CN106816316A - A kind of ultracapacitor preparation method of manganese cobalt nickel base electrode - Google Patents
A kind of ultracapacitor preparation method of manganese cobalt nickel base electrode Download PDFInfo
- Publication number
- CN106816316A CN106816316A CN201710152353.7A CN201710152353A CN106816316A CN 106816316 A CN106816316 A CN 106816316A CN 201710152353 A CN201710152353 A CN 201710152353A CN 106816316 A CN106816316 A CN 106816316A
- Authority
- CN
- China
- Prior art keywords
- manganese cobalt
- parts
- nickel base
- ultracapacitor
- base electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 39
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 36
- 239000010439 graphite Substances 0.000 claims abstract description 36
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 28
- -1 graphite alkene Chemical class 0.000 claims abstract description 28
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000005516 engineering process Methods 0.000 claims abstract description 9
- 230000003068 static effect Effects 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 16
- 239000012265 solid product Substances 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003643 water by type Substances 0.000 claims description 16
- 239000006230 acetylene black Substances 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- 235000010344 sodium nitrate Nutrition 0.000 claims description 8
- 239000004317 sodium nitrate Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 15
- 150000001336 alkenes Chemical class 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000011149 active material Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 4
- 238000011056 performance test Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004575 stone Substances 0.000 description 4
- XKYFHUXZPRFUTH-UHFFFAOYSA-N dipotassium;dioxido(dioxo)manganese Chemical class [K+].[K+].[O-][Mn]([O-])(=O)=O XKYFHUXZPRFUTH-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 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
-
- 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
-
- 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)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention discloses a kind of ultracapacitor preparation method of manganese cobalt nickel base electrode, the technique is made graphene oxide by by natural flake graphite by the step oxidation processes of low, medium and high temperature three, manganese cobalt composition and graphite oxide alkene reaction are made manganese cobalt composite graphite alkene material by the precipitation method again, active material is coated on Ni-based hearth electrode finally by pressurization pressed-disc technique, is made ultracapacitor manganese cobalt nickel base electrode.The ultracapacitor being prepared from manganese cobalt nickel base electrode, its stable performance, electric conductivity are good, electric capacity expansion capacity is strong, in addition the preparation technology environment-protection low-consumption, and safety is easy, with preferable industrial applications prospect.Also disclose simultaneously and applied in the precision instrument back-up sources such as vacuum switch, intelligent device, static memory, programme-controlled exchange as ultracapacitor manganese cobalt nickel base electrode obtained in the preparation technology.
Description
Technical field
The present invention relates to Material Field, a kind of preparation method of ultracapacitor manganese cobalt nickel base electrode is related specifically to.
Background technology
Ultracapacitor as important stand-by power supply, can prevent power breakdown simultaneously supplement energy storage with it is traditional
Electrostatic container is compared, and ultracapacitor has no too big difference in principle.Capacitance size is equally all met with facing area into just
Than the rule that the distance between two-plate is inversely proportional.But why " super " is because with porous in business for ultracapacitor
Activated carbon is electrode material, and its surface area increases rapidly, and distance between two-plate is only relevant ions radius, is typically in the range of
2-10 angstroms.The two absolute advantages cause that the storage capacity of ultracapacitor is much better than traditional electrostatic container.Certainly, it is super
Capacitor is also faced with some problems, is mainly manifested in：（1）Energy density is relatively low, it is impossible to realize the long time running of equipment；
（2）Self-discharge phenomenon is serious；（3）The operating voltage of super electric monomer is relatively low.
Used as the electrode material of ultracapacitor, manganese, cobalt, nickel are due to theoretical specific capacitance higher, unique crystal
The advantages of structure and outstanding electrical conductivity, increasingly attracts the notice of researcher.So this invention address that research manganese cobalt nickel
Base electrode, expects to overcome the defect and deficiency of ultracapacitor generally existing using the excellent chemical property of these materials,
Make qualified ultracapacitor.
