CN104252970B - Three-dimensional net structure Co3O4-Graphene@nickel cobalt double-hydroxide composite and its preparation method and application - Google Patents
Three-dimensional net structure Co3O4-Graphene@nickel cobalt double-hydroxide composite and its preparation method and application Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 98
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 82
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052803 cobalt Inorganic materials 0.000 title claims abstract description 52
- 239000010941 cobalt Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 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 claims abstract description 38
- 239000007772 electrode material Substances 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 16
- -1 nickel cobalt Chemical compound 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000002135 nanosheet Substances 0.000 claims abstract description 5
- 238000009432 framing Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000006260 foam Substances 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 16
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L Mercury(I) chloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 13
- 238000004062 sedimentation Methods 0.000 claims description 13
- UFMZWBIQTDUYBN-UHFFFAOYSA-N Cobalt(II) nitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 229960000539 carbamide Drugs 0.000 claims description 11
- 235000013877 carbamide Nutrition 0.000 claims description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 11
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N Nickel(II) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 10
- 230000005611 electricity Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical class [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 7
- 239000003990 capacitor Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 2
- 235000009508 confectionery Nutrition 0.000 claims 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims 2
- 229910052753 mercury Inorganic materials 0.000 claims 2
- AMDUMQZTBRMNMG-UHFFFAOYSA-N [Ni].O[N+]([O-])=O Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 11
- 238000004070 electrodeposition Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000012153 distilled water Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000005518 electrochemistry Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- LBFUKZWYPLNNJC-UHFFFAOYSA-N Cobalt(II,III) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 2
- 229940075397 calomel Drugs 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N Manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 210000004940 Nucleus Anatomy 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M Silver chloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002596 correlated Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004156 green chemistry Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- DLHSXQSAISCVNN-UHFFFAOYSA-M hydroxy(oxo)cobalt Chemical compound O[Co]=O DLHSXQSAISCVNN-UHFFFAOYSA-M 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 229910000468 manganese oxide Inorganic materials 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese(II,III) oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
The present invention relates to a kind of three-dimensional net structure Co3O4Graphene@nickel cobalt double-hydroxide composite and preparation method thereof, its cobaltosic oxide nano brush being unified into using ultrathin nanometer sheet is as framing structure, the surface of ultrathin nanometer sheet is glued with ultra-thin graphene film and forms Cobalto-cobaltic oxide Graphene lengthy motion picture, embeds nickel cobalt double hydroxide nano sheet between described Cobalto-cobaltic oxide Graphene two lengthy motion picture.The invention has the beneficial effects as follows: this kind of combination electrode material has the most excellent electric transmission and ion-diffusibility, finally make this kind of combination electrode material have the most excellent high rate performance.Cyclical stability have also been obtained extraordinary raising；The present invention uses simple hydro-thermal method, and sintering process combines the electro-deposition method that two steps optimize, and the material purity prepared is the highest, homogeneity the best.
Description
Technical field
The invention belongs to nano material and technical field of electrochemistry, be specifically related to a kind of three-dimensional net structure Co3O4-graphite
Alkene@nickel cobalt double-hydroxide composite and preparation method thereof, this composite can be as ultracapacitor active material.
Background technology
Along with the continuous growth of energy demand, exploration possesses the new cleaning fuel material of premium properties has become current
One challenge.Cobalto-cobaltic oxide, cobalt hydroxide and nickel hydroxide are as ultracapacitor fake capacitance material, and they have high
Theoretical specific capacity, easily prepared, advantages of environment protection, be increasingly becoming worldwide widely studied.Graphene simultaneously
It is also commonly used for being combined with electrode material for super capacitor as a kind of material with carbon element with high electrical conductivity, improves electricity with this
The high rate performance of pole material.
In order to obtain the electrode material for super capacitor possessing excellent properties, many about transition metal oxide (two
Manganese oxide, ruthenic oxide, Cobalto-cobaltic oxide, nickel oxide, molybdenum dioxide etc.)/transition metal oxide compound, burning
Thing/metal hydroxides compound, metal-oxide/carbon-based material and metal-oxide/conducting polymer compound by
Research and report, and also achieve certain achievement and solve some ultracapacitors development problems faced.But, these
Compound electrode material for super capacitor still can not reach the requirement as excellent clean energy resource material.Most important is exactly right
For current composite construction electrode material research, it is thus achieved that there is the electrode material of superelevation comprehensive electrochemical, (as high
Specific capacity, good high rate capability, fabulous discharge and recharge reversibility and cyclical stability) it is still that chooses the biggest
War.From the point of view of current reported document, also there is no research worker in the feelings meeting the high active substance load capacity of unit are
Under condition, the electrode active material obtained still has comprehensive chemical property recited above.
