CN108002370A - A kind of preparation method and application of three-dimensional porous class graphene sheet layer - Google Patents
A kind of preparation method and application of three-dimensional porous class graphene sheet layer Download PDFInfo
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- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The present invention uses low temperature graphite method, pass through coconut husk, walnut shell, hazelnut shell, the biological materials such as Fructus Pistaciae Verae shell, using the carbonate by alkali metal as catalyst, it is high to obtain a kind of purity, the good three-dimensional porous class grapheme material of pattern, the three-dimensional porous class grapheme material specific surface area are up to 1506m2/ g, reaches 91F/g applied to specific capacitance in organic system ultracapacitor.The method that the present invention uses is to enrich existing biomass as raw material in nature, synthesis technique green, it is pollution-free, the product purity prepared is high, defect is few, possess good graphene lattice, and high conductivity and high-specific surface area, a kind of ideal synthesis technique is provided for grapheme material synthesis.
Description
Technical field
The present invention relates to the preparation field of graphene, more particularly to a kind of preparation method of three-dimensional porous class graphene sheet layer
And application.
Background technology
Biological material is the carbon material that the charcoal that solid-phase pyrolysis are prepared is hard charcoal structure, due to stone in hard charcoal
Black crystallite lamella is too small, sp3The crosslinking of carbon atom is too strong, causes the specific surface area of hard charcoal and electrical conductivity all very low, and its is non-
Often it is difficult to realize graphitization.And grapheme material has the hexatomic ring lattice of large area, possess extraordinary electric conductivity and higher
Specific surface area, substantial amounts of reaction site can be provided for many physical-chemical reactions, in the energy, the multiple fields such as catalysis have
Irreplaceable effect.Preparing the common method of graphene generally has a complex process, and equipment is expensive, and it is many that product quality is not good enough etc.
Realistic problem.Reproducible biological carbon materials are converted into by the graphene that quality is good, purity is high by simple, inexpensive technique
Material is then ideal selection.
The content of the invention
For mirror with this, the present invention proposes a kind of preparation method and application of three-dimensional porous class graphene sheet layer.
The technical proposal of the invention is realized in this way：
A kind of three-dimensional porous class graphene sheet layer is interweaved by the lamella that the graphene of varying number is formed to be formed, tool
There are the cross-linked structure of three-dimensional and abundant micropore.
A kind of preparation method of three-dimensional porous class graphene sheet layer, the three-dimensional porous class graphene sheet layer use low temperature
Prepared by graphite method, comprise the following steps：
Step 1：The inner casing of biomass is separated, is crushed, less than 100 microns of powder is chosen in screening；
Step 2：The powder that step 1 is obtained is to slowly warm up to 350-900 DEG C of bar in tube furnace is placed under nitrogen protection
Carbonized under part, cooling obtains charcoal；
Step 3：The charcoal that step 2 is obtained is mixed with catalyst, ground, and is then to slowly warm up in a nitrogen atmosphere
Reacted under the conditions of 850-1000 DEG C, complete graphitization, taken out after cooling；
Step 4：The sample that step 3 is obtained is washed with deionized water to neutrality；
Step 5：The sample that step 4 is obtained, which is put into dilute hydrochloric acid, to be stirred；
Step 6：The sample that step 5 is obtained is washed with deionized water to neutrality again；
Step 7：The product that step 6 is obtained is dried, and obtains the three-dimensional porous class graphene sheet layer.
Further, in the step 2, the biomass is coconut husk, walnut shell, hazelnut shell or Fructus Pistaciae Verae shell；It is described
Catalyst be potassium carbonate or lithium carbonate, sodium carbonate.
Further, in the step 2, heating rate is 2-10 DEG C/min, carbonization time 2-4h.
Further, in the step 3, the mass ratio of charcoal and catalyst is 1:2~1:10, milling time 3-
5min, heating rate are 2-10 DEG C/min, when reaction 0.5-3 is small.
