CN107555424A - A kind of preparation method of porous class graphene active carbon material and products thereof and application - Google Patents
A kind of preparation method of porous class graphene active carbon material and products thereof and application Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of porous class graphene active carbon material and products thereof and application, belong to field of material technology, biological material is pre-processed under conditions of hydro-thermal auxiliary using oxidant and weak acid or salt in this method, realize the stripping and pore-creating to biological material, pass through high temperature pyrolysis again, it is converted into carbon material.This method is simple to operate, and the carbon material finally prepared not only has high degree of graphitization, also with high specific surface area, abundant mesoporous and micropore rate, and the characteristic of unique layer structure and Heteroatom doping.This material is used in ultracapacitor, from Electrochemical results, compared with ultracapacitor is with active Carbon Materials, the capacity that this material is showed is 4.5 times of active Carbon Materials, the material will be widely used in the field such as energy storage and conversion, electro-catalysis, bio-sensing and the depollution of environment, have important application value.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of preparation method of porous class graphene active carbon material and
Its product and application.
Background technology
With consuming excessively and using environmental disruption caused by fossil energy and pollution problem day for traditional fossil energy
It is beneficial severe, new, environmentally friendly, sustainable, high energy efficiency clean energy resource conversion and storage device are developed to substitute grinding for conventional apparatus
Study carefully direction, enjoy the concern of researcher.In recent years, the carbon material of different nanostructureds, such as carbon black, CNT, activated carbon, carbon
Aeroge, carbide-derived carbon, in multiple fields, particularly in energy conversion and energy reserves field, have a wide range of applications.
This, which is attributed to such material, has larger specific surface area, excellent electric conductivity, good physical stability.Wherein, it is two-dimentional
Carbon material, such as graphene, because the structure of its low latitudes can reduce ion transmission range and can be effective in electrochemical reaction
Accelerate electron transfer rate, cause researcher's extensive concern in recent years.For this purpose, many effort are put into controllable effective
Stripping graphite is prepared among two-dimentional carbon material.A typical case of the absorbent charcoal material as carbon material, due to its high specific surface area,
Abundant pore structure and low cost are by multiple fields extensive use.
On the whole, activated carbon in general preparation method is directly is pyrolyzed rich carbon organic matter precursor at high temperature, then
Use activator, such as KOH, ZnCl2, H3PO4Deng being activated.Although such preparation method can all obtain abundant micropore,
High specific surface area (>=1000m2g-1) and excellent absorption property, but the carbon material prepared under high temperature still has easy plate
The problem of knot.Normally, in terms of these absorbent charcoal materials are applied to energy conversion and energy storage, main problem is that block
The big density and abundant structure, electrolyte of carbon material are hardly entered in hole.Post-processing carbon material also can only be in carbon material
Surface is punched, it is difficult to the active force between destroying carbon material layer.Stratified nano materials have, such as high specific surface area, height exposure
Atomic surface, it is relatively easy to the inherent advantages such as electric transmission.Improve carbon material layer between utilization rate will be substantially improved its
The performance of energy storage, conversion and catalytic field.On the other hand, biomass refers to any renewable or recyclable organic matter,
Including all animals, plant and microorganism, and all organic matters drained and be metabolized by these life entities, have price low
Honest and clean, abundance, it is environment-friendly the features such as.If the activated carbon of Heteroatom doping can be prepared with discarded biological material, no
But the preparation method of the carbon material of a sustainable development can be developed, also with huge economy and social value, certain
Environmental problem caused by solving conventional process mode in degree.Hetero atom therein can also improve the original electronics of carbon material
Body attribute, adjust the electronics and chemical property of carbon surface.
The content of the invention
In view of this, it is an object of the invention to：(1) a kind of preparation side of porous class graphene active carbon material is provided
Method；(2) a kind of porous class graphene active carbon material is provided；(3) a kind of porous class graphene active carbon material is provided in energy storage
Application in equipment.
