CN105070523A - A preparation method of a mutually-connected porous carbon nano-sheet/nickel foam composite electrode material - Google Patents
A preparation method of a mutually-connected porous carbon nano-sheet/nickel foam composite electrode material Download PDFInfo
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- CN105070523A CN105070523A CN201510553514.4A CN201510553514A CN105070523A CN 105070523 A CN105070523 A CN 105070523A CN 201510553514 A CN201510553514 A CN 201510553514A CN 105070523 A CN105070523 A CN 105070523A
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Abstract
The invention provides a preparation method of a mutually-connected porous carbon nano-sheet/nickel foam composite electrode material and belongs to the technical field of carbon material preparation. With three-dimensional porous nickel foam soaked with anthracene oil serving as the base body and coal tar pitch as the carbon source, with zinc acetate dihydrate serving as the template, and through potassium hydroxide activation, the porous carbon nano-sheet/nickel foam composite electrode material for supercapacitors can be prepared directly through microwave heating. The preparation method has the advantages of simple process, low energy consumption and low cost and is suitable large-scale application; the obtained porous carbon nano-sheet/nickel foam composite electrode material is used for forming symmetrical supercapacitors; in 6mol/L KOH electrolyte, when the current is 2A/g or 23mA/cm<2>, the mass specific volume of the composite material can reach 490F/g, the area specific volume can reach 2846mF/cm<2>, and the available energy density is 16.6Wh/kg or 6.9mWh/cm<2>.
Description
Technical field
The invention belongs to technical field of carbon material preparation, be specifically related to a kind of preparation method of interconnective porous charcoal nanometer sheet/nickel foam combination electrode material.
Background technology
Ultracapacitor is the novel green energy-storage travelling wave tube between traditional capacitor and battery, has that power density is large, serviceability temperature wide ranges, advantages of environment protection, receives the concern of people.Electrolyte and electrode material are the principal elements affecting ultracapacitor performance.Porous charcoal is the main electrode material of ultracapacitor, but it has the shortcomings such as internal resistance is comparatively large, conductivity is poor between particle, need be improved cyclical stability and the conductivity of porous carbon electrode material by interpolation binding agent and conductive agent.This patent describes a kind of preparation method of interconnective porous charcoal nanometer sheet/nickel foam combination electrode material, and resulting materials, directly as the electrode of ultracapacitor, does not need to add binding agent and conductive agent.
Coal tar pitch is the abbreviation of coal tar asphalt, and it is the residue-accessory substance after coal tar distillation, have phosphorus content higher, be rich in the hydrocarbon construction unit of armaticity, the advantage such as cheap and easy to get.This paper is carbon source with coal tar pitch, is that coactivator generates a large amount of micropores, can increases the specific volume of super electrical equipment with potassium hydroxide.Be/macropore with zinc acetate dihydrate during template can produce, to improve the rate capability of porous carbon electrode material.What is more important, our gained porous charcoal nanometer sheet is grown directly upon to have in the nickel foam of three-dimensional structure, the binding agent and the conductive black that use insulating properties can be avoided, to shorten ion transfer distance, thus improve the conductivity of electrode material, reduce its internal resistance, final capacity and the rate capability improving electrode for super capacitor material.
The present invention is carbon source with coal tar pitch, has cheapness, is easy to get, low ash and be rich in the advantages such as the hydrocarbon construction unit of armaticity.Adopt microwave heating, there is homogeneous heating, quick and energy-conservation advantage.Using the zinc acetate dihydrate of cheapness as template, the preparation cost of super electrical electrode material can be reduced further.Literature search shows, take coal tar pitch as carbon source, is aided with activation of potassium hydroxide legal system has no report for interconnective porous charcoal nanometer sheet/this method of foam nickel electrode composite material using zinc acetate dihydrate as template.
Summary of the invention
The object of the invention is to overcome prior art deficiency, a kind of preparation method of interconnective porous charcoal nanometer sheet/nickel foam combination electrode material is provided.
In order to realize foregoing invention object, the present invention is achieved by the following technical programs.
