CN109650381A - A kind of sea urchin shape graphene and preparation method thereof - Google Patents
A kind of sea urchin shape graphene and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of sea urchin shape graphenes and preparation method thereof, are related to grapheme material preparation field.The present invention is reacted using nickel salt with reducing agent under alkaline condition, is self-assembly of sea urchin shape three-dimensional nickel substrate；By chemical vapour deposition technique, graphene is deposited in sea urchin shape three-dimensional nickel substrate；Acid removal nickel substrate is added to get sea urchin shape three-dimensional grapheme.Sea urchin shape three-dimensional grapheme of the present invention has good dispersing type, effectively prevents the problems such as stacking, is porous, configuration is unstable.Preparation process of the present invention is simple, and mild condition, raw material sources are extensive, is suitable for producing in batches, have broad application prospects.
Description
Technical field
The present invention relates to grapheme material technical fields, and in particular to a kind of sea urchin shape graphene and preparation method thereof.
Background technique
Grapheme material is a kind of monoatomic layer material with unique bi-dimensional cellular shape structure, has excellent electricity
, calorifics and mechanical characteristic.Based on its special performance, grapheme material is described as " king of 21 century new material " by scientific circles, just
It is used to include the various fields such as the energy, environment and biology.But in application process, discovery grapheme material is asked there are some
Topic, such as the graphene of two-dimensional structure easily crimp because of its own ultra-thin thickness, lead to its corresponding performance therewith
It substantially reduces, is restricted it greatly in certain practical applications.For another example because of its stronger π-π effect and Van der Waals force, graphene
Serious stacking and reunion easily occur for two-dimensional structure, have seriously affected the intrinsic property of graphene.Scientist's discovery, two dimension is tied
Structure graphene is assembled into three-dimensional grapheme structure, such as foam, hydrogel.Aeroge and spherical structure etc. can effectively solve this
A little problems.In consideration of it, people start to construct graphene three-dimensional structure, to solve the above problem present in prior art problem.
Three-dimensional structure graphene is a kind of existing way of two-dimensional graphene in three dimensions, is specifically as follows graphene
The structures such as network, graphene fiber, Graphene gel, graphene sponge.Three-dimensional grapheme not only remains two-dimensional graphene original
The various physicochemical properties having, and special microstructure imparts the specific surface area and higher electric conductivity of its super large.System at present
The method of standby three-dimensional grapheme mainly includes self-assembly method and template auxiliary law.Self-assembly method, which refers to, makes oxygen by adding crosslinking agent
Graphite alkene gelation builds as three-dimensional architecture and reduction obtains three-dimensional grapheme.
The preparation method of the three-dimensional grapheme as disclosed in Chinese patent CN 201810175676, this method is to aoxidize stone
Black alkene is starting material, and emulsifier, crosslinking agent and reducing agent is added, and spherical graphite alkene hydrogel is formed in oily phase, then through moisture
Evaporation, high-temperature calcination, obtain three-dimensional self assembly graphene.This method during the preparation process, need to introduce oily phase, emulsifier, crosslinking
The other components such as agent and reducing agent, it is clean that these components are not easy removal, and it is all to exist simultaneously that porous, interlayer is loose, is not easy to shape etc.
More defects, which has limited its performance and its applications.And template auxiliary law is three-dimensional structure to be pre-designed as template, passing through
It learns vapour deposition process and directly grows graphene in three-dimensional template, graphene defect prepared by this method is few, and having can
The pattern and performance of control.The existing three-dimensional grapheme prepared by template auxiliary chemical vapor deposition method is mostly with porous metal foam
Based on the graphene sponge prepared for substrate, structure is relatively simple.And sea is made by chemical vapour deposition technique and nickel substrate
Gallbladder shape graphene does not have temporarily related open.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of sea urchin shape graphene and preparation method thereof, above-mentioned to solve
The technical problem that two-dimensional graphene of the existing technology easily crimps, three-dimensional grapheme structure is single.
To solve the above problems, the invention provides the following technical scheme:
On the one hand, the present invention provides a kind of sea urchin shape graphene, with three-dimensional hollow sea urchin shape structure.
Further, the sea urchin shape graphene includes sphere and needle-like whisker, and needle-like whisker is distributed in spherome surface, institute
Stating sphere diameter is 500~700nm, and the whisker length is about 300nm.
