CN107630206A - The preparation method and application of array carbon nano tube foam metal composite base plate - Google Patents
The preparation method and application of array carbon nano tube foam metal composite base plate Download PDFInfo
- Publication number
- CN107630206A CN107630206A CN201710893017.8A CN201710893017A CN107630206A CN 107630206 A CN107630206 A CN 107630206A CN 201710893017 A CN201710893017 A CN 201710893017A CN 107630206 A CN107630206 A CN 107630206A
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- nano tube
- foam metal
- base plate
- array carbon
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of preparation method and application of array carbon nano tube foam metal composite base plate, belong to technical field of function materials.Specifically include growth array carbon nano tube and corona treatment is made to its surface, clean foam metal substrate, apply suitable normal pressure using tablet press machine array carbon nano tube and foam metal mechanics is compound, you can obtain array carbon nano tube foam metal composite base plate.Compared with traditional energy storage device electrode material such as foam metal, CNT base composite base plate prepared by the inventive method greatly improves the specific surface area of electrode, solve active material and conductive network loose contact, stick insecure the problems such as easily coming off, the structural stability and pliability of electrode system are added, while improves the impact resistance and security of electrode.The array carbon nano tube foam metal composite base plate being prepared is used for ultracapacitor field, the electrode being prepared has the cyclical stability of superelevation.
Description
Technical field
The invention belongs to field of functional materials, and in particular to a kind of preparation of array carbon nano tube foam metal composite base plate
The application of method and the composite base plate in energy device.
Background technology
In the application of energy storage device, because of the features such as its density is small, porosity is high, specific surface area the is big and normal quilt of foam metal
As electrode base board；Its network structure can provide good conduction and support for active material, and the three-dimensional structure of its perforate can
As electrolyte passage, be advantageous to ion transmission.However, traditional foam metal hydrophily is poor, make to stick the work on it
The electrolyte to be circulated between property material and its space can not fully react, and cause electrode capacity low.Electrode device preparation and
During use, because the adhesion strength of active material and foam metal is inadequate, the stability operation of device, cycle life have impact on
It is limited.
CNT is because of the draw ratio of its superelevation（10,000 ~ 100,0000）And with the incomparable height of traditional material
Specific surface area（100~2300）, the excellent properties such as mechanics pliability, high conductivity.Especially by Base Plate Process, carbon is received
Mitron is prepared into the array carbon nano tube macroscopic assemblies perpendicular to substrate growth（Macroscopic Assembly）And apply
When electronic device or energy device, its orderly arrangement architecture contributes to quickening and the electrode site activity of electric transmission speed
Lifting.In addition the specific surface area of its superelevation is more conducive to the infiltration of electrolyte with array form, adds living in electrode system
Contact of the property material with electrolyte, improves reaction efficiency between the two.Meanwhile array carbon nano tube has dutycycle height（>
98%）, Ultra light-weight the advantages that, can greatly lift electrode base board or collection in the case where not increasing electrode system total quality
The utilization rate of fluid volume.However, during the preparation and use of electrode device, the array structure of array carbon nano tube is easy
Destroyed, its above-mentioned advantage is played completely, limit its further application in energy field.Therefore, before
The Applied D emonstration of disclosed CNT in the electrodes, obtained more by scattered, solwution method mixing etc.；The arrangement of CNT
Form is that unordered shape is entwined state.As patent CN103434207A proposes that CNT is dispersed into organic solvent then passes through electricity
The method of swimming deposition is deposited on carbon nano-tube film in nickel foam, although or as patent CN104868134A pass through it is direct
Foamed metal catalyst and then the astaticism CNT grown are deposited on polymeric base material.
