CN104240972A - Method for manufacturing porous flaky NiCo2O4 and grapheme composite capacitive material - Google Patents
Method for manufacturing porous flaky NiCo2O4 and grapheme composite capacitive material Download PDFInfo
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- CN104240972A CN104240972A CN201410459873.9A CN201410459873A CN104240972A CN 104240972 A CN104240972 A CN 104240972A CN 201410459873 A CN201410459873 A CN 201410459873A CN 104240972 A CN104240972 A CN 104240972A
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 6
- 239000002131 composite material Substances 0.000 title abstract description 9
- 229910005949 NiCo2O4 Inorganic materials 0.000 title abstract 5
- 238000004519 manufacturing process Methods 0.000 title abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 26
- 239000010439 graphite Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 7
- 239000013049 sediment Substances 0.000 claims abstract description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910003266 NiCo Inorganic materials 0.000 claims description 49
- 229910021389 graphene Inorganic materials 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000005119 centrifugation Methods 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000012429 reaction media Substances 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 14
- 239000002114 nanocomposite Substances 0.000 abstract description 11
- 239000003990 capacitor Substances 0.000 abstract description 5
- 239000008151 electrolyte solution Substances 0.000 abstract description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 abstract 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 abstract 1
- 239000004312 hexamethylene tetramine Substances 0.000 abstract 1
- 229960004011 methenamine Drugs 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 28
- 239000007788 liquid Substances 0.000 description 28
- 238000003756 stirring Methods 0.000 description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
- 239000000243 solution Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000000227 grinding Methods 0.000 description 14
- 238000010926 purge Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- -1 Graphene compound Chemical class 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000006978 adaptation 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
- 238000011161 development Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Abstract
The invention relates to a method for manufacturing a porous flaky NiCo2O4 and grapheme composite capacitive material, and belongs to the field of nano composite material manufacturing. According to the method, a graphite oxide, cobalt nitrate and nickel nitrate are dissolved in deionized water in an ultrasonic mode and stirred, a certain amount of hexamethylene tetramine is added, a reflux reaction is carried out for 3-4 hours at the temperature of 90 DEG C, sediments are collected, the collected sediments are calcined in an air atmosphere for 2 hours at the temperature of 330 DEG C, and the porous flaky NiCo2O4 and grapheme nano composite material is obtained. In the manufactured porous flaky NiCo2O4 and grapheme composite capacitive material, porous flaky NiCo2O4 is completely attached to the surface of a grapheme piece. By means of the composite structure, conductivity of the material is improved, and the contact area of the material and an electrolyte solution is greatly improved, so that the composite material has high specific capacitance and good electrochemical stability and can be possibly used as a super-capacitor electrode material.
Description
Technical field
The invention belongs to Nano-composite materials field, particularly a kind of porous flake NiCo
2o
4the preparation method of/Graphene complex capacitance material.
Background technology
Current, along with the fast development of economy, the social concern that energy shortage causes is also more and more outstanding, makes people become more urgent for the demand continuing efficient energy accumulating device; Ultracapacitor, owing to having charging interval short, the feature such as long service life, good temp characteristic, energy savings and environmental protection, has caused the extensive concern of people, has had broad application prospects; Usually the electrode material for super capacitor used is metal oxide and conducting polymer, but this kind of electrode material is because selfcapacity amount is less and conductivity is poor, constrains its applying in ultracapacitor; In recent years, research finds electrode active material and material with carbon element compound is improve the effective way of material ultracapacitor performance.
Recently, research finds cobalt acid nickel (NiCo
2o
4) there is the capacitive property more excellent than other transition metal oxide, be considered to ideal electrode material for super capacitor; The various cobalt acid nickel electrode material come in every shape is produced out at present, but these cobalt acid nickel electrode materials still have poorly conductive, and the shortcomings such as cyclical stability is not high, can not meet the performance requirement as excellent ultracapacitor; Because porous laminated structure material can increase the contact area with electrolyte solution to greatest extent, be conducive to the raising of its capacitive property, cobalt acid nickel has been made porous laminated structure by the present invention, and with Graphene compound, because Graphene has special two-dimensional layered structure and the electric conductivity of excellence, this material can not only increase the contact area of electrode material and electrolyte, and the electric conductivity of energy intensifier electrode material, this porous flake NiCo
2o
4/ graphene composite material is used as electrode material for super capacitor, shows excellent capacitive property.
