CN108892123A - A kind of preparation method of porous graphene - Google Patents
A kind of preparation method of porous graphene Download PDFInfo
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- CN108892123A CN108892123A CN201810586526.0A CN201810586526A CN108892123A CN 108892123 A CN108892123 A CN 108892123A CN 201810586526 A CN201810586526 A CN 201810586526A CN 108892123 A CN108892123 A CN 108892123A
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- C—CHEMISTRY; METALLURGY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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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
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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 invention discloses a kind of preparation methods of porous graphene, carry out oxidation processes to graphite raw material first and obtain graphite oxide；Then secondary oxidation is carried out to graphite oxide using potassium ferrate, the oxygen of generation can convert graphene oxide for graphite oxide；Remaining Fe in solution after recycling secondary oxidation2+Fenton reagent is formed with hydrogen peroxide, third time oxidation is carried out to the graphene oxide after secondary oxidation, so that graphene oxide layer surface generates nano-pore；The graphene oxide rich in nano-pore obtained after third time is aoxidized carries out reduction reaction, obtains porous graphene.Present invention process is simple, and the preparation of porous graphene can be rapidly completed, it is easy to accomplish is mass produced, the addition of more strong acid and strong bases is avoided in preparation process, cost has been saved, has reduced the pollution to environment.Porous graphene prepared by the present invention is used as lithium ion battery negative material, and excellent chemical property is shown in terms of energy density and charge-discharge magnification.
Description
Technical field
The present invention relates to technical field of graphene, and in particular to a kind of preparation method of porous graphene, the porous graphite
Alkene material is suitable for the negative electrode material of lithium ion battery.
Background technique
Graphene be by single layer of carbon atom it is tightly packed at the carbonaceous new material with two-dimension plane structure, be building zero
Tie up the basic structural unit of fullerene, one-dimensional carbon nanotube, three-dimensional graphite.Graphene is not only one kind most thin in known materials
(theoretic throat only has 0.35nm) also possesses very high intensity (110GPa), and theoretical specific surface area is up to 2630m2/g.Graphite
The unique atomic structure of alkene assigns the excellent properties of its electricity, calorifics, mechanics etc., has a wide range of applications in numerous areas
Prospect.
Currently, having a large amount of reports using graphene as lithium ion battery negative material.Graphene is by single layer of carbon atom
Close-packed arrays are constituted, and lithium ion may be stored not only in the two sides of graphene sheet layer, can also graphene sheet layer edge and
It is stored in hole, theoretical capacity is 740~780mA h/g, about more than the 2 of conventional graphite cathode times.Use graphene as lithium
Negative electrode material lithium storage content will be greatly improved in ion battery cathode material, and then improve energy density.In addition, being made using graphene
When for lithium ion battery negative material, diffusion path of the lithium ion in grapheme material is shorter, and conductivity is higher, can be very
Big degree improves its high rate performance.So graphene has a good application prospect as lithium ion battery negative material.
But it is very important, graphene negative electrode material is expensive, and lithium ion is difficult to longitudinal transmitting, especially high
Diffusion of the lithium ion in negative electrode material can be also hindered when rate charge-discharge.Therefore, researcher has focused on preparation
On porous graphene.The sharp pore-creating on graphene in various manners, by adjusting the size and number of hole, by graphene to lithium
The inhibition of ion diffusion is preferably minimized.NaOH,KOH,HNO3、KMnO4, dense H2SO4Equal strong acid and strong bases reagent is widely used
In graphene boring technique.But the use of these strong acid and strong base oxidising agents and increased subsequent operation, not only cause
A large amount of raisings of graphene cost, but also will form a large amount of reluctant waste water, increase environmental pollution and processing cost.
Based on this, it is necessary to provide that a kind of preparation process is simple, cost is relatively low and will not aggravate the porous stone of environmental pollution
The preparation method of black alkene.
Summary of the invention
The object of the present invention is to provide a kind of preparation processes simply, cost is relatively low and will not aggravate the porous stone of environmental pollution
The preparation method of black alkene.
To achieve the above object, the technical scheme is that：A kind of preparation method of porous graphene, including walk as follows
Suddenly：
1) oxidation processes are carried out to graphite raw material and obtains graphite oxide；
2) potassium ferrate is added into graphite oxide, secondary oxidation is carried out to it, obtains graphene oxide；
3) third time oxidation is carried out to the graphene oxide after secondary oxidation using Fenton reagent, so that graphene oxide
Sheet surfaces generate nano-pore；
4) graphene oxide rich in nano-pore obtained after aoxidizing third time carries out reduction reaction, obtains porous graphite
Alkene.
