CN107967997A - A kind of three-dimensional high heat-conductivity conducting composite material, its preparation method and application - Google Patents
A kind of three-dimensional high heat-conductivity conducting composite material, its preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 113
- 239000000463 material Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 52
- 238000004070 electrodeposition Methods 0.000 claims abstract description 40
- 239000011165 3D composite Substances 0.000 claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- 239000011149 active material Substances 0.000 claims abstract description 25
- 238000000137 annealing Methods 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 61
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 52
- 239000010949 copper Substances 0.000 claims description 48
- 230000009467 reduction Effects 0.000 claims description 42
- 239000006260 foam Substances 0.000 claims description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 32
- 229910052802 copper Inorganic materials 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 29
- 229910052697 platinum Inorganic materials 0.000 claims description 26
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 26
- 239000012298 atmosphere Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 16
- 230000005611 electricity Effects 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000007772 electrode material Substances 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 229910002441 CoNi Inorganic materials 0.000 claims description 7
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 229940075397 calomel Drugs 0.000 claims description 5
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 241000208340 Araliaceae Species 0.000 claims 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims 1
- 235000003140 Panax quinquefolius Nutrition 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 235000008434 ginseng Nutrition 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000011230 binding agent Substances 0.000 abstract description 4
- 238000010422 painting Methods 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 description 10
- 229910021607 Silver chloride Inorganic materials 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 5
- -1 RuO2 Chemical class 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003032 molecular docking Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
Classifications
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- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—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
-
- 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
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- 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)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of three-dimensional high heat-conductivity conducting composite material, its preparation method and the application as electrode of super capacitor.The described method includes：1) using graphene oxide solution and/or graphene solution as electrolyte, porous current collector connects positive pole, carries out electro-deposition, obtains three-dimensional framework；2) using three-dimensional framework as working electrode, the material solution to prepare active material carries out scan round, re-annealing is handled, and obtains including the three-dimensional composite material of active material as electrolyte.The three-dimensional composite material of the present invention can avoid the use of polymer based binder directly as the electrode of ultracapacitor, this integral electrodes preparation method, and without painting work, it is simply efficient to prepare scheme.Obtained three-dimensional composite material has excellent heat conductivility and electric conductivity, has fake capacitance feature, and high rate performance is excellent, and chemical property is good, and good as the cycle performance of the ultracapacitor of electrode using the three-dimensional composite material.
Description
Technical field
The invention belongs to novel inorganic nonmetallic materials technology of preparing, it is related to a kind of three-dimensional composite material, its preparation method
With application, more particularly to a kind of three-dimensional high heat-conductivity conducting composite material, its preparation method and answering as electrode of super capacitor
With.
Background technology
Since twentieth century, this is high with power density for ultracapacitor, has extended cycle life, environmentally protective accumulator
Part receives concern and research increasingly, it has been widely used in consumer electronics, data backup memory system and industrial energy
In management and some emerging fields.From the point of view of energy storage mechnism, ultracapacitor can be divided into double layer capacitor and fake capacitance.Double electricity
Layer capacitance is that electrode material is in electrification so as to fulfill energy storage using the reversible adsorption electrostatic lotus of the active material of high-specific surface area
Redox reaction does not occur during, but is limited be subject to surface electrostatic energy storage mechnism, the energy of double layer capacitor
Density is relatively low.Fake capacitance, and redox electrochemical capacitor is properly termed as, they can occur reversible in electrochemical process
Redox reaction.Metal oxide such as RuO2, Fe3O4And MnO2, also some conducting polymers are all the electricity of common fake capacitance
Pole material.
The electrode of traditional electrochemical capacitor is prepared by rubbing method, the active material that will be prepared and is led
Electric agent acetylene carbon black also have adhesive uniformly mix after and add solvent slurry be made, be then applied on collector.Common
Collector is porous nickel, Porous Cu etc..This preparation method causes overall electrode due to the use of the adhesive of polymer matrix
Thermal conductivity is extremely low (being generally less than 1W/mK), and resistivity is big, and electrical conductivity is poor, is easily produced during high current charge-discharge a large amount of
Heat, this is all unfavorable for the stability and security of device, also, dusting easily occurs in charge and discharge process and asks
Topic, and splits away off from collector, this stability, security to whole device is all extremely disadvantageous.Filled in high current
During electric discharge, electrode easily produces amount of heat, this stability and security to electrochemical capacitance is extremely disadvantageous.
