CN107416800A - A kind of method that hydro-thermal method prepares N and S codope three-dimensional grapheme materials - Google Patents
A kind of method that hydro-thermal method prepares N and S codope three-dimensional grapheme materials Download PDFInfo
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Abstract
A kind of method that hydro-thermal method prepares N and S codope three-dimensional grapheme materials, N and S codope three-dimensional grapheme materials are prepared using hydro-thermal method, are comprised the following steps：1) graphene oxide is prepared；2) step 1) is prepared into graphene oxide solution；3) graphene oxide solution being slowly added dropwise to thiocarbamide in step 2)；4) graphene oxide solution being slowly added dropwise to ammoniacal liquor in step 3)；5) mixed liquor for obtaining step 4) is transferred in reactor, and hydrothermal reduction reaction is carried out in air dry oven；6) three-dimensional grapheme hydrogel is taken out from reactor and cleaned repeatedly with deionized water and alcohol；7) the three-dimensional grapheme hydrogel after cleaning is placed in precooling in refrigerator or liquid nitrogen；8) the graphene hydrogel after freezing is placed in freeze drier and is freeze-dried to obtain N and S codope three-dimensional graphemes.It is with a wide range of applications in fields such as ultracapacitor, electrode, lithium ion batteries.
Description
Technical field
The present invention relates to a kind of method that hydro-thermal method prepares N and S codope three-dimensional grapheme materials, belong to material science skill
Art field.
Background technology
Graphene is due to its excellent electric conductivity, translucency, conductivity of heat and mechanical property and in numerous necks such as electronics, optics
The huge potential using value of domain views.Oxidation-reduction method, which prepares graphene and turns into prepare, a large amount of graphenes and realizes its production
The most effectual way of industryization application, this method is divided into first is carried out graphite oxidation into graphene oxide, again with certain reducing agent
Reduction obtains two processes of redox graphene, and the former has tended to be ripe, and how the latter improves the specific surface area of graphene
And increase graphene oxygen-containing functional group turns into research heat to improve it in the efficiency of energy storage and the application of other field
Point and difficult point.Three-dimensional grapheme is to form three-dimensional porous structure graphene by graphene slurry, in ultracapacitor, electrode, light
The fields such as electronic device are with a wide range of applications.At present, prepare three-dimensional grapheme it is more be to use nickel foam or bubble
Foam copper carries out CVD as substrate or prepared by oxidation-reduction method, the excessive dependence substrate of this method, and be not doped
Three-dimensional grapheme performance on ultracapacitor or lithium ion battery is bad, then carrying out element doping to three-dimensional grapheme is
Improve a kind of its effective means on ultracapacitor on application performance.
This method utilizes the stage reduction method of hydro-thermal method one, and three-dimensional grapheme is entered as nitrogen source with ammoniacal liquor using thiocarbamide as sulphur source
Row doping, realizes the simple preparation that S and N is co-doped with three-dimensional grapheme material, technological process is simple, efficiently, stably, it is controllable, no
The three-dimensional structure with substrate is relied on, is with a wide range of applications in fields such as ultracapacitor, electrode, opto-electronic devices.
The content of the invention
Technical problem：It is an object of the invention to provide the side that a kind of hydro-thermal method prepares N and S codope three-dimensional grapheme materials
Method, this method technological process is simple, efficiently, stably, the preparation method of controllable three-dimensional grapheme, ultracapacitor, electrode,
The fields such as lithium ion battery are with a wide range of applications.
Technical scheme：, should the invention provides a kind of method that hydro-thermal method prepares N and S codope three-dimensional grapheme materials
Method comprises the following steps：
1) graphene oxide is dissolved in deionized water simultaneously ultrasonic disperse, it is the scattered equal of 1-5mg/mL to be prepared into concentration
Even graphene oxide solution；
2) graphene oxide solution for obtaining step 1) is poured into beaker, and it is molten that thiocarbamide is added dropwise under conditions of magnetic agitation
Liquid, obtain mixed liquor；
3) step 2) is obtained into mixed liquor, ammoniacal liquor is added dropwise under conditions of magnetic agitation and carries out element doping；
4) ammoniacal liquor that obtains step 3), thiocarbamide, graphene oxide liquid mixture are transferred in reactor；
5) reactor is placed in progress hydrothermal reduction reaction in air dry oven, obtains three-dimensional grapheme hydrogel；
6) three-dimensional grapheme hydrogel is taken out from reactor and cleaned repeatedly with deionized water and alcohol；
7) the three-dimensional grapheme hydrogel after cleaning is placed in precooling in refrigerator or liquid nitrogen；
8) the three-dimensional grapheme hydrogel after precooling is placed in freeze drier and is freeze-dried to obtain N and S is total to
Adulterate three-dimensional grapheme.