Further, in the step 5, the concentration of dilute hydrochloric acid is 2-10wt%, when mixing time is 6-12 small.
Further, in the step 7, product that step 6 is obtained be put into air dry oven dry 6-12 it is small when.
Compared with prior art, the beneficial effects of the invention are as follows：
1) the present invention provides a kind of new catalytic way, at low temperature by the relatively narrow biology of reproducible application range
Carbon material is converted into the three-dimensional porous class graphene sheet layer with good electric conductivity and high-specific surface area, there is provided a kind of new
Grapheme material preparation method；
2) preparation method simple process and low cost of the present invention, raw material sources are wide, green non-pollution；
3) the three-dimensional porous class graphene sheet layer that the present invention prepares, three be made of the different graphene sheet layer of the number of plies
Structure is tieed up, is interconnected between this three-dimensional structure, is beneficial to the transmission of electronics, in the application of ultracapacitor, this knot
Structure possesses very high electronic conductivity；
4) there is abundant microcellular structure on the class graphene sheet layer that the present invention is prepared, further increase product
Specific surface area, better than the specific surface area of same type of material；
5) microcellular structure on the class graphene sheet layer that the present invention is prepared, can provide largely for physical-chemical reaction
Reaction site, have far above same type of material electrical conductivity, have further lifting to class graphene sheet layer application value.
Brief description of the drawings
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only the preferred embodiment of the present invention, for
For those of ordinary skill in the art, without having to pay creative labor, it can also be obtained according to these attached drawings
His attached drawing.
Fig. 1 is the scanning electron microscope (SEM) photograph of the three-dimensional porous class graphene sheet layer of the present invention；
Fig. 2 is the high resolution scanning electron microscope of the three-dimensional porous class graphene sheet layer of the present invention；
Fig. 3 is the transmission electron microscope picture of the three-dimensional porous class graphene sheet layer of the present invention；
The high-resolution-ration transmission electric-lens figure of the three-dimensional porous class graphene sheet layer of Fig. 4 positions present invention；
Fig. 5 is the adsorption desorption isothermal curve of the three-dimensional porous class graphene sheet layer of case study on implementation one；
The graph of pore diameter distribution of the three-dimensional porous class graphene sheet layer of Fig. 6 positions case study on implementation one；
Fig. 7 is that electrode of super capacitor is made in the case where 20mV/s sweeps speed in the three-dimensional porous class graphene sheet layer of case study on implementation one
Cyclic voltammogram；
Fig. 8 is that electrode of super capacitor is made is close in 0.2A/g electric currents for the three-dimensional porous class graphene sheet layer of case study on implementation one
Charging and discharging curve figure under degree.
Embodiment
In order to be best understood from the technology of the present invention content, a specific embodiment is provided below, and the present invention is done with reference to attached drawing
Further instruction.
As depicted in figs. 1 and 2, which is formed by the flake layer combination of numerous three-dimensional arrangements,
It is connected with each other between these lamellas, forms the structure being integrally cross-linked with each other
As shown in Figure 3 and Figure 4, these class graphene sheet layers are actually and are made of the different graphene of the number of plies, the piece number of plies
Measure by one layer to multilayer etc., and the distance between these lamellas are 0.346nm, are the graphene layer spacing of standard.
As shown in Figure 5 and Figure 6, isothermal adsorption desorption test result shows that the specific surface area of the material is up to 1506m2/ g, contains
There is substantial amounts of micropore and a certain amount of mesoporous, these abundant pore structures have emphatically application of the material in terms of energy storage
The effect wanted.
Next the step of preparing three-dimensional porous class graphene film layer material to the present invention using specific embodiment is done
Further illustrate.