Current heat sink conception is all either to reduce electrode by the exterior devices such as some radiators that add in device
Area the methods of, but these methods timely and effectively cannot all shed heat, and preparation section is cumbersome, adds preparation
Cost.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of three-dimensional high heat-conductivity conducting to answer
Condensation material, its preparation method and the application as electrode of super capacitor.The composite material of the present invention can be directly as super electricity
The electrode of container, this integral electrodes preparation method avoid the use of polymer based binder, without painting work, system
Standby scheme is simply efficient.Obtained three-dimensional composite material has excellent heat conductivility and electric conductivity, has fake capacitance feature,
High rate performance is excellent, and chemical property is good, and using cycle performance of the three-dimensional composite material as the ultracapacitor of electrode
Well.
In the present invention, " high heat-conductivity conducting " in above-mentioned " high heat-conductivity conducting composite material " refers to：Thermal conductivity is in 501Wm-1K-1
More than；Electrical conductivity is in 37050.1Sm-1More than.
In order to achieve the above object, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of preparation method of three-dimensional composite material, especially a kind of high heat-conductivity conducting is answered
The preparation method of condensation material, described method includes following steps：
(1) using graphene oxide solution and/or graphene solution as electrolyte, porous current collector connects positive pole, carries out
Electro-deposition, obtains deposition and is coated with the graphene oxide of reduction and/or the three-dimensional framework of graphene；
(2) three-dimensional framework obtained using step (1) electro-deposition is working electrode, to prepare the material solution of active material work
For electrolyte, scan round is carried out, electroactive substance is deposited on three-dimensional framework using electrodeposition process；
(3) made annealing treatment, obtain the graphene oxide and/or graphene/active material of porous current collector/reduction,
That is three-dimensional composite material.
In the present invention, graphene oxide is referred to as GO, and the graphene oxide of reduction is referred to as RGO, and graphene is referred to as G.
In the present invention, " graphene oxide and/or graphene " refers in step (1)：It can be graphene oxide solution, also may be used
To be graphene solution, the mixed solution of graphene oxide solution and graphene solution can also be.
In the present invention, during step (1) described electro-deposition, the type of electrodes for docking power cathode is not construed as limiting, such as can be with
It is platinized platinum.
In the present invention, step (1) " the deposition cladding " refers to：Realized and coated by electro-deposition.The present invention is to coating degree
It is not construed as limiting, can is complete cladding or part cladding.
In the present invention, " material solution for preparing active material " refers to described in step (2)：Prepare former used in active material
The solution of material.
In the present invention, described in step (1) " deposition is coated with the graphene oxide of reduction and/or the three-dimensional framework of graphene "
In, the generation of the graphene oxide of reduction is due to that graphene oxide (GO) is reduced during electro-deposition, so that
The graphene oxide (RGO) reduced.
In the present invention, described in step (1) " deposition is coated with the graphene oxide of reduction and/or the three-dimensional framework of graphene "
In, " graphene oxide and/or graphene of reduction " refers to：It can be the graphene oxide or graphene of reduction, may be used also
Be reduction graphene oxide and graphene mixture.
In the present invention, during step (2) scan round, it is not construed as limiting to reference electrode and to the species of electrode, such as calomel
Electrode, or Ag/AgCl electrodes are reference electrode；Platinized platinum is to electrode.
In the present invention, described in step (3) " graphene oxide and/or graphene/active material of porous current collector/reduction "
Graphene oxide/active material of porous current collector/reduction can be referred to, porous current collector/graphene/active matter can also be referred to
Matter, can also refer to graphene oxide/graphene/active material of porous current collector/reduction.
As the optimal technical scheme of the method for the invention, step (1) graphene oxide solution and/or graphene
The concentration of solution is 1mg/mL~2mg/mL, for example, 1mg/mL, 1.2mg/mL, 1.3mg/mL, 1.5mg/mL, 1.6mg/mL,
1.7mg/mL, 1.8mg/mL or 2mg/mL etc..
It is furthermore preferred that step (1) is using graphene oxide solution as electrolyte.
Preferably, step (1) graphene oxide (GO) solution passes through traditional Hummers methods or improved
Prepared by Hummers methods, and be configured to certain density GO aqueous solutions.
Preferably, step (1) described porous current collector is any one in Porous Cu, porous nickel, porous carbon or porous aluminum
Kind or at least two combination, preferably Porous Cu, more preferably foam copper.