Summary of the invention
It is an object of the invention to provide that a kind of technique is simple, meet the requirement of Green Chemistry, have good electric chemical
The three-dimensional net structure Co of energy3O4-Graphene@nickel cobalt double-hydroxide composite and preparation method thereof.
To achieve these goals, the technical scheme is that three-dimensional net structure Co3O4The double hydrogen of-Graphene@nickel cobalt
Oxide composite, its cobaltosic oxide nano brush being unified into using ultrathin nanometer sheet is as framing structure, ultrathin nanometer sheet
Surface be glued with ultra-thin graphene film and form Cobalto-cobaltic oxide-Graphene lengthy motion picture, described Cobalto-cobaltic oxide-Graphene two
Embedding nickel cobalt double hydroxide nano sheet between lengthy motion picture, it uses following method to prepare, and includes following steps:
1) with nickel foam as electrode base sheet, be dipped into ultrasonic pretreatment in the dilute sulfuric acid of 0.1mol/L, spend after taking-up from
Sub-water supersound washing, then by washed electrode base sheet dry for standby；
2) 0.2-1.0g cabaltous nitrate hexahydrate and 0.2-1.0g carbamide are dissolved in 70ml deionized water stirring and are formed clear
Clear solution；
3) by step 2) settled solution that obtains and step 1) in the nickel foam handled well proceed to reactor reacts,
Take out reactor, naturally cool to room temperature, take out nickel foam, ultrasonic, dry, then sinter in argon and air, obtain four
Co 3 O electrode material；
4) using step 3) in the Cobalto-cobaltic oxide electrode material that obtains as working electrode, platinum electrode is as to electrode, full
With calomel electrode as reference electrode, 30 milliliters of Graphenes prepared with Ha Mofa and the 100 of 3.58 grams of disodium hydrogen phosphates
Milliliter solution as electrolyte, deposit, after terminating take out working electrode, with deionized water rinsing obtain Cobalto-cobaltic oxide-
Graphene electrodes material；
5) using step 4) in Cobalto-cobaltic oxide-Graphene electrodes material of obtaining as working electrode, platinum electrode is as right
Electrode, saturated calomel electrode, deposits as electrolyte as reference electrode, cobalt nitrate and nickel nitrate, takes out work after terminating
Make electrode, with deionized water rinsing, dry and obtain three-dimensional net structure Co3O4-Graphene@nickel cobalt double-hydroxide composite.
By such scheme, step 2) described in cabaltous nitrate hexahydrate be 0.291g, carbamide is 0.3g.
By such scheme, step 3) described in reaction temperature be 120 DEG C, the response time is 9 hours.
By such scheme, step 3) described in argon in sintering temperature be 450 DEG C, sintering time is 5 hours, in air burn
Junction temperature is 300 DEG C, and sintering time is 5 hours.
By such scheme, step 4) described in deposition current be 1mA cm-2, sedimentation time is 10 minutes.
By such scheme, step 5) described in the concentration of electrolyte be 0.01-0.05mol/L cobalt nitrate and 0.005-
0.025mol/L nickel nitrate, deposition current is 1-5mA cm-2, sedimentation time is 4-20 minute.
Described three-dimensional net structure Co3O4The preparation method of-Graphene@nickel cobalt double-hydroxide composite, include with
Lower step:
1) with nickel foam as electrode base sheet, be dipped into ultrasonic pretreatment in the dilute sulfuric acid of 0.1mol/L, spend after taking-up from
Sub-water supersound washing, then by washed electrode base sheet dry for standby；
2) 0.2-1.0g cabaltous nitrate hexahydrate and 0.2-1.0g carbamide are dissolved in 70ml deionized water stirring and are formed clear
Clear solution；
3) by step 2) settled solution that obtains and step 1) in the nickel foam handled well proceed to reactor reacts,
Take out reactor, naturally cool to room temperature, take out nickel foam, ultrasonic, dry, then sinter in argon and air, obtain four
Co 3 O electrode material；
4) using step 3) in the Cobalto-cobaltic oxide electrode material that obtains as working electrode, platinum electrode is as to electrode, full
With calomel electrode as reference electrode, 30 milliliters of Graphenes prepared with Ha Mofa and the 100 of 3.58 grams of disodium hydrogen phosphates
Milliliter solution as electrolyte, deposit, after terminating take out working electrode, with deionized water rinsing obtain Cobalto-cobaltic oxide-
Graphene electrodes material；
5) using step 4) in Cobalto-cobaltic oxide-Graphene electrodes material of obtaining as working electrode, platinum electrode is as right
Electrode, saturated calomel electrode, deposits as electrolyte as reference electrode, cobalt nitrate and nickel nitrate, takes out work after terminating
Make electrode, with deionized water rinsing, dry and obtain three-dimensional net structure Co3O4-Graphene@nickel cobalt double-hydroxide composite.