A kind of preparation method of three-dimensional porous class graphene sheet layer, the three-dimensional porous class graphene sheet layer use low temperature
Prepared by graphite method, comprise the following steps：
Step 1：The inner casing of biomass is separated, is crushed, less than 100 microns of powder is chosen in screening；
Step 2：The powder that step 1 is obtained is to slowly warm up to 350-900 DEG C of bar in tube furnace is placed under nitrogen protection
Carbonized under part, cooling obtains charcoal；
Step 3：The charcoal that step 2 is obtained is mixed with catalyst, ground, and is then to slowly warm up in a nitrogen atmosphere
Reacted under the conditions of 850-1000 DEG C, complete graphitization, taken out after cooling；
Step 4：The sample that step 3 is obtained is washed with deionized water to neutrality；
Step 5：The sample that step 4 is obtained, which is put into dilute hydrochloric acid, to be stirred；
Step 6：The sample that step 5 is obtained is washed with deionized water to neutrality again；
Step 7：The product that step 6 is obtained is dried, and obtains the three-dimensional porous class graphene sheet layer.
Further, in the step 2, the biomass is coconut husk, walnut shell, hazelnut shell or Fructus Pistaciae Verae shell；It is described
Catalyst be potassium carbonate or lithium carbonate, sodium carbonate.
Further, in the step 2, heating rate is 2-10 DEG C/min, carbonization time 2-4h.
Further, in the step 3, the mass ratio of charcoal and catalyst is 1:2~1:10, milling time 3-
5min, heating rate are 2-10 DEG C/min, when reaction 0.5-3 is small.
Further, in the step 5, the concentration of dilute hydrochloric acid is 2-10wt%, when mixing time is 6-12 small.
Further, in the step 7, product that step 6 is obtained be put into air dry oven dry 6-12 it is small when.
Embodiment 1：
(1) inner casing of coconut husk is separated first, then crushed, less than 100 microns of powder is chosen in screening；Will be above-mentioned
The powder that step (1) obtains is warming up to 400 DEG C, after then carbonizing 3h under nitrogen protection in tube furnace is placed on 10 DEG C/min
Natural cooling is taken out to obtain charcoal；The charcoal that above-mentioned steps (2) are obtained is with potassium carbonate with 1:6 ratio mixing, is grinding
5min is ground in alms bowl, then in a nitrogen atmosphere with 10 DEG C/min be warming up to 900 DEG C of reactions 2 it is small when, take out after natural cooling；Will
The sample that above-mentioned steps (3) are taken out first is washed with deionized water to neutrality；The sample that above-mentioned steps (4) are taken out is put into 2wt%'s
When stirring 12 is small in dilute hydrochloric acid；The sample that above-mentioned steps (5) are taken out is washed with deionized water to neutrality again；By above-mentioned steps
(6) product obtained be put into air dry oven drying 12 it is small when.
Embodiment 2：
(1) inner casing of coconut husk is separated first, then crushed, less than 100 microns of powder is chosen in screening；Will be above-mentioned
The powder that step (1) obtains is warming up to 500 DEG C, after then carbonizing 3h under nitrogen protection in tube furnace is placed on 10 DEG C/min
Natural cooling is taken out to obtain charcoal；The charcoal that above-mentioned steps (2) are obtained is with potassium carbonate with 1:6 ratio mixing, is grinding
5min is ground in alms bowl, then in a nitrogen atmosphere with 10 DEG C/min be warming up to 900 DEG C of reactions 2 it is small when, take out after natural cooling；Will
The sample that above-mentioned steps (3) are taken out first is washed with deionized water to neutrality；The sample that above-mentioned steps (4) are taken out is put into 2wt%'s
When stirring 12 is small in dilute hydrochloric acid；The sample that above-mentioned steps (5) are taken out is washed with deionized water to neutrality again；By above-mentioned steps
(6) product obtained be put into air dry oven drying 12 it is small when.