Preferably, the specific surface area of the porous current collector is 0.5cm2~9cm2, such as 0.5cm2、1cm2、、2cm2、
3cm2、4cm2、5cm2、7cm2、8cm2Or 10cm2Deng.
Preferably, the voltage range of step (1) described electro-deposition is 3V~5V, for example, 3V, 3.2V, 3.4V, 3.5V,
3.6V, 3.8V, 4V, 4.2V, 4.4V, 4.7V or 5V etc..
Preferably, the time of step (1) described electro-deposition is 5min~15min, for example, 5min, 8min, 10min,
12.5min, 14min or 15min etc..
As the optimal technical scheme of the method for the invention, the material solution that step (2) is described to prepare active material is
Prepare any one or at least two active materials in bimetallic oxide, bimetallic sulfide or double-metal hydroxide
The combination of material solution.
In this optimal technical scheme, the material solution of the active material for example can be to prepare CoNi2S4Raw material it is molten
Liquid, prepare CoNi2O4Material solution or prepare material solution of NiMn-LDH etc., " combination " in use, will sink by several times
Product, but cannot be used in mixed way at the same time.
Preferably, step (2) material solution for preparing active material is CoCl2·6H2O, NiCl2·6H2O and sulphur
The mixed solution of urea.
Preferably, in the mixed solution, CoCl2·6H2The concentration of O is 0.1M~3M.
Preferably, in the mixed solution, NiCl2·6H2The concentration of O is 0.1M~3M；.
Preferably, in the mixed solution, the concentration of thiocarbamide is 1M~5M.
Preferably, the voltage range of the scan round is -1.2V~0.2V, for example, -1.2V, -1V, -0.8V, -
0.5V, -0.3V, -0.1V, 0V, 0.1V or 0.2V etc..
Preferably, the sweep speed of step (2) described scan round is 3mV/s~10mV/s, such as 3mV/s, 4mV/s,
4.5mV/s, 5mV/s, 6mV/s, 6.5mV/s, 7mV/s, 8mV/s, 8.5mV/s, 9mV/s or 10mV/s etc., are preferably 5mV/s.
Preferably, the number of turns of step (2) described scan round for 4 circle~15 circle, such as 4 circle, 5 circle, 6 circle, 7 circle, 8 circle,
10 circles, 11 circles, 12 circles, 13 circles, 14 circles or 15 circles etc..
As the optimal technical scheme of the method for the invention, the method be additionally included in after step (2) step (3) it
Preceding progress step (2) '：The product of rinsing step (2) and drying.
The purpose of flushing is the RGO and/or G for rinsing out physical absorption on three-dimensional framework surface.
Preferably, step (3) annealing carries out under protective atmosphere, and the protective atmosphere is argon gas atmosphere or nitrogen
The combination of any one or two kinds in gas atmosphere.
Preferably, the temperature of step (3) described annealing be 275 DEG C~350 DEG C, such as 275 DEG C, 280 DEG C, 300 DEG C, 310
DEG C, 315 DEG C, 325 DEG C, 330 DEG C, 340 DEG C or 350 DEG C etc., be preferably 300 DEG C.
Preferably, the time of step (3) described annealing is 2h~3h, for example, 2h, 2.2h, 2.3h, 2.5h, 2.6h, 2.7h,
2.8h or 3h etc..
As the further preferred technical solution of the method for the invention, described method includes following steps：
(1) graphene oxide solution using concentration as 1mg/mL~2mg/mL is electrolyte, and foam copper connects positive pole, platinum
Plate electrode connects power cathode, in electro-deposition 5min~15min in the voltage range of 3V~5V, obtains the oxygen that deposition is coated with reduction
The three-dimensional framework of graphite alkene；
(2) for the three-dimensional framework obtained using step (1) electro-deposition as working electrode, platinum plate electrode is to electrode, calomel electrode
For reference electrode, with CoCl2·6H2O, NiCl2·6H2The mixed solution of O and thiocarbamide is as electrolyte, -1.2V~0.2V's
Voltage range encloses~15 circles with the sweep speed scan round 4 of 5mV/s, and electrochemistry is deposited on three-dimensional framework using electrodeposition process
Active material；
(2) ' product of rinsing step (2) and drying；
(3) 2h~3h is made annealing treatment in 300 DEG C under an ar atmosphere, obtains graphene oxide/CoNi of Cu/ reduction2S4, letter
Claim Cu/RGO/CoNi2S4, i.e. three-dimensional composite material.