To reach above-mentioned purpose, the present invention provides following technical scheme：
1st, a kind of preparation method of porous class graphene active carbon material, comprises the following steps：
(1) biological material is handled, in acquisition under conditions of hydro-thermal auxiliary using oxidant and weak acid or using salt
Between product；
(2) the intermediate product high temperature pyrolysis under an inert atmosphere for obtaining step (1), is made porous class graphene activated carbon
Material；
The oxidant is one kind in hydrogen peroxide, chlorate, perchlorate, nitrate, permanganate or chlorine water；Institute
Weak acid is stated as one kind in acetic acid, carbonic acid, hydrofluoric acid, hypochlorous acid, nitrous acid or organic acid；The salt is nitrate, sulfuric acid
One kind in salt or hydrochloride.
Further, step (1) concrete operations are as follows：Oxidant and weak acid are added together with biological material in solvent or
Salt and biological material are added in solvent, ultrasound obtains suspension, and it is laggard that the suspension is transferred into pyroreaction kettle
The hot assisted reaction of water-filling, reaction product is obtained, after reaction product washing is dried, obtain intermediate product.
Further, the solvent is water, and the washing is to be washed successively with secondary water and absolute ethyl alcohol.
Further, in step (1), the dosage of the oxidant is the 1-7wt% of the biological material, the weak acid
Dosage is the 4-30wt% of the biological material, and the dosage of the salt is the 5.5-15wt% of the biological material.
Further, in step (1), the biological material is the seedpod of the lotus, coconut husk, stalk, cotton bavin, peanut shell, bagasse, tree
One kind in skin, peanut seedling or wood chip.
Further, in step (1), the reaction condition of the hydro-thermal auxiliary is to react 0.5-6h at 50-160 DEG C.
Further, in step (2), the reaction condition of the high temperature pyrolysis is to exist by 0.5-10 DEG C/min programming rate
0.5-12h is reacted at 400-1700 DEG C.
2nd, the porous class graphene active carbon material prepared by described preparation method.
3rd, application of the described porous class graphene active carbon material in energy storage device.
Further, the energy storage device is ultracapacitor.
The beneficial effects of the present invention are：The present invention provide a kind of porous class graphene active carbon material preparation method and
Its product and application, biological material is entered under conditions of hydro-thermal auxiliary using oxidant and weak acid or salt in this method
Row pretreatment, realizes the stripping and pore-creating to biological material, then by high temperature pyrolysis, it is converted into carbon material, this method
Simple to operate, the carbon material finally prepared not only has high degree of graphitization, also with high specific surface area, abundant Jie
The characteristic of hole and micropore rate, unique layer structure and Heteroatom doping.Wherein, the layered porous structure of the material, will
Ion transmission range can be greatly reduced and accelerate infiltration and the electron transfer rate of electrolyte, meanwhile, hetero atom is mixed in the material
The miscellaneous hydrophily that will improve carbon material, improves its electric conductivity, so as to lift its energy reserves performance.This material is used for super electricity
In container, from Electrochemical results, compared with ultracapacitor is with active Carbon Materials, appearance that this material is showed
Amount is 4.5 times of active Carbon Materials, the material will be widely used in energy storage and conversion, electro-catalysis, bio-sensing and
The fields such as the depollution of environment, there is important application value.
Brief description of the drawings
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, the present invention provides drawings described below and carried out
Explanation：
Fig. 1 is the XRD of the porous class graphene active carbon material prepared in embodiment 1；
Fig. 2 is the SEM figures of the porous class graphene active carbon material prepared in embodiment 1；
Fig. 3 is the TEM figures of the porous class graphene active carbon material prepared in embodiment 1；
Fig. 4 is the BET figures and graph of pore diameter distribution of the porous class graphene active carbon material prepared in embodiment 1；
Fig. 5 is porous class graphene active carbon material, Standard graphite and the direct carbonization material prepared in embodiment 5
XRD；
Fig. 6 is the SEM figures of the porous class graphene active carbon material prepared in embodiment 5；
Fig. 7 is the super capacitor electrode that the porous class graphene active carbon material prepared using in embodiment 1 is prepared as raw material
The difference of pole sweeps the CV figures of speed；
Fig. 8 is the super capacitor electrode that the porous class graphene active carbon material prepared using in embodiment 1 is prepared as raw material
Impulse electricity curve of the pole under different current densities；
Fig. 9 is the super capacitor electrode that the porous class graphene active carbon material prepared using in embodiment 1 is prepared as raw material
The high rate performance test chart of pole；
Figure 10 is the super capacitor electrode that the porous class graphene active carbon material prepared using in embodiment 1 is prepared as raw material
The cyclical stability test chart of pole；
Figure 11 is the super capacitor electrode that the porous class graphene active carbon material prepared using in embodiment 5 is prepared as raw material
The difference of pole sweeps the CV figures of speed；
Figure 12 is the super capacitor electrode that the porous class graphene active carbon material prepared using in embodiment 5 is prepared as raw material
Impulse electricity curve of the pole under different current densities；
Figure 13 is the super capacitor electrode that the porous class graphene active carbon material prepared using in embodiment 5 is prepared as raw material
The high rate performance test chart of pole；
Figure 14 be commercialized absorbent charcoal material (AC) be raw material preparation electrode of super capacitor in 0.5Ag-1Electricity
Charging and discharging curve under current density.