Described three-dimensional net structure Co3O4-Graphene@nickel cobalt double-hydroxide composite is as super capacitor electrode
The application of pole active material.
The invention has the beneficial effects as follows: three-dimensional net structure Co3O4-Graphene@nickel cobalt double-hydroxide composite is abundant
Remaining Cobalto-cobaltic oxide and the advantage of the high specific capacity of nickel cobalt double-hydroxide, graphene film is as mid portion, permissible
As the high-speed channel of electronics conduction in this three-dimensional net structure.Meanwhile, this kind of structure is three-dimensional net structure, the double hydrogen-oxygen of nickel cobalt
Compound nanometer sheet is embedded between Cobalto-cobaltic oxide-Graphene two lengthy motion picture so that this kind of combination electrode material has the most excellent
Electric transmission and ion-diffusibility, finally make this kind of combination electrode material have the most excellent high rate performance.And,
Owing to double hydroxide nano sheet is well embedded between Cobalto-cobaltic oxide-Graphene two lengthy motion picture, last cyclical stability
Have also been obtained extraordinary raising；The present invention uses simple hydro-thermal method, and sintering process combines the electro-deposition side that two steps optimize
Method, and the material purity prepared is the highest, homogeneity the best.Present invention process is simple, the electrode material prepared
Material chemical property is the most excellent, meets the requirement to electrode material for super capacitor performance on market, is very beneficial for market
Change and promote.
Accompanying drawing explanation
Fig. 1 is the three-dimensional net structure Co of embodiment 13O4The synthesizer of-Graphene@nickel cobalt double-hydroxide composite
Reason figure；
Fig. 2 is the three-dimensional net structure Co of embodiment 13O4The X-ray of-Graphene@nickel cobalt double-hydroxide composite
Diffraction pattern；
Fig. 3 is step 3 in embodiment 1) Cobalto-cobaltic oxide that obtains and step 4) Cobalto-cobaltic oxide-Graphene electricity of obtaining
The Fourier infrared spectrum figure of pole material；
Fig. 4 is step 4 in embodiment 1) the X-ray energy spectrogram of Cobalto-cobaltic oxide-Graphene that obtains；
Fig. 5 is Cobalto-cobaltic oxide-Graphene and three-dimensional net structure Co3O4-Graphene@nickel cobalt double-hydroxide composite wood
The SEM figure of material, wherein Fig. 5 a and Fig. 5 b is step 4 in embodiment 1 respectively) Cobalto-cobaltic oxide-Graphene of obtaining and step 5)
The three-dimensional net structure Co obtained3O4The SEM figure of-Graphene@nickel cobalt double-hydroxide composite；
Fig. 6 is Cobalto-cobaltic oxide Graphene and three-dimensional net structure Co3O4-Graphene@nickel cobalt double-hydroxide composite
TEM figure, wherein Fig. 6 a and Fig. 6 b is step 4 in embodiment 1 respectively) the Cobalto-cobaltic oxide Graphene that obtains and step 5) obtain
Three-dimensional net structure Co3O4The TEM figure of-Graphene@nickel cobalt double-hydroxide composite；
Fig. 7 is the three-dimensional net structure Co of embodiment 13O4-Graphene nickel cobalt double-hydroxide composite the most forthright
Can figure；
Fig. 8 is step 3 in embodiment 1) Cobalto-cobaltic oxide of nanometer brush pattern that obtains, step 4) in four oxygen that obtain
Change three cobalts-Graphene and step 5) in the three-dimensional net structure Co that obtains3O4-Graphene@nickel cobalt double-hydroxide composite
Cycle performance figure.
Detailed description of the invention
In order to be more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with embodiment, but the present invention
Content is not limited solely to the following examples.