Wherein,
Graphene oxide described in step 1) is prepared by improved Hummers methods, is comprised the following steps that：
Step 1: graphite powder is added in the concentrated sulfuric acid, sodium nitrate is added sequentially afterwards and potassium permanganate carries out confined reaction,
Obtain reaction mixture I；
Step 2: adding deionized water into reaction mixture I, heating stirring, reaction mixture II is obtained；
Step 3: adding hydrogenperoxide steam generator stirring into reaction mixture II, reaction mixture III is obtained after reaction；
Step 4: standing the supernatant removed in reaction mixture III, sediment is carried out to be centrifuged repeatedly cleaning, ultrasound stripping
Graphene oxide is dried to obtain from after.
Wherein, the graphite powder described in step 1：Sodium nitrate mass ratio is (1~4)：(1~3):(1~2), graphite and Gao Meng
The ratio of sour potassium is classified as 1：(3~1)：6, the mass volume ratio of graphite powder and the concentrated sulfuric acid is 1g:(20~25) ml, described is closed anti-
It should refer to stir 90-100min after adding sodium nitrate and potassium permanganate, afterwards under the conditions of 35-40 DEG C of bath temperature, react 40-
60min。
Heating stirring described in step 2 refers to that in temperature be 93-98 DEG C, stirs 40-60min.
Described hydrogen peroxide and the volume mass ratio of graphite powder are (13~17) ml:1g, described stirring when it is a length of
15-30min。
The cleaning that is centrifuged repeatedly described in step 4 refers under 10000-14000rpm rotating speeds, centrifuges 10-15min, until
Detected with barium hydroxide untill there is no white precipitate in centrifuged supernatant；Described ultrasound, which is peeled off, refers to that in supersonic frequency be 20-
Ultrasonic 30-45min under the conditions of 40khz.
Step 1) the ultrasonic disperse power is 20-40khz, and the ultrasonic disperse time is 30-2h.
Step 2) the thiourea solution that is added dropwise is 2-10ml, concentration 10-40mg/ml.
Hydrothermal reduction reaction temperature described in step 5) is 120 DEG C -200 DEG C, and the described hydrothermal reduction reaction time is 8h-
24h。
Described precooling, time 12-36h；The time dried in freeze drier is 24-48h.
Beneficial effect：Compared with prior art, the present invention has advantages below：
1st, traditional N and S adulterates three-dimensional grapheme using CVD substrate methods, and CVD can prepare higher three of quality
Dimension graphene still compares the three-dimensional structure dependent on base foam nickel or foam copper.This method is that graphene is self-assembled into three
The effect of substrate is not needed during tieing up structure, and N and S doping prepares N and S to 2, hydro-thermal method of the present invention and is co-doped with three-dimensional stone
Black alkene material, realizes effective preparation of N and S codope three-dimensional grapheme materials, technological process is simple, efficiently, stably, can
Control, cost are had a certain impact far below the structure tool of conventional three-dimensional stone three-dimensional grapheme, and three are improved by N and S doping
The stability of graphene-structured is tieed up, and improves three-dimensional grapheme answering in terms of ultracapacitor or lithium ion battery
With.
The preparation method of black alkene, it is with a wide range of applications in fields such as ultracapacitor, electrode, lithium ion batteries.
Brief description of the drawings
Fig. 1 is the flow chart that hydro-thermal method of the present invention prepares N and S codope three-dimensional grapheme materials.
Fig. 2 is morphology characterization figure and the elementary analysis that hydro-thermal method of the present invention prepares N and S codope three-dimensional grapheme materials
Figure, wherein,
(a) N and S codopes three-dimensional grapheme material top view and front view, and load-bearing are prepared for hydro-thermal method of the present invention
Figure.
(b) and (c) is that N and S is co-doped with SEM picture of the three-dimensional grapheme material under different amplification,
(d-h) the EDS energy spectrum diagrams of three-dimensional grapheme material are co-doped with for N and S.
Fig. 3 is that hydro-thermal method of the present invention prepares CV of the N and S codope three-dimensional grapheme materials under different scanning voltage speed
Curve map.