Embodiment
The preferred embodiments of the present invention will be described in detail below.
Embodiment 1
Prepare porous class graphene active carbon material
(1) hydrogen peroxide and acetic acid are added in deionized water together with seedpod of the lotus powder, the dosage of wherein hydrogen peroxide is
The 3.5wt% of seedpod of the lotus powder, the dosage of acetic acid are the 15wt% of seedpod of the lotus powder, and ultrasound obtains suspension, and the suspension is turned
Pyroreaction kettle is moved to after reacting 2h in air dry oven at 120 DEG C, after question response kettle natural cooling, is taken out in reactor
Reaction product, successively with secondary water and absolute ethyl alcohol wash the reaction product after in vacuum drying chamber dry, obtain among
Product.
(2) by the intermediate product that step (1) obtains under argon gas protection with 2 DEG C/min programming rate at 700 DEG C it is anti-
3h is answered, porous class graphene active carbon material is made.
Embodiment 2
Prepare porous class graphene active carbon material
(1) sodium perchlorate and hypochlorous acid are added in deionized water together with stalk powder, wherein the dosage of sodium perchlorate
For the 6wt% of seedpod of the lotus powder, hypochlorous dosage is the 10wt% of stalk, and ultrasound obtains suspension, the suspension is shifted
To pyroreaction kettle after reacting 6h in air dry oven at 100 DEG C, after question response kettle natural cooling, take out in reactor
Reaction product, the reaction product is washed after being dried in vacuum drying chamber with secondary water and absolute ethyl alcohol successively, obtains middle produce
Thing.
(2) intermediate product for obtaining step (1) is under nitrogen protection with 0.5 DEG C/min programming rate at 800 DEG C
5h is reacted, porous class graphene active carbon material is made.
Embodiment 3
Prepare porous class graphene active carbon material
(1) chlorine water and carbonic acid are added in deionized water together with peanut shell, wherein the dosage of chlorine water is peanut shell
1.5wt%, the dosage of carbonic acid are the 30wt% of peanut shell, and ultrasound obtains suspension, and the suspension is transferred into pyroreaction
Kettle after question response kettle natural cooling, takes out the reaction product in reactor after reacting 0.5h in air dry oven at 90 DEG C,
The reaction product is washed after being dried in vacuum drying chamber with secondary water and absolute ethyl alcohol successively, obtains intermediate product.
(2) by the intermediate product that step (1) obtains under argon gas protection with 5 DEG C/min programming rate at 1000 DEG C it is anti-
2h is answered, porous class graphene active carbon material is made.
Embodiment 4
Prepare porous class graphene active carbon material
(1) potassium permanganate and nitrous acid are added in deionized water together with wood chip powder, wherein the dosage of potassium permanganate
For the 2.3wt% of seedpod of the lotus powder, the dosage of nitrous acid is the 8.5wt% of wood chip, and ultrasound obtains suspension, and the suspension is turned
Pyroreaction kettle is moved to after reacting 4h in air dry oven at 80 DEG C, after question response kettle natural cooling, is taken out in reactor
Reaction product, successively with secondary water and absolute ethyl alcohol wash the reaction product after in vacuum drying chamber dry, obtain among
Product.
(2) intermediate product for obtaining step (1) under nitrogen protection with 5 DEG C/min programming rate at 400 DEG C it is anti-
12h is answered, porous class graphene active carbon material is made.