The content of the invention
It is an object of the invention to provide a kind of array carbon nano tube foam metal composite base that can be applied in energy device
The preparation method of plate.The substrate can effectively improve electrode material electro-chemical activity and cyclical stability, and obtained substrate has
Certain shock resistance.Meanwhile the preparation process being related to is simple, it is easy to commercialization to mass produce.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of array carbon nano tube foam metal composite base plate, comprises the following steps：
Step 1, foam metal substrate is cleaned, removes oxide on surface；Vacuum drying chamber is put into after washing to be dried for standby；
Step 2, array carbon nano tube is grown using chemical vapour deposition technique, its height of accuracy controlling is to higher than foam metal thickness
Degree；Array carbon nano tube is put into plasma cleaner and carries out surface etch, removes the twister on array carbon nano tube surface,
Obtain acicular texture；
Step 3, the top of step 2 gained array carbon nano tube or bottom are vertically arranged in step 1 gained foam metal substrate
Side or lower section, it is put into tablet press machine and carries out pressing processing.
In step 1, the metal of foam metal substrate is copper, nickel, silver, iron, copper alloy, nickel alloy or aluminium alloy.
In step 1, porosity 90%-95%, pore size 0.15-6mm in foam metal substrate.
In step 2, array carbon nano tube is one kind in single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube
It is or several compound.
In step 2, the caliber of array carbon nano tube is 2-50nm, and the height of array carbon nano tube is more than 50 μm.
In step 2, the atmosphere of plasma etching is one or more of combinations in argon gas, oxygen and air, gas
- the 500mL/min of body flow 100.
In step 2, the power of plasma cleaner is 1-1000 W.
In step 3, the stamping pressure of tablet press machine is 1- 40MPa.
A kind of array carbon nano tube foam metal composite base plate, is prepared by above-mentioned preparation method.
In the application in energy device field, the energy device includes above-mentioned array carbon nano tube foam metal composite base plate
Ultracapacitor, lithium ion battery, the electrode base board of nickel-based battery and fuel cell.
Present invention firstly provides with the compound concept of the mechanics of array carbon nano tube and foam metal, it is intended to compound to prepare
Destruction of the step such as scattered to array form is avoided in journey；And it is support frame to utilize foam metal, suppresses array carbon nano tube
Because the characteristic of itself high-specific surface area and caused by the structure collapse in electrolyte solution the problems such as, as far as possible keep array carbon receive
The structural intergrity of mitron；Meanwhile array carbon nano tube preparation proposed by the present invention has high precision controllable, with foam metal
The technical characteristic that thickness matches, array structure extending transversely through on foam metal support can be obtained（Fig. 1）, farthest
Play the electronics conductive advantages of array carbon nano tube；It is and by the adhesion of array carbon nano tube that active material is further solid
It is fixed, it is added significantly to the cyclical stability of device.In addition, the present invention also demonstrates array carbon nano tube and device is provided with bendable
The performances such as folding, shock resistance.Every advantage as described above is that previously disclosed any structure and preparation method are unable to reach
's（Fig. 2）.
The present invention compared with prior art, has the advantages that：
First, inventive process avoids customary preparation methods（Such as scattered, liquid deposition）To array carbon nanotube structural damage, not
In the case of changing carbon pipe microscopic characteristics, the array structure of CNT is maintained；In addition in array carbon nano tube preparation
It is precisely controlled, obtains array structure and be continuous through in foam metal transverse direction, plays the excellent of its electronics conduction to greatest extent
Gesture, be advantageous to the further release of electrode performance, it is specific as follows：
Array carbon nano tube can carry out vertical orderly electric transmission, and vertical orderly electric transmission is more efficient certainly
, and unordered CNT can only carry out unordered electric transmission, inventor did the experiment similar to unordered CNT, performance
It is more far short of what is expected than array carbon nano tube；
Electrode performance refers to that Conventional electrochemical is tested, and needs quick electronics to shift in test process, to conduction needs very
Height, therefore array carbon nano tube electric conductivity vertical direction order transfer, it is more advantageous.
2nd, the present invention is removed array carbon nano tube surface wrap thing, obtained by the surface treatment to array carbon nano tube
Acicular texture；The pattern for being formed as its bottom grown of array carbon nano tube surface wrap thing, in early growth period catalyst
The difference of activationary time, lead to not produce orientation；The process is usually 0.5 ~ 1 minute, and twister is highly 10 μm or so；
In mechanics recombination process, twister can block foam metal hole, hinder the complete insertion of array carbon nano tube, while also can shadow
Ring effective transmission of electronics vertical direction in duct.And the situation that plasma etching is not destroyed in guarantee array body
Under, surface wrap thing is removed, is advantageous to obtain vertical direction biography that is uniform compound with foam metal, while being advantageous to electronics
It is defeated.
