CN108022763A - A kind of graphene/metal oxide combination electrode material and preparation method thereof - Google Patents
A kind of graphene/metal oxide combination electrode material and preparation method thereof Download PDFInfo
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- CN108022763A CN108022763A CN201711237734.1A CN201711237734A CN108022763A CN 108022763 A CN108022763 A CN 108022763A CN 201711237734 A CN201711237734 A CN 201711237734A CN 108022763 A CN108022763 A CN 108022763A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 67
- 239000007772 electrode material Substances 0.000 title claims abstract description 46
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 39
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 229920001661 Chitosan Polymers 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000011229 interlayer Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000006181 electrochemical material Substances 0.000 abstract description 2
- 239000002082 metal nanoparticle Substances 0.000 abstract 1
- 239000011572 manganese Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- -1 amino, hydroxyl Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 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
- H01G11/84—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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
Abstract
The present invention provides a kind of graphene/metal oxide combination electrode material and preparation method thereof, is related to electrochemical material technical field.This graphene/metal oxide combination electrode material, first pass through electrolytic method and graphene is prepared, then graphene is mixed with the mixing salt solution of Ru, Mn and Co, is calcined after dry under the conditions of 220 DEG C~300 DEG C, obtain graphene/metal oxide combination electrode material.The graphene/metal oxide combination electrode material is for composite by introducing metal oxide and graphene, so that metal nanoparticle is embedded in adjacent graphene film interlayer, double layer electrodes material and fake capacitance electrode material it is reasonable compound, electric conductivity and chemical stability are good, have preferable specific capacitance.
Description
Technical field
The present invention relates to electrochemical material field, and more particularly to a kind of graphene/metal oxide combination electrode material
And preparation method thereof.
Background technology
Ultracapacitor has that high power density, charging interval be short, environmentally protective and long circulation life, in electronic vapour
The fields such as car, aerospace equipment and consumer electronics are with a wide range of applications.The performance of ultracapacitor mainly depends on
In the selection of electrode material.Metal oxide can obtain very high fake capacitance based on the redox reaction of itself, wherein, oxidation
Ruthenium has preferable stability and considerable fake capacitance characteristic, is acknowledged as classic electrode material, but ruthenium is expensive, limit
Make its commercialized application.Cost of material and cost of manufacture of the reduction containing ruthenium electrode are to realize its commercialized key.By adding
Add the 2nd constituent element to improve the dispersiveness of ruthenium-oxide, increase the fault of construction of electrode, the activity of electrode can be effectively improved.2nd constituent element
Such as TiO2、MnO2、MnO2、Co3O4, SiO2Deng.
Graphene is a kind of carbon material of two-dimensional structure, it is high with preferable monoatomic layer thickness, theoretical specific surface area
Up to 2630m2·g-1, and electric conductivity and chemical stability are good, it is considered to be preferable electrode material for electric double layer capacitor.But model
The presence of De Huali makes graphene easily reunite, so as to reduce the specific surface area and specific capacity of graphene.
Inventor, which studies, to be found, introduces that metal oxide and graphene are for composite can to make nano-particle insertion adjacent
Graphene film interlayer, effectively prevents graphene film from stacking again, is maintained high charge capacity so as to make up graphene work
For the deficiency of electrode material for super capacitor.
The content of the invention
It is an object of the invention to provide a kind of graphene/metal oxide combination electrode material, this electrode material chemistry
Property is stablized, excellent electrical property.
Another object of the present invention is to provide the preparation method of graphene/metal oxide combination electrode material.
The present invention is solved its technical problem and is realized using following technical scheme.
