CN105719852A - Preparation method for three-dimensional nano-porous graphene/manganese dioxide composite electrode material - Google Patents
Preparation method for three-dimensional nano-porous graphene/manganese dioxide composite electrode material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a preparation method for a three-dimensional nano-porous graphene/manganese dioxide composite electrode material. The preparation method comprises the steps of taking an alloy foil sheet with the atomic ratio of Cu to Mn of 1:1 to 1:3, and performing dealloying processing to obtain a nano-porous metal foil sheet, wherein the nano-porous metal foil sheet changes along with the changes of dealloying time and the concentration of the dealloying corrosion liquid and is provided with a layered nano-porous structure; calcining the nano-porous metal foil sheet under an atmosphere of acetylene, argon and hydrogen at a temperature of 700-1,000 DEG C, and reducing the temperature of the sample to room temperature under the atmosphere of argon; immersing the obtained product into the corrosion liquid to remove the nano-porous metal, and then washing to obtain a self-supported three-dimensional nano-porous graphene thin film; and enabling manganese dioxide to be uniformly deposited on the surface of the three-dimensional nano-porous graphene through a multi-step current method to obtain the three-dimensional nano-porous graphene/manganese dioxide composite electrode material. By adoption of the preparation method, the volume ratio performance of the electrode material can be improved.
Description
Technical field
The invention belongs to the preparing technical field of nano material, be specifically related to a kind of three-D nano-porous Graphene/manganese dioxide and be combined
The preparation method of electrode material.
Background technology
Along with the exhaustion day by day of fossil energy, people start to be devoted to the R and D of novel energy.Wherein, ultracapacitor
Having charge-discharge velocity fast, the advantages such as service life is long, and power density is big and environmentally friendly get more and more people's extensive concerning,
Also have a very wide range of applications in power vehicle, telecommunications, Aero-Space and military field simultaneously.Tradition electrochemical capacitance point
Hitting material is mostly to be mixed by a certain percentage by powdered active agent, conductive black and insulating polymer colloid to be coated in afterwards
Metal collector surface is made.And being added in of insulating polymer colloid have impact on the electric conductivity of electrode material to a certain extent and follow
Ring stability, also makes can not well contact between active material, thus reduces the high rate performance of electrode material.Therefore, send out
Exhibition self-supporting active electrode material can avoid the incorporation of insulating polymer colloid completely, thus is effectively improved the electrification of electrode material
Learn performance.
At present, carbon nanomaterial is the most frequently used electrochemical capacitance electrode material, and they have good stability and electric conductivity and become
This is cheap, but, carbon nanomaterial there is also the shortcomings such as capacity is low, energy density is low simultaneously.Metal oxide materials is because of it
There is the highest theoretical fake capacitance capacity and become the raising very effective active material of electrochemical capacitance performance.In numerous metal-oxides,
Manganese dioxide has high theoretical specific capacity (～1370F/g) with it, with low cost, and advantages of environment protection becomes most to be applied at present
The fake capacitance active material being worth.But, the electric conductivity of manganese dioxide is the lowest, and cyclical stability is poor, more most important,
Manganese dioxide is difficult to be self-assembly of self supporting structure and is applied in electrochemical capacitance directly as electrode material.Therefore, people start
Carry out the carbon nanomaterial of nano level manganese dioxide Yu self-supporting being combined and prepare electrochemical capacitance electrode material, such as carbon fiber paper,
Carbon cloth etc..Although by the compound quality of electrode material that can largely improve of above material than performance or area ratio performance,
But owing to the carbon fiber diameter of composition carbon fiber paper or carbon cloth is relatively big, and there is the biggest gap each other so that combination electrode
Density reduce, volume increases, thus has had a strong impact on the volume ratio performance of electrode, limits the extensive application of electrode material.
Therefore, find a kind of light weight, specific surface area height, good conductivity and volume insignificant self-supporting carbon nanomaterial come and receive
Meter level manganese dioxide is combined prepares the direction that electrode material is current people effort.