3rd, array carbon nano tube foam metal composite base plate of the invention, using array carbon nano tube in pipe range advantage, shape
Into perforation effect, the space for substantially increasing foam metal utilizes, and with reference to the specific surface area advantage of carbon pipe in itself, makes electrode body
System has more preferable effect of impregnation.It is specific as follows：
The infiltration of electrolyte would generally influence the utilization to electrode base board effective volume；And electrolyte needs and electrode material contacts
Competence exertion effectiveness.For energy storage device, too low surface density can cause the infiltration for having an impact electrolyte of capillary force,
It is unfavorable for the performance of battery performance；The infiltration of material is relevant with the hydrophily of material.The hydrophily of foam metal is not so good as array carbon
Nanotube, therefore, the introducing of array carbon nano tube can regulate and control the hydrophily of array carbon nano tube foam metal composite base plate, enter
And regulate and control the infiltration of electrolyte, utilized so as to improve the volume of foam metal.
The loading of active material depends on the specific surface area of electrode material.Specific surface area of carbon nanotube is foam metal
10 ~ 50 times, equivalent to the specific surface area for greatly improving electrode system in the carbon nano-tube filled loose structure to foam metal；
The filling of active material can utilize foam metal and array carbon nano tube both sides specific surface area, larger make use of foam
The effective volume of metal；By conventional plating means, in the surface electrode active material of electrode base board, this part is attached to bubble
The structured surface of foam metal and array carbon nano tube institute, takes full advantage of the high-specific surface area of array carbon nano tube, therefore carry
The volume of high foam metal utilizes.
4th, array carbon nano tube foam metal composite base plate of the invention, compared to answering for other CNT foam metals
Close substrate（Patent CN103434207A）, because the adhesion of array carbon nano tube can further fix active material,
With bending resistance, while electrode prepared by array carbon nano tube foam metal composite base plate has well in electrolyte
Stability, it is specific as follows：
Array carbon nano tube foam metal composite base plate has bending resistance because of the adhesion of array carbon nano tube and mechanical performance
Folding endurance energy；
Aforementioned stable refers to the stability of electrode mechanical structure, compared to patent CN103434207A and patent
CN104868134A, array carbon nano tube of the invention, which has, to be sticked and array structure, adhesive attraction can consolidate active material
It is fixed, therefore structure is more firm；
Realize its adhesiveness often by the infiltration of itself and substrate surface different from common adhesion material, CNT with
The adhesion of substrate surface is that realization is brought into close contact with base material roughness at different levels, so as to reach by the flexibility of CNT itself
To adhesiving effect, this is very much like with the hierarchical level absorption in gecko vola；However, with the increase of base surface roughness,
The adhesion on array carbon nano tube and block materials surface will be introduced mechanical sealed due to the increase of contact area, and these are all
To be different under normal temperature merely with the new mechanism of Van der Waals force adhesion；And these are equally applicable to array carbon nano tube and three-dimensional
The research of foam metal.
5th, array carbon nano tube structure（Highly, arrangement degree, caliber, tube wall etc.）It is controllable, can be according to the bubble of different size
Foam metal pointedly carries out the structurally-modified of correlation, regulates and controls height, the caliber of array carbon nano tube structure, density, arrangement degree
Etc. parameter；The array carbon nano tube of Heteroatom doping can be equally prepared before compound, and then carries out the knot of array carbon nano tube
Structure regulates and controls.Further, we can also realize the regulation and control to composite base plate by the regulation and control of the structure to array carbon nano tube, right
Energy field tool is of great significance.
6th, the array structure of array carbon nano tube is easy to cave in, and three-dimensional metal foam structures can fix array carbon and receive
Mitron, so as to play a part of maintaining the stabilization of the array structure of array carbon nano tube.Simultaneously as array carbon nano tube is anti-
Impact capacity can make device have certain shock resistance.
