CN107910198A - One kind is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode - Google Patents
One kind is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode Download PDFInfo
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- CN107910198A CN107910198A CN201711084024.XA CN201711084024A CN107910198A CN 107910198 A CN107910198 A CN 107910198A CN 201711084024 A CN201711084024 A CN 201711084024A CN 107910198 A CN107910198 A CN 107910198A
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- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005864 Sulphur Substances 0.000 claims abstract description 16
- 239000003990 capacitor Substances 0.000 claims abstract description 13
- 238000009656 pre-carbonization Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 10
- 239000002608 ionic liquid Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000007654 immersion Methods 0.000 claims abstract description 8
- 239000012528 membrane Substances 0.000 claims abstract description 8
- 238000003825 pressing Methods 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- 238000005245 sintering Methods 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims 1
- 239000011812 mixed powder Substances 0.000 claims 1
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 2
- 238000000576 coating method Methods 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- QYFYUEJHZUTRKT-UHFFFAOYSA-N 1,2-diethyl-3-methyl-2h-imidazole Chemical class CCC1N(C)C=CN1CC QYFYUEJHZUTRKT-UHFFFAOYSA-N 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 125000006850 spacer group Chemical group 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
-
- 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
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses one kind with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, is comprised the following steps：Co is prepared using the method for solvent heat as raw material using cobalt salt, BTC first3(BTC)2DMF presomas；Then pre- carbonization treatment is carried out；Finally by the Co of pre- carbonization treatment3(BTC)2DMF presomas and sulphur powder mixing carry out vulcanizing treatment and Co are made9S8/ C composite；By Co obtained above9S8Coating is mixed with binding agent for/C composite and on collector material surface, dry, roll-in, is made positive plate；Porous carbon materials are mixed to coating and collector material surface with binding agent, vacuum drying roll pressing obtains negative plate；By positive plate, the membrane through ionic liquid immersion, negative plate stacking assembling, housing is then coated, ultracapacitor is made.Super capacitor energy density produced by the present invention is big, efficiency for charge-discharge is high, good cycling stability.
Description
Technical field：
The present invention relates to the preparation field of ultracapacitor, is specifically related to one kind with Co9S8/ C composite is electrode
The preparation method of ultracapacitor.
Background technology：
Ultracapacitor, also known as electrochemical capacitor, are that one kind relies primarily on electric double layer and redox fake capacitance electric charge
Store the novel energy storage apparatus of electric energy.It is different from traditional electrochmical power source, ultracapacitor be it is a kind of between traditional capacitor with
Power supply between battery, has the advantages such as power density is high, the discharge and recharge time is short, have extended cycle life, operating temperature range is wide.Cause
This, can be widely applied to the different application scenarios such as auxiliary peak power, stand-by power supply, storing, regenerating energy, substitute electric power,
In numerous necks such as Industry Control, electric power, communications and transportation, intelligence instrument, consumer electronic product, national defence, communication, new-energy automobile
There are huge application value and market potential in domain.
Ultracapacitor generally comprises four bipolar electrode, electrolyte, collector, spacer components.Wherein, electrode material is
Key, it decides the Specifeca tion speeification of capacitor.As the electrode material of ultracapacitor, high specific volume is not required nothing more than
Amount, and should possess relatively low interior resistance, to meet the requirement of high current fast charging and discharging.Meanwhile electrode material must be easy
Form electric double layer capacitance or Faraday pseudo-capacitance in electrode/electrolyte interface, and with appropriate chemistry, mechanical stability and
Good electronics, ionic conductivity.Common electrode material has carbon-based material electrode, conductive polymer electrodes and metal oxide
Electrode.
The content of the invention：
In view of the deficiencies of the prior art, it is an object of the present invention to provide one kind with Co9S8/ C composite is super for electrode
The preparation method of capacitor, the super capacitor energy density is big, and good cycling stability, preparation process is simple, and cost is low.