Embodiment 5
Prepare porous class graphene active carbon material
(1) nickel nitrate is added in deionized water together with cocoanut shell powder, wherein the dosage of nickel nitrate is coconut shell powder
End 8.1wt%, ultrasound obtain suspension, by the suspension be transferred to pyroreaction kettle after in air dry oven at 80 DEG C
Lower reaction 3h, after question response kettle natural cooling, the reaction product in reactor is taken out, is washed successively with secondary water and absolute ethyl alcohol
The reaction product obtains intermediate product after being dried in vacuum drying chamber.
(2) by the intermediate product that step (1) obtains under argon gas protection with 3 DEG C/min programming rate at 800 DEG C it is anti-
3h is answered, porous class graphene active carbon material is made.
Embodiment 6
Prepare porous class graphene active carbon material
(1) ferric sulfate is added in deionized water together with cornstalk powder, wherein the dosage of ferric sulfate is milled powders of cornstalk
End 10.5wt%, ultrasound obtain suspension, by the suspension be transferred to pyroreaction kettle after in air dry oven 50
React 6h at DEG C, after question response kettle natural cooling, take out the reaction product in reactor, washed successively with secondary water and absolute ethyl alcohol
The reaction product is washed after being dried in vacuum drying chamber, obtains intermediate product.
(2) intermediate product for obtaining step (1) is under nitrogen protection with 0.5 DEG C/min programming rate at 1200 DEG C
8h is reacted, porous class graphene active carbon material is made.
Embodiment 7
Prepare porous class graphene active carbon material
(1) calcium chloride is added in deionized water together with bagasse powder, wherein the dosage of calcium chloride is bagasse
5.5wt%, ultrasound obtain suspension, by the suspension be transferred to pyroreaction kettle after in air dry oven at 150 DEG C
4h is reacted, after question response kettle natural cooling, takes out the reaction product in reactor, successively should with secondary water and absolute ethyl alcohol washing
Reaction product obtains intermediate product after being dried in vacuum drying chamber.
(2) intermediate product for obtaining step (1) under nitrogen protection with 5 DEG C/min programming rate at 500 DEG C it is anti-
12h is answered, porous class graphene active carbon material is made.
Embodiment 8
Prepare porous class graphene active carbon material
(1) sodium nitrate is added in deionized water together with bark fines, wherein the dosage of sodium nitrate is bark fines
15wt%, ultrasound obtain suspension, by the suspension be transferred to pyroreaction kettle after in air dry oven at 160 DEG C it is anti-
Answer 2h, after question response kettle natural cooling, take out the reaction product in reactor, it is anti-that this is washed with secondary water and absolute ethyl alcohol successively
Product is answered to obtain intermediate product after being dried in vacuum drying chamber.
(2) by step (1) obtain intermediate product argon gas protection under with 10 DEG C/min programming rate at 1700 DEG C
0.5h is reacted, porous class graphene active carbon material is made.
Embodiment 9
1st, dependence test is carried out to the porous class graphene active carbon material prepared in embodiment 1 and embodiment 5
(1) by the porous class graphene active carbon material prepared in X-ray diffraction testing example 1, as a result such as Fig. 1 institutes
Show, it is known that the material has wide bag diffraction maximum at 20 degree and 42 degree or so, and does not detect the presence of other miscellaneous peaks, it was demonstrated that should
Material is class grapheme material；Electronic Speculum test is scanned to it, as a result as shown in Fig. 2 from a in Fig. 2, is scanned in low power
The material shows thin slice Rotating fields under Electronic Speculum, and from b in Fig. 2, the material surface is coarse under high power ESEM, occurs
Substantial amounts of hole；With reference to transmission electron microscope results, as shown in figure 3, from a in Fig. 3, each lamella is very thin in the material, by Fig. 3
B understands that there is abundant micropore and mesoporous on lamella；BET is carried out to it than surface test, as a result as shown in figure 4, a in Fig. 4
For the nitrogen adsorption desorption curve of porous class graphene absorbent charcoal material, b is the aperture of porous class graphene absorbent charcoal material in Fig. 4
Distribution curve, it is known that the specific surface area of the material is 1014m2/ g, pore size distribution range 2-6nm；
(2) porous class graphene active carbon material, the standard stone prepared in testing example 5 is distinguished by X-ray diffraction
Ink and direct carbonization material, as a result as shown in Figure 5, it is known that the knot of the porous class graphene active carbon material prepared in embodiment 5
Brilliant degree highest, illustrate for prepare porous class graphene active carbon material raw material after pretreatment, after can effectively improving
The crystallinity of carbon material prepared by phase, and then improve its electric conductivity；To the porous class graphene activated carbon prepared in embodiment 5
Material is scanned Electronic Speculum test, as a result as shown in fig. 6, from a in Fig. 6, the lamella being scattered occurs in the material integral material
Structure, from b in Fig. 6, the material layer has certain space with interlayer；
2nd, the porous class graphene active carbon material prepared using embodiment 1 and embodiment 5 prepares super electricity as raw material respectively
Container electrode, and correlated performance test is carried out to the electrode.