Fig. 4 is that hydro-thermal method of the present invention prepares discharge and recharge of the N and S codope three-dimensional grapheme materials under different current densities
Curve.
Embodiment
Embodiment 1
1) graphene oxide is prepared using improved Hummers methods：
Step 1: the three-necked flask that the concentrated sulfuric acid (98wt%) 20ml is added to 1L stirs 5min under the conditions of ice-water bath；
Step 2: 1g graphite is slowly added into concentrated sulfuric acid solution；
10min is reacted Step 3: 0.5g sodium nitrate is added in above-mentioned mixed liquor；
Step 4: 3g potassium permanganate is slowly slowly added to and stirs 90min, observation color is changed into blackish green from purple；
Step 5: heating, 35 DEG C of bath temperature, react 40min, observation color is changed into brown from blackish green；
Step 6: adding 46ml deionized waters, it is added dropwise, is then warming up to 98 DEG C, stirs 40min；
Step 7: 13ml hydrogen peroxide is added dropwise, 15min is stirred；
Step 8: treating that solution cools down after reaction, add deionized water, stand, remove supernatant liquor；
Step 9: centrifugation, 14000rpm, 10min, until heavy without white with the supernatant after barium hydroxide detection centrifugation
Form sediment；
Step 10: ultrasonic 45min is peeled off under the conditions of frequency is 20khz to the sediment in centrifuge tube, oxygen is obtained
Graphite alkene.
2) graphene oxide ultrasound 1h is scattered in deionized water, forms uniform dispersion, concentration is 5mg/mL and turned
Move in culture dish.
3) it is the graphene oxide solution that 20mg/ml thiocarbamides are slowly added dropwise in step 2) by 10ml concentration.
4) graphene oxide solution being slowly added dropwise to 250 μ l ammoniacal liquor in step 3).
5) thiocarbamide that obtains step 4), ammoniacal liquor, graphene oxide liquid mixture are transferred in reactor.
6) reactor is placed in air dry oven and carries out hydrothermal reduction reaction, time of hydro-thermal reaction is 24h, reaction temperature
For 200 DEG C.
7) three-dimensional grapheme hydrogel is taken out and cleaned repeatedly with deionized water and alcohol miscellaneous to taking out from reactor
Matter.
8) the three-dimensional grapheme hydrogel after cleaning is placed in refrigerator or liquid nitrogen and freezes 48h.
9) the three-dimensional grapheme hydrogel after freezing is put into freezing 36h in freeze drier and obtains N and S codopes three-dimensional
Grapheme material.
Embodiment 2
1) graphene oxide is prepared using improved Hummers methods：
Step 1: the three-necked flask that the concentrated sulfuric acid (98wt%) 23ml is added to 1L stirs 5min under the conditions of ice-water bath；
Step 2: 1g graphite is slowly added into concentrated sulfuric acid solution；
10min is reacted Step 3: 0.4g sodium nitrate is added in above-mentioned mixed liquor；
Step 4: 4g potassium permanganate is slowly slowly added to and stirs 93min, observation color is changed into blackish green from purple；
Step 5: heating, 36 DEG C or so of bath temperature, react 45min, observation color is changed into brown from blackish green；
Step 6: adding 46ml deionized waters, it is added dropwise, is then warming up to 98 DEG C, stirs 40min；
Step 7: 15ml hydrogen peroxide is added dropwise, 20min is stirred；
Step 8: treating that solution cools down after reaction, add deionized water, stand, remove supernatant liquor；
Step 9: centrifugation, 13000rpm, 12min, until heavy without white with the supernatant after barium hydroxide detection centrifugation
Form sediment；
Step 10: ultrasonic 40min is peeled off under the conditions of frequency is 30khz to the sediment in centrifuge tube, oxygen is obtained
Graphite alkene.
2) it is 3mg/mL by graphene oxide ultrasonic disperse 1.5h formation uniform dispersion concentration.
3) it is the graphene oxide solution that 10mg/ml thiocarbamides are slowly added dropwise in step 2) by 10ml concentration.
4) graphene oxide solution being slowly added dropwise to 200 μ l ammoniacal liquor in step 3).
5) thiocarbamide that obtains step 4), ammoniacal liquor, graphene oxide liquid mixture are transferred in reactor.
6) reactor is placed in air dry oven and carries out hydrothermal reduction reaction, time of hydro-thermal reaction is 10h, reaction temperature
For 140 DEG C.
7) three-dimensional grapheme hydrogel is taken out and cleaned repeatedly with deionized water and alcohol miscellaneous to taking out from reactor
Matter.
