CN104694989B - A kind of preparation method of graphene-based metallic composite - Google Patents
A kind of preparation method of graphene-based metallic composite Download PDFInfo
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- CN104694989B CN104694989B CN201510107704.3A CN201510107704A CN104694989B CN 104694989 B CN104694989 B CN 104694989B CN 201510107704 A CN201510107704 A CN 201510107704A CN 104694989 B CN104694989 B CN 104694989B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
Abstract
The invention provides a kind of preparation method of graphene-based metallic composite, first using graphene aerogel as three-electrode system in working electrode, using the method for electro-deposition, obtain graphene-based metal composite pre-product, then, the graphene-based metal composite pre-product for obtaining is again through being thermally treated resulting in graphene-based metallic composite.Due to the method using electro-deposition so that the preparation method of the graphene-based metallic composite that the present invention is provided is not related to any high energy consumption high pollution operation, environment friendly is strong.
Description
Technical field
The invention belongs to graphene-based field of compound material, and in particular to a kind of preparation of graphene-based metallic composite
Method.
Background technology
Graphene is a kind of monolayer carbon atomic plane two-dimensional material separated from graphite material, is to build other dimension charcoals
Material is such as：The basic structural unit of zero dimension fullerene, one-dimensional nano carbon pipe and graphite etc..The unique structure of Graphene has which
There are many peculiar properties, such as：Graphene has room-temperature quantum Hall effect；Its intensity is highest in current all material
, up to 130GPa；Its carrier mobility reaches 15000cm2.V-1.s-1, more than more than 10 times of commercial silicon chip mobility；Heat
Conductance is up to 5000W.m-1.K-1, it is 3 times of diamond, is more than 5 times of Carbon fibe；Additionally, the theoretical specific surface of Graphene
Product is also very high, has reached 2630m in theory2.g-1。
Three-dimensional grapheme not only partly remains the unique excellent mechanics of Graphene, calorifics and electric property, will also be to stone
The research viewpoint of black alkene is changed from microcosmic nano material to macroscopical block materials, and further macroscopical lower good using establishing for which
Basis.In three-dimensional grapheme, at most, which is integrated with Graphene and aeroge high-ratio surface, Gao Kong to the advantage of graphene aerogel
The advantages of gap rate, high conductivity and good thermal conductivity, detector, catalyst and its carrier, absorption, electrochemical energy storage with
And the field such as capacitor has great application potential.
As the intensity of simple graphite oxide aerogel is relatively low, constrain which and further apply, therefore, people are by mesh
Light is focused in the modification of three-dimensional grapheme aeroge, with graphene aerogel and the composite of metal in numerous method of modifying
Attention rate it is higher.In prior art, prepare more than the method for graphene-based metallic composite using methane, ethene as carbon
Source, is prepared under 700～1000 DEG C of hot conditions, not only high energy consumption, and the tail gas for producing causes dirt to environment
Dye.
The content of the invention
The present invention is carried out to solve the above problems, by providing a kind of new graphene-based metallic composite
Preparation method, further improves the environment friendly of graphene-based metallic composite preparation process.
Present invention employs following technical scheme：
The preparation method of the graphene-based metallic composite that the present invention is provided, has the feature that, including following step
Suddenly：
Step one, using graphene aerogel as the working electrode in three-electrode system, is 1～7 with metal in pH
In the electrolyte of ion, 0.1～24h of electro-deposition under 25～90 DEG C of temperature conditionss obtains graphene-based metal composite pre-product；
Step 2, by the graphene-based metal composite pre-product in step one in atmosphere of inert gases, is 100 in temperature
1～10h of heat treatment is carried out under conditions of～900 DEG C, the graphene-based metallic composite is obtained.
The preparation method of the graphene-based metallic composite that the present invention is provided, can also have the feature that：Also wrap
Include the graphene-based metal composite pre-product that will be obtained in step one and pH be dipped in clear water the step of being 7.
The preparation method of the graphene-based metallic composite that the present invention is provided, can also have the feature that：Step
In one, the preparation method of graphene aerogel is：Configuration concentration is the graphene oxide water solution of 0.01～10mg/mL, Jing 100
Graphene hydrogel, the freeze-drying under the conditions of -60 DEG C of Graphene hydrogel are formed under the conditions of～200 DEG C after hydro-thermal process 20h
Graphene aerogel is obtained after 72h.