On the other hand, the present invention also provides a kind of preparation methods of sea urchin shape graphene, the specific steps are as follows:
1) in a solvent, nickel salt reacts under alkali and reducing agent effect is made sea urchin shape nickel nanocrystal；
2) using nickel nanocrystal as template, by chemical vapour deposition technique in nickel nanocrystal surface apposition growth graphite
Alkene obtains nickel substrate sea urchin shape graphene；
3) by reagent erosion removal nickel substrate, sea urchin shape three-dimensional grapheme is obtained.
Further, the solvent can be ethyl alcohol, water, ethylene glycol, methanol, propyl alcohol, isopropanol, propylene glycol, glycerine,
One of kerosene, solvent naphtha or combinations thereof, further, the dissolution solvent can be ethyl alcohol, water, ethylene glycol, propyl alcohol, different
Propyl alcohol, propylene glycol, it is preferable that dissolution solvent of the present invention is ethylene glycol.
Further, the nickel salt can be NiSO4·6H2O、Ni(NO3)2·6H2O、Ni(CH3COO)2·4H2O、
NiCl2·6H2O、NiBr2、NiI2、NiF2One of or combinations thereof, it is preferable that nickel salt of the present invention is NiSO4·6H2O、
Ni(NO3)2·6H2O、NiCl2·6H2O。
Further, the alkali can be ammonium hydroxide, NaOH, KOH, Na2CO3、Na3PO4、Na3BO4、K2CO3, sodium methoxide, second
One of sodium alkoxide, potassium tert-butoxide or combinations thereof, further, the alkali can be ammonium hydroxide, NaOH, KOH, Na2CO3、Na3PO4
One of or combinations thereof, it is preferable that alkali of the present invention is NaOH.
Further, the molar ratio of the alkali and nickel salt is 1~20:1, and further, the alkali and nickel salt molar ratio are 2
~10:1, it is preferable that alkali of the present invention is 2:1,4:1,10:1 with nickel salt molar ratio.
Further, the reducing agent be hydrazine hydrate, sodium borohydride, oxalic acid, formic acid, sodium hypophosphite, L-AA,
One of citric acid, ortho phosphorous acid potassium, Lime Hypophosphate, sodium hypophosphite, sodium hypophosphite, DTT, formaldehyde or combinations thereof, preferably
Ground, reducing agent of the present invention are one of hydrazine hydrate, sodium borohydride, oxalic acid.
Further, the molar ratio of the reducing agent and the nickel salt is 1~1000:1, further, the reducing agent
Molar ratio with the nickel salt is 4~1000:1, it is preferable that the molar ratio of reducing agent of the present invention and the nickel salt is 4:1,
40:1,1000:1.
Further, the temperature of reaction described in step 1) is 10~100 DEG C, and further, the temperature is 50~100
DEG C, it is preferable that temperature of the present invention is 50 DEG C, 70 DEG C, 100 DEG C；Reaction time is 1~5 hour, it is preferable that the time
It is 1,2,4 hour.
Further, the sea urchin shape nickel nanocrystal preparation process is as follows: nickel salt is dissolved in solvent to obtain nickel salt molten
Then alkali and reducing agent are added sequentially in nickel salt solution by liquid, stirring makes it completely dissolved to obtain green solution, then by it
It is transferred in flask, heated water bath stirring, solution colour gradually becomes black, after reaction filters liquid, and gained is cotton-shaped
Object deionized water and dehydrated alcohol respectively wash three times to remove impurity, dry to get sea urchin shape nickel nanocrystal is arrived.
Further, described in step 1) after reaction, acquired solution filters, and obtains floccule, washed, dry system
Obtain sea urchin shape nickel nanocrystal.The drying temperature can be 10~100 DEG C, and further, the drying temperature is 40~100
DEG C, it is preferable that drying temperature of the present invention is 40 DEG C, 60 DEG C, 100 DEG C.
Further, in step 2), the process of the chemical vapour deposition technique is as follows: nickel nanocrystal is put into CVD pipe
In formula furnace, it is passed through the mixed atmosphere being made of hydrogen and argon gas, heat temperature raising adjusts hydrogen flow rate after the completion of heating, and is passed through
Hydrogen and carbon-source gas are closed in carbon-source gas, heat preservation, and room temperature is down in argon atmosphere, complete reaction.