To achieve the above object, the present invention uses following technical scheme：
One kind is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, it is characterised in that including following
Step：
(1) cobalt salt, BTC are added to stirring to solid in solvent to dissolve, mixed solution is made；And mixed solution is shifted
Into reaction kettle, sealing, which is placed in electrically heated drying cabinet, reacts；It is cooled to room temperature after reaction, and reaction product is centrifuged, from
The precipitation that gains in depth of comprehension arrive deionized water eccentric cleaning 2-3 times, it is dry, Co is made3(BTC)2DMF presomas；
(2) by Co obtained above3(BTC)2DMF presomas are placed in sintering crucible, and sintering crucible is put into
Into Muffle furnace, under inert gas shielding, pre-sintered processing 1-6h at 220-350 DEG C, after treatment, cools to room with the furnace
Temperature, is made the Co being carbonized in advance3(BTC)2·DMF；
(3) by the Co of pre- carbonization obtained above3(BTC)2DMF and sulphur powder ground and mixed are uniform, and by obtained mixing
Powder is put into sintering crucible, and sintering crucible is placed in atmosphere furnace, is handled at nitrogen gas protection is 450-850 DEG C lower
1-6h, after treatment are cooled to room temperature, and Co is made9S8/ C composite；
(4) by Co obtained above9S8/ C composite is mixed with binding agent to be coated on collector material surface, dry,
Roll-in, is made positive plate；Porous carbon materials are mixed with binding agent and are coated on collector material surface, vacuum drying roll pressing obtains
Negative plate；
(5) by positive plate, the membrane through ionic liquid immersion, negative plate stacking assembling, housing is then coated, is made super
Capacitor.
As the preferred of above-mentioned technical proposal, in step (1), the cobalt salt is cobalt nitrate, one in cobalt chloride, cobaltous sulfate
Kind.
As the preferred of above-mentioned technical proposal, in step (1), the cobalt salt, the molar ratio of BTC are (1-3)：2.
As the preferred of above-mentioned technical proposal, in step (1), the temperature of the reaction is 80-150 DEG C, the reaction
Time is 5-18h.
As the preferred of above-mentioned technical proposal, in step (2), the actual conditions of the pre-sintered processing is, first to horse
The oxygen being not passed through in stove in nitrogen 0.5h removing atmosphere furnaces, is then warming up to 300 DEG C, nitrogen with the heating rate of 10 DEG C/min
The lower processing 5h of protection.
As the preferred of above-mentioned technical proposal, in step (3), the Co of the pre- carbonization3(BTC)2The quality of DM and sulphur powder
Than for (10-1)：1.
As the preferred of above-mentioned technical proposal, in step (3), the actual conditions of the processing is：First into atmosphere furnace
The nitrogen of 0.5h is passed through, is then warming up to 650 DEG C with the heating rate of 5 DEG C/min, handles 5h.
As the preferred of above-mentioned technical proposal, in step (1), the solvent is the mixing of DMF, water and ethanol.
As the preferred of above-mentioned technical proposal, in step (4), the binding agent is polytetrafluoroethylene (PTFE).
As the preferred of above-mentioned technical proposal, in step (5), the ionic liquid is 1,2- diethyl -3- methylimidazoles
Fluoroform sulphonate.
The invention has the advantages that：
Co is made using the method for solvent thermal reaction first in the present invention3(BTC)2DMF presomas, are then carried out pre-
Carbonization, finally mixes vulcanizing treatment, the structure of obtained composite material is replicated in Co completely with sulphur powder3(BTC)2DMF forerunner
Body, in carbonisation, the carbon skeleton of carbonization BTC generations can effectively limit Co9S8Grow up so that generation Co9S8Nanometer
Particle is uniformly dispersed on carbon skeleton, effectively increases the electrical conductivity of obtained composite material, and good cycling stability；The opposing party
Face, composite material produced by the present invention have abundant multi-pore channel structure, have excellent high rate performance；The present invention is using self-control
Co9S8Asymmetric type supercapacitor is made as positive and negative pole material with porous carbon materials in/C composite, and energy density is big,
Good cycling stability, and it is low using the cost of raw material, prepare simpler.
Embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
The present invention is released, any restriction will not be formed to the present invention.
Embodiment 1
One kind is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, it is characterised in that including following
Step：
(1) cobalt nitrate, BTC are added to stirring to solid in solvent to dissolve, mixed solution is made；And mixed solution is turned
Move in reaction kettle, sealing is placed in electrically heated drying cabinet reacts 18h at 80 DEG C；It is cooled to room temperature after reaction, and will reaction
Product centrifuges, the precipitation centrifuged deionized water eccentric cleaning 2-3 time, dry, obtained Co3(BTC)2DMF presomas；
(2) by Co obtained above3(BTC)2DMF presomas are placed in sintering crucible, and sintering crucible is put into
Into Muffle furnace, be passed through first into Muffle furnace nitrogen 0.5h remove atmosphere furnace in oxygen, then with the heating of 10 DEG C/min
Speed is warming up to 220 DEG C, and the lower processing 6h of nitrogen protection, after treatment cools to room temperature with the furnace, the Co being carbonized in advance is made3
(BTC)2·DMF；
(3) by the Co of pre- carbonization obtained above3(BTC)2DMF and sulphur powder ground and mixed are uniform, and by obtained mixing
Powder is put into sintering crucible, and sintering crucible is placed in atmosphere furnace, is passed through the nitrogen of 0.5h into atmosphere furnace first,
Then 450 DEG C are warming up to the heating rate of 5 DEG C/min, handle 6h, after treatment is cooled to room temperature, and Co is made9S8/ C is compound
Material；Wherein, the Co being carbonized in advance3(BTC)2DM and the mass ratio of sulphur powder are 10：1；
(4) by Co obtained above9S8/ C composite is mixed with binding agent to be coated on collector material surface, dry,
Roll-in, is made positive plate；Porous carbon materials are mixed with binding agent and are coated on collector material surface, vacuum drying roll pressing obtains
Negative plate；
(5) by positive plate, the membrane through ionic liquid immersion, negative plate stacking assembling, housing is then coated, is made super
Capacitor.
Embodiment 2
One kind is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, it is characterised in that including following
Step：
(1) cobalt chloride, BTC are added to stirring to solid in solvent to dissolve, mixed solution is made；And mixed solution is turned
Move in reaction kettle, sealing is placed in electrically heated drying cabinet reacts 5h at 150 DEG C；It is cooled to room temperature after reaction, and will reaction
Product centrifuges, the precipitation centrifuged deionized water eccentric cleaning 2-3 time, dry, obtained Co3(BTC)2DMF presomas；
(2) by Co obtained above3(BTC)2DMF presomas are placed in sintering crucible, and sintering crucible is put into
Into Muffle furnace, be passed through first into Muffle furnace nitrogen 0.5h remove atmosphere furnace in oxygen, then with the heating of 10 DEG C/min
Speed is warming up to 350 DEG C, and the lower processing 1h of nitrogen protection, after treatment cools to room temperature with the furnace, the Co being carbonized in advance is made3
(BTC)2·DMF；
(3) by the Co of pre- carbonization obtained above3(BTC)2DMF and sulphur powder ground and mixed are uniform, and by obtained mixing
Powder is put into sintering crucible, and sintering crucible is placed in atmosphere furnace, is passed through the nitrogen of 0.5h into atmosphere furnace first,
Then 850 DEG C are warming up to the heating rate of 5 DEG C/min, handle 1h, after treatment is cooled to room temperature, and Co is made9S8/ C is compound
Material；Wherein, the Co being carbonized in advance3(BTC)2DM and the mass ratio of sulphur powder are 1：1；
(4) by Co obtained above9S8/ C composite is mixed with binding agent to be coated on collector material surface, dry,
Roll-in, is made positive plate；Porous carbon materials are mixed with binding agent and are coated on collector material surface, vacuum drying roll pressing obtains
Negative plate；
(5) by positive plate, the membrane through ionic liquid immersion, negative plate stacking assembling, housing is then coated, is made super
Capacitor.