Embodiment 1:
Ha Mofa prepares concretely comprising the following steps of Graphene:
A) 1g graphite is mixed with 23ml concentrated sulphuric acid in 250ml conical flask, be stirred at room temperature 24 hours；
B) under 40 DEG C of water bath condition, in conical flask, 100mg NaNO is added3, and stir 5 minutes, make NaNO3The most molten
Solve；
C) in conical flask, 500mg KMnO it is slowly added to4(controlling reaction temperature below 45 DEG C), stirs 30 minutes；
D) in conical flask, add 3ml distilled water, again add 3ml distilled water after waiting 5 minutes, add after waiting 5 minutes
Enter 40ml distilled water, stir 15 minutes；
E) stop water-bath, in conical flask, add 140ml distilled water and 10ml 30%H2O2, it is stirred at room temperature 5 minutes,
To terminate reaction；
F) use centrifuge, 10000 revs/min, 3 minutes, wash twice with 5%HCl solution, then use distilled water wash
To neutral；
G) obtained precipitate is dispersed in 100ml distilled water, and ultrasonic 60 minutes of 90Hz, water level and liquid time ultrasonic
Face is parallel, ultrasonic after wash the most at once；
H) by g) step gained solution, 5000 revs/min, within 5 minutes, it is centrifuged, takes after the supernatant 5000 revs/min again, 5 points
Twice of Zhongli's heart, gained clear liquid is graphene solution.
Three-dimensional net structure Co3O4The preparation method of-Graphene@nickel cobalt double-hydroxide composite, it includes walking as follows
Rapid:
1) nickel foam is as electrode base sheet, is first dipped into ultrasonic in the dilute sulfuric acid of 0.1mol/L (60Hz) pretreatment 20 points
Clock, washs 2 times with deionized water after taking-up under ultrasonic (60Hz), the most each 20 minutes, then by Ni-based for washed foam
Sheet dry for standby；
2) 0.291 gram of cabaltous nitrate hexahydrate and 0.3 gram of carbamide are dissolved in the deionized water of 70 milliliters stirring 1 hour
Form settled solution；
3) by step 2) in the settled solution that obtains and step 1) in the bubble that size is 20mm*60mm*0.4mm handled well
Foam nickel proceeds in reactor, reacts 9 hours under conditions of 120 DEG C, takes out reactor, naturally cools to room temperature, takes out bubble
Foam nickel, under 40Hz ultrasonic 5 minutes in deionized water, dries at 70 DEG C, sinter at 450 DEG C in argon the most respectively 5 little
Time, in air, at 300 DEG C, sintering obtains Cobalto-cobaltic oxide electrode material for 5 hours；
4) using step 3) in the length that the obtains Cobalto-cobaltic oxide in nickel foam as working electrode, platinum electrode is as to electricity
Pole, saturated calomel electrode as reference electrode, Graphene that 30 milliliters of Ha Mofa prepare and 3.58 grams of disodium hydrogen phosphates
100 milliliters of solution are as electrolyte, and cathodic deposition current value is 1mA cm-2, sedimentation time is 10 minutes, then starts electrification
Learn work station.After electrochemical workstation quits work, take out working electrode, within 10 minutes, obtain four oxidations with deionized water rinsing
Three cobalts-Graphene electrodes material
5) using step 4) in the length that the obtains Cobalto-cobaltic oxide-Graphene electrodes material in nickel foam as work electricity
Pole, platinum electrode as to electrode, saturated calomel electrode as reference electrode, 0.05 mole of every liter of cobalt nitrate and 0.025 mole every
Liter nickel nitrate is as electrolyte, and cathodic deposition current value is 5mA cm-2, sedimentation time is 4 minutes, then starts electrochemistry work
Stand.After electrochemical workstation quits work, taking out working electrode, with deionized water rinsing 10 minutes, 70 DEG C of drying obtained
Three-dimensional net structure Cobalto-cobaltic oxide-Graphene@nickel cobalt double-hydroxide combination electrode material.
As it is shown in figure 1, the synthesis mechanism of the present invention is: first pass through the hydro-thermal method of Optimal improvements, by controlling reactant
Concentration, reaction temperature and response time prepares the long Cobalto-cobaltic oxide in nickel foam with nanometer brush pattern, so
Electro-deposition method by optimizing makes graphene film be deposited on the surface of Cobalto-cobaltic oxide, finally by electrochemical deposition afterwards
Method is combined into nucleus growth and primary reconstruction mechanism obtains the final Co with three-dimensional net structure3O4-Graphene@nickel cobalt
Double-hydroxide composite material.
Product three-dimensional net structure Co with the present invention3O4As a example by-Graphene@nickel cobalt double-hydroxide composite, its group
Become to be determined by x-ray diffractometer, Fourier infrared spectrum analyser and X-ray energy disperse spectroscopy.X-ray diffraction pattern as shown in Figure 2
Spectrum (XRD) shows that the thing of composite is mutually for Cobalto-cobaltic oxide and double-hydroxide, as shown in Figure 3 Fourier infrared spectrum analysis
Instrument and have equally distributed Graphene in Fig. 4 X-ray energy disperse spectroscopy composite surface material.
