CN109383087A - A method of preparing multilayer self-supporting carbon film - Google Patents
A method of preparing multilayer self-supporting carbon film Download PDFInfo
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- CN109383087A CN109383087A CN201811408949.XA CN201811408949A CN109383087A CN 109383087 A CN109383087 A CN 109383087A CN 201811408949 A CN201811408949 A CN 201811408949A CN 109383087 A CN109383087 A CN 109383087A
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- supporting
- precursor solution
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
- B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
Abstract
The invention discloses a kind of methods for preparing multilayer self-supporting carbon film, comprising the following steps: (1) using carbon matrix precursor as raw material, is dissolved in solvent and obtains precursor solution；(2) precursor solution is laid in surface to be covered on the hard substrate of PE film or PP film, then in PE film or the PP film of newly tiling above, then tile precursor solution again, thus obtains multilayer precursor solution layer；Drying obtains multilayer precursor film；(3) carrying out pyrolysis processing to multilayer precursor film can be obtained the carbon-based films of multilayer self-supporting.The present invention is by improving the material etc. of crucial multilayer precursor film attachment, self-supporting carbon-based films easy to damage when obtaining the carbon-based films of multilayer self-supporting for the first time compared with prior art, and can effectively solve the problem that easy adhesion between self-supporting carbon-based films and substrate and lead to problems such as to separate.
Description
Technical field
The invention belongs to the preparation technical fields of self-supporting carbon film, prepare multilayer self-supporting carbon more particularly, to a kind of
The method of film is used especially for the carbon-based films such as preparation multilayer self-supporting silicon-carbon composite membrane.
Background technique
Carbon material is widely used in field of batteries, especially in lithium ion battery and sodium-ion battery negative electrode side mask
Have the features such as specific capacity high, good cycle, with other active materials it is compound can effectively reduce whole specific surface area, increase it is conductive
Property and improve cycle life.
In most cases, carbon material exists with powder, and it is limited that high-specific surface area applies it, while may also
Cause health problem.If carbon material is prepared into continuous block or self-supported membrane, its specific surface can be reduced, it is expanded
Application field.So-called self-supported membrane is able to maintain the film of membrane structure in the case where referring to no backing material or substrate.And it props up certainly
The preparation process for supportting film is often more complicated, or directlys adopt finished film and be carbonized, and structure and composition adjustment range are relatively narrow
(patent 201711370331.4)；Or need to be removed from hard substrate, it is likely to result in film and is damaged during removing
(patent 201580012433.1)；Or electrostatic spinning is needed, production efficiency is low (patent 201310578359.2).Moreover, at present
Still lack method that is a kind of while preparing multilayer self-supporting carbon film.Therefore, explore a kind of simple process, can produce in enormous quantities from
Support carbon film preparation process that there is great application value.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the purpose of the present invention is to provide a kind of multilayers for preparing from branch
The method for supportting carbon film, wherein by being improved to the material etc. of crucial multilayer precursor film attachment, compared with prior art
Obtain the carbon-based films of multilayer self-supporting for the first time, and can effectively solve the problem that between self-supporting carbon-based films and substrate be easy adhesion and
Self-supporting carbon-based films easy to damage when leading to problems such as to separate；Also, the present invention to multilayer precursor film is subsequent also by being used
Pyrolysis processing technique preferably controlled, using specific temperature and the pre-oxidation treatment and carbonization treatment of handling duration, into one
Step ensures the quality of multilayer self-supporting carbon-based films product.
To achieve the above object, it is proposed, according to the invention, provide a kind of method for preparing multilayer self-supporting carbon-based films, feature
It is, comprising the following steps:
(1) it using carbon matrix precursor as raw material, is dissolved in forming carbon matrix precursor solution in solvent；It is then based on carbon forerunner
Liquid solution obtains precursor solution；
(2) precursor solution that the step (1) obtains is laid in the hard substrate that surface is covered with PE film or PP film
On, form bottom precursor solution layer；Then, newly tile PE film or PP film on the bottom precursor solution layer, then
The precursor solution is laid on the new PE film or new PP film again, second bottom precursor solution layer is formed, before thus obtaining multilayer
Drive solution layer；Then drying and processing is carried out, multilayer precursor film is obtained；
(3) carrying out pyrolysis processing to the multilayer precursor film can be obtained the carbon-based films of multilayer self-supporting.
