CN107934953A - A kind of foam stone ink sheet and preparation method thereof, aluminium ion anode - Google Patents
A kind of foam stone ink sheet and preparation method thereof, aluminium ion anode Download PDFInfo
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- CN107934953A CN107934953A CN201711173282.5A CN201711173282A CN107934953A CN 107934953 A CN107934953 A CN 107934953A CN 201711173282 A CN201711173282 A CN 201711173282A CN 107934953 A CN107934953 A CN 107934953A
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- foamy graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- 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
Abstract
The present invention is on a kind of foam stone ink sheet and preparation method thereof, aluminium ion anode, is related to battery technology field.The technical solution mainly used for：The preparation method of foam stone ink sheet includes foamy graphite powder and Kynoar being dispersed in setting solvent, obtain foamy graphite slurry, foamy graphite slurry is coated on substrate, after drying process, foamy graphite carbon-coating is formed on substrate and is coated with the substrate of foamy graphite carbon-coating and is immersed in the first setting solution, after substrate dissolving, foamy graphite carbon-coating is post-processed to obtain foam stone ink sheet.A kind of foam stone ink sheet is prepared by the above method.Foam stone ink sheet prepared by the above method is used for the positive electrode of aluminium ion battery.The present invention mainly prepares a kind of intensity height, good toughness, carrier-free and complete foam stone ink sheet, to improve the performance of aluminium ion battery.
Description
Technical field
The present invention relates to a kind of battery technology field, more particularly to a kind of foam stone ink sheet and preparation method thereof, aluminium from
Sub- anode.
Background technology
U.S. foreign citizen of Chinese origin academician Dai Hongjie exists《Nature》On delivered one it is entitled《An ultrafast
rechargeable aluminium-ion battery》Article.It article describe the novel aluminum ion battery of its invention
Can be to complete in one minute to charge, circulation does not have obvious capacity attenuation in 7500 weeks.Aluminium ion battery not only has stable electric discharge
Voltage platform, and there is low flame properties, low cost, high power capacity, and the characteristics of these are excellent cause pass of the people to it
Note.
A kind of important positive electrode of the foamy graphite as aluminium ion battery, the prior art mainly pass through chemical gaseous phase
It is prepared by sedimentation (CVD) method.Specifically, foamy graphite carbon-coating is obtained in nickel foam by chemical vapour deposition technique, then used
Pickling, baking and high annealing and etc. the nickel that defoams, you can obtain foam stone ink sheet.
But the inventors found that the preparation method of above-mentioned existing foam stone ink sheet at least there are the following problems：
During the nickel that defoams (pickling, baking and high annealing and etc.), the more or less capital quilt of foamy graphite lamella
Damage, cause behind can not be assembled into aluminium ion battery or the stability of follow-up aluminium ion battery is substantially reduced.It is above-mentioned
The presence of problem has seriously affected the development of aluminium ion battery.
The content of the invention
In view of this, the present invention provides a kind of foam stone ink sheet and preparation method thereof, aluminium ion anode, main purpose
It is to prepare a kind of intensity height, good toughness, carrier-free and complete foamy graphite lamella.
To reach above-mentioned purpose, present invention generally provides following technical solution：
On the one hand, the embodiment of the present invention provides a kind of preparation method of foam stone ink sheet, wherein, include the following steps：
Prepare foamy graphite slurry：Foamy graphite powder and Kynoar are dispersed in setting solvent, obtain foam
Graphite slurry；
Coat foamy graphite slurry：The foamy graphite slurry is coated on substrate, after drying process, the shape on substrate
Into foamy graphite carbon-coating；
Remove substrate：The substrate for being coated with foamy graphite carbon-coating is immersed in the first setting solution, treats that the substrate is molten
Xie Hou, post-processes foamy graphite carbon-coating to obtain foam stone ink sheet.
The object of the invention to solve the technical problems can be also applied to the following technical measures to achieve further.
Preferably, the mass ratio of the foamy graphite powder and Kynoar is 9:1-19:1；
The gross mass and the mass ratio of the setting solvent of the foamy graphite powder and Kynoar be：1:1.5-
1.5:1。
Preferably, the setting solvent is selected in 1-methyl-2-pyrrolidinone (NMP), n,N-Dimethylformamide (DMF)
Any one or two kinds of mixtures.
Preferably, the substrate selects copper foil.
Preferably, in the step of coating foamy graphite slurry, the mode of the drying process is as follows：
In vacuum drying oven, the substrate coated with foamy graphite slurry is toasted；Wherein, baking temperature 90-110
DEG C, baking time 12-36h.
Preferably, in the step of removal substrate：
The first setting solution selects any of liquor ferri trichloridi, silver nitrate solution and sulfuric acid mercury solution；Its
In, the concentration of liquor ferri trichloridi is 1-3mol/L；The concentration of silver nitrate solution is 2-5mol/L；The concentration of sulfuric acid mercury solution is
2-5mol/L；Described the step of being post-processed to foamy graphite carbon-coating, includes：Using deionized water to the carbon graphite foam
After layer cleaning, drying and processing is carried out.
Preferably, before described the step of preparing foamy graphite slurry, the step of preparing foamy graphite powder is further included；
Wherein, described the step of preparing foamy graphite powder, includes：
Using chemical vapour deposition technique in substrate deposit foamy graphite carbon-coating；
The matrix that deposition has foamy graphite carbon-coating is immersed in the second setting solution, after described matrix dissolving, is obtained
Lysate；The lysate is post-processed, foamy graphite powder is made.
Preferably, described matrix selects nickel foam.
Preferably, in chemical vapor deposition unit, using absolute ethyl alcohol as carbon source, hydrogen be reducibility gas, argon gas be
Carrier gas, by chemical vapour deposition technique in substrate deposit foamy graphite carbon-coating.
Preferably, the hydrogen and the velocity ratio of argon gas being passed through into the chemical vapor deposition unit are 1:8-1:4；It is described
The addition of absolute ethyl alcohol is 2-10mL/min；Depositing temperature is 1000-1200 DEG C, sedimentation time 2-4h.
Preferably, absolute ethyl alcohol is added into the chemical vapor deposition unit using peristaltic pump.
Preferably, described second the hydrochloric acid solution that solution selects concentration as 3-6moL/L is set.
Preferably, the step of being post-processed to the lysate includes：
Suction filtration drying and processing is carried out to the lysate, obtains the foamy graphite of fragment shape；
Processing is ground to the foamy graphite of the fragment shape, obtains foamy graphite powder.
On the other hand, the embodiment of the present invention provides a kind of foam stone ink sheet, wherein, the foam stone ink sheet is by above-mentioned institute
The preparation method for the foam stone ink sheet stated is prepared.
On the other hand, the embodiment of the present invention provides a kind of aluminium ion anode, wherein, the aluminium ion anode
Including above-mentioned foam stone ink sheet.
Compared with prior art, foam stone ink sheet of the invention and preparation method thereof, aluminium ion anode at least have
Following beneficial effect：
On the one hand, the preparation method of foam stone ink sheet provided in an embodiment of the present invention in foamy graphite powder by adding
Kynoar (PVDF), can strengthen the intensity and toughness of foam stone ink sheet；And coated by using on substrate by steeping
Foam graphite composite powder and PVDF are dissolved in manufactured foamy graphite slurry in NMP, foamy graphite slurry is formed foam stone on substrate
Black carbon-coating, prepares foamy graphite lamella, this preparation method can overcome foam stone ink sheet well by the method that substrate removes
The characteristics of frangible, substantially increase the intensity and toughness of foam stone ink sheet, and also being provided for the flexible aluminium ion battery of preparation can
Energy.
Further, the preparation method of foam stone ink sheet provided in an embodiment of the present invention, which further includes, utilizes chemical vapor deposition
Method is the substrate deposit foamy graphite carbon-coating the step of, and in this step：It is carbon source to select methane relative to the prior art, should
It is carbon source that step, which selects absolute ethyl alcohol, so as to improve the security of chemical vapor deposition processes, and reduces cost；In addition,
The step adds absolute ethyl alcohol into chemical vapor deposition unit using peristaltic pump, so as to ensure that whole chemical vapor deposition mistake
The stability and controllability of journey.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate attached drawing describe in detail as after.