Further, in step 2), the hydrogen and argon gas flow rate are 1~3:20~200.
Further, in step 2), the heating up process is as follows: being warming up to 800~1000 with the rate of 5 DEG C/min
℃。
Further, hydrogen flow rate is adjusted after the completion of the heating and argon gas flow rate is 1~3:5~100.
Further, the carbon-source gas flow velocity and argon gas flow rate are 1~3:10~200.
Further, the soaking time is 10~30min, preferably 10,15,20min.
Further, reagent described in step 3) can be nitric acid, hydrochloric acid, sulfuric acid, and concentration is 5%~30%, into one
Step ground, the reagent are nitric acid, hydrochloric acid, and concentration is 5%~20%, it is preferable that the reagent is nitric acid, and concentration is
20%.
Further, after the nickel substrate of reagent erosion removal described in step 3), centrifugation, solids is washed with deionized,
It is drying to obtain sea urchin shape three-dimensional grapheme.
Further, the drying temperature is 50 DEG C~200 DEG C, and further, the drying temperature is 50 DEG C~100
DEG C, it is preferable that the drying temperature is 50 DEG C, 60 DEG C, 80 DEG C.
Further, specific step is as follows for the preparation method:
1) nickel salt is dissolved in solvent and obtains nickel salt solution, then alkali and reducing agent are added sequentially in nickel salt solution,
Stirring makes it completely dissolved to obtain green solution, is then transferred in flask, and heated water bath stirring, solution colour gradually becomes
For black, liquid is filtered after reaction, gained floccule deionized water and dehydrated alcohol respectively wash three times to go to clean
Matter is dried to get sea urchin shape nickel nanocrystal is arrived；
2) sea urchin shape nickel nanocrystal obtained by step 1) is put into CVD tube furnace, hydrogen (flow velocity is 10~
30sccm) and under argon gas (flow velocity be 600~1000sccm) mixed atmosphere, tube furnace is warming up to 800 with the rate of 5 DEG C/min~
After 1000 DEG C, then adjusting hydrogen flow rate is 80~120sccm, and is passed through carbon-source gas with the flow velocity of 10~50sccm, is kept the temperature
After 10~20min, turn off hydrogen and carbon-source gas, room temperature is down in argon atmosphere, taking-up sample obtains being grown in Ni-based
The sea urchin shape graphene of bottom surface；
3) material for obtaining step 2) immerses nitric acid (HNO3:H2O=1:4 in), after nickel substrate corrodes disappearance completely,
Liquid is centrifuged, and is washed with deionized for several times, gained black solid is in 50~80 DEG C of drying to obtain sea urchin shape graphenes.
The present invention in specific solution system, at certain pH, passes through the reduction of reducing agent, quilt by nickel salt
It is reduced to needle-shaped nickel, magnetization can occur between each other for these needle-shaped nickel, and the nickel for being self-assembly of sea urchin shape pattern is nanocrystalline
Then body using the nickel nanocrystalline structure as template, by chemical vapour deposition technique (CVD), grows graphite on its surface
Alkene, final etching remove nickel substrate, obtain sea urchin shape graphene (preparation flow is as shown in Fig. 1).
Beneficial effect
The present invention provides a kind of sea urchin shape graphene and preparation method thereof, is reacted by nickel salt and reducing agent, with sea urchin shape
Three-dimensional nickel substrate deposits graphene as template, then by CVD method on it, effectively ensures graphene and forms three-dimensional sea urchin
Shape prevents the defects of crimping, deforming, is porous existing in the prior art.
Sea urchin shape graphene prepared by the present invention can overcome the defect of the existing three-dimensional grapheme with self-assembly method preparation, can
Overcome the problems, such as that the three-dimensional grapheme structure prepared with template auxiliary chemical vapor deposition method is relatively simple；Sea urchin of the present invention
Shape graphene has the advantages that structure novel, defect counts are few, simultaneously because its structure is to be dissipated around by center, therefore have
There is good dispersibility, there is no stack, is porous, configuration is unstable；
Electronics in the sea urchin shape graphene-structured can be along all directions in its surface migration, and traditional two-dimensional slice
The electron transfer direction of layer graphene or the dimension graphene built by graphene sheet layer is limited by itself structure, is compared
For, the various physicochemical properties of graphene-structured of the present invention increase；
Sea urchin shape graphene is in hollow sea urchin shape, has the characteristics that density is small, large specific surface area, can be used as catalyst carrier
Or adsorbent material；Product micro-structure and its structural unit monodispersity are preferable, pattern is uniform, surface cleaning free from admixture, shape
Like sea urchin, 500~700nm of sphere diameter, a large amount of needle-like whisker is distributed in spherome surface, and whisker is straight along its length,
Scale is uniform, and length is about 300nm.