8) the three-dimensional grapheme hydrogel after cleaning is placed in refrigerator or liquid nitrogen and freezes 30h.
9) the three-dimensional grapheme hydrogel after freezing is put into freezing 36h in freeze drier and obtains N and S codopes three-dimensional
Grapheme material.
Embodiment 3
1) graphene oxide is prepared using improved Hummers methods：
Step 1: the three-necked flask that the concentrated sulfuric acid (98wt%) 25ml is added to 1L stirs 5min under the conditions of ice-water bath；
Step 2: 1g graphite is slowly added into concentrated sulfuric acid solution；
10min is reacted Step 3: 0.5g sodium nitrate is added in above-mentioned mixed liquor；
Step 4: 6g potassium permanganate is slowly slowly added to and stirs 96min, observation color is changed into blackish green from purple；
Step 5: heating, 38 DEG C or so of bath temperature, react 53min, observation color is changed into brown from blackish green；
Step 6: adding 46ml deionized waters, it is added dropwise, is then warming up to 98 DEG C, stirs 40min；
Step 7: 17ml hydrogen peroxide is added dropwise, 15min is stirred；
Step 8: treating that solution cools down after reaction, add deionized water, stand, remove supernatant liquor；
Step 9: centrifugation, 12000rpm, 13min, until heavy without white with the supernatant after barium hydroxide detection centrifugation
Form sediment；
Step 10: ultrasonic 30min is peeled off under the conditions of frequency is 40khz to the sediment in centrifuge tube, oxygen is obtained
Graphite alkene.
2) graphene oxide ultrasonic disperse 2h is formed into uniform dispersion concentration to be 2mg/mL and be transferred in culture dish.
3) it is the graphene oxide solution that 15mg/ml thiocarbamides are slowly added dropwise in step 2) by 15ml concentration.
4) graphene oxide solution being slowly added dropwise to 240 μ l ammoniacal liquor in step 3).
5) thiocarbamide that obtains step 4), ammoniacal liquor, graphene oxide liquid mixture are transferred in reactor.
6) reactor is placed in air dry oven and carries out hydrothermal reduction reaction, time of hydro-thermal reaction is 12h, reaction temperature
For 160 DEG C.
7) three-dimensional grapheme hydrogel is taken out and cleaned repeatedly with deionized water and alcohol miscellaneous to taking out from reactor
Matter.
8) the three-dimensional grapheme hydrogel after cleaning is placed in refrigerator or liquid nitrogen and freezes 24h.
9) the three-dimensional grapheme hydrogel after freezing is put into freezing 30h in freeze drier and obtains N and S codopes three-dimensional
Grapheme material.
Embodiment 4
1) graphene oxide is prepared using improved Hummers methods：
Step 1: the three-necked flask that the concentrated sulfuric acid (98wt%) 24ml is added to 1L stirs 5min under the conditions of ice-water bath；
Step 2: 2g graphite is slowly added into concentrated sulfuric acid solution；
10min is reacted Step 3: 0.8g sodium nitrate is added in above-mentioned mixed liquor；
Step 4: 12g potassium permanganate is slowly slowly added to and stirs 90min, observation color is changed into brown from blackish green；
Step 5: heating, 35 DEG C or so of bath temperature, react 40min, observation color is changed into brown from blackish green；
Step 6: adding 46ml deionized waters, it is added dropwise, is then warming up to 98 DEG C, stirs 40min；
Step 7: 15ml hydrogen peroxide is added dropwise, 30min is stirred；
Step 8: treating that solution cools down after reaction, add deionized water, stand, remove supernatant liquor；
Step 9: centrifugation, 10000rpm, 15min, until heavy without white with the supernatant after barium hydroxide detection centrifugation
Form sediment；
Step 10: ultrasonic 40min is peeled off under the conditions of frequency is 25khz to the sediment in centrifuge tube, oxygen is obtained
Graphite alkene.
2) graphene oxide ultrasonic disperse 2h is formed into uniform dispersion concentration to be 1mg/mL and be transferred in culture dish.
3) it is the graphene oxide solution that 20mg/ml thiocarbamides are slowly added dropwise in step 2) by 20ml concentration；
4) graphene oxide solution being slowly added dropwise to 300 μ l ammoniacal liquor in step 3)；
5) thiocarbamide that obtains step 4), ammoniacal liquor, graphene oxide liquid mixture are transferred in reactor.