Embodiment 3：
(1) inner casing of coconut husk is separated first, then crushed, less than 100 microns of powder is chosen in screening；Will be above-mentioned
The powder that step (1) obtains is warming up to 600 DEG C, after then carbonizing 3h under nitrogen protection in tube furnace is placed on 10 DEG C/min
Natural cooling is taken out to obtain charcoal；The charcoal that above-mentioned steps (2) are obtained is with potassium carbonate with 1:6 ratio mixing, is grinding
5min is ground in alms bowl, then in a nitrogen atmosphere with 10 DEG C/min be warming up to 900 DEG C of reactions 2 it is small when, take out after natural cooling；Will
The sample that above-mentioned steps (3) are taken out first is washed with deionized water to neutrality；The sample that above-mentioned steps (4) are taken out is put into 2wt%'s
When stirring 12 is small in dilute hydrochloric acid；The sample that above-mentioned steps (5) are taken out is washed with deionized water to neutrality again；By above-mentioned steps
(6) product obtained be put into air dry oven drying 12 it is small when.
Embodiment 4：
(1) inner casing of coconut husk is separated first, then crushed, less than 100 microns of powder is chosen in screening；Will be above-mentioned
The powder that step (1) obtains is warming up to 700 DEG C, after then carbonizing 3h under nitrogen protection in tube furnace is placed on 10 DEG C/min
Natural cooling is taken out to obtain charcoal；The charcoal that above-mentioned steps (2) are obtained is with potassium carbonate with 1:6 ratio mixing, is grinding
5min is ground in alms bowl, then in a nitrogen atmosphere with 10 DEG C/min be warming up to 900 DEG C of reactions 2 it is small when, take out after natural cooling；Will
The sample that above-mentioned steps (3) are taken out first is washed with deionized water to neutrality；The sample that above-mentioned steps (4) are taken out is put into 2wt%'s
When stirring 12 is small in dilute hydrochloric acid；The sample that above-mentioned steps (5) are taken out is washed with deionized water to neutrality again；By above-mentioned steps
(6) product obtained be put into air dry oven drying 12 it is small when.
Embodiment 5：
(1) inner casing of coconut husk is separated first, then crushed, less than 100 microns of powder is chosen in screening；Will be above-mentioned
The powder that step (1) obtains is warming up to 800 DEG C, after then carbonizing 3h under nitrogen protection in tube furnace is placed on 10 DEG C/min
Natural cooling is taken out to obtain charcoal；The charcoal that above-mentioned steps (2) are obtained is with potassium carbonate with 1:6 ratio mixing, is grinding
5min is ground in alms bowl, then in a nitrogen atmosphere with 10 DEG C/min be warming up to 900 DEG C of reactions 2 it is small when, take out after natural cooling；Will
The sample that above-mentioned steps (3) are taken out first is washed with deionized water to neutrality；The sample that above-mentioned steps (4) are taken out is put into 2wt%'s
When stirring 12 is small in dilute hydrochloric acid；The sample that above-mentioned steps (5) are taken out is washed with deionized water to neutrality again；By above-mentioned steps
(6) product obtained be put into air dry oven drying 12 it is small when.
Embodiment 6：
(1) inner casing of coconut husk is separated first, then crushed, less than 100 microns of powder is chosen in screening；Will be above-mentioned
The powder that step (1) obtains is warming up to 900 DEG C, after then carbonizing 3h under nitrogen protection in tube furnace is placed on 10 DEG C/min
Natural cooling is taken out to obtain charcoal；The charcoal that above-mentioned steps (2) are obtained is with potassium carbonate with 1:6 ratio mixing, is grinding
5min is ground in alms bowl, then in a nitrogen atmosphere with 10 DEG C/min be warming up to 900 DEG C of reactions 2 it is small when, take out after natural cooling；Will
The sample that above-mentioned steps (3) are taken out first is washed with deionized water to neutrality；The sample that above-mentioned steps (4) are taken out is put into 2wt%'s
When stirring 12 is small in dilute hydrochloric acid；The sample that above-mentioned steps (5) are taken out is washed with deionized water to neutrality again；By above-mentioned steps
(6) product obtained be put into air dry oven drying 12 it is small when.