Brief description of the drawings
Fig. 1 composite base plate schematic diagrames, wherein：A is array carbon nano tube foam metal composite base plate schematic diagram；B is composite base
Plate micro-structure diagram.Array carbon nano tube can run through foam metal, form conductive network, promote electric transmission.
Fig. 2 is contrast composite base plate schematic diagram, wherein：A is the directly pressing of common CNT powder and foam metal is compound shows
It is intended to；B is CVD directly in foam metal superficial growth carbon pipe schematic diagram.Compared to two kinds contrast composite base plates, array carbon nanometer
Pipe can run through whole foam metal, form conductive network.
Fig. 3 is the SEM pictures of composite base plate prepared by the embodiment of the present invention 2, wherein：A is the SEM pictures of composite base plate；
B is array carbon nano tube SEM pictures in composite base plate；C is composite base plate SEM pictures；D is top array carbon nano tube surface
SEM pictures after twister removal.
Fig. 4 is non-array CNT and the compound SEM pictures of foam metal, wherein：A schemes for low power composite base plate SEM
Piece；B is the microcosmic SEM pictures of non-array CNT.
Fig. 5 is the compound schematic diagram of array carbon nano tube foam metal, wherein：A is the array carbon nano tube table of initial growth
There is twister in face；B is that plasma removing twister obtains acicular texture；C is advantageous to compound with foam metal for acicular texture.
The Bending Stability IV test charts for the composite base plate electrode material that Fig. 6 is prepared for the embodiment of the present invention 1, IV after bending
The constant explanation adhesion effect of curve.
Fig. 7 is the electrochemical stability of composite base plate electrode material prepared by the embodiment of the present invention 2, and not compound CNT pairs
Than illustrating electrode base board stability.
Fig. 8 is the cyclic voltammetry of composite base plate electrode material prepared by the embodiment of the present invention 3.
Fig. 9 is the shock resistance test curve of composite base plate prepared by the embodiment of the present invention 4.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not
It is limited only to the following examples.
Following examples unless specific instructions, the commercially available chemical reagent of reagent or industrial products of use.
Following examples are together simply referred to as array for convenience of description, by array carbon nano tube and the compound substrate of foam metal
Composite base plate；The foam metal substrate compound not with CNT is together simply referred to as foam metal substrate.
Embodiment 1
1. select porosity 95%, pore size 6mm nickel foam（Thickness 1.4mm）, it is Ni-based using 1M HCl soak at room temperature foams
Bottom 1h, oxide on surface is removed, foam nickel material size is 0.5*3 cm2, vacuum drying chamber drying is put into after deionization washing
It is standby；
2. using Fe, Ni catalyst, CH is used4As reacting gas, 700 DEG C of reaction temperature, reaction time 20min, pass through chemistry
2000 μm of vapour deposition process growing height, caliber 20nm array carbon nano tube, array carbon nano tube is entered under oxygen atmosphere
Row 18W 20s plasma etching, the mL/min of gas flow 200；
3. the array carbon nano tube obtained by step 2 is vertically arranged in above the nickel foam obtained after step 1 is cleaned, by two
Person is placed in tablet press machine middle part, then carries out the processing of 40MPa pressure, keeps 1min.Array carbon nano tube and nickel foam
Compound schematic diagram is as shown in Figure 5.Array composite base plate crooked test is carried out from CHI electrochemical workstations, by array composite base
Plate is bent, and tests differently curved angle i-v curve.Test curve is as shown in Figure 6.Such as figure, differently curved angle
Electric current and voltage under 0 °, 60 °, 90 °, 120 °, 180 ° keep constant, it is known that array composite base plate has stability.
4. doing anode with platinum electrode, negative electrode is done with array composite base plate after bending, is put into 0.1 M Ni (NO3)3Electrolyte
Middle connection constant voltage source, the parallel spacing at negative and positive the two poles of the earth is 1 cm, the V of voltage -1, the s of sedimentation time 30, takes out negative electrode material
Material, dry, obtain array composite base plate electrode material.