Such as the scanning electron microscope of Fig. 5 a and it is deposited on uniformly as the transmission electron microscope of Fig. 6 a further demonstrates graphene film
The surface of Cobalto-cobaltic oxide, double hydroxide nano sheet is embedded between Cobalto-cobaltic oxide-Graphene two lengthy motion picture.As Fig. 5 b is
The three-dimensional net structure Co arrived3O4The scanning electron microscope (SEM) photograph of-Graphene@nickel cobalt double-hydroxide composite.If Fig. 6 b is to obtain
Three-dimensional net structure Co3O4The scanning electron microscope (SEM) photograph of-Graphene@nickel cobalt double-hydroxide composite.
The three-dimensional net structure Co that the present invention prepares3O4-Graphene@nickel cobalt double-hydroxide composite electrode is adopted
Ultracapacitor chemical property test is carried out with three-electrode system, with the combination electrode material for preparing as working electrode,
Platinum electrode is as to electrode, and silver/silver chloride electrode, as reference electrode, carries out the electrification being correlated with on occasion China electrochemical workstation
Learn test.Three-dimensional net structure Co such as Fig. 73O4-Graphene@NixCo2x(OH)6XThe electrochemistry high rate performance of electrode material is surveyed
Taking temperature, bright under the electric current density of 1A/g, capacity reaches 2550F/g, and when electric current density is 20A/g, capacity still reaches
2116F/g, tests such as the cycle performance of Fig. 8 simultaneously and shows under the electric current density of 20A/g, and the capacity after circulation 5000 circle is still
Reach the 92.7% of first lap.
Embodiment 2:
Three-dimensional net structure Co3O4The preparation method of-Graphene@nickel cobalt double-hydroxide composite, wherein, Graphene
Preparation method with reference to embodiment 1.It comprises the steps:
1) nickel foam is as electrode base sheet, is first dipped into ultrasonic in the dilute sulfuric acid of 0.1mol/L (60Hz) pretreatment 20 points
Clock, washs 2 times with deionized water after taking-up under ultrasonic (60Hz), the most each 20 minutes, then by Ni-based for washed foam
Sheet dry for standby；
2) 0.291 gram of cabaltous nitrate hexahydrate and 0.3 gram of carbamide are dissolved in the deionized water of 70 milliliters stirring 1 hour
Form settled solution；
3) by step 2) in the settled solution that obtains and step 1) in the bubble that size is 20mm*60mm*0.4mm handled well
Foam nickel proceeds in reactor, reacts 9 hours under conditions of 120 DEG C, takes out reactor, naturally cools to room temperature, takes out bubble
Foam nickel, under 40Hz ultrasonic 5 minutes in deionized water, dries at 70 DEG C, sinter at 450 DEG C in argon the most respectively 5 little
Time, in air, at 300 DEG C, sintering obtains Cobalto-cobaltic oxide electrode material for 5 hours；
4) using step 3) in the length that the obtains Cobalto-cobaltic oxide in nickel foam as working electrode, platinum electrode is as to electricity
Pole, saturated calomel electrode as reference electrode, Graphene that 30 milliliters of Ha Mofa prepare and 3.58 grams of disodium hydrogen phosphates
100 milliliters of solution are as electrolyte, and cathodic deposition current value is 1mA cm-2, sedimentation time is 10 minutes, then starts electrification
Learn work station.After electrochemical workstation quits work, take out working electrode, within 10 minutes, obtain four oxidations with deionized water rinsing
Three cobalts-Graphene electrodes material
5) using step 4) in the length that the obtains Cobalto-cobaltic oxide-Graphene electrodes material in nickel foam as work electricity
Pole, platinum electrode as to electrode, saturated calomel electrode as reference electrode, 0.05 mole of every liter of cobalt nitrate and 0.025 mole every
Liter nickel nitrate is as electrolyte, and cathodic deposition current value is 5mA cm-2, sedimentation time is 20 minutes, then starts electrochemistry work
Stand.After electrochemical workstation quits work, taking out working electrode, with deionized water rinsing 10 minutes, 70 DEG C of drying obtained
Three-dimensional net structure Cobalto-cobaltic oxide-Graphene@nickel cobalt double-hydroxide combination electrode material.
With the Co obtained in this example3O4As a example by-Graphene@nickel cobalt double-hydroxide composite, close at the electric current of 1A/g
The lower specific capacity of degree is 1100F/g, and under the electric current density of 20A/g, specific capacity is 530F/g.