As present invention further optimization, in the step (3), the pyrolysis processing includes pre-oxidation treatment and carbonization
Handle two stages, wherein the pre-oxidation treatment be 200 DEG C -300 DEG C at a temperature of heat treatment 1- is carried out in air
4 hours, the carbonization treatment be 1100 DEG C -1400 DEG C at a temperature of heat treatment 1-3 is carried out under protective gas atmosphere
Hour, the protective gas is nitrogen or argon gas；
When unstable under the conditions of hard substrate temperature locating for the carbonization treatment, the step (3) is specifically
The PE film or PP UF membrane of hard substrate and the bottom after the drying and processing that first step (2) is obtained, are attached to
Multilayer precursor film on PE film or PP film；Then it, then to the multilayer precursor film being attached on PE film or PP film carries out
Pyrolysis processing obtains the carbon-based films of multilayer self-supporting；
When stablizing under the conditions of hard substrate temperature locating for the carbonization treatment, the step (3) is specifically straight
It connects and is pyrolyzed the hard substrate after drying and processing that the step (2) obtains together with the multilayer precursor film thereon
Processing makes the reaction of multilayer precursor film generate the carbon-based films of multilayer self-supporting, finally again props up the hard substrate and the multilayer certainly
The carbon-based films of the isolated multilayer self-supporting of the carbon-based films of support.
It further include active material in the precursor solution in the step (1) as present invention further optimization, tool
Body is that active material particles are then uniformly mixed to be obtained by being added into the carbon matrix precursor solution；Preferably, active material
Material includes at least one of metal oxide, sulfide, elementary silicon, silica, metal simple-substance, Prussian blue, the activity
Material particles partial size is preferably greater than or equal to 10nm and less than 10 μm.
As present invention further optimization, in the step (2), the tiling of the precursor solution is using curtain coating
Method；
It further include repeating new tiling PE film or PP film and continuing the precursor solution that tiles in the step (2)
Thus process obtains precursor solution multilayer precursor solution layer of the number not less than three layers layer by layer.
As present invention further optimization, in the step (2), any one layer PE film or PP film with a thickness of 1-
50 microns.
As present invention further optimization, in the step (2), the drying and processing is under vacuum at 50-120 DEG C
Drying and processing 1-12 hours.
As present invention further optimization, in the step (1), the raw material carbon matrix precursor include carbohydrate,
At least one of nitrile, resin, pitch；The solvent is water or organic solvent, it is preferred that the organic solvent is N, N- bis-
Methylformamide (DMF).
Contemplated above technical scheme through the invention, compared with prior art, due to using PE film or PP film conduct
Adhere to the sacrificial layer of presoma, and multilayer high quality self-supporting hard carbon sill can be prepared using the stacking of PE film or PP film
Thick film (including carbon film and carbon composite membrane, carbon composite membrane pass through compound other active materials to carbon film according to different performance demand
It is modified), by taking the preparation of carbon film as an example, carbon film is formed in the present invention after carbon matrix precursor pyrolysis, and after PE film or the pyrolysis of PP film
It almost volatilizees, therefore can avoid adhesion between carbon film and substrate, carbon film and carbon film, and then form the discrete self-supporting of multilayer
Carbon film.It is the advantages of preparation method in the present invention: (1) simple process and low cost；(2) multilayer thick film can continuously be prepared；(3)
Can compound different active material be modified；(4) easily batch production.
Multilayer self-supporting carbon-based films have been prepared in the present invention for the first time, by the superposition of multilayer self-supporting carbon-based films, can obtain
Obtain the self-supporting carbon-based films thick film of high quality；A thick self-supporting carbon-based films are formed compared to primary coating to be pyrolyzed subsequent
Fine pore is easy to produce in journey causes thick film entirety compactness not high, and the PE film or PP film in preparation method of the present invention are in pyrolysis
It forms gas-phase carbon and secondary carbon coating is carried out to carbon film, can effectively reduce specific surface, promote the degree of graphitization of carbon surface.Also,
Since PE film or PP film being used for multiple times in preparation process of the present invention, for example, there is inside obtained multilayer precursor film to
Few PE film or PP film, so that each self-supporting carbon in the finally obtained multilayer self-supporting carbon film product of preparation method of the present invention
Separation between film layer is also easy to accomplish.PE film or PP film thickness of the present invention are preferably 1-50 microns, further really
Intensity has been protected, has been also convenient for being laid with.
The present invention due to using PE film or PP film as sacrificial layer, can be very easily by carbon film presoma from hard base
It is stripped down on plate, prior art preparation method is avoided to be easy to cause due to the adhesive between carbon film presoma and substrate
The damage of carbon film presoma when removing.It added one between substrate and carbon film presoma and carbon film presoma in the present invention
Layer PE or PP expendable film to can avoid damage when carbon film presoma is stripped down from substrate, and is also convenient for multilayer certainly
Support the separation in carbon film product between each self-supporting carbon film layer.
The present invention also passes through preferably tool, and there are two the pyrolysis processing in stage processing multilayer precursor films to obtain multilayer self-supporting
Carbon-based films, that is, by pyrolysis processing be divided into 200 DEG C -300 DEG C at a temperature of heat 1-4 hours (such as 260 in air
Heat 2 hours at DEG C) the pre-oxidation treatment stage, and 1100 DEG C -1400 DEG C at a temperature of heat 1-3 hours
The carbonization treatment stage of (heating 1 hour at such as 1100 DEG C) forms the thermostabilization structure of high-sequential in pre-oxidizing stage,
To keep its structure in high temperature cabonization constant, form is kept, other is removed in carbonation stage and does not need element, form hard carbon material
Material can obtain excellent performance in the application of power battery.
Detailed description of the invention
The thermogravimetric curve of PE film in Fig. 1 embodiment 1.
The photo of the compound carbon film of Si C in Fig. 2 embodiment 1.
The XRD curve of the compound carbon film of Si C in Fig. 3 embodiment 1.
Charging and discharging curve of the compound carbon film of Si C as negative electrode of lithium ion battery in Fig. 4 embodiment 1.
The cross-section photograph of the compound carbon film of Si C in Fig. 5 embodiment 2.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
It is in short dissolved using carbon matrix precursor as raw material that the method for multilayer self-supporting carbon film is prepared in the present invention
Carbon matrix precursor solution is formed in solvent, other active materials is then added into carbon matrix precursor solution after mixing, by carbon
Precursor solution, which is coated on polypropylene (PP) or polyethylene (PE) film, forms carbon matrix precursor film, after precursor film pyrolysis
Form self-supporting carbon film.
Wherein, carbon matrix precursor is the organic matters such as the substance that carbon can be generated, including carbohydrate, nitrile, resin, pitch
And combinations thereof；Active material refers to that (such as the organic matter containing specific objective element is pyrolyzed in this way for inorganic material or organic material
After specific objective element can be introduced into carbon-based films), including metal oxide, sulfide, silicon, silica, metal and Pu Lu
The materials such as scholar's indigo plant；Solvent refers to the organic solvents such as water or N,N-dimethylformamide (DMF).
Specifically, this method comprises the following steps:
(1) carbon matrix precursor solution is prepared；Optionally, other active materials can be added according to the composition of target product above-mentioned
It is uniformly mixed in solution；
(2) above-mentioned solution is coated uniformly on PE film or PP film and forms single layer thick film；
(3) such as need multilayer thick film, can on single layer thick film layer overlay PE film or PP film again, be then coated with one
Layer carbon matrix precursor solution, and then form the double-deck thick film；
(4) it repeats the above process, multilayer thick film can be obtained；
(5) above-mentioned thick film is by dry, pre-oxidation and carburising step, can form single layer, bilayer and three layers or more
MULTILAYER COMPOSITE carbon film.
The following are specific embodiments:
Embodiment 1
The embodiment the following steps are included:
(1) polyacrylonitrile powder 2g is weighed, is added in 10ml n,N-Dimethylformamide, the stirring and dissolving at 80 DEG C, shape
At the solution with certain viscosity.
(2) it weighs 2g silicon powder to be added in above-mentioned solution, magnetic agitation 12 hours at 80 DEG C.
(3) uniformly mixed above-mentioned solution is laid in surface using the tape casting to be covered on the glass plate of PE film, then again
In its surface tiling PE film, solution is laid on 1 micron thick of PE film using the tape casting, is gently rolled with glass bar again
It is flat.Process above is repeated, multilayer can be prepared, be placed in 60 DEG C of vacuum drying ovens later 12 hours.
(4) the PE preservative film for being coated with carbon film is taken off from glass plate, is then pre-oxidized 2 hours in 260 DEG C of air,
It is carbonized 1 hour at 1100 DEG C, finally obtains multilayer self-supporting Si@C composite membrane.
Embodiment 2
The embodiment the following steps are included:
(1) 2g sucrose is dissolved in the phenolic resin aqueous solution of 2g 48.5%, stirs 30 minutes, obtains at 60 DEG C
Precursor solution.
(2) above-mentioned solution is laid on the glass plate for the PE film that surface is covered with 20 microns thick using the tape casting, then again
It tiles PE film, solution is laid on PE film again, with glass bar gently rolling on its surface.Process above is repeated, it can
Multilayer is prepared, is placed in 100 DEG C of vacuum drying ovens later 1 hour.
(3) the PE preservative film for being coated with carbon film is taken off from glass plate, is then pre-oxidized 4 hours in 200 DEG C of air,
It is carbonized 1 hour at 1400 DEG C, finally obtains multilayer self-supporting carbon film.
Embodiment 3
The embodiment the following steps are included:
(1) polyacrylonitrile powder 1g is weighed, is added in 10ml n,N-Dimethylformamide, the stirring and dissolving at 80 DEG C, shape
At the solution with certain viscosity.
(2) 1g silicon powder/composite titania material (Si@TiO is weighed2) be added in above-mentioned solution, the magnetic force at 80 DEG C
Stirring 12 hours.
(3) above-mentioned solution surface is laid in using the tape casting to be covered on the glass plate of PE film, it is then flat on its surface again
Solution, is laid on PP film by one layer 40 microns thick of PP film of paving again, with glass bar gently rolling.Process above is repeated, it can
Multilayer is prepared, is placed in 80 DEG C of vacuum drying ovens later 12 hours.
(4) the PP film for being coated with carbon film is taken off from glass plate, is then pre-oxidized 1 hour in 300 DEG C of air,
It is carbonized 3 hours at 1100 DEG C, finally obtains multilayer self-supporting Si@TiO2Compound carbon film.
The present invention also tests and analyzes raw material used by above-described embodiment and product obtained, specific as follows:
Fig. 1 is the thermogravimetric curve of PE film used in embodiment 1.From the figure, it can be seen that PE film is weightless in pyrolytic process
Close to 100%, illustrate that PE film can sufficiently be pyrolyzed into gas phase composition and volatilize, and then avoid the adhesion between film and substrate, film and film.
Fig. 2 is the photo of the compound carbon film of Si C in embodiment 1.It can be seen that the obtained compound carbon film shape of Si C is complete
Whole, surfacing is long and wide up to 10cm and 5cm or so, illustrates that the technique is suitble to prepare self-supporting large scale carbon film.
Fig. 3 is the XRD diffracting spectrum of the compound carbon film of Si C in embodiment 1, it can be seen from the figure that synthesized composite wood
Material is the compound phase of silicon and amorphous carbon.
In addition, the compound carbon film of Si C in embodiment 1 is tested applied to negative electrode of lithium ion battery, obtain Fig. 4's
Charging and discharging curve.It can be seen from the figure that the prepared compound carbon film of Si C shows high as negative electrode of lithium ion battery
Charge/discharge capacity, discharge capacity has been more than 1600mA/g for the first time, and first charge discharge efficiency has 88.8%, shows that excellent charge and discharge is electrical
Energy.
Fig. 5 is the section SEM photograph of the compound carbon film of multilayer Si C in embodiment 2, from the figure, it can be seen that being heat-treated
In, PE film is almost pyrolyzed, therefore forms 4 layers of discrete self-supporting carbon film, and the thickness of film is from 5 microns to 90 micron.This says
The bright technique is suitble to prepare multilayer self-supporting carbon film, and the thickness of carbon film can regulate and control.
In the present invention, above embodiments are not limited to for used raw material type, quality and pyrolysis temperature, time etc.
In specific numerical value.
Other than glass substrate employed in above-described embodiment, the present invention can also be using other non-flexible substrates (such as
Common silicon substrate etc.) it is used as hard substrate.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (7)
1. a kind of method for preparing multilayer self-supporting carbon-based films, which comprises the following steps:
(1) it using carbon matrix precursor as raw material, is dissolved in forming carbon matrix precursor solution in solvent；It is molten to be then based on the carbon matrix precursor
Liquid obtains precursor solution；
(2) precursor solution that the step (1) obtains is laid in surface to be covered on the hard substrate of PE film or PP film, shape
At bottom precursor solution layer；Then, newly tile PE film or PP film on the bottom precursor solution layer, then again by institute
It states precursor solution to be laid on the new PE film or new PP film, forms second bottom precursor solution layer, thus obtain multilayer precursor solution
Layer；Then drying and processing is carried out, multilayer precursor film is obtained；
(3) carrying out pyrolysis processing to the multilayer precursor film can be obtained the carbon-based films of multilayer self-supporting.
2. the method for preparation multilayer self-supporting carbon-based films as described in claim 1, which is characterized in that described in the step (3)
Pyrolysis processing includes two stages of pre-oxidation treatment and carbonization treatment, wherein the pre-oxidation treatment is at 200 DEG C -300 DEG C
At a temperature of carried out in air heat treatment 1-4 hours, the carbonization treatment be 1100 DEG C -1400 DEG C at a temperature of in protection
Property gas atmosphere under carry out heat treatment 1-3 hour, the protective gas be nitrogen or argon gas；
When unstable under the conditions of hard substrate temperature locating for the carbonization treatment, the step (3) is specifically first will
The PE film or PP UF membrane of hard substrate and the bottom after the drying and processing that the step (2) obtains, obtain being attached to PE film
Or the multilayer precursor film on PP film；Then it, then to the multilayer precursor film being attached on PE film or PP film is pyrolyzed
Processing obtains the carbon-based films of multilayer self-supporting；
When stablizing under the conditions of hard substrate temperature locating for the carbonization treatment, the step (3) is specifically directly will
Hard substrate after the drying and processing that the step (2) obtains carries out pyrolysis processing together with the multilayer precursor film thereon
The reaction of multilayer precursor film is set to generate the carbon-based films of multilayer self-supporting, finally again by the hard substrate and the multilayer self-supporting
The carbon-based films of the isolated multilayer self-supporting of carbon-based films.
3. the method for preparation multilayer self-supporting carbon-based films as described in claim 1, which is characterized in that described in the step (1)
It further include active material in precursor solution, it is then mixed particular by active material particles are added into the carbon matrix precursor solution
What conjunction uniformly obtained；Preferably, active material includes metal oxide, sulfide, elementary silicon, silica, metal simple-substance, Pu Lu
At least one of scholar's indigo plant, the active material particles partial size are preferably greater than or equal to 10nm and less than 10 μm.
4. the method for preparation multilayer self-supporting carbon-based films as described in claim 1, which is characterized in that described in the step (2)
The tiling of precursor solution is using the tape casting；
It further include repeating new tiling PE film or PP film and continuing to tile the process of the precursor solution in the step (2),
Thus precursor solution multilayer precursor solution layer of the number not less than three layers layer by layer is obtained.
5. the method for preparation multilayer self-supporting carbon-based films as described in claim 1, which is characterized in that in the step (2), arbitrarily
One layer of PE film or PP film with a thickness of 1-50 microns.
6. the method for preparation multilayer self-supporting carbon-based films as described in claim 1, which is characterized in that described in the step (2)
Drying and processing is under vacuum drying and processing 1-12 hours at 50-120 DEG C.
7. the method for preparation multilayer self-supporting carbon-based films as described in claim 1, which is characterized in that described in the step (1)
Raw material carbon matrix precursor includes at least one of carbohydrate, nitrile, resin, pitch；The solvent be water or organic solvent,
Preferably, the organic solvent is n,N-Dimethylformamide (DMF).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114436660A (en) * | 2022-02-22 | 2022-05-06 | 合肥工业大学 | Preparation method of carbon nano tube-ceramic composite membrane |
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| CN101679788A (en) * | 2007-04-20 | 2010-03-24 | 马普科技促进协会 | Highly conductive, transparent carbon films as electrode materials |
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