Summary of the invention
For the deficiencies in the prior art, the present invention provides the three-D nano-porous of a kind of volume ratio performance that can improve electrode material
Graphene/manganese dioxide composite electrode material preparation method.The present invention with the three-D nano-porous graphene film of self-supporting as matrix,
By the method for electrochemical deposition in the method for one layer of manganese dioxide of graphenic surface uniform deposition, this preparation process is simple,
With low cost, gained petal-shaped manganese dioxide adheres to uniformly at the surfaces externally and internally of Graphene, and Graphene is at overall combination electrode
In volume be negligible, thus farthest improve the volume ratio performance of electrode material, be suitable for industrialized production.
The present invention solves the technical scheme of described technical problem,
A kind of preparation method of three-D nano-porous Graphene/manganese dioxide composite electrode material, this preparation method following technique of employing:
1) nano porous metal paillon foil is prepared
Take Cu and Mn atomic ratio alloy foil sheet between 1:1 to 1:3, carry out removal alloying process, prepare with going
After the nano porous metal paillon foil of the nano-porous structure with level of alloying time and removal alloying corrosive liquid concentration change,
Clean and dried.
2) the many Graphenes of three-dimensional manometer are prepared
The nano porous metal paillon foil that step 1 prepares is put in quartz boat, quartz boat is placed in reaction tube burner hearth perimeter,
Being passed through acetylene, argon and hydrogen, wherein, acetylene, argon, hydrogen ratio press the flow configuration of 1-20:500:200, by furnace temperature
Rise to 700-1000 DEG C；Quartz boat is quickly moved to flat-temperature zone in the middle part of reaction tube, at this temperature after furnace temperature rises to assigned temperature
Calcine 1-5 minute, after calcining by quartz boat quickly in the middle part of reaction tube flat-temperature zone move to outside burner hearth, and bell is opened,
Under the atmosphere of argon, sample is down to room temperature；Then taking out from tube furnace, immersing proportioning is 10g iron chloride: 10ml hydrochloric acid:
Nano porous metal is removed by the corrosive liquid of 100ml water, subsequently the sample deionized water obtained is cleaned up and i.e. can get certainly
Support three-D nano-porous graphene film；
3) three-D nano-porous Graphene/manganese dioxide composite electrode material is prepared
The three-D nano-porous graphene film that step 2 prepares is placed in three-electrode electro Chemical system, three-D nano-porous graphite
Alkene thin film is working electrode, and platinized platinum is to electrode, and Ag/AgCl is reference electrode, and electrolyte is 0.1-1M
Mn(CH3COO)2·4H2O and 0.1-1M Na2SO4Solution, utilizes multistep current method method at three-D nano-porous graphenic surface
Uniform deposition manganese dioxide；After having deposited, sample is taken out from electrolyte, clean up with deionized water and be i.e. available from
Support three-D nano-porous Graphene/manganese dioxide composite electrode thin film.
Preferably, the preparation method of described three-D nano-porous Graphene/manganese dioxide composite electrode material, its
Being characterised by, utilizing multistep current method method at three-D nano-porous graphenic surface uniform deposition manganese dioxide, method is as follows: first
First, at 0.1-5mA/cm2Electric current under deposit 20-60s, then under 0mA stand 10-30s, such cyclic deposition 10-240
Min, finally the surfaces externally and internally at three-D nano-porous Graphene deposits one layer of manganese dioxide uniformly.Prepare nano porous metal paper tinsel
The removal alloying processing method of sheet is: by being placed in 0.025-0.1M hydrochloric acid solution under described alloy foil sheet room temperature, by utilization
Method carries out removal alloying and processes 30-90 minute, thus prepares with removal alloying time and removal alloying corrosive liquid concentration change
The nano porous metal paillon foil of the nano-porous structure with level.
Compared with prior art, the present invention, with three-D nano-porous Graphene as matrix, utilizes multistep current method to prepare three-dimensional manometer
Porous graphene/manganese dioxide composite electrode thin film.The inventive method has the advantage that (1) technique is simple, with low cost.
Utilize simple electrochemical deposition method can synthesize three-D nano-porous Graphene/manganese dioxide composite electrode, simplify technique stream
Journey, is greatly saved cost；(2) pollution-free, environmental friendliness.Prepare Graphene/manganese dioxide composite electrode at present the most all to make
With potassium permanganate as the presoma of manganese dioxide, easily cause environmental pollution.The present invention need not use any easy system poison with strong
Oxidisability medicine, whole process is carried out in the environment of stable close friend, is a kind of green technology；(3) the used electrification of the present invention
Learn sedimentation and prepare three-D nano-porous Graphene/manganese dioxide composite electrode technical maturity, be suitable for industrial application；(4)
Three-D nano-porous Graphene/manganese dioxide composite electrode obtained by the present invention has self supporting structure, can be without any later stage
Process directly application, significantly expand the application of laminated film.