The content of the invention
In order to solve the above technical problems, the present invention provides a kind of preparation method of ultracapacitor manganese cobalt nickel base electrode,
Graphene oxide is made by the step oxidation processes of low, medium and high temperature three by by natural flake graphite, then by the precipitation method
Manganese cobalt composition and graphite oxide alkene reaction are made manganese cobalt composite graphite alkene material, finally by pressurization pressed-disc technique by active material
Material is coated on Ni-based hearth electrode, is made ultracapacitor manganese cobalt nickel base electrode.The ultracapacitor being prepared from manganese cobalt
Nickel base electrode, its stable performance, electric conductivity are good, electric capacity expansion capacity is strong, in addition the preparation technology environment-protection low-consumption, and safety is easily
OK, with preferable industrial applications prospect.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of ultracapacitor preparation method of manganese cobalt nickel base electrode, comprises the following steps：
（1）By 1L concentrated sulfuric acid ice bath 1-2h, successively to 7-9g sodium nitrate and 10-12g natural flake graphites is added in the concentrated sulfuric acid, stir
48g is slowly added to after mixing uniformly, 2-4h is persistently stirred after all adding, mixing speed is 50 revs/min；
（2）By step（1）In mixing suspension be put into heating and thermal insulation in 37 DEG C of oil bath pan, persistently stir 10-12h, stir
Speed is 50 revs/min；
（3）To step（2）In insulation suspension in add the deionized water of 1L, be heated to 95-98 DEG C, stir 15-30 minutes,
Mixing speed is 50 revs/min, then sequentially adds the hydrogen peroxide of 500ml deionized waters and 200g30%, natural cooling；
（4）By step（3）Mixture centrifugation, take solid sediment, be put in 75 DEG C of drying in oven 4-5h, aoxidized
Graphene；
（5）By 3-5 parts of manganese dioxide, 1-2 parts of potassium manganate, 1-3 parts of cobalt chloride, 2-4 parts of cobalt nitrate, 5-10 parts of graphene oxide is molten
In 8-10 parts of 1.2mM sodium hydrate aqueous solution, 1-2h is stirred, stand 12h, filter collection solid product;
（6）By step（5）The solid product being collected into is then placed into 75 DEG C of drying in oven with 3% NaCl 3 times
2-3h, obtains manganese cobalt composite graphite alkene material；
（7）Weigh step（6）5-10 parts of manganese cobalt composite graphite alkene material, conductive agent 1-2 parts, binding agent 1-2 parts, by binding agent
Add in mortar, be slowly dropped into 2ml deionized waters, after grinding is uniform, add conductive agent, 10-20min is ground, then by manganese cobalt
Composite graphite alkene material is added, and continues to be ground to pulpous state；
（8）By step（7）Slurry material stainless steel spatula be coated on Ni-based hearth electrode, then with tinfoil wrap up electrode,
It is put on tablet press machine and suppresses, pressure is 15MPa, and the duration is 2min, and the electrode that then will be suppressed is put into 75 DEG C of baking ovens
Drying 12h, takes out natural cooling, as electrode finished product.
Preferably, the step（1）The speed that middle potassium permanganate is added adds 4g according to every 5min.
Preferably, the step（5）In filter pressure for 20MPa.
Preferably, the step（7）Middle conductive agent is acetylene black.
Preferably, the step（7）Middle conductive agent is acetylene black.
Present invention also offers the ultracapacitor obtained by above-mentioned preparation technology with manganese cobalt nickel base electrode vacuum switch,
Applied in the precision instrument back-up source such as intelligent device, static memory, programme-controlled exchange.
Compared with prior art, its advantage is the present invention：
（1）Ultracapacitor of the invention with the preparation method of manganese cobalt nickel base electrode by by natural flake graphite by low temperature,
In the gentle step oxidation processes of high temperature three be made graphene oxide, then by the precipitation method by manganese cobalt composition and graphite oxide alkene reaction system
Into manganese cobalt composite graphite alkene material, active material is coated on Ni-based hearth electrode finally by pressurization pressed-disc technique, be made super
Level capacitor manganese cobalt nickel base electrode.The ultracapacitor being prepared from manganese cobalt nickel base electrode, its stable performance, electric conductivity are good
Good, electric capacity expansion capacity is strong, in addition the preparation technology environment-protection low-consumption, and safety is easy, with preferable industrial applications prospect.