5. being tested from CHI electrochemical workstations, the electrode material that step 4 is obtained is put into 1M KOH, is chosen
Hg/HgO carries out electro-chemical test as reference electrode, it is found that electrode material made from array composite base plate after bending can expire
Sufficient test request.
Embodiment 2
1. selecting porosity 90%, pore size 0.2mm nickel foam (thickness 0.5mm), 1M HCl soak at room temperature foam nickel is used
Substrate 1h, oxide on surface is removed, foam nickel material size is 0.5*3 cm2, vacuum drying chamber baking is put into after deionization washing
It is dry standby；
2. using Fe, Ni catalyst, CH is used4As reacting gas, 700 DEG C of reaction temperature, reaction time 12min, chemistry is used
The array carbon nano tube of 800 μm of vapour deposition process growing height, the nm of caliber 2, array carbon nano tube is entered under air atmosphere
Row 50W 20s plasma etching, the mL/min of gas flow 300；
3. the array carbon nano tube obtained by step 2 is vertically arranged in above the nickel foam obtained after step 1 is cleaned, by two
Person is placed in tablet press machine middle part, then carries out the processing of 1MPa pressure, keeps 1min, obtains array composite base plate.
The pattern of the array composite base plate prepared with SEM observations by above-mentioned steps 1,2 and 3, as shown in Figure 3.
As the comparative example of embodiment 2, the nm of caliber 2 non-array CNT is vertically arranged in after step 1 cleans
Above obtained nickel foam, the two is placed in tablet press machine middle part, then carries out the processing of 1MPa pressure, 1min is kept, obtains
To non-composite foam metal substrate.With SEM observe the comparative example prepare non-array CNT and foam metal it is compound
The pattern of sample, as shown in Figure 4.The obtained composite base plate of the complex method and uneven is understood by SEM image.
4. doing anode with platinum electrode, negative electrode is made with array composite base plate and foam metal substrate respectively, is put into 0.1 M Mn
(Ac)2Constant voltage source is connected in electrolyte, the parallel spacing at negative and positive the two poles of the earth is 1 cm, the V of voltage 1, the s of sedimentation time 30, is taken
Go out cathode material, dry, obtain array composite base plate electrode material and foam metal electrode of substrate material.
5. being tested from CHI electrochemical workstations, the electrode material that step 4 is obtained is put into 0.5M Na2SO4In,
Choose Ag/AgCl and carry out electro-chemical test as reference electrode.Test result is as shown in fig. 7, the electrode material of array composite base plate
The circle of material test 10000 is not decayed（See in Fig. 7 and use circle point curve）, and the test decay of the electrode material of foam metal substrate is fast
Speed（The square point curve seen in Fig. 7）, illustrate facilitation of the array composite base plate to electrochemical stability.
Embodiment 3
1. selecting porosity 90%, pore size 0.15mm (thickness 0.1mm) nickel foam, 1M HCl soak at room temperature foams are used
Nickel substrate 1h, oxide on surface is removed, foam nickel material size is 0.5*3 cm2, vacuum drying chamber is put into after deionization washing
It is dried for standby；
2. using Fe, Ni catalyst, CH is used4As reacting gas, 700 DEG C of reaction temperature, reaction time 5min, chemistry is used
The array carbon nano tube of 150 μm of vapour deposition process growing height, the nm of caliber 20, array carbon nano tube is entered under air atmosphere
Row 1W 100s plasma etching, the mL/min of gas flow 100；
3. the array carbon nano tube obtained by step 2 is vertically arranged in above the nickel foam obtained after step 1 is cleaned, by two
Person is placed in tablet press machine middle part, then carries out the processing of 10MPa pressure, keeps 1min.
4. doing anode with platinum electrode, negative electrode is made with array composite base plate, is put into 0.1 M Co (NO3)2Connected in electrolyte
Constant voltage source, the parallel spacing at negative and positive the two poles of the earth is 1 cm, the V of voltage -1, the s of sedimentation time 60, takes out cathode material, dries,
Obtain array carbon nano tube foam metal composite base electrode material.