Preparation process of the present invention is simple, and mild condition, raw material sources are extensive, and various chemical agents used are easy to
It removes, does not remain, further ensure the stability and other performances of the graphene；Sea urchin shape graphene has superelevation
Conductive, heating conduction, has potential application value in fields such as electric-heating coatings, fuel cell, sensor and supercapacitors.
Detailed description of the invention
Fig. 1 sea urchin shape three-dimensional grapheme preparation flow schematic diagram.(A) needle-shaped nickel；(B) sea urchin shape nickel；(C) Ni-based load stone
Black alkene；(D) sea urchin shape graphene.
The electrochemical alternate impedance spectrum of Fig. 2 different structure graphene.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, With reference to embodiment to this
Invention is further described.
Embodiment 1
A kind of preparation method of sea urchin shape graphene, includes the following steps:
1) by 1.19g NiCl2·6H2O is added in 100mL ethylene glycol, with 900r/min centrifugal mixer, obtains 0.05mol/
L NiCl2Solution；
0.8g NaOH is added to above-mentioned NiCl2In solution, it is ensured that deposit-free stirs 5 minutes without precipitation；
10.0g hydrazine hydrate is added in the above solution, is sufficiently stirred, obtains green mixed solution；
It is then transferred in flask, water-bath is kept the temperature in 70 DEG C, is stirred 2 hours, solution colour gradually becomes black；
After reaction, above-mentioned solution is filtered, obtains a floccule, it is right respectively with deionized water and dehydrated alcohol
It is washed three times, dries 30 minutes at 60 DEG C to get sea urchin shape nickel nanocrystal；
2) gained sea urchin shape nickel nanocrystal is put into CVD tube furnace, being passed through by flow velocity is 20sccm hydrogen and flow velocity
For the mixed atmosphere of 800sccm argon gas composition；
After tube furnace is warming up to 1000 DEG C with the rate of 5 DEG C/min, then adjusting hydrogen flow rate is 100sccm, and with
The flow velocity of 30sccm is passed through methane gas, after keeping the temperature 15min, turns off hydrogen and methane gas, room temperature is down in argon atmosphere,
It takes out sample and obtains nickel substrate sea urchin shape graphene；
3) resulting nickel substrate sea urchin shape graphene is added in 20% nitric acid of 50ml, corrodes disappearance completely to nickel substrate
Afterwards, liquid is centrifuged, takes its solids, be washed with deionized 3 times, place into drying oven, adjusting temperature is 60 DEG C, dry
30 minutes to get sea urchin shape graphene.
Embodiment 2
A kind of preparation method of sea urchin shape graphene, includes the following steps:
1) by 0.26g NiSO4·6H2O is added in 100mL ethylene glycol, with 900r/min centrifugal mixer, obtains 0.01mol/
L NiSO4Solution；
0.4g NaOH is added to above-mentioned NiSO4In solution, it is ensured that deposit-free stirs 5 minutes without precipitation；
40.0g sodium borohydride is added in the above solution, is sufficiently stirred, obtains green mixed solution；
It is then transferred in flask, water-bath is kept the temperature in 50 DEG C, is stirred 4 hours, solution colour gradually becomes black；
After reaction, above-mentioned solution is filtered, obtains a floccule, it is each to its with deionized water and dehydrated alcohol
Washing three times, dries 30 minutes at 40 DEG C to get sea urchin shape nickel nanocrystal；
2) gained sea urchin shape nickel nanocrystal is put into CVD tube furnace, being passed through by flow velocity is 10sccm hydrogen and flow velocity
For the mixed atmosphere of 600sccm argon gas composition；
After tube furnace is warming up to 800 DEG C with the rate of 5 DEG C/min, then adjusting hydrogen flow rate is 80sccm, and with
The flow velocity of 10sccm is passed through ethylene gas, after keeping the temperature 20min, turns off hydrogen and ethylene gas, room temperature is down in argon atmosphere,
It takes out sample and obtains nickel substrate sea urchin shape graphene；
3) resulting nickel substrate sea urchin shape graphene is added in 20% nitric acid of 30ml, corrodes disappearance completely to nickel substrate
Afterwards, liquid is centrifuged, takes its solids, be washed with deionized 3 times, place into drying oven, adjusting temperature is 50 DEG C, dry
30 minutes to get sea urchin shape graphene.