（2）The ultracapacitor of the invention preparation method process is simple of manganese cobalt nickel base electrode, easy to operate, raw material is easy
, environment-protection low-consumption is suitable to big rule industrialization and uses, practical.
Specific embodiment
The technical scheme invented is described in detail with reference to specific embodiment.
Embodiment 1
（1）By 1L concentrated sulfuric acid ice bath 1h, successively to 7g sodium nitrate and 10g natural flake graphites is added in the concentrated sulfuric acid, stir
After be slowly added to 48g, the speed that potassium permanganate is added adds 4g according to every 5min, and 2h is persistently stirred after all adding, and stirs
Speed is 50 revs/min；
（2）By step（1）In mixing suspension be put into heating and thermal insulation in 37 DEG C of oil bath pan, persistently stir 10h, mixing speed
It is 50 revs/min；
（3）To step（2）In insulation suspension in add the deionized water of 1L, be heated to 95 DEG C, stir 15 minutes, stirring speed
It is 50 revs/min to spend, and then sequentially adds the hydrogen peroxide of 500ml deionized waters and 200g30%, natural cooling；
（4）By step（3）Mixture centrifugation, take solid sediment, be put in 75 DEG C of drying in oven 4h, obtain aoxidize stone
Black alkene；
（5）3 parts of manganese dioxide, 1 part of potassium manganate, 1 part of cobalt chloride, 2 parts of cobalt nitrates, 5 parts of graphene oxides are dissolved in 8 parts of 1.2mM
In sodium hydrate aqueous solution, 1h is stirred, stand 12h, filter collection solid product, filter pressure for 20MPa;
（6）By step（5）The solid product being collected into is then placed into 75 DEG C of drying in oven with 3% NaCl 3 times
2h, obtains manganese cobalt composite graphite alkene material；
（7）Weigh step（6）5 parts of manganese cobalt composite graphite alkene material, 1 part of acetylene black, 1 part of tetrafluoroethene emulsion, by tetrafluoro second
Alkene emulsion is added in mortar, is slowly dropped into 2ml deionized waters, after grinding is uniform, adds acetylene black, 10min is ground, then by manganese
Cobalt composite graphite alkene material is added, and continues to be ground to pulpous state；
（8）By step（7）Slurry material stainless steel spatula be coated on Ni-based hearth electrode, then with tinfoil wrap up electrode,
It is put on tablet press machine and suppresses, pressure is 15MPa, and the duration is 2min, and the electrode that then will be suppressed is put into 75 DEG C of baking ovens
Drying 12h, takes out natural cooling, as electrode finished product.
Obtained ultracapacitor is as shown in table 1 with the performance test results of manganese cobalt nickel base electrode.
Embodiment 2
（1）By 1L concentrated sulfuric acid ice bath 1.4h, successively to 7.5g sodium nitrate and 10.5g natural flake graphites is added in the concentrated sulfuric acid, stir
48g is slowly added to after mixing uniformly, the speed that potassium permanganate is added adds 4g according to every 5min, all adds lasting stirring later
3h, mixing speed is 50 revs/min；
（2）By step（1）In mixing suspension be put into heating and thermal insulation in 37 DEG C of oil bath pan, persistently stir 10.5h, stirring speed
Spend is 50 revs/min；
（3）To step（2）In insulation suspension in add the deionized water of 1L, be heated to 96 DEG C, stir 20 minutes, stirring speed
It is 50 revs/min to spend, and then sequentially adds the hydrogen peroxide of 500ml deionized waters and 200g30%, natural cooling；
（4）By step（3）Mixture centrifugation, take solid sediment, be put in 75 DEG C of drying in oven 4.3h, aoxidized
Graphene；
（5）4 parts of manganese dioxide, 1 part of potassium manganate, 2 parts of cobalt chlorides, 2 parts of cobalt nitrates, 7 parts of graphene oxides are dissolved in 9 parts of 1.2mM
In sodium hydrate aqueous solution, 1.2h is stirred, stand 12h, filter collection solid product, filter pressure for 20MPa;
（6）By step（5）The solid product being collected into is then placed into 75 DEG C of drying in oven with 3% NaCl 3 times
2.4h, obtains manganese cobalt composite graphite alkene material；
（7）Weigh step（6）8 parts of manganese cobalt composite graphite alkene material, 1 part of acetylene black, 2 parts of tetrafluoroethene emulsion, by tetrafluoro second
Alkene emulsion is added in mortar, is slowly dropped into 2ml deionized waters, after grinding is uniform, adds acetylene black, 15min is ground, then by manganese
Cobalt composite graphite alkene material is added, and continues to be ground to pulpous state；
（8）By step（7）Slurry material stainless steel spatula be coated on Ni-based hearth electrode, then with tinfoil wrap up electrode,
It is put on tablet press machine and suppresses, pressure is 15MPa, and the duration is 2min, and the electrode that then will be suppressed is put into 75 DEG C of baking ovens
Drying 12h, takes out natural cooling, as electrode finished product.