Brief description of the drawings
Fig. 1 is a kind of preparation flow figure of the preparation method for foam stone ink sheet that the embodiment of the present invention provides；
Fig. 2A is picture of the foam stone ink sheet sample before ultrasound prepared by embodiment 2；
Fig. 2 B are picture of the foam stone ink sheet sample after ultrasound prepared by embodiment 2.
Embodiment
Further to illustrate the present invention to reach the technological means and effect that predetermined goal of the invention is taken, below in conjunction with
Attached drawing and preferred embodiment, to embodiment, structure, feature and its effect according to the present patent application, describe in detail such as
Afterwards.In the following description, what different " embodiment " or " embodiment " referred to is not necessarily the same embodiment.It is in addition, one or more
Special characteristic, structure or feature in a embodiment can be combined by any suitable form.
On the one hand, the embodiment of the present invention provides a kind of preparation method (bubble in the embodiment of the present invention of foam stone ink sheet
Foam graphite flake refers to the foamy graphite of sheet), as shown in Figure 1, the preparation method specifically comprises the following steps：
Firstth, foamy graphite slurry is prepared：Foamy graphite powder and Kynoar (PVDF) are dispersed in setting solvent
In, obtain foamy graphite slurry.
In this step, the mass ratio of foamy graphite powder and Kynoar is 9:1-19:1.
Setting solvent in the step selects any in 1-methyl-2-pyrrolidinone NMP, N,N-dimethylformamide (DMF)
Kind or two kinds of mixture.
Also, the foamy graphite powder and the gross mass of Kynoar and the mass ratio of setting solvent in the step are：
1.5:1-1:1.5。
In the step add Kynoar (PVDF), mainly strengthen foamy graphite lamella intensity and toughness, also for
Prepare flexible aluminium ion battery and provide possibility.
Here, the foamy graphite powder in the step can use the method for the prior art to be prepared, can also buy.
It is preferred that foamy graphite powder is made by the steps in the embodiment of the present invention：
1st, using chemical vapour deposition technique in substrate deposit foamy graphite carbon-coating.
It is preferred that in this step, matrix selects nickel foam.It is reducibility gas using absolute ethyl alcohol as carbon source, hydrogen, argon
Gas is carrier gas.And the step carries out in chemical vapor deposition unit (e.g., electron tubes type sintering furnace).Preferably, to chemical gas
The hydrogen and the velocity ratio of argon gas being passed through in phase precipitation equipment are 1:8-1:4.Using peristaltic pump into chemical vapor deposition unit
Add absolute ethyl alcohol.The addition of absolute ethyl alcohol is 2-10mL/min.It is preferred that the depositing temperature in the step is 1000-
1200 DEG C, sedimentation time 2-4h.
In this step, it is carbon source to select absolute ethyl alcohol, and it is carbon source to select methane relative to the prior art, improves chemistry
The security of vapor deposition processes, and reduce cost；Absolute ethyl alcohol is added into chemical vapor deposition unit using peristaltic pump,
It ensure that the stabilization of whole chemical vapor deposition processes and controllable.
2nd, the matrix that deposition has foamy graphite carbon-coating is immersed in the second setting solution, after matrix dissolution, obtained molten
Solve liquid；The lysate is post-processed, foamy graphite powder is made.
Lysate in the step refers to：The matrix that deposition has foamy graphite carbon-coating is immersed in acid solution, treats base
After body (nickel foam) dissolving, the lysate of formation.
It is preferred that second in the step sets solution selection concentration as the hydrochloric acid solution of 3-6moL/L, it is mainly used for
Remove nickel foam substrate.
It is preferred that include in the step the step of post processing to the lysate：1) Vacuum filtration device is used,
Suction filtration drying and processing is carried out to lysate, obtains the foamy graphite of fragment shape.2) bubble using planetary ball mill to fragment shape
Foam graphite is ground processing, obtains foamy graphite powder.Wherein, milling time 30-90min；The planetary ball mill
Rotating speed be 5000r/min；Preferably 5000r/min.
Secondth, foamy graphite slurry is coated：Foamy graphite slurry is coated on substrate, after drying process, on substrate
Formation is formed uniformly one layer of foamy graphite carbon-coating.
It is preferred that the substrate in the step selects copper foil.Also, to the copper clad laminate coated with foamy graphite slurry true
Toasted in empty baking oven；Wherein, baking temperature be 90-110 DEG C, baking time 12-36h.
3rd, substrate is removed：The substrate for being coated with foamy graphite carbon-coating is immersed in the first setting solution, treats the base
After plate dissolving, foamy graphite carbon-coating is post-processed to obtain foam stone ink sheet.
It is preferred that the step mainly sets solution etches substrate using first, to obtain DNAcarrier free foam stone ink sheet.
First sets the ferric trichloride (FeCl that solution selects concentration as 1-3mol/L3) solution (or the silver nitrate solution of 2-5mol/L
(AgNO3), mercuric sulfate (HgSO4) solution etc.).
It is preferred that include in the step the step of post processing to foamy graphite carbon-coating：Foamy graphite carbon-coating is soaked
Bubble in deionized water, removes the remaining first setting solution (liquor ferri trichloridi) of carbon graphite foam layer surface, after drying i.e.
High intensity, good toughness, carrier-free and complete foam stone ink sheet can be obtained.
On the other hand, the embodiment of the present invention also provides a kind of foam stone ink sheet, and the foam stone ink sheet is by above-mentioned foam
The preparation method of graphite flake is prepared；Therefore, intensity height, the good toughness of foam stone ink sheet provided in an embodiment of the present invention.
It is further described below by specific embodiment.
Embodiment 1
1) mixed gas of hydrogen and argon gas is passed through into electron tubes type sintering furnace, and (wherein, the flow velocity of hydrogen is 150ml/
Min, the flow velocity of argon gas is 600ml/min), electron tubes type sintering in-furnace temperature is increased to 1100 DEG C, treats that temperature reaches simultaneously steady
After fixed, absolute ethyl alcohol is added by peristaltic pump, the addition of absolute ethyl alcohol is 5ml/min, after a period of time, foamy graphite carbon-coating
It can be deposited in nickel foam；Sedimentation time is 3h, and obtaining deposition has the nickel foam of foamy graphite carbon-coating.
2) nickel foam that the obtained deposition of step 1) has carbon-coating is immersed in the hydrochloric acid solution of 4mol/L, treats that nickel foam is molten
Xie Hou, carries out lysate suction filtration drying and processing, obtains the foamy graphite of fragment shape；The foamy graphite of fragment shape is passed through into planet
Formula ball mill is ground, rotating speed 5000r/min, milling time 30min, you can obtains foamy graphite powder.
3) by foamy graphite powder and PVDF according to 19:1 (mass ratio) mixes, and is dispersed in nmp solvent, foam stone is made
Black slurry, coated on copper foil, in 100 DEG C of vacuum bakeout 24h.
4) copper foil for being coated with foamy graphite carbon-coating is immersed in the FeCl of 3mol/L330min in solution, then soaks again
In deionized water, the remaining FeCl of carbon graphite foam layer surface is removed3Solution, can obtain high intensity, toughness after drying
Good, carrier-free and complete foam stone ink sheet.
Embodiment 2
1) mixed gas of hydrogen and argon gas is passed through into electron tubes type sintering furnace, and (wherein, the flow velocity of hydrogen is 150ml/
Min, the flow velocity of argon gas is 600ml/min), electron tubes type sintering in-furnace temperature is increased to 1100 DEG C, treats that temperature reaches simultaneously steady
After fixed, absolute ethyl alcohol is added by peristaltic pump, the addition of absolute ethyl alcohol is 5ml/min, after a period of time, foamy graphite carbon-coating
It can be deposited in nickel foam；Sedimentation time is 3h, and obtaining deposition has the nickel foam of foamy graphite carbon-coating.
2) nickel foam that the obtained deposition of step 1) has carbon-coating is immersed in the hydrochloric acid solution of 4mol/L, treats that nickel foam is molten
Xie Hou, carries out lysate suction filtration drying and processing, obtains the foamy graphite of fragment shape；The foamy graphite of fragment shape is passed through into planet
Formula ball mill is ground, rotating speed 5000r/min, milling time 30min, you can obtains foamy graphite powder.
3) by foamy graphite powder and PVDF according to 9:1 (mass ratio) mixes, and is dispersed in nmp solvent, foam stone is made
Black slurry, coated on copper foil, in 100 DEG C of vacuum bakeout 24h.
4) copper foil for being coated with foamy graphite carbon-coating is immersed in 30min in the silver nitrate solution of 5mol/L, then soaks again
Bubble in deionized water, removes the remaining silver nitrate solution of carbon graphite foam layer surface, and high intensity, tough can be obtained after drying
The good, carrier-free of property and complete foam stone ink sheet.
Embodiment 3
1) mixed gas of hydrogen and argon gas is passed through into electron tubes type sintering furnace, and (wherein, the flow velocity of hydrogen is 150ml/
Min, the flow velocity of argon gas is 600ml/min), electron tubes type sintering in-furnace temperature is increased to 1100 DEG C, treats that temperature reaches simultaneously steady
After fixed, absolute ethyl alcohol is added by peristaltic pump, the addition of absolute ethyl alcohol is 5ml/min, after a period of time, foamy graphite carbon-coating
It can be deposited in nickel foam；Sedimentation time is 3h, and obtaining deposition has the nickel foam of foamy graphite carbon-coating.
2) nickel foam that the obtained deposition of step 1) has carbon-coating is immersed in the hydrochloric acid solution of 4mol/L, treats that nickel foam is molten
Xie Hou, carries out lysate suction filtration drying and processing, obtains the foamy graphite of fragment shape；The foamy graphite of fragment shape is passed through into planet
Formula ball mill is ground, rotating speed 5000r/min, milling time 30min, you can obtains foamy graphite powder.
3) by foamy graphite powder and PVDF according to 14:1 (mass ratio) mixes, and is dispersed in nmp solvent, foam stone is made
Black slurry, coated on copper foil, in 100 DEG C of vacuum bakeout 24h.
4) copper foil for being coated with foamy graphite carbon-coating is immersed in 30min in the sulfuric acid mercury solution of 3mol/L, then soaks again
Bubble in deionized water, removes the remaining sulfuric acid mercury solution of carbon graphite foam layer surface, and high intensity, tough can be obtained after drying
The good, carrier-free of property and complete foam stone ink sheet.
Embodiment 4
1) mixed gas of hydrogen and argon gas is passed through into electron tubes type sintering furnace, and (wherein, the flow velocity of hydrogen is 150ml/
Min, the flow velocity of argon gas is 1200ml/min), electron tubes type sintering in-furnace temperature is increased to 1000 DEG C, treats that temperature reaches simultaneously steady
After fixed, absolute ethyl alcohol is added by peristaltic pump, the addition of absolute ethyl alcohol is 2mL/min, after a period of time, foamy graphite carbon-coating
It can be deposited in nickel foam；Sedimentation time is 4h, and obtaining deposition has the nickel foam of foamy graphite carbon-coating.
2) nickel foam that the obtained deposition of step 1) has carbon-coating is immersed in the hydrochloric acid solution of 6mol/L, treats that nickel foam is molten
Xie Hou, carries out lysate suction filtration drying and processing, obtains the foamy graphite of fragment shape；The foamy graphite of fragment shape is passed through into planet
Formula ball mill is ground, rotating speed 5000r/min, milling time 60min, you can obtains foamy graphite powder.
3) by foamy graphite powder and PVDF according to 13:1 (mass ratio) mixes, and is dispersed in nmp solvent, foam stone is made
Black slurry, coated on copper foil, in 90 DEG C of vacuum bakeout 36h.
4) copper foil for being coated with foamy graphite carbon-coating is immersed in the FeCl of 2mol/L330min in solution, then soaks again
In deionized water, the remaining FeCl of carbon graphite foam layer surface is removed3Solution, can obtain high intensity, toughness after drying
Good, carrier-free and complete foam stone ink sheet.
Embodiment 5
1) mixed gas of hydrogen and argon gas is passed through into electron tubes type sintering furnace, and (wherein, the flow velocity of hydrogen is 150ml/
Min, the flow velocity of argon gas is 900ml/min), electron tubes type sintering in-furnace temperature is increased to 1200 DEG C, treats that temperature reaches simultaneously steady
After fixed, absolute ethyl alcohol is added by peristaltic pump, the addition of absolute ethyl alcohol is 10mL/min, after a period of time, carbon graphite foam
Layer can be deposited in nickel foam；Sedimentation time is 2h, and obtaining deposition has the nickel foam of foamy graphite carbon-coating.
2) nickel foam that the obtained deposition of step 1) has carbon-coating is immersed in the hydrochloric acid solution of 3mol/L, treats that nickel foam is molten
Xie Hou, carries out lysate suction filtration drying and processing, obtains the foamy graphite of fragment shape；The foamy graphite of fragment shape is passed through into planet
Formula ball mill is ground, rotating speed 5000r/min, milling time 90min, you can obtains foamy graphite powder.
3) by foamy graphite powder and PVDF according to 12:1 (mass ratio) mixes, and is dispersed in nmp solvent, foam stone is made
Black slurry, coated on copper foil, in 110 DEG C of vacuum bakeout 12h.
4) copper foil for being coated with foamy graphite carbon-coating is immersed in the FeCl of 1mol/L330min in solution, then soaks again
In deionized water, the remaining FeCl of carbon graphite foam layer surface is removed3Solution, can obtain high intensity, toughness after drying
Good, carrier-free and complete foam stone ink sheet.
Toughness, the intensity of the foam stone ink sheet prepared to embodiment 1- embodiments 5 are tested, specific as follows：It will implement
Foam stone ink sheet (2cm*2cm) sample that example 1- embodiments 5 prepare is dipped into 50ml ethanol solutions respectively, ultrasound point
30min, supersonic frequency 40Hz are dissipated, the integrality of pole piece, there is flawless etc. before and after observation is ultrasonic.
It is observed that foam stone ink sheet sample prepared by embodiment 1- embodiments 5 has almost no change after ultrasound, shape is protected
Hold completely, occur without crackle (referring to shown in Fig. 2A and Fig. 2 B), this illustrates that foamy graphite pole piece prepared by this method is compared
Integrality, the intensity of the foamy graphite pole piece directly prepared by chemical vapour deposition technique greatly improve.
The above described is only a preferred embodiment of the present invention, not make limitation in any form to the present invention, according to
Any simple modification, equivalent change and modification made according to the technical spirit of the present invention to above example, still falls within this hair
In the range of bright technical solution.
Claims (15)
1. a kind of preparation method of foam stone ink sheet, it is characterised in that include the following steps：
Prepare foamy graphite slurry：Foamy graphite powder and Kynoar are dispersed in setting solvent, obtain foamy graphite
Slurry；
Coat foamy graphite slurry：By the foamy graphite slurry coated on substrate, after drying process, bubble is formed on substrate
Foam graphite carbon-coating；
Remove substrate：The substrate for being coated with foamy graphite carbon-coating is immersed in the first setting solution, after substrate dissolving,
Foamy graphite carbon-coating is post-processed to obtain foam stone ink sheet.
2. the preparation method of foam stone ink sheet according to claim 1, it is characterised in that
The mass ratio of the foamy graphite powder and Kynoar is 9:1-19:1；
The gross mass and the mass ratio of the setting solvent of the foamy graphite powder and Kynoar be：1:1.5-1.5:1.
3. the preparation method of foam stone ink sheet according to claim 1 or 2, it is characterised in that
The setting solvent selects any of 1-methyl-2-pyrrolidinone (NMP), N,N-dimethylformamide (DMF) or two kinds
Mixture.
4. the preparation method of foam stone ink sheet according to claim 1, it is characterised in that the substrate selects copper foil.
5. the preparation method of the foam stone ink sheet according to claim 1 or 4, it is characterised in that in the coating foam stone
In the step of black slurry, the mode of the drying process is as follows：
In vacuum drying oven, the substrate coated with foamy graphite slurry is toasted；Wherein, baking temperature for 90-110 DEG C,
Baking time is 12-36h.
6. the preparation method of foam stone ink sheet according to claim 4, it is characterised in that in described the step of removing substrate
In：
The first setting solution selects any of liquor ferri trichloridi, silver nitrate solution and sulfuric acid mercury solution；Wherein, three
The concentration of ferric chloride solution is 1-3mol/L；The concentration of silver nitrate solution is 2-5mol/L；The concentration of sulfuric acid mercury solution is 2-
5mol/L；
Described the step of being post-processed to foamy graphite carbon-coating, includes：The foamy graphite carbon-coating is cleaned using deionized water
Afterwards, drying and processing is carried out.
7. the preparation method of foam stone ink sheet according to claim 1, it is characterised in that prepare foamy graphite slurry described
Before the step of material, the step of preparing foamy graphite powder is further included；Wherein, described the step of preparing foamy graphite powder, wraps
Include：
Using chemical vapour deposition technique in substrate deposit foamy graphite carbon-coating；
The matrix that deposition has foamy graphite carbon-coating is immersed in the second setting solution, after described matrix dissolving, is dissolved
Liquid；The lysate is post-processed, foamy graphite powder is made.
8. the preparation method of foam stone ink sheet according to claim 7, it is characterised in that described matrix selects nickel foam.
9. the preparation method of the foam stone ink sheet according to claim 7 or 8, it is characterised in that
In chemical vapor deposition unit, using absolute ethyl alcohol as carbon source, hydrogen be reducibility gas, argon gas be carrier gas, passing through
Vapour deposition process is learned in substrate deposit foamy graphite carbon-coating.
10. the preparation method of foam stone ink sheet according to claim 9, it is characterised in that
The hydrogen and the velocity ratio of argon gas being passed through into the chemical vapor deposition unit are 1:8-1:4；
The addition of the absolute ethyl alcohol is 2-10mL/min；
Depositing temperature is 1000-1200 DEG C, sedimentation time 2-4h.
11. the preparation method of foam stone ink sheet according to claim 9, it is characterised in that using peristaltic pump to describedization
Learn in vapor phase growing apparatus and add absolute ethyl alcohol.
12. the preparation method of foam stone ink sheet according to claim 8, it is characterised in that the second setting solution choosing
The hydrochloric acid solution for being 3-6moL/L with concentration.
13. the preparation method of the foam stone ink sheet according to claim 7 or 12, it is characterised in that to the lysate into
The step of row post processing, includes：
Suction filtration drying and processing is carried out to the lysate, obtains the foamy graphite of fragment shape；
Processing is ground to the foamy graphite of the fragment shape, obtains foamy graphite powder.
14. a kind of foam stone ink sheet, it is characterised in that the foam stone ink sheet is by claim 1-13 any one of them foams
The preparation method of graphite flake is prepared.
15. a kind of aluminium ion anode, it is characterised in that the aluminium ion anode includes the bubble described in claim 14
Foam graphite flake.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711173282.5A CN107934953A (en) | 2017-11-22 | 2017-11-22 | A kind of foam stone ink sheet and preparation method thereof, aluminium ion anode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711173282.5A CN107934953A (en) | 2017-11-22 | 2017-11-22 | A kind of foam stone ink sheet and preparation method thereof, aluminium ion anode |
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| Publication Number | Publication Date |
|---|---|
| CN107934953A true CN107934953A (en) | 2018-04-20 |
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| CN201711173282.5A Pending CN107934953A (en) | 2017-11-22 | 2017-11-22 | A kind of foam stone ink sheet and preparation method thereof, aluminium ion anode |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109734084A (en) * | 2018-12-29 | 2019-05-10 | 东莞市鸿亿导热材料有限公司 | A kind of foam stone ink sheet and preparation method thereof for cathode of lithium battery |
| RU2786676C1 (en) * | 2022-01-18 | 2022-12-23 | Акционерное Общество "Наука И Инновации" | Method for producing anisotropic heat-conducting composite sheet material and anisotropic heat-conducting composite sheet material |
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| CN109734084A (en) * | 2018-12-29 | 2019-05-10 | 东莞市鸿亿导热材料有限公司 | A kind of foam stone ink sheet and preparation method thereof for cathode of lithium battery |
| RU2786676C1 (en) * | 2022-01-18 | 2022-12-23 | Акционерное Общество "Наука И Инновации" | Method for producing anisotropic heat-conducting composite sheet material and anisotropic heat-conducting composite sheet material |
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Application publication date: 20180420 |