6) reactor is placed in air dry oven and carries out hydrothermal reduction reaction, time of hydro-thermal reaction is 24h, reaction temperature
For 180 DEG C.
7) three-dimensional grapheme hydrogel is taken out and cleaned repeatedly with deionized water and alcohol miscellaneous to taking out from reactor
Matter.
8) the three-dimensional grapheme hydrogel after cleaning is placed in refrigerator or liquid nitrogen and freezes 40h.
9) the three-dimensional grapheme hydrogel after freezing is put into freezing 4h in freeze drier and obtains N and S codopes three-dimensional
Grapheme material.
Claims (10)
1. a kind of method that hydro-thermal method prepares N and S codope three-dimensional grapheme materials, it is characterised in that this method includes following
Step：
1) graphene oxide is dissolved in deionized water simultaneously ultrasonic disperse, is prepared into the oxygen that is uniformly dispersed that concentration is 1-5mg/mL
Graphite alkene solution；
2) graphene oxide solution for obtaining step 1) is poured into beaker, and thiourea solution is added dropwise under conditions of magnetic agitation,
Obtain mixed liquor；
3) step 2) is obtained into mixed liquor, ammoniacal liquor is added dropwise under conditions of magnetic agitation and carries out element doping；
4) ammoniacal liquor that obtains step 3), thiocarbamide, graphene oxide liquid mixture are transferred in reactor；
5) reactor is placed in progress hydrothermal reduction reaction in air dry oven, obtains three-dimensional grapheme hydrogel；
6) three-dimensional grapheme hydrogel is taken out from reactor and cleaned repeatedly with deionized water and alcohol；
7) the three-dimensional grapheme hydrogel after cleaning is placed in precooling in refrigerator or liquid nitrogen；
8) the three-dimensional grapheme hydrogel after precooling is placed in freeze drier and is freeze-dried to obtain N and S codopes
Three-dimensional grapheme.
2. the method that a kind of hydro-thermal method as claimed in claim 1 prepares N and S codope three-dimensional grapheme materials, its feature exist
In the graphene oxide described in step 1) prepared by improved Hummers methods, comprised the following steps that：
Step 1: graphite powder is added in the concentrated sulfuric acid, sodium nitrate is added sequentially afterwards and potassium permanganate carries out confined reaction, is obtained
Reaction mixture I；
Step 2: adding deionized water into reaction mixture I, heating stirring, reaction mixture II is obtained；
Step 3: adding hydrogenperoxide steam generator stirring into reaction mixture II, reaction mixture III is obtained after reaction；
Step 4: standing the supernatant removed in reaction mixture III, sediment is carried out after being centrifuged repeatedly cleaning, ultrasound stripping
It is dried to obtain graphene oxide.
3. the method that a kind of hydro-thermal method as claimed in claim 2 prepares N and S codope three-dimensional grapheme materials, its feature exist
In the graphite powder described in step 1：Sodium nitrate mass ratio is (1~4)：(1~3):The ratio row of (1~2), graphite and potassium permanganate
For 1：(3~1)：6, the mass volume ratio of graphite powder and the concentrated sulfuric acid is 1g:(20~25) ml, described confined reaction refer to add
90-100min is stirred after sodium nitrate and potassium permanganate, afterwards under the conditions of 35-40 DEG C of bath temperature, reacts 40-60min.
4. the method that a kind of hydro-thermal method as claimed in claim 2 prepares N and S codope three-dimensional grapheme materials, its feature exist
Refer to that in temperature be 93-98 DEG C in the heating stirring described in step 2, stir 40-60min.
5. the method that a kind of hydro-thermal method as claimed in claim 2 prepares N and S codope three-dimensional grapheme materials, its feature exist
In：Described hydrogen peroxide and the volume mass ratio of graphite powder are (13~17) ml:1g, when a length of 15- of described stirring
30min。
6. the method that a kind of hydro-thermal method as claimed in claim 2 prepares N and S codope three-dimensional grapheme materials, its feature exist
Refer in the cleaning that is centrifuged repeatedly described in step 4 under 10000-14000rpm rotating speeds, centrifuge 10-15min, until using hydrogen-oxygen
Change untill there is no white precipitate in barium detection centrifuged supernatant；Described ultrasound, which is peeled off, refers to that in supersonic frequency be 20-40khz bars
Ultrasonic 30-45min under part.
7. the method that a kind of hydro-thermal method as claimed in claim 1 prepares N and S codope three-dimensional grapheme materials, its feature exist
In：Step 1) the ultrasonic disperse power is 20-40khz, and the ultrasonic disperse time is 30-2h.