The present invention proposes a kind of preparation method of graphene/metal oxide combination electrode material, comprises the following steps：
S1, obtains a pair of of graphite electrode and electrolyte, will be inserted into pairs in the electrolyte graphite electrode, be powered electricity
Solution, obtains the graphene that electrolysis obtains；
S2, Ru salt, Mn salt and Co salt are dissolved in solvent, obtain mixed salt solution, wherein, the hybrid metal
In salting liquid, Ru:Mn:The atomic ratio of Co is 4:1~4:2~4；
S3, in the mixed salt solution, adds the graphene, after mixing, is dried to obtain graphene-metal salt
Presoma；
S4, the graphene-metal salt presoma is calcined under the conditions of 230 DEG C~310 DEG C, obtains graphene/metal
Oxide combination electrode material.
The present invention proposes a kind of graphene/metal oxide combination electrode material, is made according to above-mentioned preparation method.
The beneficial effect of the graphene/metal oxide combination electrode material of the embodiment of the present invention and preparation method thereof is：
Double layer electrodes material graphene and fake capacitance electrode material metal oxide is compound, significantly improve electrode material
Electric conductivity and chemical stability.Meanwhile introduce that metal oxide and graphene are for composite can to make nano-particle insertion phase
Adjacent graphene film interlayer, effectively prevents graphene film from stacking again, is maintained high charge capacity, so as to make up graphite
Deficiency of the alkene as electrode material for super capacitor.
Metal oxide obtains ternary composite metal oxide, the knot of tissue of electrode material by the mixing of Mn, Co and Ru
Structure and chemical property are substantially change.The dispersiveness of ruthenium-oxide is improved, highdensity fault of construction is formed, effectively improves
The active dot density and electrochemical roughening degree of electrode, further improves the specific capacitance of electrode material.
In addition, the preparation method of the present invention is simple, and it is easily operated, suitable for industrialized production, have good market should
Use prospect.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore be not construed as pair
The restriction of scope, for those of ordinary skill in the art, without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the shape appearance figure of obtained electrode material in comparative example 1 of the present invention；
Fig. 2 is the shape appearance figure of obtained electrode material in the embodiment of the present invention 1.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer, is the conventional production that can be obtained by commercially available purchase
Product.
Graphene/metal oxide combination electrode material of the embodiment of the present invention and preparation method thereof is carried out below specific
Explanation.
The embodiment of the present invention provides a kind of preparation method of graphene/metal oxide combination electrode material, including following
Step：
S1, obtains a pair of of graphite electrode and electrolyte, will be inserted into pairs in the electrolyte graphite electrode, be powered electricity
Solution, obtains the graphene that electrolysis obtains；
S2, Ru salt, Mn salt and Co salt are dissolved in solvent, obtain mixed salt solution, wherein, the hybrid metal
In salting liquid, Ru:Mn:The atomic ratio of Co is 4:1~4:2~4；
S3, in the mixed salt solution, adds the graphene, after mixing, is dried to obtain graphene-metal salt
Presoma；
S4, the graphene-metal salt presoma is calcined under the conditions of 230 DEG C~310 DEG C, obtains graphene/metal
Oxide combination electrode material.
Further, in step S1, electrolyte is the NaCl solution that concentration is 18~22mg/L.Can using the electrolyte
It is tiny that particle is prepared, uniform in size, the graphene powder of shape comparison rule.
Further, after the completion of electrolysis, electrolysate after electrolysis is collected, after alcohol washes, is dried under the conditions of 80 DEG C
0.5h obtains graphene powder.
Further, in mixed salt solution, Ru:Mn:The atomic ratio of Co is 4:3:3.Under the special ratios, electrode
The specific capacitance value of material reaches optimal.
Further, in graphene-metal salt presoma, the content of graphene is 8~12%.Further, graphene
Content be 10%.Under the ratio, metal oxide particle is dispersed in the interlayer of graphene, keeps metal oxide
The synergistic function of high conduction performance, graphene and metal oxide reaches optimal.
Further, in step S1, the process for the electrolysis that is powered is：Power-on voltage is 8~12mV, electric current for 0.02~
0.04A, conduction time are 20~25h.Under the electrolytic condition, single-layer graphene can be formed.