Obtained ultracapacitor is as shown in table 1 with the performance test results of manganese cobalt nickel base electrode.
Embodiment 3
（1）By 1L concentrated sulfuric acid ice bath 1.8h, successively to 8g sodium nitrate and 11g natural flake graphites is added in the concentrated sulfuric acid, stirring is equal
48g is slowly added to after even, the speed that potassium permanganate is added adds 4g, 3h is persistently stirred after all adding, stirs according to every 5min
Speed is mixed for 50 revs/min；
（2）By step（1）In mixing suspension be put into heating and thermal insulation in 37 DEG C of oil bath pan, persistently stir 11h, mixing speed
It is 50 revs/min；
（3）To step（2）In insulation suspension in add the deionized water of 1L, be heated to 97 DEG C, stir 25 minutes, stirring speed
It is 50 revs/min to spend, and then sequentially adds the hydrogen peroxide of 500ml deionized waters and 200g30%, natural cooling；
（4）By step（3）Mixture centrifugation, take solid sediment, be put in 75 DEG C of drying in oven 4.7h, aoxidized
Graphene；
（5）4 parts of manganese dioxide, 2 parts of potassium manganates, 3 parts of cobalt chlorides, 3 parts of cobalt nitrates, 8 parts of graphene oxides are dissolved in 9 parts of 1.2mM
In sodium hydrate aqueous solution, 1.7h is stirred, stand 12h, filter collection solid product, filter pressure for 20MPa;
（6）By step（5）The solid product being collected into is then placed into 75 DEG C of drying in oven with 3% NaCl 3 times
2.6h, obtains manganese cobalt composite graphite alkene material；
（7）Weigh step（6）9 parts of manganese cobalt composite graphite alkene material, 2 parts of acetylene black, 1 part of tetrafluoroethene emulsion, by tetrafluoro second
Alkene emulsion is added in mortar, is slowly dropped into 2ml deionized waters, after grinding is uniform, adds acetylene black, 17min is ground, then by manganese
Cobalt composite graphite alkene material is added, and continues to be ground to pulpous state；
（8）By step（7）Slurry material stainless steel spatula be coated on Ni-based hearth electrode, then with tinfoil wrap up electrode,
It is put on tablet press machine and suppresses, pressure is 15MPa, and the duration is 2min, and the electrode that then will be suppressed is put into 75 DEG C of baking ovens
Drying 12h, takes out natural cooling, as electrode finished product.
Obtained ultracapacitor is as shown in table 1 with the performance test results of manganese cobalt nickel base electrode.