8. the method that a kind of hydro-thermal method as claimed in claim 1 prepares N and S codope three-dimensional grapheme materials, its feature exist
In step 2) it is described be added dropwise thiourea solution be 2-10ml, concentration 10-40mg/ml.
9. the method that a kind of hydro-thermal method as claimed in claim 1 prepares N and S codope three-dimensional grapheme materials, its feature exist
It it is 120 DEG C -200 DEG C in the hydrothermal reduction reaction temperature described in step 5), the described hydrothermal reduction reaction time is 8h-24h.
10. the method that a kind of hydro-thermal method as claimed in claim 1 prepares N and S codope three-dimensional grapheme materials, its feature exist
In described precooling, time 12-36h；The time dried in freeze drier is 24-48h.
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| CN108439373A (en) * | 2018-02-07 | 2018-08-24 | 山东大学 | A kind of amphiphilic Janus structure graphites alkenyl aeroge and preparation method thereof |
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| CN109037678A (en) * | 2018-06-15 | 2018-12-18 | 陕西科技大学 | A kind of preparation method of nitrogen sulphur codope three-dimensional graphene foam electrode active material |
| CN109110748A (en) * | 2018-11-07 | 2019-01-01 | 河南师范大学 | A kind of preparation method of nitrogen, the three-dimensional porous graphene of boron codope |
| CN109126793A (en) * | 2018-09-10 | 2019-01-04 | 中国工程物理研究院材料研究所 | A kind of electrochemical preparation method of monatomic copper elctro-catalyst |
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| CN108172411A (en) * | 2018-01-16 | 2018-06-15 | 武汉低维材料研究院有限公司 | A kind of preparation method of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material |
| CN108439373A (en) * | 2018-02-07 | 2018-08-24 | 山东大学 | A kind of amphiphilic Janus structure graphites alkenyl aeroge and preparation method thereof |
| CN108439373B (en) * | 2018-02-07 | 2019-12-27 | 山东大学 | Amphiphilic Janus structure graphene-based aerogel and preparation method thereof |
| CN108470890A (en) * | 2018-03-15 | 2018-08-31 | 陕西科技大学 | A kind of application of the preparation method of nitrogen sulphur codope three-dimensional grapheme, its product and the product that prepare |
| CN108745402A (en) * | 2018-06-11 | 2018-11-06 | 滨州学院 | Nitrogen sulphur codope graphene preparation method |
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| CN109110748A (en) * | 2018-11-07 | 2019-01-01 | 河南师范大学 | A kind of preparation method of nitrogen, the three-dimensional porous graphene of boron codope |
| CN109768241A (en) * | 2018-12-26 | 2019-05-17 | 格林美（无锡）能源材料有限公司 | The positive electrode and preparation method of the graphene-supported cobaltous selenide cladding of nitrogen sulphur codope |
| CN110093032A (en) * | 2019-04-28 | 2019-08-06 | 中科广化（重庆）新材料研究院有限公司 | A kind of nitrogen sulphur codope graphene/polyaniline aeroge and the preparation method and application thereof |
| CN110093032B (en) * | 2019-04-28 | 2021-09-24 | 中科广化（重庆）新材料研究院有限公司 | Nitrogen-sulfur co-doped graphene/polyaniline aerogel and preparation method and application thereof |
| CN110562970A (en) * | 2019-06-20 | 2019-12-13 | 昆明物理研究所 | Preparation method of bromine-doped graphene oxide |
| CN110841680A (en) * | 2019-11-04 | 2020-02-28 | 淮阴师范学院 | Preparation method of nitrogen and sulfur-doped graphene-CuS composite material |
| CN112226780A (en) * | 2020-10-17 | 2021-01-15 | 石河子大学 | NiCo for total water splitting2S4Preparation method of/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst |
| CN112226780B (en) * | 2020-10-17 | 2023-09-29 | 石河子大学 | NiCo for full water dissolution 2 S 4 Preparation method of nitrogen/sulfur co-doped reduced graphene oxide bifunctional electrocatalyst |
| CN113526494A (en) * | 2021-06-28 | 2021-10-22 | 合肥国轩高科动力能源有限公司 | Method for preparing graphene hydrogel |
| CN113526494B (en) * | 2021-06-28 | 2023-09-08 | 合肥国轩高科动力能源有限公司 | Method for preparing graphene hydrogel |
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