Embodiment 3
One kind is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, it is characterised in that including following
Step：
(1) cobalt nitrate, cobalt chloride, cobaltous sulfate, BTC are added to stirring to solid in solvent to dissolve, mixed solution is made；
And mixed solution is transferred in reaction kettle, sealing is placed in electrically heated drying cabinet reacts 8h at 100 DEG C；It is cooled to after reaction
Room temperature, and reaction product is centrifuged, the precipitation centrifuged deionized water eccentric cleaning 2-3 times is dry, and Co is made3
(BTC)2DMF presomas；
(2) by Co obtained above3(BTC)2DMF presomas are placed in sintering crucible, and sintering crucible is put into
Into Muffle furnace, be passed through first into Muffle furnace nitrogen 0.5h remove atmosphere furnace in oxygen, then with the heating of 10 DEG C/min
Speed is warming up to 240 DEG C, and the lower processing 2h of nitrogen protection, after treatment cools to room temperature with the furnace, the Co being carbonized in advance is made3
(BTC)2·DMF；
(3) by the Co of pre- carbonization obtained above3(BTC)2DMF and sulphur powder ground and mixed are uniform, and by obtained mixing
Powder is put into sintering crucible, and sintering crucible is placed in atmosphere furnace, is passed through the nitrogen of 0.5h into atmosphere furnace first,
Then 550 DEG C are warming up to the heating rate of 5 DEG C/min, handle 2h, after treatment is cooled to room temperature, and Co is made9S8/ C is compound
Material；Wherein, the Co being carbonized in advance3(BTC)2DM and the mass ratio of sulphur powder are 3：1；
(4) by Co obtained above9S8/ C composite is mixed with binding agent to be coated on collector material surface, dry,
Roll-in, is made positive plate；Porous carbon materials are mixed with binding agent and are coated on collector material surface, vacuum drying roll pressing obtains
Negative plate；
(5) by positive plate, the membrane through ionic liquid immersion, negative plate stacking assembling, housing is then coated, is made super
Capacitor.
Embodiment 4
One kind is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, it is characterised in that including following
Step：
(1) cobaltous sulfate, BTC are added to stirring to solid in solvent to dissolve, mixed solution is made；And mixed solution is turned
Move in reaction kettle, sealing is placed in electrically heated drying cabinet reacts 10h at 120 DEG C；It is cooled to room temperature after reaction, and will reaction
Product centrifuges, the precipitation centrifuged deionized water eccentric cleaning 2-3 time, dry, obtained Co3(BTC)2DMF presomas；
(2) by Co obtained above3(BTC)2DMF presomas are placed in sintering crucible, and sintering crucible is put into
Into Muffle furnace, be passed through first into Muffle furnace nitrogen 0.5h remove atmosphere furnace in oxygen, then with the heating of 10 DEG C/min
Speed is warming up to 310 DEG C, and the lower processing 5h of nitrogen protection, after treatment cools to room temperature with the furnace, the Co being carbonized in advance is made3
(BTC)2·DMF；
(3) by the Co of pre- carbonization obtained above3(BTC)2DMF and sulphur powder ground and mixed are uniform, and by obtained mixing
Powder is put into sintering crucible, and sintering crucible is placed in atmosphere furnace, is passed through the nitrogen of 0.5h into atmosphere furnace first,
Then 820 DEG C are warming up to the heating rate of 5 DEG C/min, handle 4h, after treatment is cooled to room temperature, and Co is made9S8/ C is compound
Material；Wherein, the Co being carbonized in advance3(BTC)2DM and the mass ratio of sulphur powder are 5：1；
(4) by Co obtained above9S8/ C composite is mixed with binding agent to be coated on collector material surface, dry,
Roll-in, is made positive plate；Porous carbon materials are mixed with binding agent and are coated on collector material surface, vacuum drying roll pressing obtains
Negative plate；
(5) by positive plate, the membrane through ionic liquid immersion, negative plate stacking assembling, housing is then coated, is made super
Capacitor.