Accompanying drawing explanation
Fig. 1 is that the present invention prepares three-D nano-porous Graphene/manganese dioxide schematic diagram；
Fig. 2 is the three-D nano-porous Graphene SEM image prepared by the present invention；
Fig. 3 is the three-D nano-porous Graphene/manganese dioxide composite electrode SEM image prepared by the present invention；
Fig. 4 is the three-D nano-porous Graphene/manganese dioxide composite electrode TEM image prepared by the present invention.
The present invention does not addresses part and is applicable to prior art.
The specific embodiment of preparation method of the present invention given below.These embodiments are only used for describing preparation method of the present invention in detail,
It is not limiting as the application scope of the claims.
Detailed description of the invention
The preparation method of the three-D nano-porous Graphene/manganese dioxide composite electrode material of the present invention, below the employing of this preparation method
Technique:
1) nano porous metal is prepared
The Cu selecting thickness to be 10-200um thickness30Mn70、Cu40Mn60Alloy foil sheet (above ratio is atomic ratio), so
After by above alloy foil sheet intercept appropriate size, alloy foil sheet is placed in 0.025-0.1M hydrochloric acid solution under room temperature, by utilization
Method carries out removal alloying and processes 30-90 minute, thus prepares with removal alloying time and removal alloying corrosive liquid concentration change
The nano porous metal paillon foil of the nano-porous structure with level.Prepared nano porous metal paillon foil is first used deionization
Water cleans, then with washes of absolute alcohol, then standby by carrying out vacuum drying 12h under clean nano porous metal paillon foil room temperature.
2) the many Graphenes of three-dimensional manometer are prepared
The nano porous copper that step 1 prepares is put in quartz boat, quartz boat is placed in reaction tube burner hearth perimeter, is passed through second
Alkynes, argon and hydrogen, wherein, acetylene, argon, hydrogen ratio press the flow configuration of 1-20:500:200.Now by furnace temperature liter
To 700-1000 DEG C.After furnace temperature rises to assigned temperature, quartz boat is quickly moved to flat-temperature zone in the middle part of reaction tube, forges at this temperature
Burn 1-5 minute.After calcining by quartz boat quickly in the middle part of reaction tube flat-temperature zone move to outside burner hearth, and bell is opened,
Under the atmosphere of argon, sample is down to room temperature.Then being taken out from tube furnace by sample, immersing proportioning is 10g iron chloride+10ml
Being removed by nano porous metal in the corrosive liquid of hydrochloric acid (containing the concentrated hydrochloric acid of 38% hydrogen chloride)+100ml water, etching time is 12
Hour.Subsequently the sample deionized water obtained is cleaned up and i.e. can get the three-D nano-porous graphene film of self-supporting.
3) three-D nano-porous Graphene/manganese dioxide composite electrode material is prepared
The three-D nano-porous graphene film that step 2 prepares is placed in three-electrode electro Chemical system, three-D nano-porous graphite
Alkene thin film is working electrode, and platinized platinum is to electrode, and Ag/AgCl is reference electrode, and electrolyte is 0.1-1M
Mn(CH3COO)2·4H2O+0.1-1M Na2SO4Solution, utilizes multistep current method method equal at three-D nano-porous graphenic surface
Even deposition petal-shaped manganese dioxide.First, at 0.1-5mA/cm2Electric current under deposit 20-60s, then under 0mA stand
10-30s makes electrolyte can fully diffuse to three-D nano-porous Graphene pore interior.So cyclic deposition 10-240min,
Finally the surfaces externally and internally at three-D nano-porous Graphene can deposit one layer of manganese dioxide uniformly.After having deposited, by sample
Take out from electrolyte, clean up with deionized water and be i.e. available from supporting three-D nano-porous Graphene/manganese dioxide compound electric
Very thin films.