Embodiment 3
A kind of preparation method of sea urchin shape graphene, includes the following steps:
1) by 2.91g Ni (NO3)2·6H2O is added in 100mL ethylene glycol, with 900r/min centrifugal mixer, obtains
0.1mol/L NiCl2Solution；
0.8g NaOH is added to above-mentioned NiCl2In solution, it is ensured that deposit-free stirs 5 minutes without precipitation；
4.0g oxalic acid is added in the above solution, is sufficiently stirred, obtains green mixed solution；
It is then transferred in flask, water-bath is kept the temperature in 100 DEG C, is stirred 1 hour, solution colour gradually becomes black
Color；
After reaction, above-mentioned solution is filtered, obtains floccule, it is respectively washed with deionized water and dehydrated alcohol
It washs three times, is dried in 80 DEG C to get sea urchin shape nickel nanocrystal is arrived.
2) gained sea urchin shape nickel nanocrystal is put into CVD tube furnace, being passed through by flow velocity is 30sccm hydrogen and flow velocity
For the mixed atmosphere of 1000sccm argon gas composition；
After tube furnace is warming up to 900 DEG C with the rate of 5 DEG C/min, then adjusting hydrogen flow rate is 120sccm, and with
The flow velocity of 50sccm is passed through acetylene gas, after keeping the temperature 10min, turns off hydrogen and acetylene gas, room temperature is down in argon atmosphere,
It takes out sample and obtains nickel substrate sea urchin shape graphene；
3) resulting nickel substrate sea urchin shape graphene is added in 20% nitric acid of 100ml, corrodes disappearance completely to nickel substrate
Afterwards, liquid is centrifuged, takes its solids, be washed with deionized 3 times, place into drying oven, adjusting temperature is 80 DEG C, dry
30 minutes to get arrive sea urchin shape graphene.
Embodiment 4
Sea urchin shape nickel nanocrystal in embodiment 1 is replaced with into nickel sheet, and as substrate, similarly to Example 1
Under conditions of graphene prepared using CVD method, finally obtain two-dimensional slice graphene.
Specific surface area is carried out to graphene prepared by embodiment 1 and the present embodiment 4 respectively and electrochemical AC impedance is surveyed
Examination, wherein specific surface area uses U.S. Micromeritics company ASAP2010MC type BET nitrogen adsorption specific surface instrument
Measurement, electrochemical AC impedance test carries out on CHI 660D type electrochemical workstation (BeiJing, China), using three electrode bodies
System, using graphene as working electrode, platinum filament is auxiliary electrode, and saturated calomel electrode is reference electrode.Acquired results such as table 1 and figure
2
Table 1
| Group | Embodiment 1 | Embodiment 4 |
| Material | Sea urchin shape graphene | Two-dimensional slice graphene |
| Specific surface area (m2/g) | 1764 | 537 |
Due to being influenced by many empirical factors and graphene nature, graphene prepared by laboratory can exist
Different degrees of reunion makes its actual specific surface area far below theoretical value (2630m2/ g), seen from table 1, sea urchin of the present invention
Shape graphene is due to its special microstructure, though specific surface area is apparently higher than conventional two-dimensional lamella stone lower than theoretical value
Black alkene shows its good dispersibility.
In electrochemical alternate impedance spectrum, half circular diameter corresponds to interfacial charge transfer resistance, it is possible thereby to characterize leading for material
Electrically, half circular diameter is smaller, i.e. interfacial charge transfer resistance is smaller, i.e., electric conductivity is better, as seen from Figure 2, sea urchin shape stone
The electric conductivity of black alkene is better than two-dimensional slice graphene.
It is understood that the principle that embodiment of above is intended to be merely illustrative of the present and the exemplary implementation that uses
Mode, however the present invention is not limited thereto.For those skilled in the art, essence of the invention is not being departed from
Mind and essence in the case where, various changes and modifications can be made therein, these variations and modifications be also considered as be comprised in it is of the invention
In protection scope.
Claims (10)
1. a kind of sea urchin shape graphene, which is characterized in that have three-dimensional hollow sea urchin shape structure.
2. a kind of preparation method of sea urchin shape graphene, which is characterized in that specific step is as follows:
1) in a solvent, nickel salt reacts under alkali and reducing agent effect is made sea urchin shape nickel nanocrystal；
2) it using nickel nanocrystal as template, by chemical vapour deposition technique in nickel nanocrystal surface apposition growth graphene, obtains
To nickel substrate sea urchin shape graphene；
3) by reagent erosion removal nickel substrate, sea urchin shape three-dimensional grapheme is obtained.
3. preparation method according to claim 2, which is characterized in that the solvent is ethyl alcohol, water, ethylene glycol, methanol, third
One of alcohol, isopropanol, propylene glycol, glycerine, kerosene, solvent naphtha or combinations thereof；
The nickel salt is NiSO4·6H2O、Ni(NO3)2·6H2O、Ni(CH3COO)2·4H2O、NiCl2·6H2O、NiBr2、
NiI2、NiF2One of or combinations thereof；
The alkali is ammonium hydroxide, NaOH, KOH, Na2CO3、Na3PO4、Na3BO4、K2CO3, sodium methoxide, sodium ethoxide, in potassium tert-butoxide
One kind or combinations thereof.
4. preparation method according to claim 2, which is characterized in that the molar ratio of the alkali and nickel salt is 1~20:1.
5. preparation method according to claim 2, which is characterized in that the reducing agent is hydrazine hydrate, sodium borohydride, grass
Acid, formic acid, sodium hypophosphite, L-AA, citric acid, ortho phosphorous acid potassium, Lime Hypophosphate, sodium hypophosphite, sodium hypophosphite,
One of DTT, formaldehyde or combinations thereof；
The molar ratio of the reducing agent and the nickel salt is 1~1000:1.
6. preparation method according to claim 2, which is characterized in that the temperature of reaction described in step 1) is 10~100
℃；Reaction time is 1~5 hour；
Described in step 1) after reaction, acquired solution filters, and obtains floccule, and washed, dry obtained sea urchin shape nickel is received
Meter Jing Ti.
7. preparation method according to claim 2, which is characterized in that in step 2), the mistake of the chemical vapour deposition technique
Journey is as follows: nickel nanocrystal being put into CVD tube furnace, the mixed atmosphere being made of hydrogen and argon gas is passed through, heat temperature raising rises
Hydrogen flow rate is adjusted after the completion of temperature, and is passed through carbon-source gas, is kept the temperature, and is closed hydrogen and carbon-source gas, is down in argon atmosphere
Room temperature completes reaction.
8. preparation method according to claim 7, which is characterized in that in step 2), the hydrogen and argon gas flow rate
For 1~3:20~200；
The heating up process is as follows: being warming up to 800~1000 DEG C with the rate of 5 DEG C/min.
9. preparation method according to claim 8, which is characterized in that adjust hydrogen flow rate and argon gas after the completion of the heating
Flow rate is 1~3:5~100；
The carbon-source gas flow velocity and argon gas flow rate are 1~3:10~200；
The soaking time is 10~30min.
10. preparation method according to claim 2, which is characterized in that reagent described in step 3) is nitric acid, hydrochloric acid or sulphur
Acid, concentration are 5%~30%；
After the reagent erosion removal nickel substrate, centrifugation, solids is washed with deionized, and is drying to obtain sea urchin shape three-dimensional stone
Black alkene.
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| CN111424257A (en) * | 2020-03-20 | 2020-07-17 | 西安交通大学 | Three-dimensional reticular graphene with biomass structure and preparation method thereof |
| CN112573509A (en) * | 2020-12-23 | 2021-03-30 | 湖南医家智烯新材料科技有限公司 | Cage-shaped graphene material and preparation method thereof |
| CN112624097A (en) * | 2020-12-30 | 2021-04-09 | 北京新能源汽车技术创新中心有限公司 | Graphene pore-forming method |
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