Embodiment 4
（1）By 1L concentrated sulfuric acid ice bath 2h, successively to 9g sodium nitrate and 12g natural flake graphites is added in the concentrated sulfuric acid, stir
After be slowly added to 48g, the speed that potassium permanganate is added adds 4g according to every 5min, and 4h is persistently stirred after all adding, and stirs
Speed is 50 revs/min；
（2）By step（1）In mixing suspension be put into heating and thermal insulation in 37 DEG C of oil bath pan, persistently stir 12h, mixing speed
It is 50 revs/min；
（3）To step（2）In insulation suspension in add the deionized water of 1L, be heated to 98 DEG C, stir 30 minutes, stirring speed
It is 50 revs/min to spend, and then sequentially adds the hydrogen peroxide of 500ml deionized waters and 200g30%, natural cooling；
（4）By step（3）Mixture centrifugation, take solid sediment, be put in 75 DEG C of drying in oven 5h, obtain aoxidize stone
Black alkene；
（5）5 parts of manganese dioxide, 2 parts of potassium manganates, 3 parts of cobalt chlorides, 4 parts of cobalt nitrates, 10 parts of graphene oxides are dissolved in 10 parts
In 1.2mM sodium hydrate aqueous solutions, 2h is stirred, stand 12h, filter collection solid product, filter pressure for 20MPa;
（6）By step（5）The solid product being collected into is then placed into 75 DEG C of drying in oven with 3% NaCl 3 times
3h, obtains manganese cobalt composite graphite alkene material；
（7）Weigh step（6）10 parts of manganese cobalt composite graphite alkene material, 2 parts of acetylene black, 2 parts of tetrafluoroethene emulsion, by tetrafluoro second
Alkene emulsion is added in mortar, is slowly dropped into 2ml deionized waters, after grinding is uniform, adds acetylene black, 20min is ground, then by manganese
Cobalt composite graphite alkene material is added, and continues to be ground to pulpous state；
（8）By step（7）Slurry material stainless steel spatula be coated on Ni-based hearth electrode, then with tinfoil wrap up electrode,
It is put on tablet press machine and suppresses, pressure is 15MPa, and the duration is 2min, and the electrode that then will be suppressed is put into 75 DEG C of baking ovens
Drying 12h, takes out natural cooling, as electrode finished product.
Obtained ultracapacitor is as shown in table 1 with the performance test results of manganese cobalt nickel base electrode.
Comparative example 1
（1）By 1L concentrated sulfuric acid ice bath 1h, successively to 7g sodium nitrate and 10g natural flake graphites is added in the concentrated sulfuric acid, stir
After be slowly added to 48g, the speed that potassium permanganate is added adds 8g according to every 5min, and 2h is persistently stirred after all adding, and stirs
Speed is 50 revs/min；
（2）By step（1）In mixing suspension be put into heating and thermal insulation in 37 DEG C of oil bath pan, persistently stir 10h, mixing speed
It is 50 revs/min；
（3）To step（2）In insulation suspension in add the deionized water of 1L, be heated to 95 DEG C, stir 15 minutes, stirring speed
It is 50 revs/min to spend, and then sequentially adds the hydrogen peroxide of 500ml deionized waters and 200g30%, natural cooling；
（4）By step（3）Mixture centrifugation, take solid sediment, be put in 75 DEG C of drying in oven 4h, obtain aoxidize stone
Black alkene；
（5）3 parts of manganese dioxide, 1 part of cobalt chloride, 5 parts of graphene oxides are dissolved in 8 parts of 1.2mM sodium hydrate aqueous solutions, are stirred
1h, stands 12h, filters collection solid product, filters pressure for 20MPa;
（6）By step（5）The solid product being collected into is then placed into 75 DEG C of drying in oven with 3% NaCl 3 times
2h, obtains manganese cobalt composite graphite alkene material；
（7）Weigh step（6）5 parts of manganese cobalt composite graphite alkene material, 1 part of acetylene black, 1 part of tetrafluoroethene emulsion, by tetrafluoro second
Alkene emulsion is added in mortar, is slowly dropped into 2ml deionized waters, after grinding is uniform, adds acetylene black, 10min is ground, then by manganese
Cobalt composite graphite alkene material is added, and continues to be ground to pulpous state；
（8）By step（7）Slurry material stainless steel spatula be coated on Ni-based hearth electrode, then with tinfoil wrap up electrode,
It is put on tablet press machine and suppresses, pressure is 15MPa, and the duration is 2min, and the electrode that then will be suppressed is put into 75 DEG C of baking ovens
Drying 12h, takes out natural cooling, as electrode finished product.
Obtained ultracapacitor is as shown in table 1 with the performance test results of manganese cobalt nickel base electrode.