Embodiment 3:
Three-dimensional net structure Co3O4The preparation method of-Graphene@nickel cobalt double-hydroxide composite, wherein, Graphene
Preparation method with reference to embodiment 1, it comprises the steps:
1) nickel foam is as electrode base sheet, is first dipped into ultrasonic in the dilute sulfuric acid of 0.1mol/L (60Hz) pretreatment 20 points
Clock, washs 2 times with deionized water after taking-up under ultrasonic (60Hz), the most each 20 minutes, then by Ni-based for washed foam
Sheet dry for standby；
2) 0.291 gram of cabaltous nitrate hexahydrate and 0.3 gram of carbamide are dissolved in the deionized water of 70 milliliters stirring 1 hour
Form settled solution；
3) by step 2) in the settled solution that obtains and step 1) in the bubble that size is 20mm*60mm*0.4mm handled well
Foam nickel proceeds in reactor, reacts 9 hours under conditions of 120 DEG C, takes out reactor, naturally cools to room temperature, takes out bubble
Foam nickel, under 40Hz ultrasonic 5 minutes in deionized water, dries at 70 DEG C, sinter at 450 DEG C in argon the most respectively 5 little
Time, in air, at 300 DEG C, sintering obtains Cobalto-cobaltic oxide electrode material for 5 hours；
4) using step 3) in the length that the obtains Cobalto-cobaltic oxide in nickel foam as working electrode, platinum electrode is as to electricity
Pole, saturated calomel electrode as reference electrode, Graphene that 30 milliliters of Ha Mofa prepare and 3.58 grams of disodium hydrogen phosphates
100 milliliters of solution are as electrolyte, and cathodic deposition current value is 1mA cm-2, sedimentation time is 10 minutes, then starts electrification
Learn work station.After electrochemical workstation quits work, take out working electrode, within 10 minutes, obtain four oxidations with deionized water rinsing
Three cobalts-Graphene electrodes material.
5) using step 4) in the length that the obtains Cobalto-cobaltic oxide-Graphene electrodes material in nickel foam as work electricity
Pole, platinum electrode as to electrode, saturated calomel electrode as reference electrode, 0.01 mole of every liter of cobalt nitrate and 0.005 mole every
Liter nickel nitrate is as electrolyte, and cathodic deposition current value is 1mA cm-2, sedimentation time is 20 minutes, then starts electrochemistry work
Stand.After electrochemical workstation quits work, taking out working electrode, with deionized water rinsing 10 minutes, 70 DEG C of drying obtained
Cobalto-cobaltic oxide-Graphene@nickel cobalt double-hydroxide combination electrode material.
The preparation method of Graphene is with reference to embodiment 1.
With the Co obtained in this example3O4As a example by-Graphene@nickel cobalt double-hydroxide composite, close at the electric current of 1A/g
The lower specific capacity of degree is 1553F/g, and under the electric current density of 20A/g, specific capacity is 1126F/g.
Comparative example 4:
Three-dimensional net structure Co3O4The preparation method of@nickel cobalt double-hydroxide composite, it comprises the steps:
1) nickel foam is as electrode base sheet, is first dipped into ultrasonic in the dilute sulfuric acid of 0.1mol/L (60Hz) pretreatment 20 points
Clock, washs 2 times with deionized water after taking-up under ultrasonic (60Hz), the most each 20 minutes, then by Ni-based for washed foam
Sheet dry for standby；
2) 0.291 gram of cabaltous nitrate hexahydrate and 0.3 gram of carbamide are dissolved in the deionized water of 70 milliliters stirring 1 hour
Form settled solution；
3) by step 2) in the settled solution that obtains and step 1) in the bubble that size is 20mm*60mm*0.4mm handled well
Foam nickel proceeds in reactor, reacts 9 hours under conditions of 120 DEG C, takes out reactor, naturally cools to room temperature, takes out bubble
Foam nickel, under 40Hz ultrasonic 5 minutes in deionized water, dries at 70 DEG C, sinter at 450 DEG C in argon the most respectively 5 little
Time, in air, at 300 DEG C, sintering obtains Cobalto-cobaltic oxide electrode material for 5 hours；
4) using step 3) in the length that the obtains Cobalto-cobaltic oxide electrode material in nickel foam as working electrode, platinum electrode
As to electrode, saturated calomel electrode is as reference electrode, and 0.05 mole of every liter of cobalt nitrate and 0.025 mole of every liter of nickel nitrate are made
For electrolyte, cathodic deposition current value is 5mA cm-2, sedimentation time is 4 minutes, then starts electrochemical workstation.Treat electrification
Learning after work station quits work, take out working electrode, with deionized water rinsing 10 minutes, 70 DEG C of drying obtained three-dimensional net structure
Cobalto-cobaltic oxide@nickel cobalt double-hydroxide combination electrode material.