Three-dimensional porous class graphene sheet layer obtained by testing example 1-6, specific data are as shown in table 1：
Table 1：
| Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Specific surface area | m2/g | 1506 | 1473 | 1329 | 1337 | 1232 | 1050 |
| Most probable pore size | nm | 0.83 | 0.81 | 0.82 | 0.79 | 0.8 | 0.8 |
| Pore volume | cm3/g | 0.8 | 0.76 | 0.75 | 0.7 | 0.68 | 0.55 |
As it can be seen from table 1 three-dimensional porous class graphene sheet layer is prepared using low temperature graphitization method provided by the present invention
Method, purity height, specific surface area, most probable pore size and the proper class graphene film layer material of pore volume can be obtained.
According to above-mentioned preparation method, using the raw material and preparation process in table 2, table 3, embodiment 7-10, contrast are obtained
The class grapheme material of example 1-5：
Table 2：
| Unit | Embodiment 1 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | |
| Biomass | —— | Coconut husk | Walnut shell | Coconut husk | Hazelnut shell | Fructus Pistaciae Verae shell |
| Catalyst | —— | Potassium carbonate | Sodium carbonate | Lithium carbonate | Sodium carbonate | Potassium carbonate |
| Heating rate | ℃/min | 10 | 5 | 5 | 2 | 8 |
| Maximum temperature | ℃ | 400 | 400 | 500 | 500 | 400 |
| Carbonization time | h | 3 | 2 | 4 | 5 | 3 |
| Mass ratio | —— | 1:6 | 1:2 | 1:4 | 1:8 | 1:10 |
| Milling time | min | 5 | 4 | 3 | 4 | 5 |
| Heating rate | ℃/min | 10 | 2 | 8 | 2 | 5 |
| Maximum temperature | ℃ | 900 | 850 | 1000 | 950 | 900 |
| Reaction time | h | 2 | 0.5 | 3 | 3 | 1 |
| Dilute hydrochloric acid concentration | Wt% | 2 | 5 | 8 | 10 | 2 |
| Mixing time | h | 12 | 6 | 8 | 10 | 12 |
Table 3：
| Unit | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Biomass | —— | Fructus Pistaciae Verae shell | Coconut husk | Hazelnut shell | Fructus Pistaciae Verae shell | Walnut shell |
| Catalyst | —— | Potassium carbonate | Lithium carbonate | Sodium carbonate | Potassium carbonate | Sodium carbonate |
| Heating rate | ℃/min | 10 | 1 | 15 | 5 | 5 |
| Maximum temperature | ℃ | 600 | 500 | 500 | 1000 | 300 |
| Carbonization time | h | 4 | 5 | 3 | 1 | 3 |
| Mass ratio | —— | 1:11 | 1:12 | 1:7 | 1:4 | 1:1 |
| Milling time | min | 2 | 7 | 3 | 4 | 5 |
| Heating rate | ℃/min | 10 | 10 | 15 | 1 | 5 |
| Maximum temperature | ℃ | 1050 | 800 | 900 | 1000 | 1000 |
| Reaction time | h | 3 | 2 | 0.25 | 4 | 2 |
| Dilute hydrochloric acid concentration | Wt% | 2 | 1 | 7 | 8 | 12 |
| Mixing time | h | 4 | 8 | 7 | 8 | 14 |
Three-dimensional porous class graphene sheet layer, specific data such as table 4, the institute of table 5 obtained by test comparison example 1-5, embodiment 7-10
Show：
Table 4：
| Unit | Embodiment 1 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | |
| Specific surface area | m2/g | 1506 | 587 | 1080 | 1054 | 967 |
| Most probable pore size | nm | 0.83 | 0.73 | 0.77 | 0.76 | 0.80 |
| Pore volume | cm3/g | 0.8 | 0.35 | 0.56 | 0.53 | 0.50 |
Table 5：
| Unit | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Specific surface area | m2/g | 829 | 659 | 482 | 696 | 654 |
| Most probable pore size | nm | 0.77 | 0.78 | 0.64 | 0.76 | 0.73 |
| Pore volume | cm3/g | 0.48 | 0.33 | 0.30 | 0.42 | 0.40 |
The specific surface area of the three-dimensional porous class grapheme material of the gained of embodiment 1 is can be seen that from above experimental result, most may be used
Several apertures and pore volume are relatively optimal, it is seen that optimal preparation method is：(1) inner casing of coconut husk is separated first, then powder
Broken, less than 100 microns of powder is chosen in screening；The powder that above-mentioned steps (1) are obtained is in tube furnace is placed on, under nitrogen protection