Concrete steps of the present invention are as follows:
(1) preliminary treatment of reactant: nickel foam is washed, after drying, is washed into disk and weighs, to be placed in carbolineum after soaking 5min carbolineum soak after nickel foam; Heat in tube furnace after a certain amount of coal tar pitch and zinc acetate dihydrate are ground, after cool to room temperature, grinding, obtain mixture A; Take the potassium hydroxide grinding of certain mass and mix with mixture A, obtaining mixture B; Mixture B is pressed into uniformly in the hole of the nickel foam after carbolineum immersion, and the nickel foam after being filled is put into corundum crucible together with remaining mixture B, obtain reactant C;
Wherein: the quality of zinc acetate dihydrate accounts for 50% ~ 65% of nickel foam, coal tar pitch and zinc acetate dihydrate three mixture gross mass; The mass ratio of potassium hydroxide and zinc acetate dihydrate is between 5/12 ~ 10/12; The mass ratio of carbolineum and nickel foam is 3/2;
(2) preparation of interconnective porous charcoal nanometer sheet/nickel foam combination electrode material: reactant C is placed in quartz cover, and quartz cover is put into microwave oven; Under the argon gas atmosphere of flowing, microwave heating is adopted to prepare porous charcoal nanometer sheet/nickel foam composite material; After reaction terminates, porous charcoal nanometer sheet/nickel foam is taken out, is placed in dilute hydrochloric acid solution and soaks more than 2h, be washed with distilled water to neutrality, after drying, obtain porous charcoal nanometer sheet/nickel foam combination electrode material.
As one optimization, in step (1), the quality of coal tar pitch is 3g, and the quality of zinc acetate dihydrate is 18g, and the quality of potassium hydroxide is 10g, and nickel foam is 0.26g, and the quality of carbolineum is 0.39g.Now preparing gained composite material in 6mol/LKOH electrolyte, is 2A/g or 23mA/cm at electric current
2time, its quality specific volume is 490F/g, and area specific volume is 2846mF/cm
2.The available energy density of the symmetric form ultracapacitor prepared by composite material is 16.6Wh/kg or 6.9mWh/cm
2.
The principles of science of the present invention:
Take coal tar pitch as carbon source, by template coupling activation of potassium hydroxide method, adopt microwave fast heating can realize the original position preparation of interconnective porous charcoal nanometer sheet/nickel foam combination electrode material.Wherein, nickel foam is on the one hand as the collector of ultracapacitor, on the other hand as the support frame of three-dimensional porous charcoal, the close contact of porous charcoal and nickel foam can be realized, reduce the internal resistance of electrode material, and save the conductive agent and binding agent that electrode for super capacitor material was used in the past, thus simplify the preparation technology of electrode for super capacitor material, save production cost, and capacity and the rate capability of electrode for super capacitor material can be improved.
Compared with prior art, the present invention has the following advantages:
(1) carbon source coal tar pitch and the template zinc acetate dihydrate advantage that all there is cheapness, be easy to get.
(2) raw material is pressed in nickel foam hole after the mode that is dry mixed mixes, and material treatment process is simple.
(3) adopt the heating of microwave one step directly to prepare interconnective porous charcoal nanometer sheet/nickel foam combination electrode material, there is efficient, quick, energy-conservation advantage.
(4) this patent saves the conductive agent used of electrode of super capacitor in the past and binding agent, direct is conducting matrix grain with nickel foam, the coal tar pitch of post liquefaction and three-dimensional netted nickel foam combine fully, reduce the internal resistance of electrode material, the electrode material for super capacitor of high power capacity and two-forty performance can be obtained.
Accompanying drawing explanation
Microwave heating curve when Fig. 1 is the embodiment of the present invention 1,2,3,4 preparation interconnective porous charcoal nanometer sheet/nickel foam combination electrode material.
Fig. 2 is the electromicroscopic photograph of the embodiment of the present invention 3 interconnective nickel foam used.
Fig. 3 is the electromicroscopic photograph of the interconnective porous charcoal nanometer sheet/nickel foam combination electrode material of the embodiment of the present invention 3 gained.
Fig. 4 is the electromicroscopic photograph of the interconnective porous charcoal nanometer sheet of the embodiment of the present invention 3 gained.
Fig. 5 is the variation diagram of area specific volume with current density of interconnective porous charcoal nanometer sheet/nickel foam combination electrode material prepared by the embodiment of the present invention 1,2,3,4.
Fig. 6 is the variation diagram of Area Power Density with power density of interconnective porous charcoal nanometer sheet/nickel foam combination electrode material prepared by the embodiment of the present invention 1,2,3,4.
Embodiment
Below in conjunction with specific embodiment in detail the present invention is described in detail, but the present invention is not limited to following embodiment, should be understood to example, those skilled in the art can carry out changing and revising on the basis of spirit and scope of the invention, and all such changes and modifications are included in the scope of the present invention.