Further, in step S2, solvent is ethanol solution.Further, solvent is that mass fraction is 75%~95%
Ethanol solution.
In step S3, first graphene is dissolved in the dimethyl formamide solution containing chitosan and acetic acid, Ran Houzai
It is added in mixed salt solution.Further, the mass ratio of graphene and chitosan is 1:0.2~0.4.Further,
In dimethyl formamide solution, chitosan, acetic acid, the ratio of dimethylformamide are 0.5g：3g：1L.
Chitosan is a kind of a large amount of natural polymers for being present in nature, has nontoxic, high intensity, high adhesive ability etc.
Advantage.A large amount of amino, hydroxyl, acetylamino etc. are contained in chitosan surface, by graphene dispersion in the solution of chitosan-containing, energy
It is enough to form functional membrane on the surface of graphene, during follow-up graphene and metal ion are compound, enable to metal
Uniform ion is compounded on graphene, forms graphene layer after calcining on an metal oxide.Graphene layer can suppress metal
The volume deformation of oxide, and metal oxide particle is protected, be conducive to the lifting of electrode material chemical property.
Further, in step S4, in the calcination process of graphene-metal salt presoma, including with the next stage：
First stage：240~250 DEG C are warming up to the heating rate of 15~20 DEG C/min, keeps the temperature 10~15min；Second
Stage：290~310 DEG C are warming up to the heating rate of 2~5 DEG C/min, keeps the temperature 25~40min；Phase III：With 4~6 DEG C/
The rate of temperature fall of min is cooled to 230~240 DEG C, keeps the temperature 10~15min.
First heated up with faster speed, solvent quickly removes, and avoids the formation of hole, and then slowly heating, may advantageously facilitate
Form the electrode material of uniform and smooth.Finally, by temperature-fall period, the compound of metal oxide and graphene is conducive to, can
Effectively avoid electrode material that volume deformation occurs in follow-up charge and discharge process, improve cycle performance.
Present invention also offers black alkene blended metal oxide electrode material made from above-mentioned preparation method.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of black alkene blended metal oxide electrode material provided in this embodiment, it is made according to following steps：
(1) by the NaCl electrolyte of paired graphite electrode insertion 20mg/L, be powered electrolysis, power-on voltage 10mv, electricity
Flow for 0.03A, conduction time 24h, after electrolysis, extract powder alcohol washes and be put into drying box and dry, dry
Temperature is 80 DEG C, dries 0.5h, it is stand-by that collection obtains graphene；
(2) will be by Ru：Mn：The atomic ratio of Co is 4:3:3 are dissolved in ruthenium trichloride, manganese chloride and cobalt chloride in alcohol,
Obtain mixed salt solution；
(3) in mixed salt solution (total amount of metal salt is 60mg), 6mg graphenes are added, after mixing, dry
To graphene-metal salt presoma；
(4) graphene-metal salt presoma is kept into 10min at 240 DEG C, is warming up to 290 DEG C of holding 30min, then
Being cooled to 230 DEG C keeps 10min to obtain graphene/metal oxide combination electrode material.
Embodiment 2
A kind of black alkene blended metal oxide electrode material provided in this embodiment, is with the difference of embodiment 1,
Graphene-metal salt presoma is kept into 10min at 240 DEG C, 300 DEG C of holding 30min is warming up to, is then cooled to 230 DEG C
10min is kept to obtain graphene/metal oxide combination electrode material.
Embodiment 3
A kind of black alkene blended metal oxide electrode material provided in this embodiment, is with the difference of embodiment 1,
Graphene-metal salt presoma is kept into 10min at 240 DEG C, 310 DEG C of holding 30min is warming up to, is then cooled to 230 DEG C
10min is kept to obtain graphene/metal oxide combination electrode material.