Comparative example 2
（1）By 1L concentrated sulfuric acid ice bath 2h, successively to 9g sodium nitrate and 12g natural flake graphites is added in the concentrated sulfuric acid, stir
After be slowly added to 48g, the speed that potassium permanganate is added adds 4g according to every 5min, and 1h is persistently stirred after all adding, and stirs
Speed is 50 revs/min；
（2）By step（1）In mixing suspension be put into heating and thermal insulation in 37 DEG C of oil bath pan, persistently stir 12h, mixing speed
It is 50 revs/min；
（3）To step（2）In insulation suspension in add the deionized water of 1L, be heated to 98 DEG C, stir 30 minutes, stirring speed
It is 50 revs/min to spend, and is subsequently adding 500ml deionized waters, natural cooling；
（4）By step（3）Mixture centrifugation, take solid sediment, be put in 75 DEG C of drying in oven 5h, obtain aoxidize stone
Black alkene；
（5）2 parts of potassium manganates, 3 parts of cobalt chlorides, 10 parts of graphene oxides are dissolved in 10 parts of 1.2mM sodium hydrate aqueous solutions, are stirred
2h, stands 12h, filters collection solid product, filters pressure for 20MPa;
（6）By step（5）The solid product being collected into is then placed into 75 DEG C of drying in oven with 3% NaCl 3 times
3h, obtains manganese cobalt composite graphite alkene material；
（7）Weigh step（6）10 parts of manganese cobalt composite graphite alkene material, 2 parts of acetylene black, 2 parts of tetrafluoroethene emulsion, by tetrafluoro second
Alkene emulsion is added in mortar, is slowly dropped into 2ml deionized waters, after grinding is uniform, adds acetylene black, 20min is ground, then by manganese
Cobalt composite graphite alkene material is added, and continues to be ground to pulpous state；
（8）By step（7）Slurry material stainless steel spatula be coated on Ni-based hearth electrode, then with tinfoil wrap up electrode,
It is put on tablet press machine and suppresses, pressure is 15MPa, and the duration is 2min, and the electrode that then will be suppressed is put into 75 DEG C of baking ovens
Drying 12h, takes out natural cooling, as electrode finished product.
Obtained ultracapacitor is as shown in table 1 with the performance test results of manganese cobalt nickel base electrode.
The obtained ultracapacitor of embodiment 1-4 and comparative example 1-2 is carried out into specific capacitance, capacity with manganese cobalt nickel base electrode
Retention rate, electric charge transfer internal resistance, this several performance tests of energy density.
Table 1
| Specific capacitance（F/g,1A/g） | Capacity retention rate（%, 1000 cyclic voltammetries） | Electric charge transfer internal resistance（Ω） | Energy density（Wh/kg） | |
| Embodiment 1 | 379 | 92.3 | 1.41 | 10.11 |
| Embodiment 2 | 373 | 91.4 | 1.39 | 10.03 |
| Embodiment 3 | 376 | 91.8 | 1.45 | 10.09 |
| Embodiment 4 | 375 | 92.1 | 1.37 | 9.99 |
| Comparative example 1 | 217 | 61.4 | 1.93 | 4.78 |
| Comparative example 2 | 208 | 56.7 | 1.89 | 6.39 |
Ultracapacitor of the invention with the preparation method of manganese cobalt nickel base electrode by by natural flake graphite by low temperature, middle temperature
Graphene oxide is made with the step oxidation processes of high temperature three, then manganese cobalt composition and graphite oxide alkene reaction are made manganese by the precipitation method
, be coated on active material on Ni-based hearth electrode finally by pressurization pressed-disc technique by cobalt composite graphite alkene material, is made super electricity
Container manganese cobalt nickel base electrode.The ultracapacitor being prepared from manganese cobalt nickel base electrode, its stable performance, electric conductivity is good,
Electric capacity expansion capacity is strong, in addition the preparation technology environment-protection low-consumption, and safety is easy, with preferable industrial applications prospect.This hair
The bright ultracapacitor preparation method process is simple of manganese cobalt nickel base electrode, easy to operate, raw material is easy to get, environment-protection low-consumption, fits
Used in big rule industrialization, it is practical.
Embodiments of the invention are the foregoing is only, the scope of the claims of the invention is not thereby limited, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright description is made, or directly or indirectly it is used in other related technology necks
Domain, is included within the scope of the present invention.