Embodiment 1
Selecting thickness is the Cu of 100um40Mn60Alloy foil sheet, and it is cut into 1*1cm2Size.Then configuration concentration is
The hydrochloric acid solution of 0.05M, immerses alloy foil sheet in hydrochloric acid solution, at room temperature carries out removal alloying, and the removal alloying time is
40 minutes, paillon foil was sequentially passed through deionized water-alcohol washes after terminating by removal alloying, puts in vacuum drying oven after cleaning up,
At room temperature vacuum drying 12 hours, obtain nano porous copper.Put into being dried nano porous copper completely in quartz Noah's ark, and
Noah's ark being placed in reaction tube burner hearth perimeter, is passed through acetylene, argon and hydrogen, the ratio of three kinds of gases is
C2H2:Ar:H2=5:500:200sccm.Meanwhile, tube furnace temperature is risen to 900 DEG C, when furnace temperature arrival 900 DEG C by stone
Britain side's boat is quickly moved to flat-temperature zone in the middle part of reaction tube, at this temperature reaction 2 minutes outside burner hearth.After reaction reception terminates,
By quartz boat, quickly in the middle part of reaction tube, flat-temperature zone moves to outside burner hearth, and is opened by bell, closes acetylene and hydrogen, at argon
Atmosphere under sample is down to room temperature.Then being taken out from tube furnace by sample, immersing proportioning is 10g iron chloride+10ml hydrochloric acid
Being removed by nano porous copper in the corrosive liquid of+100ml water, etching time is 12 hours.The sample deionization that will obtain subsequently
Water cleans up and obtains the three-D nano-porous graphene film of self-supporting.Then three-D nano-porous Graphene is placed in three electrode body
In system, platinized platinum is to electrode, and Ag/AgCl is reference electrode, and electrolyte is 0.2M Mn (CH3COO)2·4H2O+0.2M
Na2SO4Solution, first at 0.5mA/cm2Electric current under deposit 20s, then under 0mA stand 10s make electrolyte energy
Enough fully diffuse to three-D nano-porous Graphene pore interior, then at 0.5mA/cm2Electric current under deposit 20s, so circulate
Deposition 60min, deposits one layer of manganese dioxide uniformly at three-D nano-porous graphenic surface.After having deposited, by sample from electricity
Solve in liquid and take out, clean up with deionized water that to be i.e. available from supporting three-D nano-porous Graphene/manganese dioxide composite electrode thin
Film.
Embodiment 2
Selecting thickness is the Cu of 50um30Mn70Alloy foil sheet, and it is cut into 2*1cm2Size.Then configuration concentration is
The hydrochloric acid solution of 0.025M, immerses alloy foil sheet in hydrochloric acid solution, at room temperature carries out removal alloying, and the removal alloying time is
60 minutes, paillon foil was sequentially passed through deionized water-alcohol washes after terminating by removal alloying, puts in vacuum drying oven after cleaning up,
At room temperature vacuum drying 12 hours, obtain nano porous copper.Put into being dried nano porous copper completely in quartz Noah's ark, and
Noah's ark being placed in reaction tube burner hearth perimeter, is passed through acetylene, argon and hydrogen, the ratio of three kinds of gases is
C2H2:Ar:H2=20:500:200sccm.Meanwhile, tube furnace temperature is risen to 800 DEG C, when furnace temperature arrival 800 DEG C by stone
Britain side's boat is quickly moved to flat-temperature zone in the middle part of reaction tube, at this temperature reaction 1 minute outside burner hearth.After reaction reception terminates,
By quartz boat, quickly in the middle part of reaction tube, flat-temperature zone moves to outside burner hearth, and is opened by bell, closes acetylene and hydrogen, at argon
Atmosphere under sample is down to room temperature.Then being taken out from tube furnace by sample, immersing proportioning is 10g iron chloride+10ml hydrochloric acid
Being removed by nano porous copper in the corrosive liquid of+100ml water, etching time is 12 hours.The sample deionization that will obtain subsequently
Water cleans up and obtains the three-D nano-porous graphene film of self-supporting.Then three-D nano-porous Graphene is placed in three electrode body
In system, platinized platinum is to electrode, and Ag/AgCl is reference electrode, and electrolyte is 0.1M Mn (CH3COO)2·4H2O+2M Na2SO4
Solution, first at 0.1mA/cm2Electric current under deposit 60s, under 0mA, then stand 30s make the electrolyte can be abundant
Diffuse to three-D nano-porous Graphene pore interior, then at 0.1mA/cm2Electric current under deposit 60s, such cyclic deposition
30min, deposits one layer of manganese dioxide uniformly at three-D nano-porous graphenic surface.After having deposited, by sample from electrolyte
Middle taking-up, cleans up with deionized water and is i.e. available from supporting three-D nano-porous Graphene/manganese dioxide composite electrode thin film.