The people such as Peng disclose one and prepare sheet NiCo
2o
4the preparation method of/graphene complex, prepared compound is as demonstrating good capacitive property during electrode material for super capacitor; But this preparation method is hydro thermal method, operation comparatively bothers, and in the present invention, we adopt simple heat reflow method successfully to prepare NiCo
2o
4/ Graphene complex capacitance material, greatly reduces the difficulty of operation.Meanwhile, prepared compound compares NiCo as demonstrating during electrode material
2s
4the capacitive property that/Graphene is higher, is more suitable for practical application.
Summary of the invention
The present invention has considered produced problem in prior art, and object is to provide a kind of porous flake NiCo
2o
4the preparation method of/Graphene complex capacitance material, adopts following technical scheme:
1) by graphite oxide ultrasonic dissolution in water, add cobalt nitrate and nickel nitrate, the concentration of graphite oxide is
0.5 ~ 1.0 g/L, the concentration of cobalt nitrate is 1.0 ~ 2.0 g/L, and the mol ratio of cobalt nitrate and nickel nitrate is 2:1.
2) drop in above-mentioned mixed solution by the hexa aqueous solution, maintenance hexa concentration is
5~20?g/L。
3) by mixed solution back flow reaction; Naturally, after cooling, centrifugation, gained sediment washing final vacuum is done
Dry.
4) using dried material as presoma, calcine in air atmosphere, can porous flake be obtained
NiCo
2o
4/ Graphene complex capacitance material.
Described graphite oxide take native graphite as raw material, is oxidized obtains by the Hummers method improved.
Described washing is that gained sediment is used deionized water and absolute ethanol washing respectively.
Described vacuumize refers to 45 DEG C of drying 24 h.
Described back flow reaction refers at 90 DEG C of back flow reaction 3 ~ 4 h.
Described calcining refers to 330 DEG C of calcining 2 h.
Porous flake NiCo prepared by the present invention
2o
4/ Graphene complex capacitance material use NiCo
2o
4with the characteristic of Graphene layer structure, make both perfect adaptations, porous flake NiCo
2o
4all be attached to the surface of graphene film; Meanwhile, the existence in hole ensure that NiCo
2o
4contact with the effective of electrolyte solution in electro-chemical test, make NiCo
2o
4give play to due capacitive property; This composite construction can not only improve the electric conductivity of material, and greatly can improve the contact area of itself and electrolyte solution, and thus this composite material demonstrates very high ratio capacitance and good electrochemical stability.
Accompanying drawing explanation
Fig. 1 is porous flake NiCo prepared by the present invention
2o
4x-ray diffraction (XRD) collection of illustrative plates of/graphene nanocomposite material, wherein abscissa is the angle of diffraction (2
θ), unit for degree (
0), ordinate is diffracted intensity, and unit is cps.
Porous flake NiCo prepared by Fig. 2 the present invention
2o
4the power spectrum (EDS) of/graphene nanocomposite material is analyzed.Wherein abscissa is energy, and unit is KeV, and ordinate is intensity, and unit is cps.
Fig. 3 is porous flake NiCo prepared by the present invention
2o
4transmission electron microscope (TEM) photo of/graphene nanocomposite material.
Fig. 4 is porous flake NiCo prepared by the present invention
2o
4the infrared spectrogram of/graphene nanocomposite material.Wherein abscissa is wave number, and unit is cm
-1, ordinate is transmitance, and unit is cps.
Fig. 5 is porous flake NiCo prepared by the present invention
2o
4/ graphene nanocomposite material be 0.5 A g in current density in 3 M KOH solution
-1time charging and discharging curve.Wherein abscissa is the time, and unit is s, and ordinate is voltage, and unit is V.
Fig. 6 is porous flake NiCo prepared by the present invention
2o
4/ graphene nanocomposite material is 0.5 A g in current density
-1time cyclical stability figure.Wherein abscissa is cycle-index, and ordinate is ratio capacitance, and unit is F g
-1.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are described in detail, but protection scope of the present invention is not limited to these embodiments.