Embodiment 5
One kind is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, it is characterised in that including following
Step：
(1) cobalt nitrate, BTC are added to stirring to solid in solvent to dissolve, mixed solution is made；And mixed solution is turned
Move in reaction kettle, sealing is placed in electrically heated drying cabinet reacts 15h at 130 DEG C；It is cooled to room temperature after reaction, and will reaction
Product centrifuges, the precipitation centrifuged deionized water eccentric cleaning 2-3 time, dry, obtained Co3(BTC)2DMF presomas；
(2) by Co obtained above3(BTC)2DMF presomas are placed in sintering crucible, and sintering crucible is put into
Into Muffle furnace, be passed through first into Muffle furnace nitrogen 0.5h remove atmosphere furnace in oxygen, then with the heating of 10 DEG C/min
Speed is warming up to 320 DEG C, and the lower processing 5h of nitrogen protection, after treatment cools to room temperature with the furnace, the Co being carbonized in advance is made3
(BTC)2·DMF；
(3) by the Co of pre- carbonization obtained above3(BTC)2DMF and sulphur powder ground and mixed are uniform, and by obtained mixing
Powder is put into sintering crucible, and sintering crucible is placed in atmosphere furnace, is passed through the nitrogen of 0.5h into atmosphere furnace first,
Then 800 DEG C are warming up to the heating rate of 5 DEG C/min, handle 5h, after treatment is cooled to room temperature, and Co is made9S8/ C is compound
Material；Wherein, the Co being carbonized in advance3(BTC)2DM and the mass ratio of sulphur powder are 7：1；
(4) by Co obtained above9S8/ C composite is mixed with binding agent to be coated on collector material surface, dry,
Roll-in, is made positive plate；Porous carbon materials are mixed with binding agent and are coated on collector material surface, vacuum drying roll pressing obtains
Negative plate；
(5) by positive plate, the membrane through ionic liquid immersion, negative plate stacking assembling, housing is then coated, is made super
Capacitor.
Ultracapacitor obtained above is passed through into electro-chemical test, test result shows：The energy of ultracapacitor is close
Degree is up to 58.5Wh/kg, and corresponding power density is 800W/kg；And ultracapacitor produced by the present invention is in 3.5A/g
Current density under after constant current charge-discharge test 10000 times, specific capacitance conservation rate is more than 99%；And pass through three electrode tests,
Co produced by the present invention9S8/ C composite list gram volume is up to 1810F/g.
Claims (10)
1. one kind is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, it is characterised in that including following step
Suddenly：
(1) cobalt salt, BTC are added to stirring to solid in solvent to dissolve, mixed solution is made；And mixed solution is transferred to instead
Answer in kettle, sealing, which is placed in electrically heated drying cabinet, reacts；It is cooled to room temperature after reaction, and reaction product is centrifuged, centrifuges
The precipitation arrived deionized water eccentric cleaning 2-3 times, it is dry, Co is made3(BTC)2DMF presomas；
(2) by Co obtained above3(BTC)2DMF presomas are placed in sintering crucible, and sintering crucible is put into horse
Not in stove, under inert gas shielding, pre-sintered processing 1-6h at 220-350 DEG C, after treatment, cools to room temperature with the furnace, system
Obtain the Co being carbonized in advance3(BTC)2·DMF；
(3) by the Co of pre- carbonization obtained above3(BTC)2DMF and sulphur powder ground and mixed are uniform, and by obtained mixed-powder
It is put into sintering crucible, sintering crucible is placed in atmosphere furnace, 1- is handled at nitrogen gas protection is 450-850 DEG C lower
6h, after treatment are cooled to room temperature, and Co is made9S8/ C composite；
(4) by Co obtained above9S8/ C composite is mixed with binding agent to be coated on collector material surface, dry, roller
Pressure, is made positive plate；Porous carbon materials are mixed with binding agent and are coated on collector material surface, vacuum drying roll pressing must be born
Pole piece；
(5) by positive plate, the membrane through ionic liquid immersion, negative plate stacking assembling, housing is then coated, super capacitor is made
Device.
