-05-16 | 2022-08-30 | 天能新能源(湖州)有限公司 | Preparation method of lithium iron phosphate positive plate for energy storage |
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