CN108172411A - A kind of preparation method of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material - Google Patents
A kind of preparation method of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material Download PDFInfo
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- CN108172411A CN108172411A CN201810038664.5A CN201810038664A CN108172411A CN 108172411 A CN108172411 A CN 108172411A CN 201810038664 A CN201810038664 A CN 201810038664A CN 108172411 A CN108172411 A CN 108172411A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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
Abstract
The present invention provides a kind of preparation method of the sulfur and nitrogen co-doped graphene nanocomposite material of cobalt manganese alloy oxide, and preparation method mainly includes：Doped graphene at the beginning of preparing sulphur nitrogen with hydro-thermal method, sulfur and nitrogen co-doped graphene is made in the secondary doping process through high-temperature heat treatment again, Co-Mn metal salt mixture and ammonium hydroxide are introduced in sulfur and nitrogen co-doped graphene, hydro-thermal reaction realizes the preparation of cobalt manganese alloy oxide nano-slice/sulfur and nitrogen co-doped graphene nanocomposite material later.Nanocomposite prepared by the present invention can be applicable on electrode of super capacitor, show the capacitance of superelevation, outstanding high rate performance and good cyclical stability, and a cheap route easily extended is provided for using energy source.
Description
Technical field
The invention belongs to new energy and field of material technology, specifically a kind of cobalt manganese alloy oxide-sulfur and nitrogen co-doped stone
The preparation method of black alkene nanocomposite.
Background technology
Graphene possesses huge potential in the respective applications because of its unique electronic property.It is atom doped to change
The part composition and electronic structure of graphene, change its Electronic Performance.Recently, nitrogen-doped graphene because its in electronic device it is good
Performance cause the very big of people and pay attention to graphene nitrating usually there are three types of implementation methods：Increase in chemical vapor deposition (CVD)
It is added during length, the high-temperature heat treatment of nitrogen containing species or decomposition, NH3/N2The high-temperature heat treatment of plasma or decomposition.These sides
For method because of the limitation of reaction condition and equipment, cost is excessively high, can not carry out large-scale application.
The characteristics of due to business carbon electricity double layer capacitor low-voltage capacity, the faradic fake capacitance electricity of metal oxide base
Pole is considered as a kind of most promising electrode of super capacitor.Metal oxide resistor usually contains relatively low conductivity, with
The electronics transfer and capacitive property that the hydridization of conductance stent is expected to improve electrode.N- graphenes are because the doping of N improves it
Electronic conductivity, and possess two-dimensional structure.In terms of hybrid super capacitor electrode is made, N- graphenes are one good
Selection.
Invention content
In view of the above-mentioned problems, the present invention provides a kind of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nano composite wood
The preparation method of material, cobalt manganese alloy oxide nano-slice/sulfur and nitrogen co-doped graphite that this method can carry out in low temperature and solution
The preparation method of alkene nanocomposite overcomes tradition to prepare complex process, the shortcomings that cost is higher during nitrogen-doped graphene,
Gained nanocomposite shows capacitance (the 1551F g of superelevation-1), outstanding high rate performance and good stable circulation
Property.
Technical solution provided by the invention：A kind of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material
Preparation method, include the following steps：
(1) the graphite oxide powder of certain mass is taken to be dissolved in deionized water, adds sulfur-containing compound, anionic surface
Activating agent, nitrogenous compound A, after ultrasonic disperse dissolves, then by hydro-thermal reaction after, through filter be dried to obtain sulphur nitrogen just adulterate
Graphene；
(2) by the sulphur nitrogen obtained by step (1), just doped graphene is mixed with nitrogenous compound B, after tube furnace is calcined
To sulfur and nitrogen co-doped graphene (S, N- graphene)；
(3) cobalt salt and manganese salt mixed configuration cobalt-manganese salt mixture, then the sulfur and nitrogen co-doped stone obtained by by itself and step (2) are taken
Black alkene is dissolved in deionized water, is mixed evenly to obtain mixed liquor；
(4) ammonium hydroxide is added in into the mixed liquor obtained by step (3), it is dry through filtering in hydrothermal reaction kettle after heating reaction
It is dry to obtain cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material.
Further, the one kind or two of sulfur-containing compound in thioacetic acid, 2 mercapto ethanol described in step (1)
Kind, anion surfactant be selected from neopelex, dodecyl sodium sulfate, lauryl sodium sulfate one kind or
It is a variety of.
Further, nitrogenous compound A described in step (1) is selected from ammonium hydroxide, hexamethylenetetramine, urea, melamine
In it is one or more.
Further, graphite oxide powder, sulfur-containing compound, anion surfactant, nitrogen described in step (1)
The mass ratio for closing object A is 1：(1~10)：(0.5~5)：(2~15).
Further, hydrothermal temperature is 60~250 DEG C in the step (1), 5~72h of reaction time.
Further, 0.5~5h of ultrasonic time in the step (1), drying condition are：60-80 DEG C of temperature, time 1-
12h。
Further, in the step (2) nitrogenous compound B in hexamethylenetetramine, urea, melamine one
Kind is a variety of, the mass ratio (1~20) of nitrogenous compound B and the first doped graphene of sulphur nitrogen:1.
Further, the step (2) reaction temperature in tube furnace is 150~750 DEG C, the reaction time for 0.5~
10h。
Further, in the step (3), sulfur and nitrogen co-doped a concentration of 1~100mg/ml of graphene, cobalt salt is nitric acid
One kind in cobalt, cobaltous sulfate, cobalt chloride, cobalt oxalate, manganese salt is manganese nitrate, one kind in manganese sulfate, manganese chloride, manganese oxalate, two
Person in mass ratio 1:1 mixing.
Further, in the step (4), the ratio of sulfur and nitrogen co-doped graphene, ammonia and cobalt-manganese salt mixture for (1~
5)g：(10~18) g：(0.01~0.05) mol, reaction temperature is 150~250 DEG C in hydrothermal reaction kettle, the reaction time for 2~
5h。
Sulfur and nitrogen co-doped graphene (S, N- graphene) is prepared with solwution method the present invention provides a kind of, is added at low temperature
The method of the laminated nano composition of cobalt manganese alloy.Co-Mn metal salt possesses very high capacitance in theory, adds in sulfur-bearing
Reducing agent carries out redox reaction with graphene oxide, and the electronation graphene carried out in cryogenic fluid method also can
It realizes a large amount of doping of N, in addition, being used as the medium increased by adding in negatively charged surfactant, can close cobalt manganese
Gold and S, N- graphene are in close contact.Particularly secondary doping increases the doping of nitrogen so that prepared is sulfur and nitrogen co-doped
Graphene has higher capacitance and good high rate performance.Co-Mn metal salt mixture is introduced in sulfur and nitrogen co-doped graphene
When add in ammonium hydroxide as dispersant, ensure that hydro-thermal reaction fully carries out, make made from composite property it is more stable.The layer of synthesis
The nanocomposite of shape structure shows capacitance (the 1551F g of superelevation-1), outstanding high rate performance and good cycle
Stability.In energy storage and conversion, this low temperature method can provide a kind of novel route come it is extensive prepare containing
The nanocomposite high-performance electrode of sulfur and nitrogen co-doped graphene.
Description of the drawings
Fig. 1 is S, transmission electron microscope (TEM) image of N- graphenes.
Fig. 2 is the TEM image of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material.
Fig. 3 is that cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanometer composite electrode, pure cobalt manganese alloy oxide are received
Rice piece crystalline electrode and cobalt manganese alloy oxide nano-slice/sulfur and nitrogen co-doped graphene mixture electrode are under different discharge currents
The comparison of capacitance.
Fig. 4 is the cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanometer composite calculated under different scanning rates
The specific capacitor of electrode.
Fig. 5 is the electrochemical cycle stability of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanometer composite electrode
Curve.
Specific embodiment
Doped graphene at the beginning of the present invention prepares sulphur nitrogen with hydro-thermal method, using the reducing agent of sulfur-bearing, dispersant and some contain
Nitrogen compound completes the preliminary doping of sulphur nitrogen, then two through high-temperature heat treatment while reaction is promoted to be normally carried out
Sulfur and nitrogen co-doped graphene is made in secondary doping process.Then it is mixed with sulfur and nitrogen co-doped graphene with cobalt, manganese presoma, adds in ammonia
Water washs drying after hydro-thermal reaction.With reference to specific embodiments and the drawings, the present invention is described further.
Embodiment 1
Graphite oxide powder, thioacetic acid, neopelex, hexamethylenetetramine (mass ratio 1 are taken at room temperature:
1:0.5:2) the ultrasonic disperse 0.5h in 50ml deionized waters, later in reaction kettle 60 DEG C reaction 5h, through filter, dry (60 DEG C,
Sulphur nitrogen just doped graphene is obtained after 12h).By doped graphene at the beginning of sulphur nitrogen and melamine in mass ratio 1:2 mixing, are being connected with
400 DEG C of reaction 2h obtain sulfur and nitrogen co-doped graphene (S, N- graphene) in the tube furnace of nitrogen.Take cobalt-manganese salt mixture (Co
(NO 3)2、MnSO4Mass ratio 1:1 mixing) 0.01mol, S, N- graphenes 3g dissolves in 50ml deionized waters, is mixed evenly
After add 10g ammonium hydroxide, mixed solution reacts in hydrothermal reaction kettle at 200 DEG C is dried to obtain final product cobalt after 2h through filtering
Manganese alloy oxide nano-slice/sulfur and nitrogen co-doped graphene nanocomposite material.
Embodiment 2
Graphite oxide powder, 2 mercapto ethanol, lauryl sodium sulfate, ammonium hydroxide (mass ratio 1 are taken at room temperature:5:2:10) in
Ultrasonic disperse 2h in 50ml deionized waters, 100 DEG C of reaction 10h of reaction kettle, sulphur is obtained after filtering, drying (80 DEG C, 12h) later
The first doped graphene of nitrogen.By doped graphene at the beginning of sulphur nitrogen and hexamethylenetetramine in mass ratio 1:5 mixing, in the pipe for being connected with nitrogen
300 DEG C of reaction 5h obtain sulfur and nitrogen co-doped graphene (S, N- graphene) in formula stove.Take cobalt-manganese salt mixture (CoSO4、MnCl2Matter
Measure ratio 1:1 mixing) 0.05mol, S, N- graphenes 5g dissolved in 80ml deionized waters, and 16g ammonia is added after being mixed evenly
Water, mixed solution are dried to obtain final product cobalt manganese alloy oxide after reaction 5h at 230 DEG C in hydrothermal reaction kettle through filtering
Nanometer sheet/sulfur and nitrogen co-doped graphene nanocomposite material.
Embodiment 3
Graphite oxide powder, 2 mercapto ethanol, dodecyl sodium sulfate, melamine (mass ratio 1 are taken at room temperature:8:5:
15) the ultrasonic disperse 5h in 50ml deionized waters, 200 DEG C of reaction kettle reaction later for 24 hours, after filtering, drying (60 DEG C, 12h)
Obtain sulphur nitrogen just doped graphene.By doped graphene at the beginning of sulphur nitrogen and urea in mass ratio 1:15 mixing, in the pipe for being connected with nitrogen
500 DEG C of reaction 10h obtain sulfur and nitrogen co-doped graphene (S, N- graphene) in formula stove.Take cobalt-manganese salt mixture (CoCl2、MnC2O4
Mass ratio 1:1 mixing) 0.02mol, S, N- graphenes 2g dissolved in 80ml deionized waters, and 20g is added after being mixed evenly
Ammonium hydroxide, mixed solution are dried to obtain the oxidation of final product cobalt manganese alloy after reaction 3h at 250 DEG C in hydrothermal reaction kettle through filtering
Object nanometer sheet/sulfur and nitrogen co-doped graphene nanocomposite material.
Application example 1
The cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material obtained in embodiment 1 is configured to
The solution of 8mg/mL, applied in electrode of super capacitor.Wherein electrolyte is 0.5molL-1H2SO4, diaphragm is
Celgard3501, binding agent nafion ratio are 5%, deionized water and isopropanol ratios 1:4.By solution drop coating in graphitic carbon
As electrode slice on paper, using two electrode slices identical in quality as cathode and anode, it is assembled into button capacitor.It measures different
The specific capacity of capacitor under current density, the results are shown in Table 1, and when current density is in 2A/g, specific capacity reaches 1510Fg-1.When current density increases to 30Ag-1, still remain in 990Fg-1.Pure cobalt manganese alloy oxide nano-slice is used simultaneously
Crystalline electrode and cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene mixture as a control group, capacitance under different discharge currents
Comparison as shown in figure 3, the capacitance of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material for preparing of the present invention
Amount is significantly higher than control group.
The capacitance of 1 cobalt manganese alloy oxide of table-sulfur and nitrogen co-doped graphene nanocomposite material
Application example 2
The cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material obtained in embodiment 1 is configured to
The solution of 10mg/mL, in 0.5molL-1H2SO4As carrying out electro-chemical test, Ag/AgCl in the three-electrode system of electrolyte
For reference electrode, platinum electrode is auxiliary electrode.Binding agent nafion mass accounts for the 5% of active material, deionized water and isopropyl
Alcohol ratio 1:4, by solution drop coating on vitreous carbon, working electrode is used as after dry.CV is carried out under voltage 0-1.1V ranges to follow
Ring volt-ampere is tested, the cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material calculated under different scanning rates
The specific capacitor of electrode, test result are shown in Table 2, Fig. 4.
The capacitance of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material under 2 different scanning rates of table
Application example 3
The cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material obtained in embodiment 2 is configured to
The solution of 10mg/mL, applied in electrode of super capacitor.In 2molL-1Li2SO4For in the three-electrode system of electrolyte into
Row electrochemical cycle stability is tested, and wherein Ag/AgCl is reference electrode, and platinum electrode is auxiliary electrode.Binding agent PVDF
(polyvinylidene fluoride) ratio is 5%, deionized water and isopropanol ratios 1:4, by solution drop coating in vitreous carbon
On, it is used as working electrode after dry.Fig. 5 is the electricity of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanometer composite electrode
Chemical cycle stability curve, the capacitance of result show electrode are gradually increased due to activation when starting, and
It is not deteriorated significantly in 10000 cycles.
The foregoing is merely the detailed descriptions of specific embodiments of the present invention, do not limit the present invention with this, all at this
All any modification, equivalent and improvement made in the mentality of designing of invention etc., should be included in protection scope of the present invention it
It is interior.
Claims (10)
- A kind of 1. preparation method of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material, it is characterised in that packet Include following steps：(1) graphite oxide powder, sulfur-containing compound, anion surfactant, the nitrogenous compound A of certain mass are taken, is dissolved in In deionized water, after ultrasonic disperse dissolves, then doped graphene at the beginning of by being dried to obtain sulphur nitrogen through suction filtration after hydro-thermal reaction；(2) by the sulphur nitrogen obtained by step (1), just doped graphene is mixed with nitrogenous compound B, and sulphur is obtained after tube furnace is calcined Nitrogen co-doped graphene；(3) take cobalt salt and manganese salt mixed configuration cobalt-manganese salt mixture, then by its with step (2) obtained by sulfur and nitrogen co-doped graphene It is dissolved in deionized water, is mixed evenly to obtain mixed liquor；(4) ammonium hydroxide is added in into the mixed liquor obtained by step (3), in hydrothermal reaction kettle after heating reaction, dry through suction filtration To cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material.
- 2. the preparation side of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material according to claim 1 Method, it is characterised in that：Sulfur-containing compound described in step (1) is the reducing agent of sulfur-bearing, in thioacetic acid, 2 mercapto ethanol One or two, anion surfactant be selected from neopelex, dodecyl sodium sulfate, dodecyl sulphate Sodium it is one or more.
- 3. the preparation side of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material according to claim 1 Method, it is characterised in that：Nitrogenous compound A is in ammonium hydroxide, hexamethylenetetramine, urea, melamine described in step (1) It is one or more.
- 4. the preparation side of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material according to claim 2 Method, it is characterised in that：Graphite oxide powder, sulfur-containing compound, anion surfactant, nitrogenous chemical combination described in step (1) The mass ratio of object A is 1：(1~10)：(0.5~5)：(2~15).
- 5. the preparation side of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material according to claim 1 Method, it is characterised in that：Hydrothermal temperature is 60~250 DEG C in the step (1), 5~72h of reaction time.
- 6. the preparation side of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material according to claim 1 Method, it is characterised in that：0.5~5h of ultrasonic time in the step (1), drying condition are：60-80 DEG C of temperature, time 1-12h.
- 7. the preparation side of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material according to claim 1 Method, it is characterised in that：The one kind of nitrogenous compound B in hexamethylenetetramine, urea, melamine in the step (2) Or a variety of, the mass ratio (1~20) of nitrogenous compound B and the first doped graphene of sulphur nitrogen:1.
- 8. the preparation of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material according to claim 1 or 7 Method, it is characterised in that：The step (2) reaction temperature in tube furnace is 150~750 DEG C, and the reaction time is 0.5~10h.
- 9. the preparation side of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material according to claim 1 Method, it is characterised in that：Sulfur and nitrogen co-doped a concentration of 1~100mg/ml of graphene in the mixed liquor of the step (3), cobalt salt is nitre One kind in sour cobalt, cobaltous sulfate, cobalt chloride, cobalt oxalate, manganese salt is manganese nitrate, one kind in manganese sulfate, manganese chloride, manganese oxalate, The two in mass ratio 1:1 mixing.
- 10. the preparation side of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material according to claim 1 Method, it is characterised in that：In the step (4), the ratio of sulfur and nitrogen co-doped graphene, ammonium hydroxide and cobalt-manganese salt mixture is (1~5) g：(10~18) g：(0.01~0.05) mol, reaction temperature is 150~250 DEG C in hydrothermal reaction kettle, and the reaction time is 2~5h.
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| CN112824886A (en) * | 2019-11-21 | 2021-05-21 | 中国石油化工股份有限公司 | Gold-copper oxide nano composite electrode taking nitrogen-sulfur doped graphene paper as substrate and preparation method and application thereof |
| CN113912816A (en) * | 2021-11-13 | 2022-01-11 | 深圳前海石墨烯产业有限公司 | Graphene polyurethane composite sponge material and preparation method and application thereof |
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