Further, it is low to be carried out with Hummers method to graphite to carry out the method for oxidation processes to graphite raw material for step 1)
Temperature oxidation；Graphite is the natural flake graphite that purity is more than or equal to 99.5%；Hummers method the specific steps are：By scale stone
Black raw material is added into 1 DEG C or less the beaker equipped with the concentrated sulfuric acid, is stirred to react 1-5h, is then slow added into potassium permanganate reaction
1-12h, the additional amount of potassium permanganate are 2-10 times of graphite quality, and system temperature is maintained at 4 DEG C hereinafter, being aoxidized after reaction
Graphite.
Further, secondary oxidation is carried out to graphite oxide using potassium ferrate in step 2), meanwhile, utilize potassium ferrate
A large amount of oxygen that reaction generates make graphite oxide removing be graphene oxide；Wherein, the purity of potassium ferrate used is greater than 97%,
The additive amount of potassium ferrate is 0.1-8 times of graphite quality, reaction time 0.1-48h.
Further, after step 3) is secondary oxidation, appropriate hydrogen peroxide is added into graphene oxide solution, in solution
Fe2+Reaction forms Fenton reagent, third time oxidation is carried out to the graphite oxide after secondary oxidation, so that oxidized graphite flake
Layer surface generates nano-pore；
Specifically, graphene oxide solution after secondary oxidation is slowly added to foot after 38 DEG C of 0.3~0.8h of constant temperature oil bath
After reacting 20~40min, hydrogen peroxide, the Fe after reacting with potassium ferrate in solution is added in the deionized water of amount2+Reaction generates
Fenton reagent carries out third time oxidation to the graphene oxide after secondary oxidation；Feton reagent presses following parameter configuration：It is double
Oxygen water concentration is 0.5~2mmol/L, (H2O2)：(Fe2+) molar ratio be 1:1~8, pH value aoxidizes for the third time between 2-5
Reaction time is 10-120min.
Further, the step 4) is to be rich in using chemical reagent or high-temperature process to what is obtained after third time oxidation
The graphene oxide of nano-pore is restored, and porous graphene is obtained.
Wherein, the chemical reagent of reduction includes in hydrazine hydrate, hydroiodic acid, sodium borohydride, vitamin C, alcohols and phenols
One kind or 2-6 kind arbitrary proportion mixing；Reaction time can be 0.1-12h.
Wherein, high-temperature process is to will be enriched in the graphene oxide powder of nano-pore to be put under 200-800 DEG C of vacuum environment
Processing, vacuum tank or hydrogen, nitrogen, argon gas, hydrogen/argon mixture gas (hydrogen in atmosphere furnace or Muffle furnace：Argon gas=1：1) gas
Processing in tube furnace under atmosphere；Handling the time can be 0.1-5h.
Compared with prior art, beneficial effects of the present invention：
The preparation method of porous graphene of the present invention, simple process, it is easy to accomplish large-scale production has been simply added into one kind
Once oxidation in original Hummers method is become and is aoxidized three times by cheap potassium ferrate, and intermediate medium temperature is omitted
The step of reaction and highest temperature reaction, the addition of more strong acid and strong bases is avoided in preparation process, has saved cost, reduce pair
The pollution of environment.
It is directly used in lithium cell cathode material using porous graphene prepared by the method for the present invention, specific capacity is up to 800mA
Still there is the reversible specific capacity of 645mAh/g under the current density of h/g, 3C (1C=372mA h/g), in energy density and again
Rate aspect of performance shows excellent chemical property.
Detailed description of the invention
Fig. 1 be embodiment 1 prepare porous graphene charging and discharging curve (in ordinate VS Li/Li+ indicate graphene
Current potential of the cathode relative to lithium anode)；
Fig. 2 is the curve of double curvature of porous graphene prepared by embodiment 1；
Fig. 3 is that (mass ratio of porous graphene and graphite is the porous graphene/graphite composite material for preparing of embodiment 2
1：7) and the charging and discharging curve comparison diagram of graphite (VS Li/Li+ indicates that graphene cathode is negative relative to lithium metal in ordinate
The current potential of pole)；
Wherein, A1 and A2 is the charging and discharging curve of graphite, and B1 and B2 are the charge and discharge of porous graphene/graphite composite material
Curve；
Fig. 4 is porous graphene/graphite composite material cyclic curve prepared by embodiment 2.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that
The described embodiments are merely a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiment of the present invention,
Those skilled in the art's other embodiments obtained without making creative work, belong to guarantor of the present invention
The range of shield.
Concentrated sulfuric acid mass concentration is 80% in various embodiments of the present invention step 1), and graphite powder is that purity is greater than 99.5%
Natural flake graphite.