Embodiment 1:60 mg graphite oxide is dispersed in the deionized water solution of 40 mL, the uniform dispersion liquid of ultrasonic formation; 10 mL are contained 0.250 mmol Co (NO
3)
2 . 6H
2o and 0.125 mmol Ni (NO
3)
2 . 6H
2the aqueous solution of O slowly drops in above-mentioned dispersion liquid, fully stirs; The aqueous solution again 10 mL being contained 0.21 g hexa slowly drops in above-mentioned mixed liquor, continues stirring 10 min; Mixed solution is transferred in back flow reaction device, 90
o3 h are reacted under C; The black product that centrifugation obtains, and use water and ethanol purge 3 times respectively, 45
ovacuumize under C; Powdered substance after grinding is calcined 2 h in air atmosphere at 330 DEG C, porous flake NiCo can be obtained
2o
4/ Graphene complex capacitance material.
Embodiment 2:60 mg graphite oxide is dispersed in the deionized water solution of 40 mL, the uniform dispersion liquid of ultrasonic formation; 10 mL are contained 0.250 mmol Co (NO
3)
2 . 6H
2o and 0.125 mmol Ni (NO
3)
2 . 6H
2the aqueous solution of O slowly drops in above-mentioned dispersion liquid, fully stirs; The aqueous solution again 10 mL being contained 0.21 g hexa slowly drops in above-mentioned mixed liquor, continues stirring 10 min; Mixed solution is transferred in back flow reaction device, 90
o4 h are reacted under C; The black product that centrifugation obtains, and use water and ethanol purge 3 times respectively, 45
ovacuumize under C; Powdered substance after grinding is calcined 2 h in air atmosphere at 330 DEG C, porous flake NiCo can be obtained
2o
4/ Graphene complex capacitance material.
Embodiment 3:60 mg graphite oxide is dispersed in the deionized water solution of 40 mL, the uniform dispersion liquid of ultrasonic formation; 10 mL are contained 0.500 mmol Co (NO
3)
2 . 6H
2o and 0.250 mmol Ni (NO
3)
2 . 6H
2the aqueous solution of O slowly drops in above-mentioned dispersion liquid, fully stirs; The aqueous solution again 10 mL being contained 0.21 g hexa slowly drops in above-mentioned mixed liquor, continues stirring 10 min; Mixed solution is transferred in back flow reaction device, 90
o3 h are reacted under C; The black product that centrifugation obtains, and use water and ethanol purge 3 times respectively, 45
ovacuumize under C; Powdered substance after grinding is calcined 2 h in air atmosphere at 330 DEG C, porous flake NiCo can be obtained
2o
4/ Graphene complex capacitance material.
Embodiment 4:60 mg graphite oxide is dispersed in the deionized water solution of 40 mL, the uniform dispersion liquid of ultrasonic formation; 10 mL are contained 0.500 mmol Co (NO
3)
2 . 6H
2o and 0.250 mmol Ni (NO
3)
2 . 6H
2the aqueous solution of O slowly drops in above-mentioned dispersion liquid, fully stirs; The aqueous solution again 10 mL being contained 0.21 g hexa slowly drops in above-mentioned mixed liquor, continues stirring 10 min; Mixed solution is transferred in back flow reaction device, 90
o4 h are reacted under C; The black product that centrifugation obtains, and use water and ethanol purge 3 times respectively, 45
ovacuumize under C; Powdered substance after grinding is calcined 2 h in air atmosphere at 330 DEG C, porous flake NiCo can be obtained
2o
4/ Graphene complex capacitance material.
Embodiment 5:60 mg graphite oxide is dispersed in the deionized water solution of 40 mL, the uniform dispersion liquid of ultrasonic formation; 10 mL are contained 0.750 mmol Co (NO
3)
2 . 6H
2o and 0.375 mmol Ni (NO
3)
2 . 6H
2the aqueous solution of O slowly drops in above-mentioned dispersion liquid, fully stirs; The aqueous solution again 10 mL being contained 0.21 g hexa slowly drops in above-mentioned mixed liquor, continues stirring 10 min; Mixed solution is transferred in back flow reaction device, 90
o3 h are reacted under C; The black product that centrifugation obtains, and use water and ethanol purge 3 times respectively, 45
ovacuumize under C; Powdered substance after grinding is calcined 2 h in air atmosphere at 330 DEG C, porous flake NiCo can be obtained
2o
4/ Graphene complex capacitance material.
Embodiment 6:60 mg graphite oxide is dispersed in the deionized water solution of 40 mL, the uniform dispersion liquid of ultrasonic formation; 10 mL are contained 0.750 mmol Co (NO
3)
2 . 6H
2o and 0.375 mmol Ni (NO
3)
2 . 6H
2the aqueous solution of O slowly drops in above-mentioned dispersion liquid, fully stirs; The aqueous solution again 10 mL being contained 0.21 g hexa slowly drops in above-mentioned mixed liquor, continues stirring 10 min; Mixed solution is transferred in back flow reaction device, 90
o4 h are reacted under C.The black product that centrifugation obtains, and use water and ethanol purge 3 times respectively, 45
ovacuumize under C; Powdered substance after grinding is calcined 2 h in air atmosphere at 330 DEG C, porous flake NiCo can be obtained
2o
4/ Graphene complex capacitance material.
Embodiment 7:60 mg graphite oxide is dispersed in the deionized water solution of 40 mL, the uniform dispersion liquid of ultrasonic formation; 10 mL are contained 1.00 mmol Co (NO
3)
2 . 6H
2o and 0.500 mmol Ni (NO
3)
2 . 6H
2the aqueous solution of O slowly drops in above-mentioned dispersion liquid, fully stirs; The aqueous solution again 10 mL being contained 0.21 g hexa slowly drops in above-mentioned mixed liquor, continues stirring 10 min; Mixed solution is transferred in back flow reaction device, 90
o3 h are reacted under C; The black product that centrifugation obtains, and use water and ethanol purge 3 times respectively, 45
ovacuumize under C; Powdered substance after grinding is calcined 2 h in air atmosphere at 330 DEG C, porous flake NiCo can be obtained
2o
4/ Graphene complex capacitance material.
Embodiment 8:60 mg graphite oxide is dispersed in the deionized water solution of 40 mL, the uniform dispersion liquid of ultrasonic formation; 10 mL are contained 1.00 mmol Co (NO
3)
2 . 6H
2o and 0.500 mmol Ni (NO
3)
2 . 6H
2the aqueous solution of O slowly drops in above-mentioned dispersion liquid, fully stirs; The aqueous solution again 10 mL being contained 0.21 g hexa slowly drops in above-mentioned mixed liquor, continues stirring 10 min; Mixed solution is transferred in back flow reaction device, 90
o4 h are reacted under C.The black product that centrifugation obtains, and use water and ethanol purge 3 times respectively, 45
ovacuumize under C; Powdered substance after grinding is calcined 2 h in air atmosphere at 330 DEG C, porous flake NiCo can be obtained
2o
4/ Graphene complex capacitance material.
Embodiment 9:60 mg graphite oxide is dispersed in the deionized water solution of 40 mL, the uniform dispersion liquid of ultrasonic formation; 10 mL are contained 0.250 mmol Co (NO
3)
2 . 6H
2o and 0.125 mmol Ni (NO
3)
2 . 6H
2the aqueous solution of O slowly drops in above-mentioned dispersion liquid, fully stirs; The aqueous solution again 10 mL being contained 0.42 g hexa slowly drops in above-mentioned mixed liquor, continues stirring 10 min; Mixed solution is transferred in back flow reaction device, 90
o3 h are reacted under C; The black product that centrifugation obtains, and use water and ethanol purge 3 times respectively, 45
ovacuumize under C; Powdered substance after grinding is calcined 2 h in air atmosphere at 330 DEG C, porous flake NiCo can be obtained
2o
4/ Graphene complex capacitance material.
Embodiment 10:60 mg graphite oxide is dispersed in the deionized water solution of 40 mL, the uniform dispersion liquid of ultrasonic formation; 10 mL are contained 0.250 mmol Co (NO
3)
2 . 6H
2o and 0.125 mmol Ni (NO
3)
2 . 6H
2the aqueous solution of O slowly drops in above-mentioned dispersion liquid, fully stirs; The aqueous solution again 10 mL being contained 0.42 g hexa slowly drops in above-mentioned mixed liquor, continues stirring 10 min; Mixed solution is transferred in back flow reaction device, 90
o4 h are reacted under C; The black product that centrifugation obtains, and use water and ethanol purge 3 times respectively, 45
ovacuumize under C; Powdered substance after grinding is calcined 2 h in air atmosphere at 330 DEG C, porous flake NiCo can be obtained
2o
4/ Graphene complex capacitance material.
Embodiment 11:60 mg graphite oxide is dispersed in the deionized water solution of 40 mL, the uniform dispersion liquid of ultrasonic formation; 10 mL are contained 0.250 mmol Co (NO
3)
2 . 6H
2o and 0.125 mmol Ni (NO
3)
2 . 6H
2the aqueous solution of O slowly drops in above-mentioned dispersion liquid, fully stirs; The aqueous solution again 10 mL being contained 0.63 g hexa slowly drops in above-mentioned mixed liquor, continues stirring 10 min; Mixed solution is transferred in back flow reaction device, 90
o3 h are reacted under C; The black product that centrifugation obtains, and use water and ethanol purge 3 times respectively, 45
ovacuumize under C; Powdered substance after grinding is calcined 2 h in air atmosphere at 330 DEG C, porous flake NiCo can be obtained
2o
4/ Graphene complex capacitance material.
Embodiment 12:60 mg graphite oxide is dispersed in the deionized water solution of 40 mL, the uniform dispersion liquid of ultrasonic formation; 10 mL are contained 0.250 mmol Co (NO
3)
2 . 6H
2o and 0.125 mmol Ni (NO
3)
2 . 6H
2the aqueous solution of O slowly drops in above-mentioned dispersion liquid, fully stirs; The aqueous solution again 10 mL being contained 0.63 g hexa slowly drops in above-mentioned mixed liquor, continues stirring 10 min; Mixed solution is transferred in back flow reaction device, 90
o4 h are reacted under C; The black product that centrifugation obtains, and use water and ethanol purge 3 times respectively, 45
ovacuumize under C; Powdered substance after grinding is calcined 2 h in air atmosphere at 330 DEG C, porous flake NiCo can be obtained
2o
4/ Graphene complex capacitance material.
Embodiment 13:60 mg graphite oxide is dispersed in the deionized water solution of 40 mL, the uniform dispersion liquid of ultrasonic formation; 10 mL are contained 0.250 mmol Co (NO
3)
2 . 6H
2o and 0.125 mmol Ni (NO
3)
2 . 6H
2the aqueous solution of O slowly drops in above-mentioned dispersion liquid, fully stirs; The aqueous solution again 10 mL being contained 0.84 g hexa slowly drops in above-mentioned mixed liquor, continues stirring 10 min; Mixed solution is transferred in back flow reaction device, 90
o3 h are reacted under C; The black product that centrifugation obtains, and use water and ethanol purge 3 times respectively, 45
ovacuumize under C; Powdered substance after grinding is calcined 2 h in air atmosphere at 330 DEG C, porous flake NiCo can be obtained
2o
4/ Graphene complex capacitance material.
Embodiment 14:60 mg graphite oxide is dispersed in the deionized water solution of 40 mL, the uniform dispersion liquid of ultrasonic formation; 10 mL are contained 0.250 mmol Co (NO
3)
2 . 6H
2o and 0.125 mmol Ni (NO
3)
2 . 6H
2the aqueous solution of O slowly drops in above-mentioned dispersion liquid, fully stirs; The aqueous solution again 10 mL being contained 0.84 g hexa slowly drops in above-mentioned mixed liquor, continues stirring 10 min; Mixed solution is transferred in back flow reaction device, 90
o4 h are reacted under C; The black product that centrifugation obtains, and use water and ethanol purge 3 times respectively, 45
ovacuumize under C; Powdered substance after grinding is calcined 2 h in air atmosphere at 330 DEG C, porous flake NiCo can be obtained
2o
4/ Graphene complex capacitance material.
Fig. 1 is the XRD figure of product, except NiCo in figure
2o
4outside the diffraction maximum of diffraction maximum and substrate silicon dioxide, not observe other peak.
Fig. 2 is the EDS collection of illustrative plates of product, and containing Co, Ni, C, O element in sample, wherein C element derives from Graphene, and oxygen element derives from the oxygen-containing functional group of redox graphene remnants.
As can be seen from Figure 3, the NiCo of porous flake
2o
4be attached to the surface of graphene film closely, and be evenly distributed, in conjunction with respond well, illustrate that product is porous flake NiCo
2o
4/ graphene nanocomposite material.
Infrared spectrum as can be seen from Fig. 4, in graphite oxide, the absworption peak of oxy radical disappears substantially, illustrates that graphite oxide is effectively reduced, and can observe the infrared signature absworption peak of cobalt acid nickel simultaneously.
Fig. 5 is porous flake NiCo
2o
4the charging and discharging curve of/graphene nanocomposite material in 3 M KOH solution, the material synthesized by explanation has very high ratio capacitance, is 0.5 A g in current density
-1time can reach 1186.3 F g
-1.
Fig. 6 shows porous flake NiCo
2o
4/ graphene composite material has good stability as electrode material, and after 100 discharge and recharges, ratio capacitance only loses 3.1%.
Claims (8)
1. a porous flake NiCo
2o
4the preparation method of/Graphene complex capacitance material, is characterized in that, comprise the following steps:
1) by graphite oxide ultrasonic dissolution in water, add cobalt nitrate and nickel nitrate, the concentration of graphite oxide is 0.5 ~ 1.0 g/L, and the concentration of cobalt nitrate is 1.0 ~ 2.0 g/L, and the mol ratio of cobalt nitrate and nickel nitrate is 2:1;
2) the hexa aqueous solution is dropped in above-mentioned mixed solution, keep hexa concentration to be 5 ~ 20 g/L;
3) by mixed solution back flow reaction; Naturally after cooling, centrifugation, the drying of gained sediment washing final vacuum obtains sheet presoma;
4) sheet presoma is calcined in air atmosphere, porous flake NiCo can be obtained
2o
4/ Graphene complex capacitance material.
2. a kind of porous flake NiCo as claimed in claim 1
2o
4the preparation method of/Graphene complex capacitance material, is characterized in that: described graphite oxide take native graphite as raw material, is oxidized obtains by the Hummers method improved.
3. a kind of porous flake NiCo as claimed in claim 1
2o
4the preparation method of/Graphene complex capacitance material, is characterized in that: described washing is that gained sediment is used deionized water and absolute ethanol washing respectively.
4. a kind of porous flake NiCo as claimed in claim 1
2o
4the preparation method of/Graphene complex capacitance material, is characterized in that: described vacuumize refers to 45 DEG C of drying 24 h.
5. a kind of porous flake NiCo as claimed in claim 1
2o
4the preparation method of/Graphene complex capacitance material, is characterized in that: described back flow reaction refers at 90 DEG C of back flow reaction 3 ~ 4 h.
6. a kind of porous flake NiCo as claimed in claim 1
2o
4the preparation method of/Graphene complex capacitance material, is characterized in that: described calcining refers to 330 DEG C of calcining 2 h.
7. a kind of porous flake NiCo as claimed in claim 1
2o
4the preparation method of/Graphene complex capacitance material, is characterized in that: preparation NiCo
2o
4sheet presoma time, hexa provides hydroxide ion, and simultaneously hexa is also as the reducing agent of reduction-oxidation graphite.
8. a kind of porous flake NiCo as claimed in claim 1
2o
4the preparation method of/Graphene complex capacitance material, is characterized in that: use water as reaction medium.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410459873.9A CN104240972B (en) | 2014-09-11 | 2014-09-11 | A kind of porous flake NiCo2O4The preparation method of/graphene complex capacitance material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410459873.9A CN104240972B (en) | 2014-09-11 | 2014-09-11 | A kind of porous flake NiCo2O4The preparation method of/graphene complex capacitance material |
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| Publication Number | Publication Date |
|---|---|
| CN104240972A true CN104240972A (en) | 2014-12-24 |
| CN104240972B CN104240972B (en) | 2018-12-14 |
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ID=52228864
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| CN201410459873.9A Active CN104240972B (en) | 2014-09-11 | 2014-09-11 | A kind of porous flake NiCo2O4The preparation method of/graphene complex capacitance material |
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| CN104599851A (en) * | 2014-12-31 | 2015-05-06 | 江苏江大环保科技开发有限公司 | Application of 3D coralline graphene/NiCo2O4 composite material |
| CN104616914A (en) * | 2014-12-31 | 2015-05-13 | 江苏江大环保科技开发有限公司 | Preparation method for 3D coralloid grapheme/NiCo2O4 composite materials |
| CN104658766A (en) * | 2015-02-12 | 2015-05-27 | 南京工业大学 | Nickel cobaltate doped with silicon nanosheet and preparation method of nickel cobaltate |
| CN104766725A (en) * | 2015-03-12 | 2015-07-08 | 广东工业大学 | Preparation method for electrode material used for supercapacitor and application of electrode material |
| CN106067383A (en) * | 2016-08-23 | 2016-11-02 | 中国科学院重庆绿色智能技术研究院 | A kind of pseudocapacitors positive pole based on cobalt sulfide nickel nucleocapsid three-dimensional multistage nanostructured and preparation method thereof |
| CN106169384A (en) * | 2016-08-30 | 2016-11-30 | 江苏大学 | A kind of three-dimensional meso-hole NiCo2o4the preparation method of/nitrogen-doped graphene combination electrode material |
| CN107248457A (en) * | 2017-07-26 | 2017-10-13 | 徐靖才 | One kind has caged NiCo2S4The preparation method of@carbon ball electrode materials |
| CN107393725A (en) * | 2017-06-20 | 2017-11-24 | 中国科学院福建物质结构研究所 | A kind of carbon material supported NiCo of porous, electrically conductive2O4Composite and its preparation method and application |
| CN108439370A (en) * | 2018-04-25 | 2018-08-24 | 江苏大学 | A kind of preparation method and its usage of two dimension porous boron nitrogen codope carbon nanomaterial |
| CN108520827A (en) * | 2018-01-29 | 2018-09-11 | 江苏大学 | Carbon fiber/NiCo2O4The preparation method of/graphene composite material |
| CN105845889B (en) * | 2016-04-18 | 2019-06-18 | 中南大学 | A kind of NiCo2O4Composite material and preparation method and its application on lithium ion battery |
| CN110033955A (en) * | 2019-04-18 | 2019-07-19 | 上海应用技术大学 | A kind of preparation method based on graphene building nickel cobalt mine binary composite |
| CN112229885A (en) * | 2020-10-17 | 2021-01-15 | 石河子大学 | Porous flaky NiCo2O4Preparation method and application of/nitrogen and sulfur co-doped reduced graphene oxide composite electrode material |
| CN114212779A (en) * | 2021-12-28 | 2022-03-22 | 洛阳尖端技术研究院 | Preparation method of composite wave-absorbing material and composite wave-absorbing material |
| CN114284509A (en) * | 2021-08-05 | 2022-04-05 | 先进能源产业研究院(广州)有限公司 | Preparation method of trimetal oxygen evolution electrocatalyst |
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| CN107248457A (en) * | 2017-07-26 | 2017-10-13 | 徐靖才 | One kind has caged NiCo2S4The preparation method of@carbon ball electrode materials |
| CN107248457B (en) * | 2017-07-26 | 2018-11-13 | 中国计量大学 | One kind having caged NiCo2S4The preparation method of@carbon ball electrode materials |
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| CN110033955A (en) * | 2019-04-18 | 2019-07-19 | 上海应用技术大学 | A kind of preparation method based on graphene building nickel cobalt mine binary composite |
| CN112229885A (en) * | 2020-10-17 | 2021-01-15 | 石河子大学 | Porous flaky NiCo2O4Preparation method and application of/nitrogen and sulfur co-doped reduced graphene oxide composite electrode material |
| CN112229885B (en) * | 2020-10-17 | 2023-11-24 | 石河子大学 | Porous sheet NiCo 2 O 4 Preparation method and application of nitrogen and sulfur co-doped reduced graphene oxide composite electrode material |
| CN114284509A (en) * | 2021-08-05 | 2022-04-05 | 先进能源产业研究院(广州)有限公司 | Preparation method of trimetal oxygen evolution electrocatalyst |
| CN114212779A (en) * | 2021-12-28 | 2022-03-22 | 洛阳尖端技术研究院 | Preparation method of composite wave-absorbing material and composite wave-absorbing material |
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