2. one kind as claimed in claim 1 is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, it is special
Sign is：In step (1), the cobalt salt is cobalt nitrate, one kind in cobalt chloride, cobaltous sulfate.
3. one kind as claimed in claim 1 is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, it is special
Sign is：In step (1), the cobalt salt, the molar ratio of BTC are (1-3)：2.
4. one kind as claimed in claim 1 is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, it is special
Sign is：In step (1), the temperature of the reaction is 80-150 DEG C, and the time of the reaction is 5-18h.
5. one kind as claimed in claim 1 is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, it is special
Sign is：In step (2), the actual conditions of the pre-sintered processing is to be passed through nitrogen 0.5h into Muffle furnace first to remove degassing
Oxygen in atmosphere stove, is then warming up to 300 DEG C, the lower processing 5h of nitrogen protection with the heating rate of 10 DEG C/min.
6. one kind as claimed in claim 1 is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, it is special
Sign is：In step (3), the Co of the pre- carbonization3(BTC)2DM and the mass ratio of sulphur powder are (10-1)：1.
7. one kind as claimed in claim 1 is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, it is special
Sign is：In step (3), the actual conditions of the processing is：The nitrogen of 0.5h is passed through into atmosphere furnace first, then with 5 DEG C/
The heating rate of min is warming up to 650 DEG C, handles 5h.
8. one kind as claimed in claim 1 is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, it is special
Sign is：In step (1), the solvent is the mixing of DMF, water and ethanol.
9. one kind as claimed in claim 1 is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, it is special
Sign is：In step (4), the binding agent is polytetrafluoroethylene (PTFE).
10. one kind as claimed in claim 1 is with Co9S8/ C composite is the preparation method of the ultracapacitor of electrode, it is special
Sign is：In step (5), the ionic liquid is 1,2- diethyl -3- methylimidazole fluoroform sulphonates.
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| CN110311131A (en) * | 2019-06-28 | 2019-10-08 | 江苏大学 | Aluminium ion battery, its positive electrode and production method |
| CN110676441A (en) * | 2018-07-03 | 2020-01-10 | 中国科学院福建物质结构研究所 | Battery negative electrode material, sodium ion battery and preparation method thereof |
| US11342552B2 (en) * | 2019-08-06 | 2022-05-24 | Korea University Research And Business Foundation | Method of preparing cathode active material and cathode active material |
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| CN103816905A (en) * | 2014-03-21 | 2014-05-28 | 南开大学 | Preparation method of carbon nano-tube loaded nano-cobalt catalyst |
| CN105895886A (en) * | 2016-06-21 | 2016-08-24 | 中南大学 | Transition metal phosphide/porous carbon anode composite material for sodium-ion battery and preparation method thereof |
| CN106531999A (en) * | 2016-11-25 | 2017-03-22 | 武汉理工大学 | Embedded cobalt sulfide and porous carbon nanorod composite electrode material and preparation method and application thereof |
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| CN103456929A (en) * | 2013-09-04 | 2013-12-18 | 中南大学 | Anode material of lithium-sulfur battery and preparation method thereof |
| CN103816905A (en) * | 2014-03-21 | 2014-05-28 | 南开大学 | Preparation method of carbon nano-tube loaded nano-cobalt catalyst |
| CN105895886A (en) * | 2016-06-21 | 2016-08-24 | 中南大学 | Transition metal phosphide/porous carbon anode composite material for sodium-ion battery and preparation method thereof |
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| CN110676441A (en) * | 2018-07-03 | 2020-01-10 | 中国科学院福建物质结构研究所 | Battery negative electrode material, sodium ion battery and preparation method thereof |
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| CN110311131A (en) * | 2019-06-28 | 2019-10-08 | 江苏大学 | Aluminium ion battery, its positive electrode and production method |
| US11342552B2 (en) * | 2019-08-06 | 2022-05-24 | Korea University Research And Business Foundation | Method of preparing cathode active material and cathode active material |
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