5. being tested from CHI electrochemical workstations, the electrode material that step 4 is obtained is put into 1M KOH, is chosen
Hg/HgO carries out electro-chemical test as reference electrode.Cyclic voltammetry result is as shown in figure 8, obtain cyclic voltammetry knot
Fruit does not occur compared with Strong oxdiative reduction peak, illustrating that array composite base plate have impact on the facilitation of electric transmission array structure
The course of reaction.
Embodiment 4
1. selecting porosity 92%, pore size 0.2mm (thickness 0.45mm) foam copper, 50 DEG C of immersion foams of 1M HCl are used
Nickel substrate 1h, oxide on surface is removed, foam nickel material size is 0.5*3 cm2, vacuum drying chamber is put into after deionization washing
It is dried for standby；
2. using Fe, Ni catalyst, CH is used4As reacting gas, 700 DEG C of reaction temperature, reaction time 10min, chemistry is used
The array carbon nano tube of 600 μm of vapour deposition process growing height, the nm of caliber 20, array carbon nano tube is entered under argon atmosphere
Row 1000W 2s plasma etching, the mL/min of gas flow 500；
3. the array carbon nano tube obtained by step 2 is vertically arranged in above the nickel foam obtained after step 1 is cleaned, by two
Person is placed in tablet press machine middle part, then carries out the processing of 30MPa pressure, keeps 1min.By gained array composite base plate and bubble
Foam metal substrate carries out shock resistance test respectively, and related data, shock resistance test curve such as Fig. 9 institutes are recorded using mechanics sensor
Show.As illustrated, the response curve of array composite base plate（See Grey curves in Fig. 9）Less than the response curve of foam metal substrate
（See black curve in Fig. 9）, illustrate that array composite base plate has more preferable shock resistance.
4. doing anode with platinum electrode, negative electrode is made with the array composite base plate Jing Guo shock-testing, is put into 0.1 M Ni
(NO3)2Connect constant voltage source in electrolyte, the parallel spacing at negative and positive the two poles of the earth is 1 cm, the V of voltage -1, the s of sedimentation time 80,
Cathode material is taken out, dries, obtains array carbon nano tube foam metal composite base electrode material.
5. being tested from CHI electrochemical workstations, the electrode material that step 4 is obtained is put into 1M KOH, is chosen
Hg/HgO carries out electrochemistry liberation of hydrogen test as reference electrode, illustrates that the array composite base plate after shock-testing can still provide for
Electrocatalytic hydrogen evolution is tested.
Claims (10)
1. a kind of preparation method of array carbon nano tube foam metal composite base plate, it is characterised in that comprise the following steps：
Step 1, foam metal is cleaned, removes oxide on surface；Vacuum drying chamber is put into after washing to be dried for standby；
Step 2, array carbon nano tube is grown using chemical vapour deposition technique, its height of accuracy controlling is to higher than selected foam metal
Thickness；Array carbon nano tube surface is handled using plasma etching, array carbon nano tube surface wrap thing is removed, obtains
To acicular texture；
Step 3, the top of step 2 gained array carbon nano tube or bottom are vertically arranged in step 1 gained foam metal substrate
Side or lower section, it is put into tablet press machine and carries out pressing processing.
2. the preparation method of array carbon nano tube foam metal composite base plate according to claim 1, it is characterised in that：
In step 1, the metal of foam metal substrate is copper, nickel, silver, iron, copper alloy, nickel alloy or aluminium alloy.
3. the preparation method of array carbon nano tube foam metal composite base plate according to claim 1, it is characterised in that：
In step 1, porosity 90%-95%, pore size 0.15-6mm in foam metal substrate.
4. the preparation method of array carbon nano tube foam metal composite base plate according to claim 1, it is characterised in that：
In step 2, array carbon nano tube is one kind or several in single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube
That plants is compound.
5. the preparation method of array carbon nano tube foam metal composite base plate according to claim 1, it is characterised in that：
In step 2, the caliber of array carbon nano tube is 2-50nm, and the height of array carbon nano tube is more than 50 μm.