This optimal technical scheme is template using the foam copper of high conductivity, and electrolyte is used as using graphene oxide solution
Electro-deposition is carried out, graphene oxide is changed into the graphene oxide of reduction in deposition process, deposited so as to be powered in foam copper
RGO, further deposits cobalt sulfide nickel, finally makes annealing treatment, obtain the three-dimensional composite material containing cobalt sulfide nickel hydroxide active material, its
Can be directly as electrode.The electrode preparation method of this monoblock type, which avoids polymer based binder in prepared by conventional electrodes, to be made
With, meanwhile, the three-dimensional grapheme being electrodeposited on foam copper realizes the lifting of the thermal conductivity on three dimension scale, effectively lifting electricity
The thermal conductivity and electrical conductivity of pole, so as to improve the stability of whole device.
Second aspect, the present invention provide a kind of three-dimensional composite material, and the three-dimensional composite material is by first aspect institute
What the method stated was prepared.
The third aspect, the present invention provide a kind of ultracapacitor, and the ultracapacitor is using three described in second aspect
Composite material is tieed up as electrode material.
Preferably, three-dimensional combination electrode material (referred to as Cu/RGO/CoNi is tested under three-electrode system2S4)。
Compared with the prior art, the present invention has the advantages that：
(1) present invention is template using the porous current collector of high conductivity, using graphene oxide solution and/or graphene
Solution carries out electro-deposition on porous current collector, obtains the graphene oxide (RGO) that deposition is coated with reduction as electrolyte
And/or the three-dimensional framework of graphene (G), then position activity material is powered in the three-dimensional framework by scan round, finally anneal
Processing, obtains the three-dimensional composite material containing active material, which can be directly as application of electrode in super electricity
In container.The electrode preparation method of this monoblock type avoids the use of polymer based binder, without painting work, prepares
Scheme is simply efficient.
(2) in the present invention, the three-dimensional RGO and/or G that are electrodeposited on the porous current collector of high-specific surface area cause three-dimensional electricity
Pole is greatly promoted in each upward thermal conductivity, realizes the lifting of the thermal conductivity on three dimension scale, effectively lifts the thermal conductivity of electrode
Rate and electrical conductivity, thermal conductivity is in 501Wm-1K-1More than；Electrical conductivity is in 37050.1Sm-1More than；The RGO being coated on three-dimensional framework
And/or G can protect porous current collector not by electrolytic corrosion, the stability of whole device is improved；Moreover, growth in situ exists
Contact of the active material with three-dimensional framework on RGO/G is good, avoids the use of adhesive.
Good electric conductivity can ensure the good chemical property of electrode material；Good heat conductivility can incite somebody to action
The heat that capacitor produces in charge and discharge process timely and effectively distributes, and in practical applications, can not only lead rapidly
Heat heat dissipation, is conducive to the heat management of ultracapacitor, improves the security performance of capacitor, also show good electrochemistry
Energy.
(3) preparation method of monolithic three-dimensional electrode (i.e. the three-dimensional composite material comprising active material) of the invention has
Easily operated, cost is low, and yield is high, and reaction condition is gentle, low power consumption and other advantages, can effectively lift the thermal conductivity and electricity of material
Conductance.
(4) show that good circulation is steady in ultracapacitor using the three-dimensional composite material of the present invention as application of electrode
It is qualitative.
Brief description of the drawings
Fig. 1 is the Cu/RGO/CoNi that embodiment 1 obtains2S4It is 2Ag in current density-1, 3Ag-1,5Ag-1,8Ag-1,10Ag-1,20Ag-1Constant current charge-discharge curve.
Three-diemsnional electrode Cu/RGO/CoNi made from Fig. 2 embodiments 12S4It is directly used as electrode material for super capacitor cyclicity
Can result figure.
Embodiment
Further illustrate technical scheme below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
(1) graphene oxide is prepared using improved Hummer methods.Prepare the graphene oxide solution of 2mg/ml.
(2) using the graphene oxide solution of 2mg/ml as electrolyte, foam copper connects positive pole, and platinum plate electrode connects negative
Pole, the electro-deposition 10min under the constant pressure of 3V.The graphene of the reduction of electrode surface physical absorption is rinsed out, and electrode is put into
It is dried overnight in vacuum drying oven, obtains deposited the foam copper of the graphene of reduction, i.e. three-dimensional framework.