The preparation method of the graphene-based metallic composite that the present invention is provided, can also have the feature that：Step
In two, electrolyte is made up of buffer solution and metal ion liquid,
Buffer solution includes 0.01～1mol/L Na3C6H5O7·2H2O, 0.01～1mol/L H3BO3And 0.01～
1mol/L NaH2PO2·H2O,
Metal ion liquid includes 0.01～1mol/L FeSO4·7H2O, 0.01～1mol/L CoSO4·7H2O、0.01
～1mol/L CuSO4·5H2O and 0.01～1mol/L MnSO4In any one or a few.
The preparation method of the graphene-based metallic composite that the present invention is provided, can also have the feature that：Step
In two, atmosphere of inert gases is any one in nitrogen atmosphere and argon atmosphere.
The preparation method of the graphene-based metallic composite that the present invention is provided, can also have the feature that：Three
In electrode system, platinized platinum and the dry mercury electrode of saturation are respectively as to electrode and reference electrode.
Invention effect and effect
The invention provides a kind of preparation method of graphene-based metallic composite, first using graphene aerogel as
Working electrode in three-electrode system, using the method for electro-deposition, obtains graphene-based metal composite pre-product, then, obtains
Graphene-based metal composite pre-product again through being thermally treated resulting in graphene-based metallic composite.Due to using electro-deposition
Method so that the preparation method of the graphene-based metallic composite that the present invention is provided is not related to any high energy consumption high pollution behaviour
Make, environment friendly is strong.
Description of the drawings
Fig. 1 is the SEM figures of graphene aerogel in embodiments of the invention one；
Fig. 2 is the SEM figures of graphene-based metallic composite in embodiments of the invention two；
Fig. 3 is the Raman collection of illustrative plates of the graphene-based metallic composite in embodiments of the invention two；
Fig. 4 is the infrared spectrogram of the graphene-based metallic composite in embodiments of the invention two；
Fig. 5 is the intensity map of the graphene-based metallic composite in embodiments of the invention four；
Fig. 6 is the SEM figures of the graphene-based metallic composite in embodiments of the invention seven.
Specific embodiment
The specific embodiment of the present invention is illustrated below in conjunction with accompanying drawing.
The preparation method of graphene aerogel
Embodiment one
Present embodiments provide the preparation method of graphene aerogel：Configuration concentration is the oxidation stone of 0.01～10mg/mL
Black aqueous solution, forms Graphene hydrogel Jing after hydro-thermal process 20h under the conditions of 100～200 DEG C, and Graphene hydrogel is -60
Under the conditions of DEG C after freeze-drying 72h to graphene aerogel.
SEM figures of the Fig. 1 for the graphene aerogel of the present embodiment.
As shown in figure 1, graphene sheet layer is continuous in the microstructure of graphene aerogel, it is hierarchical porous structure.
The preparation method of graphene-based metallic composite
Embodiment two
The preparation method of the graphene-based metallic composite in the present embodiment is method for optimizing, is comprised the following steps：
Graphene aerogel in embodiment one is carried out electro-deposition in three-electrode system by step one, wherein, embodiment
Graphene aerogel in one is working electrode, and Pt pieces and the dry mercury electrode of saturation are respectively to electrode and reference electrode, electrolysis
Liquid system is 0.24mol/L FeSO4·7H2O、0.16mol/L CoSO4·7H2O、0.8mol/L Na3C6H5O7·2H2O、
0.2mol/L H3BO3And 0.8mol/L NaH2PO2·H2The mixed liquor of O, pH are 3, and depositing temperature is 60 DEG C, and sedimentation time is
2h, obtains graphene-based metal composite pre-product；
Step 2, it is 7 that the graphene-based metal composite pre-product in step one is dipped in clear water pH, obtains time stone
Mertenyl metallic composite；
Step 3, by the schungite thiazolinyl metallic composite in step 2 under the protection of condition of nitrogen gas, in temperature be
Heat treatment 5h is carried out under conditions of 500 DEG C, graphene-based metallic composite is obtained.
The compression strength of the graphene-based metallic composite prepared according to the method for the present embodiment is 100KPa, and resistance is
10-100Ω。
SEM figures of the Fig. 2 for the graphene-based metallic composite in the present embodiment.
As shown in Fig. 2 by the electro-deposition techniques in the present embodiment, metallic particles can be made uniformly to be grown in Graphene
In the pore structure of aeroge.
Raman spectrograms of the Fig. 3 for the graphene-based metallic composite in the present embodiment.
As shown in figure 3, electro-deposition techniques cause metallic particles to produce physical absorption with graphene aerogel, do not produce new
Chemical bond, remains the excellent physicochemical properties of graphene aerogel.
Infrared spectrograms of the Fig. 4 for the graphene-based metallic composite of the present embodiment.
As shown in figure 4, the electro-deposition techniques through different time are processed, graphene aerogel does not produce new chemistry
Key, remains itself good physicochemical properties.
Embodiment three
The preparation method of graphene-based metallic composite, comprises the following steps：
Graphene aerogel in embodiment one is carried out electro-deposition in three-electrode system by step one, wherein, embodiment
Graphene aerogel in one is working electrode, and Pt pieces and the dry mercury electrode of saturation are respectively to electrode and reference electrode, electrolysis
Liquid system is 0.5mol/L FeSO4·7H2O、0.5mol/L MnSO4、1.0mol/L Na3C6H5O7·2H2O、0.3mol/L
H3BO3And 0.5mol/L NaH2PO2·H2The mixed liquor of O, pH are 4, and depositing temperature is 60 DEG C, and sedimentation time is 6h, obtains stone
Mertenyl metal composite pre-product；
Step 2, it is 7 that the graphene-based metal composite pre-product in step one is dipped in clear water pH, obtains time stone
Mertenyl metallic composite；
Step 3, by the schungite thiazolinyl metallic composite in step 2 under the protection of condition of nitrogen gas, in temperature be
Heat treatment 10h is carried out under conditions of 100 DEG C, graphene-based metallic composite is obtained.
The compression strength of the graphene-based metallic composite prepared according to the method for the present embodiment is 50KPa or so, electric
Hinder for 10-100 Ω.
Example IV
The preparation method of graphene-based metallic composite, comprises the following steps：
Graphene aerogel in embodiment one is carried out electro-deposition in three-electrode system by step one, wherein, embodiment
Graphene aerogel in one is working electrode, and Pt pieces and the dry mercury electrode of saturation are respectively to electrode and reference electrode, electrolysis
Liquid system is 1.0mol/L FeSO4·7H2O、1mol/L CuSO4·5H2O、0.5mol/L Na3C6H5O7·2H2O、0.5mol/
L H3BO3And 0.8mol/L NaH2PO2·H2The mixed liquor of O, pH are 2, and depositing temperature is 25 DEG C, and sedimentation time is 24h, is obtained
To graphene-based metal composite pre-product；
Step 2, it is 7 that the graphene-based metal composite pre-product in step one is dipped in clear water pH, obtains time stone
Mertenyl metallic composite；
Step 3, by the schungite thiazolinyl metallic composite in step 2 under the protection of condition of nitrogen gas, in temperature be
Heat treatment 0.1h is carried out under conditions of 900 DEG C, graphene-based metallic composite is obtained.
The compression strength of the graphene-based metallic composite prepared according to the method for the present embodiment is 5KPa or so, resistance
For 10-100 Ω.
Fig. 5 is the graphene-based metallic composite stress strain diagram in the present embodiment.
Shown in Fig. 5, graphene-based metallic composite mechanical strength can reach 5KPa.
Embodiment five
The preparation method of graphene-based metallic composite, comprises the following steps：
Graphene aerogel in embodiment one is carried out electro-deposition in three-electrode system by step one, wherein, embodiment
Graphene aerogel in one is working electrode, and Pt pieces and the dry mercury electrode of saturation are respectively to electrode and reference electrode, electrolysis
Liquid system is 0.5mol/L CoSO4·5H2O、1mol/L MnSO4、0.01mol/L Na3C6H5O7·2H2O、0.8mol/L
H3BO3And 1mol/L NaH2PO2·H2The mixed liquor of O, pH are 2, and depositing temperature is 90 DEG C, and sedimentation time is 0.01h, is obtained
Graphene-based metal composite pre-product；
Step 2, it is 7 that the graphene-based metal composite pre-product in step one is dipped in clear water pH, obtains time stone
Mertenyl metallic composite；
Step 3, by the schungite thiazolinyl metallic composite in step 2 under the protection of condition of nitrogen gas, in temperature be
Heat treatment 5h is carried out under conditions of 500 DEG C, graphene-based metallic composite is obtained.
The compression strength of the graphene-based metallic composite prepared according to the method for the present embodiment is 30KPa or so, electric
Hinder for 10-100 Ω.
Embodiment six
The preparation method of graphene-based metallic composite, comprises the following steps：
Graphene aerogel in embodiment one is carried out electro-deposition in three-electrode system by step one, wherein, embodiment
Graphene aerogel in one is working electrode, and Pt pieces and the dry mercury electrode of saturation are respectively to electrode and reference electrode, electrolysis
Liquid system is 1mol/L CoSO4·5H2O、0.5mol/L CuSO4·5H2O、0.5mol/L Na3C6H5O7·2H2O、0.9mol/
L H3BO3And 0.01mol/L NaH2PO2·H2The mixed liquor of O, pH are 2, and depositing temperature is 60 DEG C, and sedimentation time is 10h, is obtained
To graphene-based metal composite pre-product；
Step 2, it is 7 that the graphene-based metal composite pre-product in step one is dipped in clear water pH, obtains time stone
Mertenyl metallic composite；
Step 3, by the schungite thiazolinyl metallic composite in step 2 under the protection of argon gas condition, in temperature be
Heat treatment 5h is carried out under conditions of 500 DEG C, graphene-based metallic composite is obtained.
The compression strength of the graphene-based metallic composite prepared according to the method for the present embodiment is 70KPa or so, electric
Hinder for 10-100 Ω.
Embodiment seven
The preparation method of graphene-based metallic composite, comprises the following steps：
Graphene aerogel in embodiment one is carried out electro-deposition in three-electrode system by step one, wherein, embodiment
Graphene aerogel in one is working electrode, and Pt pieces and the dry mercury electrode of saturation are respectively to electrode and reference electrode, electrolysis
Liquid system is 0.75mol/L FeSO47H2O、0.75mol/L CoSO4·7H2O、0.01mol/L MnSO4、0.8mol/L
Na3C6H5O7·2H2O、0.01mol/L H3BO3And 0.8mol/L NaH2PO2·H2The mixed liquor of O, pH are 7, depositing temperature
For 60 DEG C, sedimentation time is 12h, obtains graphene-based metal composite pre-product；
Step 2, it is 7 that the graphene-based metal composite pre-product in step one is dipped in clear water pH, obtains time stone
Mertenyl metallic composite；
Step 3, by the schungite thiazolinyl metallic composite in step 2 under the protection of argon gas condition, in temperature be
Heat treatment 5h is carried out under conditions of 500 DEG C, graphene-based metallic composite is obtained.
The compression strength of the graphene-based metallic composite prepared according to the method for the present embodiment is 20KPa or so, electric
Hinder for 10-100 Ω.
SEM figures of the Fig. 6 for the graphene-based metallic composite in the present embodiment.
As shown in fig. 6, graphenic surface is completely covered by metallic.
Embodiment eight
The preparation method of graphene-based metallic composite, comprises the following steps：
Graphene aerogel in embodiment one is carried out electro-deposition in three-electrode system by step one, wherein, embodiment
Graphene aerogel in one is working electrode, and Pt pieces and the dry mercury electrode of saturation are respectively to electrode and reference electrode, electrolysis
Liquid system is 0.01mol/L FeSO47H2O、0.75mol/L CuSO4·5H2O、1mol/L MnSO4、0.25mol/L
Na3C6H5O7·2H2O、1mol/L H3BO3And 0.25mol/L NaH2PO2·H2The mixed liquor of O, pH are 1, and depositing temperature is
60 DEG C, sedimentation time is 12h, obtains graphene-based metal composite pre-product；
Step 2, it is 7 that the graphene-based metal composite pre-product in step one is dipped in clear water pH, obtains time stone
Mertenyl metallic composite；
Step 3, by the schungite thiazolinyl metallic composite in step 2 under the protection of argon gas condition, in temperature be
Heat treatment 5h is carried out under conditions of 500 DEG C, graphene-based metallic composite is obtained.
The compression strength of the graphene-based metallic composite prepared according to the method for the present embodiment is 80KPa or so, electric
Hinder for 10-100 Ω.
Embodiment nine
The preparation method of graphene-based metallic composite, comprises the following steps：
Graphene aerogel in embodiment one is carried out electro-deposition in three-electrode system by step one, wherein, embodiment
Graphene aerogel in one is working electrode, and Pt pieces and the dry mercury electrode of saturation are respectively to electrode and reference electrode, electrolysis
Liquid system is 1mol/L CoSO4·7H2O、0.01mol/L CuSO4·5H2O、0.25mol/L MnSO4、0.5mol/L
Na3C6H5O7·2H2O、0.9mol/L H3BO3And 0.01mol/L NaH2PO2·H2The mixed liquor of O, pH are 2, depositing temperature
For 60 DEG C, sedimentation time is 12h, obtains graphene-based metal composite pre-product；
Step 2, it is 7 that the graphene-based metal composite pre-product in step one is dipped in clear water pH, obtains time stone
Mertenyl metallic composite；
Step 3, by the schungite thiazolinyl metallic composite in step 2 under the protection of argon gas condition, in temperature be
Heat treatment 5h is carried out under conditions of 500 DEG C, graphene-based metallic composite is obtained.
The compression strength of the graphene-based metallic composite prepared according to the method for the present embodiment is 100KPa or so, electric
Hinder for 10-100 Ω.
Embodiment ten
The preparation method of graphene-based metallic composite, comprises the following steps：
Graphene aerogel in embodiment one is carried out electro-deposition in three-electrode system by step one, wherein, embodiment
Graphene aerogel in one is working electrode, and Pt pieces and the dry mercury electrode of saturation are respectively to electrode and reference electrode, electrolysis
Liquid system is 0.25mol/L FeSO47H2O、0.25mol/L CoSO4·5H2O、0.25mol/L CuSO4·5H2O、
0.25mol/L MnSO4、0.8mol/L Na3C6H5O7·2H2O、0.2mol/L H3BO3And 0.8mol/L NaH2PO2·H2O
Mixed liquor, pH is 3, depositing temperature be 60 DEG C, sedimentation time is 2h, obtains graphene-based metal composite pre-product；
Step 2, it is 7 that the graphene-based metal composite pre-product in step one is dipped in clear water pH, obtains time stone
Mertenyl metallic composite；
Step 3, by the schungite thiazolinyl metallic composite in step 2 under the protection of argon gas condition, in temperature be
Heat treatment 5h is carried out under conditions of 500 DEG C, graphene-based metallic composite is obtained.
The compression strength of the graphene-based metallic composite prepared according to the method for the present embodiment is 100KPa or so, electric
Hinder for 10-100 Ω.
Embodiment is acted on and effect
Embodiment provides a kind of preparation method of graphene-based metallic composite, electric as three using graphene aerogel
Working electrode in polar body system, using the method for electro-deposition, obtains graphene-based metal composite pre-product, and graphene-based metal is multiple
Pre-product is closed again through soaking and being thermally treated resulting in graphene-based metallic composite.Due to the method using electro-deposition, make
The preparation process for obtaining graphene-based metallic composite is not related to any high energy consumption high pollution operation, and environment friendly is strong.
The graphene-based metallic composite prepared according to the method for embodiment removes the bigger serface with general gel
Outward, also with good mechanical strength, its anti-pressure ability can graphene-based metallic composite more of the prior art resistance to compression
Ability improves several to more than ten times, and the composite shapes are controllable, and electric conductivity is strong, and resistance is become by kilo-ohm level of graphene aerogel
For 10～100 Ω so that the graphene-based metallic composite has larger application prospect in terms of absorption and catalysis, also may be used
As electrode of super capacitor.
The invention is not restricted to the scope of specific embodiment, for those skilled in the art, as long as respectively
Kind of change described claim limit and the spirit and scope of the present invention that determine in, these changes be it will be apparent that
All are using the innovation and creation of present inventive concept in the row of protection.
Claims (6)
1. a kind of preparation method of graphene-based metallic composite, it is characterised in that comprise the following steps：
Step one, using graphene aerogel as the working electrode in three-electrode system, pH be in 1～7 with metal from
0.1～24h of electro-deposition in the electrolyte of son, under 25～90 DEG C of temperature conditionss, obtains graphene-based metal composite pre-product；
Step 2, by the described graphene-based metal composite pre-product in step one atmosphere of inert gases, temperature be 100～
1～10h of heat treatment is carried out under conditions of 900 DEG C, the graphene-based metallic composite is obtained.
2. the preparation method of graphene-based metallic composite according to claim 1, it is characterised in that：
In the step 2, before the heat treatment, also include that the described graphene-based metal composite that will be obtained in step one is produced in advance
Thing be dipped in clear water pH for 7 the step of.
3. the preparation method of graphene-based metallic composite according to claim 1, it is characterised in that：
Wherein, in step one, the preparation method of the graphene aerogel is：Configuration concentration is the oxidation of 0.01～10mg/mL
Graphene aqueous solution, forms Graphene hydrogel, the Graphene hydrogel after hydrothermal treatment 20h under the conditions of 100～200 DEG C
The graphene aerogel is being obtained after freeze-drying 72h under the conditions of -60 DEG C.
4. the preparation method of graphene-based metallic composite according to claim 1, it is characterised in that：
Wherein, in step one, the electrolyte is made up of buffer solution and metal ion liquid,
The buffer solution includes 0.01～1mol/L Na3C6H5O7·2H2O, 0.01～1mol/L H3BO3And 0.01～1mol/
L NaH2PO2·H2O,
The metal ion liquid includes 0.01～1mol/L FeSO4·7H2O, 0.01～1mol/L CoSO4·7H2O、0.01
～1mol/L CuSO4·5H2O and 0.01～1mol/L MnSO4In any one or a few.
5. the preparation method of graphene-based metallic composite according to claim 1, it is characterised in that：
Wherein, in the step 2, the atmosphere of inert gases is any one in nitrogen atmosphere and argon atmosphere.
6. the preparation method of graphene-based metallic composite according to claim 1, it is characterised in that：
Wherein, in the three-electrode system, platinized platinum and saturated calomel electrode are respectively as to electrode and reference electrode.
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| CN104973594B (en) * | 2015-06-26 | 2017-01-18 | 江苏大学 | Preparation method and applications of graphene aerogel |
| CN105420794B (en) * | 2015-11-13 | 2018-01-26 | 上海应用技术学院 | A kind of preparation method of graphene/ferriferrous oxide composite material |
| CN105800597B (en) * | 2016-02-26 | 2018-04-17 | 成都新柯力化工科技有限公司 | A kind of preparation method of mechanical stripping high conductivity composite graphite alkene |
| CN105923627B (en) * | 2016-06-07 | 2018-11-30 | 南京邮电大学 | A kind of preparation method of porous graphene |
| CN107513745B (en) * | 2016-06-15 | 2020-01-03 | 中国科学院兰州化学物理研究所苏州研究院 | Preparation method of graphene-metal oxide three-dimensional porous composite material |
| CN107256803A (en) * | 2017-06-29 | 2017-10-17 | 天津师范大学 | A kind of preparation method of graphene/carbon aerogel composite |
| CN110106534B (en) * | 2019-05-15 | 2021-03-26 | 南京理工大学 | Method for preparing super-hydrophobic nickel surface with wood mirror structure |
| CN111101172B (en) * | 2019-12-31 | 2021-02-09 | 新疆烯金石墨烯科技有限公司 | Graphene-aluminum composite material and preparation method thereof |
| CN113235130B (en) * | 2021-04-12 | 2022-09-06 | 中山大学 | Low-platinum composite material based on tungsten oxide/graphene aerogel and preparation method and application thereof |
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