6. the preparation method of array carbon nano tube foam metal composite base plate according to claim 1, it is characterised in that：
In step 2, the atmosphere of plasma etching is one or more of combinations in argon gas, oxygen and air, gas stream
Measure 100-500mL/min.
7. the preparation method of array carbon nano tube foam metal composite base plate according to claim 1, it is characterised in that：
In step 2, the power of plasma etching is 1-1000W.
8. the preparation method of array carbon nano tube foam metal composite base plate according to claim 1, it is characterised in that：
In step 3, the stamping pressure of tablet press machine is 1-40MPa.
A kind of 9. array carbon nano tube foam metal composite base plate, it is characterised in that：As any one of claim 1-8
Preparation method is prepared.
10. array carbon nano tube foam metal composite base plate according to claim 9 is in the application in energy device field, institute
Stating energy device includes the electrode base board of ultracapacitor, lithium ion battery, nickel-based battery and fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710893017.8A CN107630206B (en) | 2017-09-27 | 2017-09-27 | The preparation method and application of array carbon nano tube foam metal composite substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710893017.8A CN107630206B (en) | 2017-09-27 | 2017-09-27 | The preparation method and application of array carbon nano tube foam metal composite substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107630206A true CN107630206A (en) | 2018-01-26 |
| CN107630206B CN107630206B (en) | 2019-06-11 |
Family
ID=61102742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710893017.8A Active CN107630206B (en) | 2017-09-27 | 2017-09-27 | The preparation method and application of array carbon nano tube foam metal composite substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107630206B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060093642A1 (en) * | 2004-11-03 | 2006-05-04 | Ranade Shrirang V | Method of incorporating carbon nanotubes in a medical appliance, a carbon nanotube medical appliance, and a medical appliance coated using carbon nanotube technology |
| CN101764213A (en) * | 2010-01-04 | 2010-06-30 | 北京航空航天大学 | Method for preparing stannic oxide battery anode material on carbon nano tube by using electro-deposition process |
| CN102385994A (en) * | 2011-10-19 | 2012-03-21 | 沈阳建筑大学 | Deformed photovoltaic component flexible dye sensitization solar cell as well as preparation method and application thereof |
| US20120213918A1 (en) * | 2011-02-17 | 2012-08-23 | Hyundai Motor Company | Vertically aligning a carbon nanotubes array |
| CN103434207A (en) * | 2013-08-19 | 2013-12-11 | 南京航空航天大学 | Foam metal-carbon nanotube composite material and preparation method thereof |
| CN104745976A (en) * | 2015-03-27 | 2015-07-01 | 中国民航大学 | Preparation method of carbon-nanotube-reinforced foamed aluminum-base composite material |
| CN105439117A (en) * | 2014-09-19 | 2016-03-30 | 中国科学院苏州纳米技术与纳米仿生研究所 | Rapid losses transfer method for large-area carbon nanotube vertical array |
-
2017
- 2017-09-27 CN CN201710893017.8A patent/CN107630206B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060093642A1 (en) * | 2004-11-03 | 2006-05-04 | Ranade Shrirang V | Method of incorporating carbon nanotubes in a medical appliance, a carbon nanotube medical appliance, and a medical appliance coated using carbon nanotube technology |
| CN101764213A (en) * | 2010-01-04 | 2010-06-30 | 北京航空航天大学 | Method for preparing stannic oxide battery anode material on carbon nano tube by using electro-deposition process |
| US20120213918A1 (en) * | 2011-02-17 | 2012-08-23 | Hyundai Motor Company | Vertically aligning a carbon nanotubes array |
| CN102385994A (en) * | 2011-10-19 | 2012-03-21 | 沈阳建筑大学 | Deformed photovoltaic component flexible dye sensitization solar cell as well as preparation method and application thereof |
| CN103434207A (en) * | 2013-08-19 | 2013-12-11 | 南京航空航天大学 | Foam metal-carbon nanotube composite material and preparation method thereof |