Each embodiment step 2) in potassium ferrate purity be greater than 97%.
Embodiment 1
A kind of preparation method of porous graphene, includes the following steps：
1) it measures the 150mL concentrated sulfuric acid to pour into 500ml beaker, beaker is put into ice bath and is cooled to 1 DEG C hereinafter, weighing 5g
Graphite powder is put into beaker, is stirred to react after 1h, is slowly added to 10g potassium permanganate, and control temperature is no more than 4 DEG C, the reaction time
About 2h altogether；
2) 0.5g potassium ferrate is then added, the reaction was continued 2h carries out second to graphite oxide and aoxidizes, make its surface into
Row local corrosion.
3) beaker is moved to thermostatical oil bath, 38 DEG C of temperature control, reacts 0.5h, be finally slowly added in gained mixed liquor
The deionized water of 100mL reacts the hydrogen peroxide of addition 5mL (0.5mol/L) after 30min, after reacting with potassium ferrate in solution
Fe2+Reaction generates Fenton reagent, and control pH value is 2, carries out third time oxidation to obtained graphite oxide, oxidization time is
60min forms it into more nano aperture.
4) the porous oxidation graphene of preparation is put into vacuum oven, is evacuated to 0.1Mpa, 200 DEG C of reaction 1h,
Obtain porous graphene.
By obtained porous graphene and conductive agent Super-P and binder LA132 according to 8:1:1 mass ratio mixing is equal
Even, homogeneous paste is made in grinding in mortar, is coated on 12 microns thick of the bright copper foil as collector, to moisture evaporation
After completely, electrode slice is rolled with roll squeezer, then be punched into the electrode slice of required diameter, in 105 DEG C dry 12 in vacuum drying oven
Hour, after removing micro-moisture contained in electrode slice, it is transferred quickly in glove box.With lithium metal be to electrode,
Celgard 2400 is diaphragm, and electrolyte is the 1mol/l LiPF6 containing 2%VC (vinylene carbonate), solvent EC/DMC/
EMC (volume ratio 1:1:1) CR2032 type button cell, is assembled.(electric current is close for the specific capacity and high rate performance for testing electrode respectively
Degree be 0.2C, 1C and 3C, wherein 1C be equal to 372mAh/g, test voltage range be 0.01~3.0V), test result such as Fig. 1 and
Shown in Fig. 2.
As shown in Figure 1, under the current density of 0.2C, negative electrode material of the above-mentioned porous graphene as lithium ion battery,
Its specific capacity is up to 800mAh/g, is that twice of conventional graphite negative material is had a surplus, and shows in terms of energy density apparent
Advantage.In addition, carry out 1C and 3C multiplying power discharging respectively to above-mentioned material, their specific capacity also respectively reach 750mAh/g and
650mAh/g shows excellent multiplying power property (as shown in Figure 2).
Embodiment 2
A kind of preparation method of porous graphene, includes the following steps：
1) it measures the 150mL concentrated sulfuric acid to pour into 500ml beaker, beaker is put into ice bath and is cooled to 1 DEG C hereinafter, weighing 5g
Graphite powder is put into beaker, and 15g potassium permanganate is slowly added to after 5h, and control temperature is no more than 4 DEG C, and the reaction time is total to about 12h；
2) 20g potassium ferrate is then added, the reaction was continued, and 0.1h makes its surface to second of oxidation of graphite oxide progress
Carry out local corrosion.
3) beaker is moved to thermostatical oil bath, 38 DEG C of temperature control, reacts 0.2h, be finally slowly added in gained mixed liquor
The deionized water of 100mL reacts the hydrogen peroxide of addition 6.3mL (2mol/L) after 40min, after reacting with potassium ferrate in solution
Fe2+Reaction generates Fenton reagent, controls the pH of reaction system between 2~3, carries out third time oxygen to obtained graphite oxide
Change, oxidization time 120min forms it into more nano aperture, this elementary reaction controls temperature and is higher than 95 DEG C.
4) the porous oxidation graphene of preparation is put into 800 DEG C of tube furnaces full of argon gas, reacts 5min, obtains porous
Graphene.