400 DEG C are warming up to 10 DEG C/min, natural cooling is taken out to obtain charcoal after then carbonizing 3h；Above-mentioned steps (2) are obtained
Charcoal is with potassium carbonate with 1:6 ratio mixing, 5min is ground in mortar, is then heated up in a nitrogen atmosphere with 10 DEG C/min
To 900 DEG C of reactions 2 it is small when, take out after natural cooling；The sample that above-mentioned steps (3) are taken out first is washed with deionized water to neutrality；
By the sample that above-mentioned steps (4) are taken out be put into the dilute hydrochloric acid of 2wt% stirring 12 it is small when；The sample that above-mentioned steps (5) are taken out
It is washed with deionized water again to neutrality；By the product that above-mentioned steps (6) obtain be put into air dry oven drying 12 it is small when.
The class grapheme material that embodiment 1 is prepared is characterized, its pattern as shown in Figs 1-4, from scanning electron microscope
As can be seen that the pattern of gained class grapheme material is preferable, lamella is spaced about 0.35nm.To the three-dimensional porous of case study on implementation one
Class graphene sheet layer expansion further test, gained adsorption desorption isothermal curve is as shown in figure 5, graph of pore diameter distribution is as shown in Figure 6.Will
Electrode of super capacitor is made in the three-dimensional porous class graphene sheet layer of case study on implementation one, its cyclic voltammetric in the case where 20mV/s sweeps speed
Figure as shown in fig. 7, charging and discharging curve figure under 0.2A/g current densities as shown in figure 8, by one three-dimensional porous class of case study on implementation
Electrode of super capacitor is made in graphene sheet layer, and applied in organic system ultracapacitor, its specific capacitance reaches 91F/g.
In conclusion using method provided by the invention, that low temperature graphitization method prepares three-dimensional porous class graphene sheet layer,
It is high that a kind of purity can be obtained, the good three-dimensional porous class grapheme material of pattern.And preparation method technique letter of the present invention
Single, of low cost, green non-pollution, is easy to industrialized production.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on, should all be included in the protection scope of the present invention god.
Claims (7)
- A kind of 1. preparation method of three-dimensional porous class graphene sheet layer, it is characterised in that the three-dimensional porous class graphene film Layer is prepared using low temperature graphite method, is comprised the following steps：Step 1：The inner casing of biomass is separated, is crushed, less than 100 microns of powder is chosen in screening；Step 2：The powder that step 1 is obtained is to slowly warm up under the conditions of 350-900 DEG C in tube furnace is placed under nitrogen protection Charing, cooling obtain charcoal；Step 3：The charcoal that step 2 is obtained is mixed with catalyst, ground, and is then to slowly warm up to 850- in a nitrogen atmosphere Reacted under the conditions of 1000 DEG C, complete graphitization, taken out after cooling；Step 4：The sample that step 3 is obtained is washed with deionized water to neutrality；Step 5：The sample that step 4 is obtained, which is put into dilute hydrochloric acid, to be stirred；Step 6：The sample that step 5 is obtained is washed with deionized water to neutrality again；Step 7：The product that step 6 is obtained is dried, and obtains the three-dimensional porous class graphene sheet layer.
- 2. the preparation method of three-dimensional porous class graphene sheet layer according to claim 1, it is characterised in that the step 2 In, the biomass is coconut husk, walnut shell, hazelnut shell or Fructus Pistaciae Verae shell；The catalyst is potassium carbonate or lithium carbonate, Sodium carbonate.