With the three-dimensional net structure Co obtained in this example3O4As a example by@nickel cobalt double-hydroxide composite, 1A/g's
Under electric current density, specific capacity is 1947F/g, and under the electric current density of 20A/g, specific capacity is 1201F/g.
Embodiment 4 is not add the three-dimensional net structure Co that Graphene obtains3O4@nickel cobalt double-hydroxide composite.From
Can draw on chemical property, the specific capacity of the combination electrode material that addition Graphene prepares and high rate performance ratio are not
Add the combination electrode material raising many that Graphene prepares.
Claims (13)
1. three-dimensional net structure Co3O4-Graphene@nickel cobalt double-hydroxide composite, its four oxygen being unified into ultrathin nanometer sheet
Changing three cobalt nanometer brushes as framing structure, the surface of ultrathin nanometer sheet is glued with ultra-thin graphene film and forms four oxidations three
Cobalt-Graphene lengthy motion picture, embeds nickel cobalt double hydroxide nano sheet between described Cobalto-cobaltic oxide-Graphene two lengthy motion picture, it is adopted
Prepare by following method, include following steps:
1) with nickel foam as electrode base sheet, it is dipped into ultrasonic pretreatment in the dilute sulfuric acid of 0.1mol/L, after taking-up, uses deionized water
Supersound washing, then by washed electrode base sheet dry for standby；
2) 0.2-1.0g cabaltous nitrate hexahydrate and 0.2-1.0g carbamide are dissolved in 70ml deionized water stirring and form settled solution；
3) by step 2) settled solution that obtains and step 1) in the nickel foam handled well proceed to reactor reacts, take out
Reactor, naturally cools to room temperature, takes out nickel foam, ultrasonic, dries, then sinters in argon and air, obtain four oxidations
Three cobalt electrode materials；
4) using step 3) in the Cobalto-cobaltic oxide electrode material that obtains as working electrode, platinum electrode is as to electrode, saturated sweet
Mercury electrode is as reference electrode, 30 milliliters of Graphenes prepared with Ha Mofa and 100 milliliters of 3.58 grams of disodium hydrogen phosphates
Solution, as electrolyte, deposits, and takes out working electrode, obtain Cobalto-cobaltic oxide-graphite with deionized water rinsing after terminating
Alkene electrode material；
5) using step 4) in Cobalto-cobaltic oxide-Graphene electrodes material of obtaining as working electrode, platinum electrode as to electrode,
Saturated calomel electrode, deposits as electrolyte as reference electrode, cobalt nitrate and nickel nitrate, takes out work electricity after terminating
Pole, with deionized water rinsing, dries and obtains three-dimensional net structure Co3O4-Graphene@nickel cobalt double-hydroxide composite.
Three-dimensional net structure Co the most according to claim 13O4-Graphene@nickel cobalt double-hydroxide composite, it is special
Levy and be, step 2) described in cabaltous nitrate hexahydrate be 0.291g, carbamide is 0.3g.
Three-dimensional net structure Co the most according to claim 13O4-Graphene@nickel cobalt double-hydroxide composite, it is special
Levy and be, step 3) described in reactor in carry out reacting reaction temperature be 120 DEG C, the response time is 9 hours.
Three-dimensional net structure Co the most according to claim 13O4-Graphene@nickel cobalt double-hydroxide composite, it is special
Levy and be, step 3) described in argon in sintering temperature be 450 DEG C, sintering time is 5 hours, and in air, sintering temperature is 300
DEG C, sintering time is 5 hours.
Three-dimensional net structure Co the most according to claim 13O4-Graphene@nickel cobalt double-hydroxide composite, it is special
Levy and be, step 4) described in deposition current be 1mA cm-2, sedimentation time is 10 minutes.
Three-dimensional net structure Co the most according to claim 13O4-Graphene@nickel cobalt double-hydroxide composite, it is special
Levy and be, step 5) described in the concentration of electrolyte be 0.01-0.05mol/L cobalt nitrate and 0.005-0.025mol/L nitric acid
Nickel, deposition current is 1-5mA cm-2, sedimentation time is 4-20 minute.
7. three-dimensional net structure Co described in claim 13O4The preparation method of-Graphene@nickel cobalt double-hydroxide composite,
Include following steps:
1) with nickel foam as electrode base sheet, it is dipped into ultrasonic pretreatment in the dilute sulfuric acid of 0.1mol/L, after taking-up, uses deionized water
Supersound washing, then by washed electrode base sheet dry for standby；
2) 0.2-1.0g cabaltous nitrate hexahydrate and 0.2-1.0g carbamide are dissolved in 70ml deionized water stirring and form settled solution；
3) by step 2) settled solution that obtains and step 1) in the nickel foam handled well proceed to reactor reacts, take out
Reactor, naturally cools to room temperature, takes out nickel foam, ultrasonic, dries, then sinters in argon and air, obtain four oxidations
Three cobalt electrode materials；
4) using step 3) in the Cobalto-cobaltic oxide electrode material that obtains as working electrode, platinum electrode is as to electrode, saturated sweet
Mercury electrode is as reference electrode, 30 milliliters of Graphenes prepared with Ha Mofa and 100 milliliters of 3.58 grams of disodium hydrogen phosphates
Solution, as electrolyte, deposits, and takes out working electrode, obtain Cobalto-cobaltic oxide-graphite with deionized water rinsing after terminating
Alkene electrode material；
5) using step 4) in Cobalto-cobaltic oxide-Graphene electrodes material of obtaining as working electrode, platinum electrode as to electrode,
Saturated calomel electrode, deposits as electrolyte as reference electrode, cobalt nitrate and nickel nitrate, takes out work electricity after terminating
Pole, with deionized water rinsing, dries and obtains three-dimensional net structure Co3O4-Graphene@nickel cobalt double-hydroxide composite.
Three-dimensional net structure Co the most according to claim 73O4The preparation of-Graphene@nickel cobalt double-hydroxide composite
Method, it is characterised in that step 2) described in cabaltous nitrate hexahydrate be 0.291g, carbamide is 0.3g.
Three-dimensional net structure Co the most according to claim 73O4The preparation of-Graphene@nickel cobalt double-hydroxide composite
Method, it is characterised in that step 3) described in reactor in carry out reacting reaction temperature be 120 DEG C, the response time is 9 little
Time.
Three-dimensional net structure Co the most according to claim 73O4The system of-Graphene@nickel cobalt double-hydroxide composite
Preparation Method, it is characterised in that step 3) described in argon in sintering temperature be 450 DEG C, sintering time is 5 hours, in air burn
Junction temperature is 300 DEG C, and sintering time is 5 hours.
11. three-dimensional net structure Co according to claim 73O4The system of-Graphene@nickel cobalt double-hydroxide composite
Preparation Method, it is characterised in that step 4) described in deposition current be 1mA cm-2, sedimentation time is 10 minutes.
12. three-dimensional net structure Co according to claim 73O4The system of-Graphene@nickel cobalt double-hydroxide composite
Preparation Method, it is characterised in that step 5) described in the concentration of electrolyte be 0.01-0.05mol/L cobalt nitrate and 0.005-
0.025mol/L nickel nitrate, deposition current is 1-5mA cm-2, sedimentation time is 4-20 minute.
Three-dimensional net structure Co described in 13. claim 13O4-Graphene@nickel cobalt double-hydroxide composite is as super
The application of electrode for capacitors active material.
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| CN102324503A (en) * | 2011-09-19 | 2012-01-18 | 上海大学 | Method for preparing cobalt oxide nanosheet and graphene composite lithium battery cathode material through single-mode microwave |
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| CN103347377A (en) * | 2013-06-08 | 2013-10-09 | 西北工业大学 | Method for preparing graphene/Co3O4 wave-absorbing material through hydrothermal method |
| CN103972496A (en) * | 2014-04-10 | 2014-08-06 | 山东润昇电源科技有限公司 | Co3O4/graphene electrode material preparation method through hydro-thermal coupling spray pyrolysis |
| CN103985561A (en) * | 2014-05-28 | 2014-08-13 | 中国工程物理研究院化工材料研究所 | Graphene in-situ load needle-shaped Co3O4 composite electrode material and manufacturing method thereof |
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| CN102324503A (en) * | 2011-09-19 | 2012-01-18 | 上海大学 | Method for preparing cobalt oxide nanosheet and graphene composite lithium battery cathode material through single-mode microwave |
| CN102842710A (en) * | 2012-07-18 | 2012-12-26 | 上海大学 | Preparation method of Co3O4/graphene nanocomposite material |
| CN103347377A (en) * | 2013-06-08 | 2013-10-09 | 西北工业大学 | Method for preparing graphene/Co3O4 wave-absorbing material through hydrothermal method |
| CN103972496A (en) * | 2014-04-10 | 2014-08-06 | 山东润昇电源科技有限公司 | Co3O4/graphene electrode material preparation method through hydro-thermal coupling spray pyrolysis |
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