Embodiment 3
Selecting thickness is the Cu of 100um40Mn60Alloy foil sheet, and it is cut into 1*1cm2Size.Then configuration concentration is
The hydrochloric acid solution of 0.5M, immerses alloy foil sheet in hydrochloric acid solution, at room temperature carries out removal alloying, and the removal alloying time is 60
Minute, paillon foil is sequentially passed through deionized water-alcohol washes after terminating by removal alloying, puts in vacuum drying oven after cleaning up,
At room temperature vacuum drying 12 hours, obtain nano porous copper.Put into being dried nano porous copper completely in quartz Noah's ark, and
Noah's ark being placed in reaction tube burner hearth perimeter, is passed through acetylene, argon and hydrogen, the ratio of three kinds of gases is
C2H2:Ar:H2=1:500:200sccm.Meanwhile, tube furnace temperature is risen to 1000 DEG C, will when furnace temperature arrival 1000 DEG C
Quartz Noah's ark is quickly moved to flat-temperature zone in the middle part of reaction tube, at this temperature reaction 1 minute outside burner hearth.After reaction reception terminates,
By quartz boat, quickly in the middle part of reaction tube, flat-temperature zone moves to outside burner hearth, and is opened by bell, closes acetylene and hydrogen, at argon
Atmosphere under sample is down to room temperature.Then being taken out from tube furnace by sample, immersing proportioning is 10g iron chloride+10ml hydrochloric acid
Being removed by nano porous copper in the corrosive liquid of+100ml water, etching time is 12 hours.The sample deionization that will obtain subsequently
Water cleans up and obtains the three-D nano-porous graphene film of self-supporting.Then three-D nano-porous Graphene is placed in three electrode body
In system, platinized platinum is to electrode, and Ag/AgCl is reference electrode, and electrolyte is 0.5M Mn (CH3COO)2·4H2O+0.2M
Na2SO4Solution, first at 1mA/cm2Electric current under deposit 30s, under 0mA, then stand 30s make the electrolyte can
Fully diffuse to three-D nano-porous Graphene pore interior, then at 1mA/cm2Electric current under deposit 30s, such cyclic deposition
120min, deposits one layer of manganese dioxide uniformly at three-D nano-porous graphenic surface.After having deposited, by sample from electrolysis
Liquid takes out, cleans up with deionized water and be i.e. available from supporting three-D nano-porous Graphene/manganese dioxide composite electrode thin film.
Embodiment 4
Selecting thickness is the Cu of 200um30Mn70Alloy foil sheet, and it is cut into 2*1cm2Size.Then configuration concentration is
The hydrochloric acid solution of 0.1M, immerses alloy foil sheet in hydrochloric acid solution, at room temperature carries out removal alloying, and the removal alloying time is 90
Minute, paillon foil is sequentially passed through deionized water-alcohol washes after terminating by removal alloying, puts in vacuum drying oven after cleaning up,
At room temperature vacuum drying 12 hours, obtain nano porous copper.Put into being dried nano porous copper completely in quartz Noah's ark, and
Noah's ark being placed in reaction tube burner hearth perimeter, is passed through acetylene, argon and hydrogen, the ratio of three kinds of gases is
C2H4:Ar:H2=5:500:200sccm.Meanwhile, tube furnace temperature is risen to 1050 DEG C, will when furnace temperature arrival 1050 DEG C
Quartz Noah's ark is quickly moved to flat-temperature zone in the middle part of reaction tube, at this temperature reaction 5 minutes outside burner hearth.After reaction reception terminates,
By quartz boat, quickly in the middle part of reaction tube, flat-temperature zone moves to outside burner hearth, and is opened by bell, closes acetylene and hydrogen, at argon
Atmosphere under sample is down to room temperature.Then being taken out from tube furnace by sample, immersing proportioning is 10g iron chloride+10ml hydrochloric acid
Being removed by nano porous copper in the corrosive liquid of+100ml water, etching time is 12 hours.The sample deionization that will obtain subsequently
Water cleans up and obtains the three-D nano-porous graphene film of self-supporting.Then three-D nano-porous Graphene is placed in three electrode body
In system, platinized platinum is to electrode, and Ag/AgCl is reference electrode, and electrolyte is 1M Mn (CH3COO)2·4H2O+0.2M Na2SO4
Solution, first at 0.5mA/cm2Electric current under deposit 20s, under 0mA, then stand 10s make the electrolyte can be abundant
Diffuse to three-D nano-porous Graphene pore interior, then at 0.5mA/cm2Electric current under deposit 30s, such cyclic deposition
240min, deposits one layer of manganese dioxide uniformly at three-D nano-porous graphenic surface.After having deposited, by sample from electrolysis
Liquid takes out, cleans up with deionized water and be i.e. available from supporting three-D nano-porous Graphene/manganese dioxide composite electrode thin film.