Embodiment 1
Interconnective porous charcoal nanometer sheet/concrete preparation process of nickel foam combination electrode material C/Ni-1 is as follows:
(1) preliminary treatment of reactant: by aperture be 75 object nickel foam in the NaOH solution of 0.1mol/L after sonic oscillation 1h, be washed with distilled water to the nickel foam after neutral alkali treatment; By the nickel foam after alkali treatment in 0.05mol/L hydrochloric acid after sonic oscillation 1h, then washed to neutral with distilled water.Nickel foam after washing taken out after 110 DEG C of dry 24h in an oven, be washed into disc-shaped, weigh, stand-by soak 5min in carbolineum after, wherein, the quality of carbolineum and the mass ratio of nickel foam are 3/2.3g coal tar pitch and 24g zinc acetate dihydrate are ground, with 5 DEG C/min ramp to 150 DEG C in tube furnace, constant temperature is cooled to room temperature after half an hour, obtains mixture A after grinding.Take 10g potassium hydroxide, mix with A, obtain mixture B.Mixture B is pressed into uniformly in nickel foam duct, the nickel foam pressed is put into corundum crucible together with remaining mixture B, obtains reactant C;
(2) preparation of interconnective porous charcoal nanometer sheet/nickel foam combination electrode material: reactant C is put into protective quartz jacket; passing into argon gas 10min with the flow of 60mL/min gets rid of clean, after then heating 20min under the power of 600W by the air in protective quartz jacket.After naturally cooling to room temperature, porous charcoal nanometer sheet/nickel foam is taken out, puts into 0.5MHCl solution and soak 12h, then be washed with distilled water to neutrality.Porous charcoal/nickel foam composite material after washing is put into drying box after 110 DEG C of dry 24h, obtains porous charcoal/nickel foam combination electrode material called after C/Ni-1.
(3) above-mentioned gained C/Ni-1 being assembled into symmetrical ultracapacitor, in 6mol/LKOH electrolyte, is 2A/g or 33mA/cm in current density
2time, the quality specific volume of gained composite material is 199F/g, and area specific volume is 1652mF/cm
2, the available energy density of symmetric form ultracapacitor that thus prepared by composite material is 6.0Wh/kg or 3.6mWh/cm
2.
Embodiment 2
Interconnective porous charcoal nanometer sheet/concrete preparation process of nickel foam combination electrode material C/Ni-2 is as follows:
(1) preliminary treatment of reactant: as the step (1) in embodiment 1; Its difference just changes the quality of zinc acetate dihydrate and potassium hydroxide into 24g and 15g respectively.
(2) preparation of interconnective porous charcoal nanometer sheet/nickel foam combination electrode material: with step (2) in embodiment 1, gained porous charcoal/nickel foam combination electrode material called after C/Ni-2.
(3) with step 3 in embodiment 1, be 2A/g or 20mA/cm in current density
2time, the quality specific volume of gained composite material is 262F/g, and area specific volume is 1371mF/cm
2, available energy density is 6.2Wh/kg or 2.6mWh/cm
2.
Embodiment 3
Interconnective porous charcoal nanometer sheet/concrete preparation process of nickel foam combination electrode material C/Ni-3 is as follows:
(1) preliminary treatment of reactant: as the step (1) in embodiment 1; Its difference just changes the quality of zinc acetate dihydrate and potassium hydroxide into 18g and 10g respectively.
(2) preparation of interconnective porous charcoal nanometer sheet/nickel foam combination electrode material: with step (2) in embodiment 1, gained porous charcoal/nickel foam combination electrode material called after C/Ni-3.
(3) with step 3 in embodiment 1, be 2A/g or 23mA/cm in current density
2time, the quality specific volume of gained composite material is 490F/g, and area specific volume is 2846mF/cm
2, available energy density is 16.6Wh/kg or 6.9mWh/cm
2.
Embodiment 4
Interconnective porous charcoal nanometer sheet/concrete preparation process of nickel foam combination electrode material C/Ni-4 is as follows:
(1) reactant preliminary treatment: as the step (1) in embodiment 1; Its difference just changes the quality of zinc acetate dihydrate and potassium hydroxide into 18g and 15g respectively.
(2) preparation of interconnective porous charcoal nanometer sheet/nickel foam combination electrode material: with step (2) in embodiment 1, gained porous charcoal/nickel foam combination electrode material called after C/Ni-4.
(3) with step 3 in embodiment 1, be 2A/g or 24mA/cm in current density
2time, the quality specific volume of gained composite material is 417F/g, and area specific volume is 2582mF/cm
2, available energy density is 13.7Wh/kg or 6.1mWh/cm
2.