(3) CoCl of 0.012g is weighed2·6H2The NiCl of O, 0.178g2·6H2The thiocarbamide of O and 5.6g, and they are molten
Solution obtains mixed solution in the deionized water of 100ml.
(4) using deposited reduction graphene foam copper as working electrode, platinized platinum is is to electrode, Ag/AgCl electrodes
Reference electrode, the mixed solution of step (3) as electrolyte, -1.2V-0.2V voltage range with the sweep speed of 5mV/s
Scan round 15 is enclosed, and electroactive substance is deposited on three-dimensional framework using electrodeposition process.
(5) finally, when annealing 3 is small at 300 DEG C in an ar atmosphere, three-dimensional composite material is obtained, is named as Cu/RGO/
CoNi2S4, it can be directly as combination electrode (i.e. three-diemsnional electrode).
Fig. 1 is the Cu/RGO/CoNi that embodiment 1 obtains2S4It is 2Ag in current density-1, 3Ag-1,5Ag-1,8Ag-1,10Ag-1,20Ag-1Constant current charge-discharge curve.As seen from Figure 1, Cu/RGO/CoNi2S4Show the feature of fake capacitance, multiplying power
Performance is excellent, discharge and recharge time length, and chemical property is good.It is pointed out that in 2~20Ag-1Between other current density bars
The constant current charge-discharge curve tested under part is also similar with Fig. 1, has excellent chemical property.
Three-diemsnional electrode Cu/RGO/CoNi made from Fig. 2 embodiments 12S4It is directly used as electrode material for super capacitor cyclicity
Can result figure.As seen from Figure 2, Cu/RGO/CoNi2S4It is directly used as electrode material for super capacitor and shows good follow
Ring stability.
The three-dimensional composite material that the present embodiment obtains has good thermal conductivity and conductivity, and thermal conductivity is in 501Wm-1K-1
More than；Electrical conductivity is in 37050.1Sm-1More than.
Embodiment 2
(1) graphene oxide is prepared using improved Hummer methods.Prepare the graphene oxide solution of 2mg/ml.
(2) using the graphene oxide solution of 2mg/ml as electrolyte, foam copper connects positive pole, and platinum plate electrode connects negative
Pole, the electro-deposition 5min under the constant pressure of 5V.The graphene of the reduction of electrode surface physical absorption is rinsed out, and electrode is put into very
It is dried overnight in empty baking oven, obtains deposited the foam copper of the graphene of reduction, i.e. three-dimensional framework.
(3) CoCl of 0.012g is weighed2·6H2The NiCl of O, 0.178g2The thiocarbamide of 6H2O and 5.6g, and they are molten
Solution obtains mixed solution in the deionized water of 100ml.
(4) using deposited reduction graphene foam copper as working electrode, platinized platinum is is to electrode, Ag/AgCl electrodes
Reference electrode, the mixed solution of step (3) as electrolyte, -1.2V-0.2V voltage range with the sweep speed of 5mV/s
Scan round 15 is enclosed, and electroactive substance is deposited on three-dimensional framework using electrodeposition process.
(5) finally, when annealing 3 is small at 300 DEG C in an ar atmosphere, three-dimensional composite material is obtained, it can be directly as compound
Electrode (i.e. three-diemsnional electrode).
Embodiment 3
(1) graphene oxide is prepared using improved Hummer methods.Prepare the graphene oxide solution of 1mg/ml.
(2) using the graphene oxide solution of 1mg/ml as electrolyte, foam copper connects positive pole, and platinum plate electrode connects negative
Pole, the electro-deposition 5min under the constant pressure of 5V.The graphene of the reduction of electrode surface physical absorption is rinsed out, and electrode is put into very
It is dried overnight in empty baking oven, obtains deposited the foam copper of the graphene of reduction, i.e. three-dimensional framework.
(3) CoCl of 0.012g is weighed2·6H2The NiCl of O, 0.178g2·6H2The thiocarbamide of O and 5.6g, and they are molten
Solution obtains mixed solution in the deionized water of 100ml.