Claims (6)
1. a kind of ultracapacitor preparation method of manganese cobalt nickel base electrode, it is characterised in that comprise the following steps：
（1）By 1L concentrated sulfuric acid ice bath 1-2h, successively to 7-9g sodium nitrate and 10-12g natural flake graphites is added in the concentrated sulfuric acid, stir
48g is slowly added to after mixing uniformly, 2-4h is persistently stirred after all adding, mixing speed is 50 revs/min；
（2）By step（1）In mixing suspension be put into heating and thermal insulation in 37 DEG C of oil bath pan, persistently stir 10-12h, stir
Speed is 50 revs/min；
（3）To step（2）In insulation suspension in add the deionized water of 1L, be heated to 95-98 DEG C, stir 15-30 minutes,
Mixing speed is 50 revs/min, then sequentially adds the hydrogen peroxide of 500ml deionized waters and 200g30%, natural cooling；
（4）By step（3）Mixture centrifugation, take solid sediment, be put in 75 DEG C of drying in oven 4-5h, aoxidized
Graphene；
（5）By 3-5 parts of manganese dioxide, 1-2 parts of potassium manganate, 1-3 parts of cobalt chloride, 2-4 parts of cobalt nitrate, 5-10 parts of graphene oxide is molten
In 8-10 parts of 1.2mM sodium hydrate aqueous solution, 1-2h is stirred, stand 12h, filter collection solid product;
（6）By step（5）The solid product being collected into is then placed into 75 DEG C of drying in oven with 3% NaCl 3 times
2-3h, obtains manganese cobalt composite graphite alkene material；
（7）Weigh step（6）5-10 parts of manganese cobalt composite graphite alkene material, conductive agent 1-2 parts, binding agent 1-2 parts, by binding agent
Add in mortar, be slowly dropped into 2ml deionized waters, after grinding is uniform, add conductive agent, 10-20min is ground, then by manganese cobalt
Composite graphite alkene material is added, and continues to be ground to pulpous state；
（8）By step（7）Slurry material stainless steel spatula be coated on Ni-based hearth electrode, then with tinfoil wrap up electrode,
It is put on tablet press machine and suppresses, pressure is 15MPa, and the duration is 2min, and the electrode that then will be suppressed is put into 75 DEG C of baking ovens
Drying 12h, takes out natural cooling, as electrode finished product.
2. the ultracapacitor according to claim 1 preparation method of manganese cobalt nickel base electrode, it is characterised in that the step
Suddenly（1）The speed that middle potassium permanganate is added adds 4g according to every 5min.
3. the ultracapacitor according to claim 1 preparation method of manganese cobalt nickel base electrode, it is characterised in that the step
Suddenly（5）In filter pressure for 20Mpa.
4. the ultracapacitor according to claim 1 preparation method of manganese cobalt nickel base electrode, it is characterised in that the step
Suddenly（7）Middle conductive agent is acetylene black.
5. the ultracapacitor according to claim 1 preparation method of manganese cobalt nickel base electrode, it is characterised in that the step
Suddenly（7）Middle binding agent is tetrafluoroethene emulsion.