Claims (2)
1. a preparation method for interconnective porous charcoal nanometer sheet/nickel foam combination electrode material, is characterized in that the method concrete steps are as follows:
(1) preliminary treatment of reactant: nickel foam is washed, after drying, is washed into disk and weighs, to be placed in carbolineum after soaking 5min carbolineum soak after nickel foam; Heat in tube furnace after a certain amount of coal tar pitch and zinc acetate dihydrate are ground, after cool to room temperature, grinding, obtain mixture A; Take the potassium hydroxide grinding of certain mass and mix with mixture A, obtaining mixture B; Mixture B is pressed into uniformly in the hole of the nickel foam after carbolineum immersion, and the nickel foam after being filled is put into corundum crucible together with remaining mixture B, obtain reactant C;
Wherein: the quality of zinc acetate dihydrate accounts for 50% ~ 65% of nickel foam, coal tar pitch and zinc acetate dihydrate three mixture gross mass; The mass ratio of potassium hydroxide and zinc acetate dihydrate is between 5/12 ~ 10/12; The mass ratio of carbolineum and nickel foam is 3/2;
(2) preparation of interconnective porous charcoal nanometer sheet/nickel foam combination electrode material: reactant C is placed in quartz cover, and quartz cover is put into microwave oven; Under the argon gas atmosphere of flowing, microwave heating is adopted to prepare porous charcoal nanometer sheet/nickel foam composite material; After reaction terminates, porous charcoal nanometer sheet/nickel foam is taken out, is placed in dilute hydrochloric acid solution and soaks more than 2h, be washed with distilled water to neutrality, after drying, obtain porous charcoal nanometer sheet/nickel foam combination electrode material.
2. the preparation method of a kind of interconnective porous charcoal nanometer sheet/nickel foam combination electrode material as claimed in claim 1, it is characterized in that, in step (1), the quality of coal tar pitch is 3g, the quality of zinc acetate dihydrate is 18g, the quality of potassium hydroxide is 10g, and nickel foam is 0.26g, and the quality of carbolineum is 0.39g.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105366661A (en) * | 2015-12-15 | 2016-03-02 | 安徽工业大学 | Preparation method of curled porous carbon nanometer sheet for supercapacitor |
| CN108630454A (en) * | 2018-04-28 | 2018-10-09 | 辽宁大学 | A kind of method that combined techniques prepare super capacitor carbon electrode material |
| CN110073523A (en) * | 2016-10-18 | 2019-07-30 | Jenax股份有限公司 | Surface aggregate has the metal non-woven fabrics electrode of Dopaminergics monomer and the surface modifying method for it |
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| CN102431992A (en) * | 2011-09-22 | 2012-05-02 | 安徽工业大学 | Method for preparing porous carbon material by using magnesium oxide template in cooperation with activation of potassium hydroxide |
| CN102838105A (en) * | 2012-09-11 | 2012-12-26 | 安徽工业大学 | Preparation method of grading porous carbon material |
| KR20140087534A (en) * | 2012-12-31 | 2014-07-09 | 인하대학교 산학협력단 | Alkali-activated carbon and electrode for supercapacitor using the samer |
| CN104600307A (en) * | 2015-01-13 | 2015-05-06 | 上海交通大学 | Preparation method of multiwalled carbon nanotube for lithium air battery positive electrode |
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2015
- 2015-08-28 CN CN201510553514.4A patent/CN105070523B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102431992A (en) * | 2011-09-22 | 2012-05-02 | 安徽工业大学 | Method for preparing porous carbon material by using magnesium oxide template in cooperation with activation of potassium hydroxide |
| CN102838105A (en) * | 2012-09-11 | 2012-12-26 | 安徽工业大学 | Preparation method of grading porous carbon material |
| KR20140087534A (en) * | 2012-12-31 | 2014-07-09 | 인하대학교 산학협력단 | Alkali-activated carbon and electrode for supercapacitor using the samer |
| CN104600307A (en) * | 2015-01-13 | 2015-05-06 | 上海交通大学 | Preparation method of multiwalled carbon nanotube for lithium air battery positive electrode |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105366661A (en) * | 2015-12-15 | 2016-03-02 | 安徽工业大学 | Preparation method of curled porous carbon nanometer sheet for supercapacitor |
| CN110073523A (en) * | 2016-10-18 | 2019-07-30 | Jenax股份有限公司 | Surface aggregate has the metal non-woven fabrics electrode of Dopaminergics monomer and the surface modifying method for it |
| CN108630454A (en) * | 2018-04-28 | 2018-10-09 | 辽宁大学 | A kind of method that combined techniques prepare super capacitor carbon electrode material |
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