- 3. the preparation method of three-dimensional porous class graphene sheet layer according to claim 1, it is characterised in that the step 2 In, heating rate is 2-10 DEG C/min, carbonization time 2-4h.
- 4. the preparation method of three-dimensional porous class graphene sheet layer according to claim 1, it is characterised in that the step 3 In, the mass ratio of charcoal and catalyst is 1:2~1:10, milling time 3-5min, heating rate are 2-10 DEG C/min, instead When answering 0.5-3 small.
- 5. the preparation method of three-dimensional porous class graphene sheet layer according to claim 1, it is characterised in that the step 5 In, the concentration of dilute hydrochloric acid is 2-10wt%, when mixing time is 6-12 small.
- 6. the preparation method of three-dimensional porous class graphene sheet layer according to claim 1, it is characterised in that the step 7 In, product that step 6 is obtained be put into air dry oven dry 6-12 it is small when.
- 7. the three-dimensional porous class graphene sheet layer that low temperature graphite method as claimed in claim 1 prepares is preparing super electricity Application on container.
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| CN109750316A (en) * | 2018-09-12 | 2019-05-14 | 东莞理工学院 | Electrochemistry formated ammonia catalyst based on graphene quantum dot and preparation method thereof |
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| CN109824034A (en) * | 2019-03-07 | 2019-05-31 | 南方科技大学 | Graphene with regular nanohole array and preparation method thereof and lithium battery |
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| CN109087816A (en) * | 2018-08-24 | 2018-12-25 | 亳州学院 | A kind of electrode composite material and the preparation method and application thereof |
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| CN109824034A (en) * | 2019-03-07 | 2019-05-31 | 南方科技大学 | Graphene with regular nanohole array and preparation method thereof and lithium battery |
| CN109761215A (en) * | 2019-03-11 | 2019-05-17 | 大连理工大学 | A kind of preparation method of the conductive porous carbon material of kitchen garbage base complex defect type |
| 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 |
| CN111072007A (en) * | 2019-12-12 | 2020-04-28 | 广西大学 | Preparation method and application of biomass-based three-dimensional multi-cavity graphene-like carbon capsule |
| CN112246220A (en) * | 2020-10-30 | 2021-01-22 | 井冈山大学 | Graphene-like biochar prepared from bidens tripartita and method for treating printing and dyeing wastewater by using graphene-like biochar |
| CN112279240A (en) * | 2020-10-30 | 2021-01-29 | 井冈山大学 | Graphene-like biochar prepared from allium aviculare and method for removing sulfonamide antibiotics by graphene-like biochar |
| CN112678809A (en) * | 2020-12-30 | 2021-04-20 | 安徽工程大学 | Method for synthesizing graphene with hierarchical structure by catalyzing biomass |
| CN113307254A (en) * | 2021-06-24 | 2021-08-27 | 武汉科技大学 | Method for preparing three-dimensional porous graphene sheet by using low-temperature double-salt compound and application |
| CN114014315A (en) * | 2021-10-22 | 2022-02-08 | 海南大学 | Molten salt chemical activation method for preparing macroporous graphitized biomass carbon |
| CN114340371A (en) * | 2022-01-21 | 2022-04-12 | 中星(广州)纳米材料有限公司 | Graphene oxide-high-entropy alloy nanocomposite for electromagnetic wave shielding and preparation method and application thereof |
| CN114380285A (en) * | 2022-02-17 | 2022-04-22 | 湘潭大学 | One-dimensional and two-dimensional biological carbon synergistically enhanced carbon aerogel material and preparation method and application thereof |
| CN114380285B (en) * | 2022-02-17 | 2023-10-20 | 湘潭大学 | Carbon aerogel material with synergistic enhancement of one-dimensional biological carbon and two-dimensional biological carbon, and preparation method and application thereof |
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