(4) using deposited reduction graphene foam copper as working electrode, platinized platinum is is to electrode, Ag/AgCl electrodes
Reference electrode, the mixed solution of step (3) as electrolyte, -1.2V-0.2V voltage range with the sweep speed of 5mV/s
Scan round 15 is enclosed, and electroactive substance is deposited on three-dimensional framework using electrodeposition process.
(5) finally, when annealing 3 is small at 300 DEG C in an ar atmosphere, three-dimensional composite material is obtained, it can be directly as compound
Electrode (i.e. three-diemsnional electrode).
Embodiment 4
(1) graphene oxide is prepared using improved Hummer methods.Prepare the graphene oxide solution of 1mg/ml.
(2) using the graphene oxide solution of 1mg/ml as electrolyte, foam copper connects positive pole, and platinum plate electrode connects negative
Pole, the electro-deposition 10min under the constant pressure of 3V.The graphene of the reduction of electrode surface physical absorption is rinsed out, and electrode is put into
It is dried overnight in vacuum drying oven, obtains deposited the foam copper of the graphene of reduction, i.e. three-dimensional framework.
(3) CoCl of 0.012g is weighed2·6H2The NiCl of O, 0.178g2·6H2The thiocarbamide of O and 5.6g, and they are molten
Solution obtains mixed solution in the deionized water of 100ml.
(4) using deposited reduction graphene foam copper as working electrode, platinized platinum is is to electrode, Ag/AgCl electrodes
Reference electrode, the mixed solution of step (3) as electrolyte, -1.2V-0.2V voltage range with the sweep speed of 5mV/s
Scan round 4 is enclosed, and electroactive substance is deposited on three-dimensional framework using electrodeposition process.
(5) finally, when annealing 3 is small at 300 DEG C in an ar atmosphere, three-dimensional composite material is obtained, it can be directly as compound
Electrode (i.e. three-diemsnional electrode).
Embodiment 5
(1) graphene oxide is prepared using improved Hummer methods.Prepare the graphene oxide solution of 2mg/ml.
(2) using the graphene oxide solution of 2mg/ml as electrolyte, to connect positive pole, platinum plate electrode connects negative foam copper
Pole, the electro-deposition 15min under the constant pressure of 3V.The graphene of the reduction of electrode surface physical absorption is rinsed out, and electrode is put into
It is dried overnight in vacuum drying oven, obtains deposited the foam copper of the graphene of reduction, i.e. three-dimensional framework.
(3) CoCl of 0.012g is weighed2·6H2The NiCl of O, 0.178g2·6H2The thiocarbamide of O and 5.6g, and they are molten
Solution obtains mixed solution in the deionized water of 100ml.
(4) using deposited reduction graphene foam copper as working electrode, platinized platinum is is to electrode, Ag/AgCl electrodes
Reference electrode, the mixed solution of step (3) as electrolyte, -1.2V-0.2V voltage range with the sweep speed of 5mV/s
Scan round 10 is enclosed, and electroactive substance is deposited on three-dimensional framework using electrodeposition process.
(5) finally, when annealing 3 is small at 300 DEG C in an ar atmosphere, three-dimensional composite material is obtained, it can be directly as compound
Electrode (i.e. three-diemsnional electrode).
Embodiment 6
(1) graphene oxide is prepared using improved Hummer methods.Prepare the graphene oxide solution of 1mg/ml.
(2) using the graphene oxide solution of 1mg/ml as electrolyte, to connect positive pole, platinum plate electrode connects negative foam copper
Pole, the electro-deposition 15min under the constant pressure of 5V.The graphene of the reduction of electrode surface physical absorption is rinsed out, and electrode is put into
It is dried overnight in vacuum drying oven, obtains deposited the foam copper of the graphene of reduction, i.e. three-dimensional framework.
(3) CoCl of 0.012g is weighed2·6H2The NiCl of O, 0.178g2·6H2The thiocarbamide of O and 5.6g, and they are molten
Solution obtains mixed solution in the deionized water of 100ml.
(4) using deposited reduction graphene foam copper as working electrode, platinized platinum is is to electrode, Ag/AgCl electrodes
Reference electrode, the mixed solution of step (3) as electrolyte, -1.2V-0.2V voltage range with the sweep speed of 5mV/s
Scan round 4 is enclosed, and electroactive substance is deposited on three-dimensional framework using electrodeposition process.
(5) finally, when annealing 2 is small at 300 DEG C in an ar atmosphere, three-dimensional composite material is obtained, it can be directly as compound
Electrode (i.e. three-diemsnional electrode).