Claims (3)
1. a preparation method for three-D nano-porous Graphene/manganese dioxide composite electrode material, this preparation method following technique of employing:
1) nano porous metal paillon foil is prepared
Take Cu and Mn atomic ratio alloy foil sheet between 1:1 to 1:3, carry out removal alloying process, prepare with the removal alloying time and
After the nano porous metal paillon foil of the nano-porous structure with level of removal alloying corrosive liquid concentration change, clean and dried.
2) the many Graphenes of three-dimensional manometer are prepared
The nano porous metal paillon foil that step 1 prepares is put in quartz boat, quartz boat is placed in reaction tube burner hearth perimeter, is passed through acetylene, argon
Gas and hydrogen, wherein, acetylene, argon, hydrogen ratio press the flow configuration of 1-20:500:200, and furnace temperature is risen to 700-1000 DEG C；Treat furnace temperature liter
Quartz boat is quickly moved to assigned temperature flat-temperature zone in the middle part of reaction tube, and calcining 1-5 minute, quick by quartz boat after calcining at this temperature
In the middle part of reaction tube, flat-temperature zone moves to outside burner hearth, and is opened by bell, under the atmosphere of argon, sample is down to room temperature；Then take from tube furnace
Going out, immersing proportioning is 10g iron chloride: 10ml hydrochloric acid: removed by nano porous metal in the corrosive liquid of 100ml water, is used by the sample obtained subsequently
Deionized water cleans up and i.e. can get the three-D nano-porous graphene film of self-supporting；
3) three-D nano-porous Graphene/manganese dioxide composite electrode material is prepared
Being placed in three-electrode electro Chemical system by the three-D nano-porous graphene film that step 2 prepares, three-D nano-porous graphene film is work
Electrode, platinized platinum is to electrode, and Ag/AgCl is reference electrode, and electrolyte is 0.1-1M Mn (CH3COO)2·4H2O and 0.1-1M Na2SO4
Solution, utilizes multistep current method method at three-D nano-porous graphenic surface uniform deposition manganese dioxide；After having deposited, by sample from electrolyte
Take out, clean up with deionized water and be i.e. available from supporting three-D nano-porous Graphene/manganese dioxide composite electrode thin film.
The preparation method of three-D nano-porous Graphene/manganese dioxide composite electrode material the most according to claim 1, it is characterised in that profit
By multistep current method method at three-D nano-porous graphenic surface uniform deposition manganese dioxide, method is as follows: first, at 0.1-5mA/cm2Electric current
Lower deposition 20-60s, then stands 10-30s under 0mA, and such cyclic deposition 10-240min, finally in three-D nano-porous Graphene
Outer surface deposits one layer of manganese dioxide uniformly.