Porous class graphene active carbon material made from Example 1 and 5, press quality with carbon black, PVDF binding agents respectively
Than 85:10:5 mixing, add appropriate ethanol, pasty state are ground in agate mortar, and electrode active material is made, starches the electricity
For pole active material coated on stainless steel collector, coated area is 1.0 × 1.0cm2, coating quality is about 2mg.Then will
Steel plate coated with electrode active material is dried in vacuo 8 hours in 70 DEG C, and electrode of super capacitor is made.Test platform is electrification
Work station CHI760E is learned, uses the correlated performance of standard three electrode system, respectively two kinds of electrodes of test.
(1) super capacitor electrode to being prepared using the porous class graphene active carbon material prepared in embodiment 1 as raw material
Pole carries out the CV that difference is swept under speed and scanned, as a result as shown with 7, it is known that in the case where difference sweeps speed, the shape of CV curves all approximating squares
Shape, and with being continuously increased for speed is swept, curve shape keeps fine, shows that material has preferable electric conductivity and forthright again
Energy；Charge-discharge characteristic of the electrode of super capacitor under different current densities is tested, as a result as shown in Figure 8, it is known that
Under different current densities, more symmetrical triangle is all presented in impulse electricity curve, illustrates that electric double layer capacitance accounts for master in the electrode
Body；The high rate performance of the electrode of super capacitor is tested, as a result as shown in Figure 9, it is known that the electrode is in 0.5Ag-1Electric current it is close
Specific capacitance under degree is 340Fg-1, in 20Ag-1Current density under the electrode specific capacitance 223Fg-1, illustrate the electricity
Has preferable high rate performance；The electrode of super capacitor is tested in 1Ag-1Current density under cyclical stability, knot
Fruit is as shown in Figure 10, it is known that after putting circulation electric discharge by 10000 punchings, the capacity that the electrode still has 97% is kept, explanation
The electrode has good cyclical stability.
(2) electrode of super capacitor to being prepared using the porous class graphene active carbon material prepared in example 5 as raw material
The CV scannings under different scanning speed are carried out, as a result as shown in figure 11, although sweeping speed (100mVs in height-1) under, CV curves are still
Good rectangle is so presented, and without there is any polarization, presentation materials have good electric conductivity；To the ultracapacitor
Charge-discharge characteristic of the electrode under different current densities is tested, as a result as shown in figure 12, under different current densities, charge and discharge
The triangle of electric curve symmetric, it is the electrode material that electric double layer capacitance is main body to illustrate it；Test the electrode of super capacitor
High rate performance, as a result as shown in figure 13, the electrode is in 1Ag-1Current density under specific capacitance be 234Fg-1, and
20A·g-1Current density under still there is 180Fg-1Specific capacitance, illustrate that the electrode has excellent high rate performance.
3rd, it is that raw material prepares electrode of super capacitor with commercialized activated carbon (AC), and the electrode capacitance amount is surveyed
Examination, i.e., in 0.5Ag-1Current density under carry out discharge and recharge, as a result as shown in figure 14, it is known that close in 0.5Ag-1 electric current
Under degree, its specific capacitance is 75Fg-1, and the porous class graphene active carbon material to be prepared in embodiment 1 is prepared as raw material
Electrode of super capacitor, under 0.5Ag-1 current density, its specific capacitance is 340Fg-1, it is commercial activated carbon (AC)
4.5 again.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
Cross above preferred embodiment the present invention is described in detail, it is to be understood by those skilled in the art that can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (10)
1. a kind of preparation method of porous class graphene active carbon material, it is characterised in that comprise the following steps：
(1) using oxidant and weak acid or using salt under conditions of hydro-thermal auxiliary, biological material is handled, is produced among acquisition
Thing；
(2) the intermediate product high temperature pyrolysis under an inert atmosphere for obtaining step (1), is made porous class graphene activity carbon materials
Material；
The oxidant is one kind in hydrogen peroxide, chlorate, perchlorate, nitrate, permanganate or chlorine water；It is described weak
Acid is one kind in acetic acid, carbonic acid, hydrofluoric acid, hypochlorous acid, nitrous acid or organic acid；The salt be nitrate, sulfate or
One kind in hydrochloride.
A kind of 2. preparation method of porous class graphene active carbon material as claimed in claim 1, it is characterised in that step
(1) concrete operations are as follows：Oxidant and weak acid are added together with biological material in solvent or by salt and biological material
Add in solvent, ultrasound obtains suspension, and the suspension is transferred into the hot assisted reaction of the laggard water-filling of pyroreaction kettle, obtains
Reaction product, after reaction product washing is dried, obtain intermediate product.
3. a kind of preparation method of porous class graphene active carbon material as claimed in claim 2, it is characterised in that described molten
Agent is water, and the washing is to be washed successively with secondary water and absolute ethyl alcohol.
4. a kind of preparation method of porous class graphene active carbon material as described in claim any one of 1-3, its feature exist
In in step (1), the dosage of the oxidant is the 1-7wt% of the biological material, and the dosage of the weak acid is the life
The 4-30% of material, the dosage of the salt are the 5.5-15wt% of the biological material.
5. a kind of preparation method of porous class graphene active carbon material as described in claim any one of 1-3, its feature exist
In, in step (1), the biological material be the seedpod of the lotus, coconut husk, stalk, cotton bavin, peanut shell, bagasse, bark, peanut seedling or
One kind in wood chip.
6. a kind of preparation method of porous class graphene active carbon material as described in claim any one of 1-3, its feature exist
In in step (1), the reaction condition of the hydro-thermal auxiliary is to react 0.5-6h at 50-160 DEG C.
7. a kind of preparation method of porous class graphene active carbon material as described in claim any one of 1-3, its feature exist
In, in step (2), the reaction condition of the high temperature pyrolysis be by 0.5-10 DEG C/min programming rate at 400-1700 DEG C it is anti-
Answer 0.5-12h.
8. the porous class graphene active carbon material prepared as the preparation method described in claim any one of 1-7.
9. application of the porous class graphene active carbon material in energy storage device described in claim 8.
10. application as claimed in claim 9, it is characterised in that the energy storage device is ultracapacitor.
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| CN108178156A (en) * | 2016-12-08 | 2018-06-19 | 中国科学院大连化学物理研究所 | A kind of high graphitization active carbon electrode material and its preparation and application |
| CN108178156B (en) * | 2016-12-08 | 2021-04-13 | 中国科学院大连化学物理研究所 | High-graphitization activated carbon electrode material and preparation and application thereof |
| CN108417408A (en) * | 2018-01-17 | 2018-08-17 | 莆田市超维二维科技发展有限公司 | A kind of ultracapacitor and preparation method thereof |
| CN109860644A (en) * | 2019-01-24 | 2019-06-07 | 江苏大学 | A kind of application of linden three-dimensional carbon electrode in microbiological fuel cell |
| CN110364369A (en) * | 2019-06-05 | 2019-10-22 | 华东理工大学 | It is a kind of using shredded coconut meat as active carbon capacitor electrode material of carbon source and preparation method thereof |
| CN110937596A (en) * | 2019-11-05 | 2020-03-31 | 北华大学 | Method for preparing graphene-like material based on biomass waste and application of graphene-like material |
| CN110898805A (en) * | 2019-11-28 | 2020-03-24 | 广东省生态环境技术研究所 | Preparation method and application of graphene-like structure biochar loaded nano zero-valent iron composite material |
| CN111009648A (en) * | 2019-12-10 | 2020-04-14 | 华南农业大学 | Silicon-carbon composite material and preparation method thereof |
| CN112138664A (en) * | 2020-09-10 | 2020-12-29 | 广州大学 | Carbon-based electrocatalyst and preparation method thereof |
| CN112138664B (en) * | 2020-09-10 | 2022-12-20 | 广州大学 | Carbon-based electrocatalyst and preparation method thereof |
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