Embodiment 7
(1) graphene oxide is prepared using improved Hummer methods.Prepare the graphene oxide solution of 2mg/ml.
(2) using the graphene oxide solution of 2mg/ml as electrolyte, foam copper connects positive pole, and platinum plate electrode connects negative
Pole, the electro-deposition 5min under the constant pressure of 5V.The graphene of the reduction of electrode surface physical absorption is rinsed out, and electrode is put into very
It is dried overnight in empty baking oven, obtains deposited the foam copper of the graphene of reduction, i.e. three-dimensional framework.
(3) CoCl of 0.012g is weighed2·6H2The NiCl of O, 0.178g2·6H2The thiocarbamide of O and 5.6g, and they are molten
Solution obtains mixed solution in the deionized water of 100ml.
(4) using deposited reduction graphene foam copper as working electrode, platinized platinum is is to electrode, Ag/AgCl electrodes
Reference electrode, the mixed solution of step (3) as electrolyte, -1.2V-0.2V voltage range with the sweep speed of 5mV/s
Scan round 15 is enclosed, and electroactive substance is deposited on three-dimensional framework using electrodeposition process.
(5) finally, when annealing 3 is small at 300 DEG C in an ar atmosphere, three-dimensional composite material is obtained, it can be directly as compound
Electrode (i.e. three-diemsnional electrode).
Embodiment 8
(1) graphene oxide is prepared using improved Hummer methods.Prepare the graphene oxide solution of 1.5mg/ml.
(2) using the graphene oxide solution of 1.5mg/ml as electrolyte, foam copper connects positive pole, and platinum plate electrode connects negative
Pole, the electro-deposition 8min under the constant pressure of 4V.The graphene of the reduction of electrode surface physical absorption is rinsed out, and electrode is put into very
It is dried overnight in empty baking oven, obtains deposited the foam copper of the graphene of reduction, i.e. three-dimensional framework.
(3) CoCl of 0.012g is weighed2·6H2The NiCl of O, 0.178g2·6H2The thiocarbamide of O and 5.6g, and they are molten
Solution obtains mixed solution in the deionized water of 100ml.
(4) using deposited reduction graphene foam copper as working electrode, platinized platinum be to electrode, calomel electrode is reference
Electrode, the mixed solution of step (3) are circulated as electrolyte in the voltage range of -1.2V-0.2V with the sweep speed of 4mV/s
The circle of scanning 12, electroactive substance is deposited using electrodeposition process on three-dimensional framework.
(5) finally, when annealing 2.5 is small at 325 DEG C in an ar atmosphere, three-dimensional composite material is obtained, it can be directly as multiple
Composite electrode (i.e. three-diemsnional electrode).
Embodiment 9
(1) graphene solution of 2mg/ml is prepared.
(2) using the graphene solution of 2mg/ml as electrolyte, nickel foam connects positive pole, and platinum plate electrode connects anode,
Electro-deposition 13min under the constant pressure of 4.5V.The graphene of electrode surface physical absorption is rinsed out, and electrode is put into vacuum drying oven
It is dried overnight, obtains deposited the foam copper of graphene, i.e. three-dimensional framework.
(3) NiCl of 0.1M is weighed2·6H2The NH of O, 2M4The Mn (COOH) of Cl and 0.01M2·6H2O, and they are dissolved
In the deionized water of 100ml, mixed solution is obtained.
(4) deposited the nickel foam of graphene as working electrode, platinized platinum is to electrode, and Ag/AgCl electrodes are reference electricity
Pole, the mixed solution of step (3) are swept as electrolyte in the voltage range of -1.2V-0.2V with the sweep speed circulation of 7mV/s
9 circles are retouched, electroactive substance is deposited on three-dimensional framework using electrodeposition process.
(5) finally, when annealing 2.8 is small at 285 DEG C in an ar atmosphere, three-dimensional composite material is obtained, it can be directly as multiple
Composite electrode (i.e. three-diemsnional electrode).
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all fall within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of preparation method of three-dimensional composite material, it is characterised in that described method includes following steps：
(1) using graphene oxide solution and/or graphene solution as electrolyte, porous current collector connects positive pole, and it is heavy to carry out electricity
Product, obtains deposition and is coated with the graphene oxide of reduction and/or the three-dimensional framework of graphene；
(2) for the three-dimensional framework obtained using step (1) electro-deposition as working electrode, the material solution to prepare active material is used as electricity
Liquid is solved, scan round is carried out, electroactive substance is deposited on three-dimensional framework using electrodeposition process；
(3) made annealing treatment, obtain the graphene oxide and/or graphene/active material of porous current collector/reduction, i.e., three
Tie up composite material.