The preparation method of three-D nano-porous Graphene/manganese dioxide composite electrode material the most according to claim 1, it is characterised in that system
The removal alloying processing method of standby nano porous metal paillon foil is: will be placed in 0.025-0.1M hydrochloric acid solution under described alloy foil sheet room temperature, will
Utilize chemical method to carry out removal alloying to process 30-90 minute, thus prepare having with removal alloying time and removal alloying corrosive liquid concentration change
The nano porous metal paillon foil of the nano-porous structure of level.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610084136.4A CN105719852A (en) | 2016-02-04 | 2016-02-04 | Preparation method for three-dimensional nano-porous graphene/manganese dioxide composite electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610084136.4A CN105719852A (en) | 2016-02-04 | 2016-02-04 | Preparation method for three-dimensional nano-porous graphene/manganese dioxide composite electrode material |
Publications (1)
| Publication Number | Publication Date |
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| CN106927418A (en) * | 2017-03-29 | 2017-07-07 | 广东工业大学 | A kind of micro-nano engine and preparation method thereof |
| CN107416807A (en) * | 2017-08-28 | 2017-12-01 | 天津大学 | A kind of preparation method of the three-D nano-porous graphene of nitrogen oxygen codope |
| CN107502886A (en) * | 2017-07-13 | 2017-12-22 | 天津大学 | The preparation method of fabricated in situ sheet metal hydroxide/oxide composite |
| CN107644743A (en) * | 2017-08-25 | 2018-01-30 | 天津大学 | A kind of preparation method of the three-dimensional porous nitrogen-doped graphene of self-supporting-nickel hydroxide electrochemical capacitance electrode material |
| CN107785586A (en) * | 2017-09-19 | 2018-03-09 | 天津大学 | Three-dimensional porous copper/graphene composite current collector for secondary metals cathode of lithium battery |
| CN108242530A (en) * | 2016-12-23 | 2018-07-03 | 北京好风光储能技术有限公司 | A kind of lithium slurry battery and its negative plate |
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| CN110706939A (en) * | 2019-09-06 | 2020-01-17 | 暨南大学 | Nano porous nickel alloy/manganese dioxide electrode material and preparation method and application thereof |
| CN110706938A (en) * | 2018-07-10 | 2020-01-17 | 中国科学院上海硅酸盐研究所 | Preparation method of supercapacitor electrode material |
| CN110970234A (en) * | 2019-11-20 | 2020-04-07 | 南通纺织丝绸产业技术研究院 | Preparation method of vinylon fabric-based graphene/manganese dioxide electrode material |
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| CN108242530A (en) * | 2016-12-23 | 2018-07-03 | 北京好风光储能技术有限公司 | A kind of lithium slurry battery and its negative plate |
| CN106927418A (en) * | 2017-03-29 | 2017-07-07 | 广东工业大学 | A kind of micro-nano engine and preparation method thereof |
| CN107502886A (en) * | 2017-07-13 | 2017-12-22 | 天津大学 | The preparation method of fabricated in situ sheet metal hydroxide/oxide composite |
| CN107644743A (en) * | 2017-08-25 | 2018-01-30 | 天津大学 | A kind of preparation method of the three-dimensional porous nitrogen-doped graphene of self-supporting-nickel hydroxide electrochemical capacitance electrode material |
| CN107416807A (en) * | 2017-08-28 | 2017-12-01 | 天津大学 | A kind of preparation method of the three-D nano-porous graphene of nitrogen oxygen codope |
| CN107785586A (en) * | 2017-09-19 | 2018-03-09 | 天津大学 | Three-dimensional porous copper/graphene composite current collector for secondary metals cathode of lithium battery |
| CN108831750A (en) * | 2018-05-24 | 2018-11-16 | 天津大学 | Three-dimensional porous Ni-Co film/CoMoO4The preparation method of composite material |
| CN110706938A (en) * | 2018-07-10 | 2020-01-17 | 中国科学院上海硅酸盐研究所 | Preparation method of supercapacitor electrode material |
| CN110706939A (en) * | 2019-09-06 | 2020-01-17 | 暨南大学 | Nano porous nickel alloy/manganese dioxide electrode material and preparation method and application thereof |
| CN111009644A (en) * | 2019-11-13 | 2020-04-14 | 天津工业大学 | Preparation method of nano-porous copper surface modified MnO/graphene composite electrode |
| CN111009644B (en) * | 2019-11-13 | 2023-09-22 | 天津工业大学 | Preparation method of nano-porous copper surface modified MnO/graphene composite electrode |
| CN110970234A (en) * | 2019-11-20 | 2020-04-07 | 南通纺织丝绸产业技术研究院 | Preparation method of vinylon fabric-based graphene/manganese dioxide electrode material |
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