By obtained porous graphene and graphite cathode, conductive agent Super-P and binder LA132 according to 1:7:1:1
Mass ratio is uniformly mixed, and homogeneous paste is made in grinding in mortar, is coated in 12 microns thick of the bright copper foil as collector
On, after moisture evaporation is complete, electrode slice is rolled with roll squeezer, then be punched into the electrode slice of required diameter, in vacuum drying oven
It is 12 hours dry in 105 DEG C, after removing micro-moisture contained in electrode slice, it is transferred quickly in glove box.With lithium metal
For to electrode, Celgard 2400 is diaphragm, electrolyte is the 1mol/l LiPF6 containing 2%VC (vinylene carbonate), solvent
For EC/DMC/EMC (volume ratio 1:1:1) CR2032 type button cell, is assembled.The specific capacity of electrode and forthright again is tested respectively
Energy (current density 0.2C, 1C and 3C, wherein 1C is equal to 372mAh/g, and test voltage range is 0.01~3.0V), test knot
Fruit is as shown in Figure 3 and Figure 4.
As shown in figure 3, porous graphene/graphite is as lithium ion battery negative material, specific capacity under 0.2 multiplying power
Up to 450mAh/g is 1.3 times of conventional graphite cathode specific capacity.In addition, under 1C multiplying power, porous graphene/graphite ratio
Capacity is up to 355mAh/g, still has 328mAh/g after circulation 600 times, capacity retention rate is up to 92% (as shown in Figure 4).
It is less by graphene used in this present embodiment, be conducive to control material cost, more be expected to negative as conventional graphite
The substitute of pole.
Embodiment 3
A kind of preparation method of porous graphene, includes the following steps：
1) it measures the 150mL concentrated sulfuric acid to pour into 500ml beaker, beaker is put into ice bath and is cooled to 1 DEG C hereinafter, weighing 5g
Graphite powder is put into beaker, and 50g potassium permanganate is slowly added to after 2h, and control temperature is no more than 4 DEG C, and the reaction time is total to about 3h；
2) 30g potassium ferrate is then added, the reaction was continued 48h carries out second to graphite oxide and aoxidizes, make its surface into
Row local corrosion.
3) beaker is moved to thermostatical oil bath, 38 DEG C of temperature control, reacts 0.8h, be finally slowly added in gained mixed liquor
The deionized water of 100mL reacts the hydrogen peroxide of addition 38mL (1mol/L) after 10min, after reacting with potassium ferrate in solution
Fe2+Reaction generates Fenton reagent, controls the pH of reaction system between 2~3, carries out third time oxygen to obtained graphite oxide
Change, oxidization time is that 10min forms it into more nano aperture, this elementary reaction controls temperature and is higher than 95 DEG C.
4) the porous oxidation graphene of preparation is soluble in water, the porous oxidation graphene solution 100ml of 1mg/ml is configured,
0.1g hydrazine hydrate is added dropwise in above-mentioned solution, 90 DEG C of reaction 1h are freeze-dried after filtering, obtain porous graphene.
By obtained porous graphene and graphite cathode, conductive agent Super-P and binder LA132 according to 1:7:1:1
Mass ratio is uniformly mixed, and homogeneous paste is made in grinding in mortar, is coated in 12 microns thick of the bright copper foil as collector
On, after moisture evaporation is complete, electrode slice is rolled with roll squeezer, then be punched into the electrode slice of required diameter, in vacuum drying oven
It is 12 hours dry in 105 DEG C, after removing micro-moisture contained in electrode slice, it is transferred quickly in glove box.With lithium metal
For to electrode, Celgard 2400 is diaphragm, electrolyte is the 1mol/l LiPF6 containing 2%VC (vinylene carbonate), solvent
For EC/DMC/EMC (volume ratio 1:1:1) CR2032 type button cell, is assembled.The specific capacity of electrode and forthright again is tested respectively
Energy (current density 0.2C, 1C and 3C, wherein 1C is equal to 372mAh/g, and test voltage range is 0.01~3.0V).
Under 0.2 multiplying power, porous graphene/graphite is up to 510mAh/ as lithium ion battery negative material, specific capacity
G is 1.4 times of conventional graphite cathode specific capacity.In addition, porous graphene/graphite specific capacity is up under 1C multiplying power
395mAh/g still has 358mAh/g after recycling 600 times, and capacity retention rate is up to 90%.
Embodiment 4
The present embodiment difference from Example 3 is：Use in step 4) mass concentration for 55% HI solution 20ml,
Reaction temperature is 100 DEG C, reaction time 60s, solution after then being reacted with ethanol washing rapidly, to remove extra HI.