2. according to the method described in claim 1, it is characterized in that, step (1) graphene oxide solution and/or graphene
The concentration of solution is 1mg/mL~2mg/mL；
Preferably, step (1) is using graphene oxide solution as electrolyte.
3. method according to claim 1 or 2, it is characterised in that step (1) described porous current collector is Porous Cu, more
In hole nickel, porous carbon or porous aluminum any one or at least two combination, preferred Porous Cu, more preferably foam
Copper；
Preferably, the specific surface area of the porous current collector is 0.5cm2~9cm2；
Preferably, the voltage range of step (1) described electro-deposition is 3V~5V；
Preferably, the time of step (1) described electro-deposition is 5min~15min；
Preferably, during step (1) described electro-deposition, platinum plate electrode connects power cathode.
4. according to claim 1-3 any one of them methods, it is characterised in that step (2) original for preparing active material
Material solution be in the material solution for prepare bimetallic oxide, bimetallic sulfide or double-metal hydroxide any one or
The combination of the material solution of at least two active materials.
5. according to claim 1-4 any one of them methods, it is characterised in that step (2) original for preparing active material
Material solution is CoCl2·6H2O, NiCl2·6H2The mixed solution of O and thiocarbamide；
Preferably, in the mixed solution, CoCl2·6H2The concentration of O is 0.1M~3M；
Preferably, in the mixed solution, NiCl2·6H2The concentration of O is 0.1M~3M；
Preferably, in the mixed solution, the concentration of thiocarbamide is 1M~5M.
6. according to claim 1-5 any one of them methods, it is characterised in that the voltage model of step (2) described scan round
Enclose for -1.2V~0.2V；
Preferably, the sweep speed of step (2) described scan round is 3mV/s~10mV/s, is preferably 5mV/s；
Preferably, the number of turns of step (2) described scan round is~15 circle of 4 circle；
Preferably, during step (2) described scan round, platinized platinum is that calomel electrode is reference electrode to electrode；
Preferably, step (3) carries out step (2) ' before after the method is additionally included in step (2)：The production of rinsing step (2)
Thing and drying.
7. according to claim 1-6 any one of them methods, it is characterised in that step (3) annealing is in protective atmosphere
Lower progress, the protective atmosphere for any one or two kinds of argon gas atmosphere or nitrogen atmosphere combination；
Preferably, the temperature of step (3) described annealing is 275 DEG C~350 DEG C, is preferably 300 DEG C；
Preferably, the time of step (3) described annealing is 2h~3h.
8. according to claim 1-7 any one of them methods, it is characterised in that described method includes following steps：
(1) graphene oxide solution using concentration as 1mg/mL~2mg/mL is electrolyte, and foam copper connects positive pole, platinized platinum electricity
Pole connects power cathode, in electro-deposition 5min~15min in the voltage range of 3V~5V, obtains the oxidation stone that deposition is coated with reduction
The three-dimensional framework of black alkene；
(2) three-dimensional framework obtained using step (1) electro-deposition is working electrode, and platinum plate electrode is to electrode, and calomel electrode is ginseng
Than electrode, with CoCl2·6H2O, NiCl2·6H2The mixed solution of O and thiocarbamide is as electrolyte, in the voltage of -1.2V~0.2V
Scope encloses~15 circles with the sweep speed scan round 4 of 5mV/s, and electro-chemical activity is deposited on three-dimensional framework using electrodeposition process
Material；
(2) ' product of rinsing step (2) and drying；
(3) 2h~3h is made annealing treatment in 300 DEG C under an ar atmosphere, obtains graphene oxide/CoNi of Cu/ reduction2S4, i.e., it is three-dimensional
Composite material.
9. a kind of three-dimensional composite material, it is characterised in that the three-dimensional composite material is by described in claim any one of 1-8
Method be prepared.
10. a kind of ultracapacitor, it is characterised in that the ultracapacitor is using the three-dimensional composite wood described in claim 9
Material is used as electrode material；
Preferably, three-dimensional combination electrode material is tested under three-electrode system.
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Application publication date: 20180427 |