Embodiment 4
A kind of black alkene blended metal oxide electrode material provided in this embodiment, is with the difference of embodiment 1,
Step (3) is：In mixed salt solution (total amount of metal salt is 60mg), graphene solution is added, after mixing, dry
To graphene-metal salt presoma, wherein graphene solution is：6mg graphenes are added to containing chitosan (1.5mg) and vinegar
In the dimethyl formamide solution of acid.
Comparative example 1
This comparative example provides a kind of electrode material, it is made according to following steps：
Will be by Ru：Mn：The atomic ratio of Co is 4:3:3 are dissolved in ruthenium trichloride, manganese chloride and cobalt chloride in alcohol, obtain
Mixed salt solution；After drying, calcine 30min at 290 DEG C and obtain.
It is the shape appearance figure of obtained electrode material in comparative example 1 of the present invention as shown in Figure 1, Fig. 2 comparative examples 1 of the present invention are made
Electrode material shape appearance figure.It can see clearly that the covering of graphene in Fig. 2, form more homogeneous mud crack shape and split
Line, hence it is evident that be conducive to the infiltration of electrolyte, and electrode surface uniform and smooth.
The specific capacitance of embodiment 1~4 and comparative example 1 is measured, the results are shown in Table 1.
Embodiments described above is part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of graphene/metal oxide combination electrode material, it is characterised in that comprise the following steps：
S1, obtains a pair of of graphite electrode and electrolyte, will be inserted into pairs in the electrolyte graphite electrode, and be powered electrolysis,
Obtain the graphene that electrolysis obtains；
S2, Ru salt, Mn salt and Co salt are dissolved in solvent, obtain mixed salt solution, wherein, the mixed metal salt is molten
In liquid, Ru:Mn:The atomic ratio of Co is 4:1~4:2~4；
S3, in the mixed salt solution, adds the graphene, after mixing, is dried to obtain graphene-metal salt precursor
Body；
S4, the graphene-metal salt presoma is calcined under the conditions of 230 DEG C~310 DEG C, obtains graphene/metal oxidation
Thing combination electrode material.
2. preparation method according to claim 1, it is characterised in that in step S1, the electrolyte be concentration be 18~
The NaCl solution of 22mg/L.
3. preparation method according to claim 1, it is characterised in that in the mixed salt solution, Ru:Mn:Co's
Atomic ratio is 4:3:3.
4. preparation method according to claim 1, it is characterised in that in the graphene-metal salt presoma, the stone
The content of black alkene is 8~12%.
5. preparation method according to claim 1, it is characterised in that in step S1, the process for the electrolysis that is powered is：Be powered electricity
It is 0.02~0.04A to press as 8~12mV, electric current, and conduction time is 20~25h.
6. preparation method according to claim 1, it is characterised in that in step S2, the solvent is ethanol solution.
7. preparation method according to claim 1, it is characterised in that in step S3, first the graphene is dissolved in and is contained
In the dimethyl formamide solution for having chitosan and acetic acid, the mixed salt solution is then then added to.
8. preparation method according to claim 7, it is characterised in that the mass ratio of the graphene and the chitosan is
1：0.5~0.8.
9. preparation method according to claim 1, it is characterised in that in step S4, the graphene-metal salt presoma
Calcination process in, including with the next stage：
First stage：240~250 DEG C are warming up to the heating rate of 15~20 DEG C/min, keeps the temperature 10~15min；
Second stage：290~310 DEG C are warming up to the heating rate of 2~5 DEG C/min, keeps the temperature 25~40min；
Phase III：230~240 DEG C are cooled to the rate of temperature fall of 4~6 DEG C/min, keeps the temperature 10~15min.
10. a kind of graphene/metal oxide combination electrode material, it is characterised in that according to claim 1~9 any one
The preparation method is made.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102112393A (en) * | 2008-07-28 | 2011-06-29 | 巴特尔纪念研究院 | Nanocomposite of graphene and metal oxide materials |
| CN107359054A (en) * | 2016-05-09 | 2017-11-17 | 国家纳米科学中心 | Composite electrode material, preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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