By obtained porous graphene and graphite cathode, conductive agent Super-P and binder LA132 according to 1:7:1:1
Mass ratio is uniformly mixed, and homogeneous paste is made in grinding in mortar, is coated in 12 microns thick of the bright copper foil as collector
On, after moisture evaporation is complete, electrode slice is rolled with roll squeezer, then be punched into the electrode slice of required diameter, in vacuum drying oven
It is 12 hours dry in 105 DEG C, after removing micro-moisture contained in electrode slice, it is transferred quickly in glove box.With lithium metal
For to electrode, Celgard 2400 is diaphragm, electrolyte is the 1mol/l LiPF6 containing 2%VC (vinylene carbonate), solvent
For EC/DMC/EMC (volume ratio 1:1:1) CR2032 type button cell, is assembled.The specific capacity of electrode and forthright again is tested respectively
Energy (current density 0.2C, 1C and 3C, wherein 1C is equal to 372mAh/g, and test voltage range is 0.01~3.0V).
Under 0.2 multiplying power, porous graphene/graphite is up to 490mAh/ as lithium ion battery negative material, specific capacity
G is 1.36 times of conventional graphite cathode specific capacity.In addition, porous graphene/graphite specific capacity is up under 1C multiplying power
375mAh/g still has 343mAh/g after recycling 600 times, and capacity retention rate is up to 91%.
Claims (10)
1. a kind of preparation method of porous graphene, it is characterised in that：Include the following steps：
1) oxidation processes are carried out to graphite raw material and obtains graphite oxide；
2) potassium ferrate is added into graphite oxide, secondary oxidation is carried out to it, obtains graphene oxide；
3) third time oxidation is carried out to the graphene oxide after secondary oxidation using Fenton reagent, so that graphene oxide layer
Surface generates nano-pore；
4) graphene oxide rich in nano-pore obtained after aoxidizing third time carries out reduction reaction, obtains porous graphene.
2. a kind of preparation method of porous graphene as described in claim 1, it is characterised in that：The step 1) is to graphite original
The method that material carries out oxidation processes is to carry out low-temperature oxidation to graphite with Hummers method.
3. a kind of preparation method of porous graphene as claimed in claim 2, it is characterised in that：The tool of the Hummers method
Body step is：Crystalline flake graphite raw material is added into 1 DEG C or less the beaker equipped with the concentrated sulfuric acid, 1-5h is stirred to react, then delays again
The slow potassium permanganate that is added reacts 1-12h, and the additional amount of potassium permanganate is 2-10 times of graphite quality, and system temperature is maintained at 4 DEG C
Hereinafter, obtaining graphite oxide after reaction.
4. a kind of preparation method of porous graphene as described in claim 1, it is characterised in that：Ferric acid in the step 2)
The additive amount of potassium is 0.1-8 times of graphite quality, reaction time 0.1-48h.
5. a kind of preparation method of porous graphene as described in claim 1, it is characterised in that：Ferric acid in the step 2)
Potassium purity is not less than 97%.
6. a kind of preparation method of porous graphene as described in any one in claim 1-5, it is characterised in that：The step 3)
For graphene oxide solution after secondary oxidation after 38 DEG C of 0.3~0.8h of constant temperature oil bath, is slowly added to suitable deionized water,
After reacting 20~40min, hydrogen peroxide, the Fe after reacting with potassium ferrate in solution is added2+Reaction generates Fenton reagent, to two
Graphene oxide after secondary oxidation carries out third time oxidation.
7. a kind of preparation method of porous graphene as claimed in claim 6, it is characterised in that：The Feton reagent is by such as
Lower parameter configuration：Hydrogen peroxide concentration is 0.5~2mol/L, (H2O2)：(Fe2+) molar ratio be 1:1~8, pH value between 2-5,
The reaction time of the third time oxidation is 10-120min.
8. a kind of preparation method of porous graphene as described in claim 1, it is characterised in that：The step 4) is to utilize change
It learns the graphene oxide rich in nano-pore obtained after reagent or high-temperature process aoxidize third time to restore, obtain porous
Graphene.
9. a kind of preparation method of porous graphene as claimed in claim 8, it is characterised in that：The chemical reagent of the reduction
Comprising one of hydrazine hydrate, hydroiodic acid, sodium borohydride, vitamin C, alcohols and phenols or it is above it is several between any ratio
Example mixing.
10. a kind of preparation method of porous graphene as claimed in claim 8, it is characterised in that：The high-temperature process be by
Graphene oxide powder rich in nano-pore is put into 200-800 DEG C of vacuum tank or hydrogen, nitrogen, argon gas, hydrogen/argon mixture gas
(hydrogen：Argon gas=1：1) processing in the tube furnace under atmosphere.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112357909A (en) * | 2020-11-11 | 2021-02-12 | 四川恒瑞天成科技有限公司 | Preparation method and application of graphene porous membrane |
| CN114014306A (en) * | 2021-12-15 | 2022-02-08 | 陇东学院 | Preparation method and application of oxygen-enriched layered porous graphene |
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