6. the ultracapacitor that the preparation technology according to claim any one of 1-5 is obtained is with manganese cobalt nickel base electrode in vacuum
Applied in the precision instrument back-up sources such as switch, intelligent device, static memory, programme-controlled exchange.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710152353.7A CN106816316B (en) | 2017-03-15 | 2017-03-15 | A kind of preparation method of supercapacitor manganese cobalt nickel base electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710152353.7A CN106816316B (en) | 2017-03-15 | 2017-03-15 | A kind of preparation method of supercapacitor manganese cobalt nickel base electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106816316A true CN106816316A (en) | 2017-06-09 |
| CN106816316B CN106816316B (en) | 2019-01-18 |
Family
ID=59114938
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710152353.7A Active CN106816316B (en) | 2017-03-15 | 2017-03-15 | A kind of preparation method of supercapacitor manganese cobalt nickel base electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106816316B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102938325A (en) * | 2011-08-15 | 2013-02-20 | 海洋王照明科技股份有限公司 | Hybrid capacitor and preparation method thereof |
| CN103474251A (en) * | 2013-08-13 | 2013-12-25 | 常州大学 | Organic electrolyte system asymmetric electrochemistry capacitor and preparation method thereof |
| CN105632787A (en) * | 2016-01-20 | 2016-06-01 | 安徽大学 | Preparation method of cobaltosic oxide/graphene nano composite electrode material for super capacitor |
-
2017
- 2017-03-15 CN CN201710152353.7A patent/CN106816316B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102938325A (en) * | 2011-08-15 | 2013-02-20 | 海洋王照明科技股份有限公司 | Hybrid capacitor and preparation method thereof |
| CN103474251A (en) * | 2013-08-13 | 2013-12-25 | 常州大学 | Organic electrolyte system asymmetric electrochemistry capacitor and preparation method thereof |
| CN105632787A (en) * | 2016-01-20 | 2016-06-01 | 安徽大学 | Preparation method of cobaltosic oxide/graphene nano composite electrode material for super capacitor |
Non-Patent Citations (1)
| Title |
|---|
| M. LI等: "3D-architectured nickel-cobalt-manganese layered double hydroxide/reduced graphene oxide composite for high-performance supercapacitor", 《CHEMICAL PHYSICS LETTERS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106816316B (en) | 2019-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103346301B (en) | The preparation method of the graphene-based metal oxide composite of three-dimensional structure and application thereof | |
| Wang et al. | Low-cost, green synthesis of highly porous carbons derived from lotus root shell as superior performance electrode materials in supercapacitor | |
| CN108538641B (en) | Three-dimensional porous inorganic non-metallic element doped graphene aerogel composite material and preparation method and application thereof | |
| Zhou et al. | Boron and nitrogen co-doped porous carbon for supercapacitors: A comparison between a microwave-assisted and a conventional hydrothermal process | |
| CN109941997B (en) | Hemoglobin-like Co3O4/Ti3C2Preparation method and application of nano composite material | |
| CN104810165B (en) | A kind of method for preparing nickel phosphide/Graphene composite thin film material | |
| CN108288547B (en) | Preparation method of nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material | |
| CN105914358A (en) | Preparation method of yolk-eggshell structured nitrogen-doped carbon-coated Fe3O4@SnO2 magnetic nanometer box | |
| CN105489397A (en) | Preparation method and application of chemically-modified carbon material/graphene/RuO2 ternary composite material | |
| Liu et al. | Biotemplate-assisted hydrothermal synthesis of tubular porous Co3O4 with excellent charge-discharge cycle stability for supercapacitive electrodes | |
| CN105374575A (en) | Method for preparing surface-functionalized porous carbon super capacitor electrode material | |
| CN103545491A (en) | Preparation method of graphene/titanium dioxide composite material for lithium ion battery cathode material | |
| CN115642038A (en) | Nitrogen-phosphorus co-doped porous biomass carbon material and preparation method and application thereof | |
| Tang et al. | Facile synthesis of Ni–Mn layered double hydroxide nanopetals on 3D reduced graphene oxide/Ni foam for high-performance supercapacitors | |
| CN103523776A (en) | Preparation method for activated carbon for super capacitor | |
| CN106006630A (en) | Method for preparing activated carbon materials | |
| CN106356203B (en) | A kind of cobalt acid nickel nano film/graphite felt composite material and its preparation and application | |
| CN105957732B (en) | For the ceria of capacitor and the preparation method of activated carbon composite electrode material | |
| CN108400022A (en) | A kind of preparation method of manganous silicate/carbon supercapacitor electrode material | |
| CN108539149A (en) | A kind of graphene composite nitrogen, oxygen codope biomass carbon material and preparation method thereof | |
| CN106298287A (en) | Its ultracapacitor of composite of a kind of multi-layer graphene and ferrum cobalt layered double hydroxide and preparation method and application | |
| CN106683895B (en) | Anthraquinone-based modified composite electrode material, preparation method and application thereof, and electronic component containing anthraquinone-based modified composite electrode material | |
| CN106816316B (en) | A kind of preparation method of supercapacitor manganese cobalt nickel base electrode | |
| CN107017089B (en) | The preparation method and applications of supercapacitor nickel oxide combination electrode material | |
| CN115763096A (en) | Ni-MOF based on urotropine and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |