CN102683040A - Preparation method for graphene/alpha nickel hydroxide nanometer compound material - Google Patents
Preparation method for graphene/alpha nickel hydroxide nanometer compound material Download PDFInfo
- Publication number
- CN102683040A CN102683040A CN2012101515222A CN201210151522A CN102683040A CN 102683040 A CN102683040 A CN 102683040A CN 2012101515222 A CN2012101515222 A CN 2012101515222A CN 201210151522 A CN201210151522 A CN 201210151522A CN 102683040 A CN102683040 A CN 102683040A
- Authority
- CN
- China
- Prior art keywords
- graphene
- solution
- nickel hydroxide
- preparation
- graphite oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to a preparation method for a graphene/alpha nickel hydroxide nanometer compound material. The preparation method comprises the following steps of: preparing a graphite oxide aqueous solution; performing chemical reduction by using hydrazine hydrate, thereby obtaining graphene; mixing and reflowing the reduced graphene, divalent soluble nickel and urea in water and alcohol solvents; and leaching, cleaning and drying, thereby obtaining the graphene/alpha nickel hydroxide nanometer compound material. The preparation method provided by the invention is simple in preparation process, high in production efficiency and short in period. The prepared graphene/alpha nickel hydroxide nanometer compound material is excellent in electrochemical property.
Description
Technical field
The present invention relates to the preparation method of a kind of Graphene/α nickel hydroxide nano composite material, belong to nano material and electrochemical energy technical field.
Background technology
In recent years, Ni (OH)
2Cheap as electrode material for super capacitor because of it, electrochemical redox stability of characteristics etc. and receive increasing concern.Ni (OH)
2Electrochemical capacitor characteristic and size, pattern and the lattice types of its particle be closely related.In order to improve its ratio capacitance, people have made many effort, have synthesized many Ni (OH) with different nanostructures
2Material, like nano belt, three-dimensional manometer flower, hollow-core construction and nano-porous films or the like.Yet to having the Ni (OH) of big effective ratio area
2Nano particle then is difficult for synthetic because of taking place easily to reunite.Occur and raising dispersion of nano-particles degree in order to alleviate to reunite, Vidottim etc. utilize organic molecule to modify Ni (OH)
2Particle makes and forms protective layer to stop the mutual gathering of particle.But so outer organic molecule can hinder Ni (OH) undoubtedly
2Electron transport between particle and the electrode basement is used.
Graphene is that carbon atom is with sp
2The tightly packed cellular two-dimensional crystal lattice structural carbon nano material that forms of hybrid systems has good electricity, mechanics and thermal property, is the energy storage material that has potentiality.And Graphene has the electron conduction and very big specific area of superelevation, and theoretical value is up to 2600 m
2/ g, this makes Graphene be suitable as very much the host material of composite material.Synergistic function between nano material makes graphene-based material have the good power characteristic of material with carbon element, fake capacitance material high energy density and good electrochemistry cyclical stability, is expected to aspect electrode material for super capacitor, obtain to use.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of Graphene/α nickel hydroxide nano composite material.
The preparation method of Graphene of the present invention/α nickel hydroxide nano composite material may further comprise the steps:
1) under the sonic oscillation, that graphite oxide is soluble in water, the preparation mass concentration is 0.05% ~ 0.2% the graphite oxide aqueous solution, and regulates pH value to 10;
2) hydrazine hydrate solution with mass concentration 80% is poured in the above-mentioned graphite oxide aqueous solution, and the volume ratio of the hydrazine hydrate solution and the graphite oxide aqueous solution is 1:100, behind 80-100 ℃ of refluxing and stirring 5-24h, filters, washs, drying, obtains Graphene;
3) with step 2) Graphene that obtains is mixed with the ethanolic solution that concentration is the Graphene of 5g/L, is called solution A; Prepare the divalence soluble nickel of 0.12mol/L and the mixed aqueous solution of 2.4mol/L urea simultaneously, be called solution B;
4) stir down, solution A is splashed in the solution B, the volume ratio of solution A and solution B is 6:10, stirred 3-5 hour 100 ℃ of refluxed, and suction filtration, washing, drying obtains Graphene/α nickel hydroxide nano composite material.
Above-mentioned steps 3) said divalence soluble nickel can be NiCl in
2, Ni (NO
3) or NiSO
4
Compare with existing technical method, operation of the present invention and equipment are simple, are easy to control; With short production cycle, output is big, and the material composite effect for preparing is good; Have good electrochemical, its electrode material as the commercialization ultracapacitor has great application prospect.
Description of drawings
Fig. 1 is the SEM figure of Graphene/α nickel hydroxide nano composite material of obtaining of embodiment 1.
Fig. 2 be Graphene/α nickel hydroxide nano composite material of obtaining of embodiment 2 XRD figure.
Fig. 3 is the cyclic voltammetry curve figure under different scanning speed of Graphene/α nickel hydroxide nano composite material of obtaining of embodiment 3.
Fig. 4 be Graphene/α nickel hydroxide nano composite material of obtaining of embodiment 3 under the 10A/g current density than electric capacity with discharging and recharging the curve that number of times changes.
Embodiment
Embodiment 1:
1) in the 300ml deionized water for ultrasonic it is fully disperseed the 0.6g graphite oxide, regulate pH value to 10 with NaOH then;
2) hydrazine hydrate solution with 3ml mass concentration 80% is poured in the above-mentioned graphite oxide aqueous solution, behind 100 ℃ of refluxing and stirring 8h, filters, washs, drying, obtains Graphene;
3) take by weighing the above-mentioned Graphene of 300mg, join in the 60ml ethanol and it fully to be disperseed in ultrasonic 2 hours, obtain the ethanolic solution of Graphene, be called solution A; Simultaneously with 0.0012mol NiCl
2Be dissolved in the 100ml deionized water with 0.24mol urea, obtain mixed solution, be called solution B;
4) stir down, solution A is splashed in the solution B, stirred 3 hours 100 ℃ of refluxed, suction filtration, washing, drying obtains Graphene/α nickel hydroxide nano composite material, and its SEM figure sees Fig. 1.
By mass ratio is that 8:1:1 takes by weighing Graphene/α nickel hydroxide nano composite material 0.16g, acetylene black 0.02g, and PVDF (binding agent) 0.02g evenly is mixed and made into slurry in the N-methyl pyrrolidone.Subsequently the slurry that makes is evenly spread upon nickel foam (on the 1.5cm * 1.5cm); With the composite electrode sheet is work electrode; Platinized platinum is to electrode, and saturated calomel electrode is that electrolyte carries out the test of chemical property to it as reference electrode with 6mol/L KOH solution.The result: in the scanning voltage scope be-0.15V is to 0.35V, records than capacitance 1025F/g under the sweep speed of 2mv/s; And discharge and recharge the capacity that still can keep after 200 times more than 90% at the 10A/g high current density.
Embodiment 2:
1) in the 300ml deionized water for ultrasonic it is fully disperseed 0.15 g graphite oxide, regulate pH value to 10 with NaOH then;
2) hydrazine hydrate solution with 3ml mass concentration 80% is poured in the above-mentioned graphite oxide aqueous solution, behind 100 ℃ of refluxing and stirring 5h, filters, washs, drying, obtains Graphene;
3) take by weighing the above-mentioned Graphene of 75mg, join in the 15ml ethanol and it fully to be disperseed in ultrasonic 2 hours, obtain the ethanolic solution of Graphene, be called solution A; Simultaneously with 0.003mol Ni (NO
3)
2Be dissolved in the 25ml deionized water with 0.06mol urea, obtain mixed solution, be called solution B;
4) stir down, solution A is splashed in the solution B, stirred 5 hours 100 ℃ of refluxed, suction filtration, washing, drying obtains Graphene/α nickel hydroxide nano composite material, and its XRD figure is seen Fig. 2.
By mass ratio is that 8:1:1 takes by weighing Graphene/α nickel hydroxide nano composite material 0.16g, acetylene black 0.02g, and PVDF (binding agent) 0.02g evenly is mixed and made into slurry in the N-methyl pyrrolidone.Subsequently the slurry that makes is evenly spread upon nickel foam (on the 1.5cm * 1.5cm); With the composite electrode sheet is work electrode; Platinized platinum is to electrode, and saturated calomel electrode is that electrolyte carries out the test of chemical property to it as reference electrode with 6mol/L KOH solution.The result: in the scanning voltage scope be-0.15V is to 0.35V, records than capacitance 1040F/g under the sweep speed of 2mv/s; And discharge and recharge the capacity that still can keep after 200 times more than 90% at the 10A/g high current density.
Embodiment 3:
1) in the 300ml deionized water for ultrasonic it is fully disperseed 0.3 g graphite oxide, regulate pH value to 10 with NaOH then;
2) hydrazine hydrate solution with 3ml mass concentration 80% is poured in the above-mentioned graphite oxide aqueous solution, behind 100 ℃ of refluxing and stirring 24h, filters, washs, drying, obtains Graphene;
3) take by weighing the above-mentioned Graphene of 150mg, join in the 30ml ethanol and it fully to be disperseed in ultrasonic 2 hours, obtain the ethanolic solution of Graphene, be called solution A; Simultaneously with 0.006mol NiSO
4Be dissolved in the 50ml deionized water with 0.12mol urea, obtain mixed solution, be called solution B;
4) stir down, solution A is splashed in the solution B, stirred 4 hours 100 ℃ of refluxed, suction filtration, washing, drying obtains Graphene/α nickel hydroxide nano composite material.
By mass ratio is that 8:1:1 takes by weighing Graphene/α nickel hydroxide nano composite material 0.16g, acetylene black 0.02g, and PVDF (binding agent) 0.02g evenly is mixed and made into slurry in the N-methyl pyrrolidone.Subsequently the slurry that makes is evenly spread upon nickel foam (on the 1.5cm * 1.5cm); With the composite electrode sheet is work electrode; Platinized platinum is to electrode, and saturated calomel electrode is that electrolyte carries out the test of chemical property to it as reference electrode with 6mol/L KOH solution.The result: in the scanning voltage scope be-0.15V is to 0.35V, records than capacitance 1037F/g under the sweep speed of 2mv/s; And discharge and recharge the capacity that still can keep after 200 times more than 90% at the 10A/g high current density.
The cyclic voltammetry curve under different scanning speed of Graphene/α nickel hydroxide nano composite material is seen Fig. 3.Under the 10A/g current density, see Fig. 4 with the curve that discharges and recharges the number of times variation than electric capacity.
Claims (2)
1. the preparation method of Graphene/α nickel hydroxide nano composite material is characterized in that may further comprise the steps:
1) under the sonic oscillation, that graphite oxide is soluble in water, the preparation mass concentration is 0.05% ~ 0.2% the graphite oxide aqueous solution, and regulates pH value to 10;
2) hydrazine hydrate solution with mass concentration 80% is poured in the above-mentioned graphite oxide aqueous solution, and the volume ratio of the hydrazine hydrate solution and the graphite oxide aqueous solution is 1:100, behind 80-100 ℃ of refluxing and stirring 5-24h, filters, washs, drying, obtains Graphene;
3) with step 2) Graphene that obtains is mixed with the ethanolic solution that concentration is the Graphene of 5g/L, is called solution A; Prepare the divalence soluble nickel of 0.12mol/L and the mixed aqueous solution of 2.4mol/L urea simultaneously, be called solution B;
4) stir down, solution A is splashed in the solution B, the volume ratio of solution A and solution B is 6:10, stirred 3-5 hour 100 ℃ of refluxed, and suction filtration, washing, drying obtains Graphene/α nickel hydroxide nano composite material.
2. by the preparation method of the said Graphene of claim 1/α nickel hydroxide nano composite material, it is characterized in that the divalence soluble nickel in the step 3) is NiCl
2, Ni (NO
3)
2Or NiSO
4
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101515222A CN102683040A (en) | 2012-05-16 | 2012-05-16 | Preparation method for graphene/alpha nickel hydroxide nanometer compound material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101515222A CN102683040A (en) | 2012-05-16 | 2012-05-16 | Preparation method for graphene/alpha nickel hydroxide nanometer compound material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102683040A true CN102683040A (en) | 2012-09-19 |
Family
ID=46814797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101515222A Pending CN102683040A (en) | 2012-05-16 | 2012-05-16 | Preparation method for graphene/alpha nickel hydroxide nanometer compound material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102683040A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103065814A (en) * | 2012-12-24 | 2013-04-24 | 新疆大学 | Electrochemical application of synthesis of nickelous hydroxide and graphene compound with single-step reflux reaction adopted |
| CN103980978A (en) * | 2014-05-15 | 2014-08-13 | 张孝彬 | Graphene/nano carbon sphere compound engineering plastic with high lubricity and preparation method thereof |
| CN104599863A (en) * | 2015-01-15 | 2015-05-06 | 华东理工大学 | Method for preparation of composite material, composite material and application thereof |
| CN105513835A (en) * | 2015-12-25 | 2016-04-20 | 哈尔滨工业大学 | Preparation method and application of nickel hydroxide/graphene flexible electrode material |
| CN105591087A (en) * | 2016-03-21 | 2016-05-18 | 内蒙古科技大学 | Preparation method of nickel hydroxide/graphene composite material for nickel-metal hydride battery positive pole |
| CN106179205A (en) * | 2016-07-13 | 2016-12-07 | 安徽师范大学 | A kind of Ni (OH)2the preparation method of graphene composite nano materials |
| CN108922789A (en) * | 2018-06-28 | 2018-11-30 | 陕西科技大学 | The hollow tubular Ni (OH) of one step solvent structure2/ rGO combination electrode material and its methods and applications |
| CN110112381A (en) * | 2019-04-08 | 2019-08-09 | 河南超力新能源有限公司 | Nickel combination electrode material and preparation method, nickel hydroxide positive plate and preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101992303A (en) * | 2010-10-29 | 2011-03-30 | 江苏大学 | Method for preparing graphene/Ni nano composite material |
-
2012
- 2012-05-16 CN CN2012101515222A patent/CN102683040A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101992303A (en) * | 2010-10-29 | 2011-03-30 | 江苏大学 | Method for preparing graphene/Ni nano composite material |
Non-Patent Citations (2)
| Title |
|---|
| JUN YAN: "advanced asymmetric supercapacitors based on Ni(OH)2/grapheme and porous grapheme electrodes with high energy density", 《ADVANCED FUNCTIONAL MATERIALS》 * |
| 杨勇辉: "石墨烯的氧化还原法制备及结构表征", 《无机化学学报》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103065814A (en) * | 2012-12-24 | 2013-04-24 | 新疆大学 | Electrochemical application of synthesis of nickelous hydroxide and graphene compound with single-step reflux reaction adopted |
| CN103980978A (en) * | 2014-05-15 | 2014-08-13 | 张孝彬 | Graphene/nano carbon sphere compound engineering plastic with high lubricity and preparation method thereof |
| CN103980978B (en) * | 2014-05-15 | 2016-03-02 | 张孝彬 | Engineering plastics of a kind of graphene/nanometer carbon ball compound of high lubricity and preparation method thereof |
| CN104599863A (en) * | 2015-01-15 | 2015-05-06 | 华东理工大学 | Method for preparation of composite material, composite material and application thereof |
| CN104599863B (en) * | 2015-01-15 | 2017-07-18 | 华东理工大学 | A kind of method for preparing composite, composite and its application |
| CN105513835A (en) * | 2015-12-25 | 2016-04-20 | 哈尔滨工业大学 | Preparation method and application of nickel hydroxide/graphene flexible electrode material |
| CN105513835B (en) * | 2015-12-25 | 2018-07-03 | 哈尔滨工业大学 | A kind of preparation method and applications of nickel hydroxide/graphene flexible electrode material |
| CN105591087A (en) * | 2016-03-21 | 2016-05-18 | 内蒙古科技大学 | Preparation method of nickel hydroxide/graphene composite material for nickel-metal hydride battery positive pole |
| CN105591087B (en) * | 2016-03-21 | 2017-12-12 | 内蒙古科技大学 | A kind of preparation method of anode of nickel-metal hydride battery nickel hydroxide/graphene composite material |
| CN106179205A (en) * | 2016-07-13 | 2016-12-07 | 安徽师范大学 | A kind of Ni (OH)2the preparation method of graphene composite nano materials |
| CN108922789A (en) * | 2018-06-28 | 2018-11-30 | 陕西科技大学 | The hollow tubular Ni (OH) of one step solvent structure2/ rGO combination electrode material and its methods and applications |
| CN110112381A (en) * | 2019-04-08 | 2019-08-09 | 河南超力新能源有限公司 | Nickel combination electrode material and preparation method, nickel hydroxide positive plate and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102683040A (en) | Preparation method for graphene/alpha nickel hydroxide nanometer compound material | |
| Zhao et al. | An overview of oxygen reduction electrocatalysts for rechargeable zinc-air batteries enabled by carbon and carbon composites | |
| Venkatachalam et al. | Double hydroxide mediated synthesis of nanostructured ZnCo2O4 as high performance electrode material for supercapacitor applications | |
| Zhou et al. | Sulfuration of NiV-layered double hydroxide towards novel supercapacitor electrode with enhanced performance | |
| Ouyang et al. | Hierarchically structured spherical nickel cobalt layered double hydroxides particles grown on biomass porous carbon as an advanced electrode for high specific energy asymmetric supercapacitor | |
| Wu et al. | Construction of self-supported porous TiO2/NiO core/shell nanorod arrays for electrochemical capacitor application | |
| Acharya et al. | Leaf-like integrated hierarchical NiCo2O4 nanorods@ Ni-Co-LDH nanosheets electrodes for high-rate asymmetric supercapacitors | |
| Tian et al. | Preparation of CoS2 supported flower-like NiFe layered double hydroxides nanospheres for high-performance supercapacitors | |
| Shinde et al. | Flower-like NiCo2O4/NiCo2S4 electrodes on Ni mesh for higher supercapacitor applications | |
| Li et al. | Hierarchically nanostructured Ni (OH) 2–MnO2@ C ternary composites derived from Ni-MOFs grown on nickel foam as high-performance integrated electrodes for hybrid supercapacitors | |
| CN101840792B (en) | Hybrid super capacitor and manufacture method thereof | |
| Zhao et al. | Morphology controllable NiCo2O4 nanostructure for excellent energy storage device and overall water splitting | |
| Zhang et al. | Alcoholic hydroxyl functionalized partially reduced graphene oxides for symmetric supercapacitors with long-term cycle stability | |
| Xing et al. | High-performance supercapacitor based on three-dimensional flower-shaped Li4Ti5O12-graphene hybrid and pine needles derived honeycomb carbon | |
| CN103787320B (en) | The Synthesis and applications of the carbon nanosheet material of one kind graphene sheet layer structure | |
| CN105590754A (en) | Production method of multi-element transition metal hydroxide nuclear shell composite carbon filter electrode material | |
| CN102664107B (en) | Preparation method of nano-manganese dioxide electrode | |
| CN106981377B (en) | A kind of Co3O4The preparation method of@graphene fiber super capacitor electrode material | |
| CN107201573A (en) | A kind of preparation method and applications of cobalt disulfide and carbon nano-fiber composite material | |
| CN103985563B (en) | Lithium intercalation manganese dioxide-titanium nitride nanotube composite material and preparing method and application thereof | |
| CN107045948B (en) | NaxMnO2Positive electrode, preparation method and applications | |
| Chen et al. | In-situ growth of core-shell NiCo2O4@ Ni-Co layered double hydroxides for all-solid-state flexible hybrid supercapacitor | |
| Wang et al. | Hierarchical Cu0. 92Co2. 08O4@ NiCo-layered double hydroxide nanoarchitecture for asymmetric flexible storage device | |
| Zhu et al. | Dual-defect site regulation on MOF-derived P-Co 3 O 4@ NC@ O v-NiMnLDH carbon arrays for high-performance supercapacitors | |
| Baral et al. | Crumpled graphene oxide/spinel cobalt oxide composite based high performance supercapacitive energy storage device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120919 |