| CN105439117A (en) * | 2014-09-19 | 2016-03-30 | 中国科学院苏州纳米技术与纳米仿生研究所 | Rapid losses transfer method for large-area carbon nanotube vertical array |
| CN104745976A (en) * | 2015-03-27 | 2015-07-01 | 中国民航大学 | Preparation method of carbon-nanotube-reinforced foamed aluminum-base composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107630206B (en) | 2019-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lin et al. | Core-branched CoSe 2/Ni 0.85 Se nanotube arrays on Ni foam with remarkable electrochemical performance for hybrid supercapacitors | |
| Chen et al. | Three-dimensional NiCo 2 O 4@ NiWO 4 core–shell nanowire arrays for high performance supercapacitors | |
| CN107235472B (en) | Porous vertical graphene nano wall array of N doping and the preparation method and application thereof | |
| Chen et al. | Multi-walled carbon nanotube papers as binder-free cathodes for large capacity and reversible non-aqueous Li–O 2 batteries | |
| CN102282706B (en) | High efficiency energy conversion and storage systems using carbon nanostructured materials | |
| Salunkhe et al. | Binary metal hydroxide nanorods and multi-walled carbon nanotube composites for electrochemical energy storage applications | |
| Chen et al. | Electrochemical conversion of Ni 2 (OH) 2 CO 3 into Ni (OH) 2 hierarchical nanostructures loaded on a carbon nanotube paper with high electrochemical energy storage performance | |
| Cheng et al. | Nitrogen-doped herringbone carbon nanofibers with large lattice spacings and abundant edges: catalytic growth and their applications in lithium ion batteries and oxygen reduction reactions | |
| Guan et al. | Atomic‐Layer‐Deposition‐Assisted Formation of Carbon Nanoflakes on Metal Oxides and Energy Storage Application | |
| CN105047427B (en) | Ultracapacitor combination electrode material and preparation method thereof and ultracapacitor | |
| CN106449132B (en) | A kind of mesoporous Co3O4Nano wire@NiCo2O4Nanometer sheet is classified nucleocapsid array material, preparation method and application | |
| Sun et al. | MnO 2 nanoflakes grown on 3D graphite network for enhanced electrocapacitive performance | |
| Xie et al. | A novel TiO2-wrapped activated carbon fiber/sulfur hybrid cathode for high performance lithium sulfur batteries | |
| CN108172781A (en) | A kind of Si-C composite material of Argent grain doping and its preparation method and application | |
| Tu et al. | Highly-efficient MnO2/carbon array-type catalytic cathode enabling confined Li2O2 growth for long-life Li–O2 batteries | |
| CN110773233A (en) | Preparation method of electrocatalytic full-hydrolytic nanosheet array material | |
| Pan et al. | Facile synthesis of ZnCo2O4 micro-flowers and micro-sheets on Ni foam for pseudocapacitor electrodes | |
| CN107196020A (en) | The preparation method of nitrogen-doped carbon nanometer pipe array/carbon fibre material air electrode | |
| Cheng et al. | Plasma-Assisted Synthesis of Defect-Rich O and N Codoped Carbon Nanofibers Loaded with Manganese Oxides as an Efficient Oxygen Reduction Electrocatalyst for Aluminum–Air Batteries | |
| Liu et al. | A permselective and multifunctional 3D N-doped carbon nanotubes interlayer for high-performance lithium-sulfur batteries | |
| Youn et al. | Effect of nitrogen functionalization of graphite felt electrode by ultrasonication on the electrochemical performance of vanadium redox flow battery | |
| CN101521273B (en) | In-situ synthesis method for preparing tin-carbon/core-shell nano-particle fully filled carbon nano-tube composite anode material | |
| CN109273672A (en) | SEI film cladding Na-K liquid alloy electrode in situ and its preparation method and application | |
| Moni et al. | One-dimensional polymer-derived ceramic nanowires with electrocatalytically active metallic silicide tips as cathode catalysts for Zn–air batteries | |
| Han et al. | Green bridge between waste and energy: conversion the rotten wood into cathode for functional Zn-air battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |