CN102530910A - Method for preparing fluorinated graphene - Google Patents
Method for preparing fluorinated graphene Download PDFInfo
- Publication number
- CN102530910A CN102530910A CN2010106004239A CN201010600423A CN102530910A CN 102530910 A CN102530910 A CN 102530910A CN 2010106004239 A CN2010106004239 A CN 2010106004239A CN 201010600423 A CN201010600423 A CN 201010600423A CN 102530910 A CN102530910 A CN 102530910A
- Authority
- CN
- China
- Prior art keywords
- graphene
- fluorographite alkene
- fluorographite
- alkene
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing fluorinated graphene, which comprises the following steps: providing graphite; preparing graphene oxide by using the graphite; reducing the graphene oxide by a liquid phase to obtain graphene; and reacting the graphene with a fluorine-containing matter to obtain fluorinated graphene. The fluorinated graphene is obtained by reacting the graphene with the fluorine-containing matter, particularly a fluorine-containing gas or fluorine-containing compound. The preparation method has fewer steps, adopts simple process and has a good application prospect.
Description
[technical field]
The invention belongs to the organic semiconductor material technical field, be specifically related to the preparation method of fluorographite alkene.
[background technology]
Prepared grapheme material in 2004 since the strong K of the peace moral of Univ Manchester UK sea nurse (Andre K.Geim) waits, pay attention to widely owing to its particular structure and photoelectric property have received people.Graphene is called " nova " that is rising in Materials science and Condensed Matter Physics field, many novelties that it had and unique character is just attracting many scientific workers with the potential application.Single-layer graphene has big specific surface area, good conduction, heat conductivility and low thermal expansivity.As: 1. HS, the Young molar weight, (1,100GPa), breaking tenacity: (125GPa); 2. high heat conductance, (5,000W/mK); 3. high conductivity, carrier transport rate, (200,000cm2/V*s); 4. high specific surface area, (calculated value: 2,630m
2/ g).Especially its high conductivity matter, the textural property of the big specific surface character and the nanoscale of its unimolecular layer two dimension can be used as electrode materials in ultracapacitor and lithium ion battery.
Fluorographite has caused mechanism of new electrochemical power sources investigators' very big interest and attention as the active substance of high-performance lithium ion battery, and has succeeded in developing corresponding high tension battery.Fluorographite-lithium cell has the performance of following excellence: (1) voltage is high, energy density is high.The actual nominal voltage of general manganese cell is 3V, and energy density is 360wh/kg, and the nominal voltage of cylindrical fluorographite-lithium cell is two times of manganese cell, and energy density is that 5～10 times of (2) utilization ratios of manganese cell are high, voltage is steady.According to exoelectrical reaction, owing to generate the carbon of electroconductibility, utilization ratio is almost 100%, and internal resistance does not increase during discharge, and sparking voltage is stabilized to the latter stage of discharging.Shelf lives is long, the Applicable temperature scope is wide.
Fluorographite alkene is that a kind of physical strength is high, chemistry and the stable compound of thermal property.The very similar tetrafluoroethylene of this novel material performance is referred to as two-dimentional tetrafluoroethylene usually.
Yet how obtaining fluorographite alkene easily is a present difficult problem.
[summary of the invention]
Based on this, be necessary to provide the preparation method of the simple fluorographite alkene of a kind of technology
A kind of method of fluorographite alkene comprises the steps:
Graphite is provided;
Use said graphite to prepare graphene oxide;
The said graphene oxide of liquid-phase reduction makes Graphene;
Graphene and fluorine-containing material reaction make fluorographite alkene.
Preferably, the reaction of said Graphene and fluorine-containing material is for said Graphene and by N
2And F
2The mixed gas of forming is 50～500 ℃ in temperature, and the reaction times is to make said fluorographite alkene under the condition of 3～120h.
Preferably, F in the said mixed gas
2Volume(tric)fraction be 10%～30%.
Preferably, F in the said mixed gas
2Volume(tric)fraction be 20%.
Preferably, the step of using said graphite to prepare graphene oxide comprises:
Said graphite, Potassium Persulphate and Vanadium Pentoxide in FLAKES joined according to mass ratio at 2: 1: 1 in 75～95 ℃ the vitriol oil, the back naturally cooling that stirs, washing to neutral after drying obtains pretreated mixture;
Said pretreated mixture and potassium permanganate are joined temperature be lower than in 20 ℃ the vitriol oil,, add deionized water, add the ydrogen peroxide 50 reaction behind the 15min, suction filtration, collect solid then at 30～40 ℃ of following oil bath 1.5～2.5h;
Said solid washs with Hydrogen chloride, and drying obtains said graphene oxide.
Preferably, the said graphene oxide of the liquid-phase reduction step that makes Graphene comprises:
Said graphene oxide is mixed with deionized water and is dispersed into suspension liquid;
In said suspension liquid, add reductive agent, 90～100 ℃ of thermal reduction 24～28h obtain the Graphene suspension;
Said Graphene suspension liquid filters the back and collects filter residue, and water, methanol wash after drying obtain said Graphene successively.
Preferably, said reductive agent is a Hydrazine Hydrate 80.
Preferably, said Graphene and fluorine-containing material reaction are that said Graphene and fluorochemicals are 1: 1～1: 100 processing 1～10h postcooling under 200～1000 ℃ with mass ratio, and water and washing with alcohol, drying obtain said fluorographite alkene successively.
Preferably, said fluorochemicals is at least a in Neutral ammonium fluoride, Sodium tetrafluoroborate, potassium fluoborate, potassium fluoroaluminate and the Sodium Silicofluoride 98min.
Preferably, said fluorochemicals is at least a in tetrafluoroethylene, polyhexafluoropropylene and the pvdf.
The preparation method of above-mentioned fluorographite alkene uses graphite to prepare graphene oxide, and the liquid-phase reduction graphene oxide obtains Graphene again, utilizes Graphene and N at last
2And F
2Mixed gas or the fluorochemicals formed react at a certain temperature, prepare fluorographite alkene, and this preparing method's step is few, technology is simple, has stronger application prospect.
[description of drawings]
Fig. 1 is preparing method's the schema of the fluorographite alkene of an embodiment;
Fig. 2 is preparing method's the schema of the fluorographite alkene of another embodiment;
Fig. 3 is the XPS collection of illustrative plates of C1s of the fluorographite alkene of embodiment one preparation;
Fig. 4 is the XPS collection of illustrative plates of F1s of the fluorographite alkene of embodiment one preparation;
Fig. 5 is the SEM Electronic Speculum picture of the fluorographite alkene of embodiment one preparation.
[embodiment]
Below in conjunction with accompanying drawing and embodiment the preparation method of fluorographite alkene is done further and to explain.
A kind of fluorographite alkene, wherein, the mass percent of F is 0.5＜F%＜30%, the shared mass percent of C is 70%＜C%＜99.5%.
This fluorographite alkene is made by Graphene generation fluoro-reaction.
Under Electronic Speculum, can find out, this fluorographite alkene surface have can increasing specific surface area fold-like structures.
A kind of preparation method of above-mentioned fluorographite alkene as shown in Figure 1 comprises the steps:
S110, graphite is provided
Buy purity and surpass 99.5% graphite.
S120, use graphite prepare graphene oxide
General; Can be equipped with graphite oxide through the Hummers legal system; Be about to graphite, potassium permanganate and high density acid with strong oxidizing property (sulfuric acid or nitric acid) and place same container water-bath or oil bath heating, treat to take out after the abundant oxidation, reduce potassium permanganate with ydrogen peroxide 50 earlier; With zero(ppm) water or hydrochloric acid washed product several, obtain graphite oxide after the drying.
In order to prepare graphene oxide, can carry out some to the Hummers method and improve, the preparation process after the improvement comprises the steps.
At first, with graphite, Potassium Persulphate and Vanadium Pentoxide in FLAKES according to mass ratio join at 2: 1: 1 75～95 ℃ the vitriol oil in, the back naturally cooling that stirs, washing obtains pretreated mixture to neutral after drying.
Next joins said pretreated mixture and potassium permanganate in the vitriol oil, keeps temperature to be lower than 20 ℃, and 30～40 ℃ of oil bath 1.5～2.5h add deionized water afterwards, adds the ydrogen peroxide 50 reaction behind the 15min, suction filtration, collection solid.
At last, above-mentioned solid is washed with Hydrogen chloride, drying obtains graphene oxide.
The purpose of oil bath is for better control reaction temperature, in other embodiment, also can adopt water-bath.
S130, liquid-phase reduction graphene oxide make Graphene
At first, the graphene oxide that S120 is obtained mixes with deionized water and is dispersed into suspension liquid.Generally can adopt ultrasonic echography to disperse graphene oxide.
Secondly, in above-mentioned suspension liquid, add reductive agent, be heated to 90～100 ℃ and carry out thermal reduction, obtain the Graphene suspension behind 24～28h.Reductive agent adopts the soluble compound with certain thermostability, and general can enumerate: Hydrazine Hydrate 80, Peng Qinghuana and to benzene two ammoniums are preferably Hydrazine Hydrate 80.
At last, the Graphene suspension is filtered the back collect filter residue, water, methanol wash after drying obtain Graphene successively.
S140, Graphene and the reaction of fluorine simple substance obtain fluorographite alkene
Graphene that the drying of utilizing the S130 step to obtain is crossed and fluorine simple substance (F
2) prepared in reaction fluorographite alkene, this method is called vapor phase process, adopts N
2And F
2Mixed gas, concrete steps are following:
The Graphene that the S130 step obtains is put into reactor drum, feed exsiccant nitrogen 0.5～4h, feed N again
2And F
2Mixed gas (F
2Volume(tric)fraction be 10%～30%), holding temperature is 50～500 ℃, the reaction 3～120h, obtain fluorographite alkene.
Through test of many times, find F
2Volume(tric)fraction gets 20%, temperature of reaction is got 250 ℃, reaction times to get 6h be optimum reaction condition.
The another kind of preparation method of above-mentioned fluorographite alkene as shown in Figure 2 comprises the steps:
S210, graphite is provided
Buy purity and surpass 99.5% graphite.
S220, use graphite prepare graphene oxide
General; Can be equipped with graphite oxide through the Hummers legal system; Be about to graphite, potassium permanganate and high density acid with strong oxidizing property (sulfuric acid or nitric acid) and place same container water-bath or oil bath heating, treat to take out after the abundant oxidation, reduce potassium permanganate with ydrogen peroxide 50 earlier; With zero(ppm) water or hydrochloric acid washed product several, obtain graphite oxide after the drying.
In order to prepare graphene oxide, can carry out some to the Hummers method and improve, the preparation process after the improvement comprises the steps.
At first, with graphite, Potassium Persulphate and Vanadium Pentoxide in FLAKES according to mass ratio join at 2: 1: 1 75～95 ℃ the vitriol oil in, the back naturally cooling that stirs, washing obtains pretreated mixture to neutral after drying.
Next joins said pretreated mixture and potassium permanganate in the vitriol oil, keeps temperature to be lower than 20 ℃, and 30～40 ℃ of oil bath 1.5～2.5h add deionized water afterwards, adds the ydrogen peroxide 50 reaction behind the 15min, suction filtration, collection solid.
At last, above-mentioned solid is washed with Hydrogen chloride, drying obtains graphene oxide.
The purpose of oil bath is for better control reaction temperature, in other embodiment, also can adopt water-bath.
S230, liquid-phase reduction graphene oxide make Graphene
At first, the graphene oxide that S220 is obtained mixes with deionized water and is dispersed into suspension liquid.Generally can adopt ultrasonic echography to disperse graphene oxide.
Secondly, in above-mentioned suspension liquid, add reductive agent, be heated to 90～100 ℃ and carry out thermal reduction, obtain the Graphene suspension behind 24～28h.Reductive agent adopts the soluble compound with certain thermostability, and general can enumerate: Hydrazine Hydrate 80, Peng Qinghuana and to benzene two ammoniums are preferably Hydrazine Hydrate 80.
At last, the Graphene suspension is filtered the back collect filter residue, water, methanol wash after drying obtain Graphene successively.
S240, Graphene and fluorochemicals reaction obtain fluorographite alkene
Graphene that the drying of utilizing the S230 step to obtain is crossed and fluorochemicals prepared in reaction fluorographite alkene; This method is called solid phase method; Be divided into fluorine-containing inorganics and fluoropolymer according to fluorochemicals, solid phase method comprises inorganic solid phase method and organic solid phase method again, specifically introduces one by one below.
Inorganic solid phase method prepares fluorographite alkene
The reaction of Graphene that the drying that present method adopts heat decomposable fluorine-containing inorganics and S230 step to obtain is crossed, the fluorine-containing inorganics of employing is general can enumerate like Neutral ammonium fluoride, Sodium tetrafluoroborate, potassium fluoborate, potassium fluoroaluminate and Sodium Silicofluoride 98min.During actually operating, can select wherein a kind ofly, also can select multiple mixing.
At first, fluorine-containing inorganics is carried out drying treatment, drying temperature is lower than its decomposition temperature.
Then; According to Graphene and fluorine-containing inorganics quality ratio be 1: 1～1: 100 with the reactor drum of packing into behind Graphene and the fluorine-containing inorganics mixing; 200～1000 ℃ of thermal treatment 1～10h; Abundant reaction postcooling takes out reactant and successively after water and the washing with alcohol, 80 ℃ of vacuum-drying 24h obtain fluorographite alkene.
The thermal treatment actual temp is decided according to the fluorine-containing inorganics of actual selection.
Organic solid phase method prepares fluorographite alkene
The reaction of Graphene that the drying that present method adopts heat decomposable fluoropolymer and S230 step to obtain is crossed, the fluoropolymer of employing is general can enumerate like tetrafluoroethylene, polyhexafluoropropylene and pvdf.During actually operating, can select wherein a kind ofly, also can select multiple mixing.
At first, fluoropolymer is boiled in boiling water more than the 3h, again oven dry.
Then; According to Graphene and fluoropolymer mass ratio is Graphene and fluoropolymer to be dried behind the mixing in organic solvent in 1: 1～1: 100; Behind the compressing tablet under oxygen free condition 200～800 ℃ of thermal treatment 1～10h, fully react postcooling, obtain fluorographite alkene.
General, oxygen free condition can be realized through rare gas element or nitrogen protection.
The preparation method of above-mentioned fluorographite alkene uses graphite to prepare graphene oxide, and the liquid-phase reduction graphene oxide obtains Graphene again, utilizes Graphene and N at last again
2And F
2Mixed gas or the fluorochemicals formed react at a certain temperature, prepare fluorographite alkene.This preparing method's step is few, technology is simple, has stronger application prospect.
The fluorographite alkene for preparing can be used the electrode materials as ultracapacitor, lithium-ion secondary cell.
It below is the specific embodiment part.
Embodiment 1
Present embodiment is following through the technical process that Graphene prepares fluorographite alkene:
Graphite → graphene oxide → Graphene → fluorographite alkene
(1) graphite: purity 99.5%.
(2) graphene oxide: be equipped with graphene oxide through improved Hummers legal system.Its concrete steps are that 20g 50 order Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in 80 ℃ the vitriol oil, stir, and more than the cooling 6h, washing is to neutral, drying.In the vitriol oil with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate again, the temperature of mixture remains on below 20 ℃, in 35 ℃ oil bath, behind the maintenance 1.5h, slowly adds the 920mL deionized water then.Behind the 15min; Add 2.8L deionized water (wherein contain 50mL concentration be 30% ydrogen peroxide 50) again; The mixture color becomes glassy yellow afterwards, and suction filtration while hot uses that 5L concentration is that 10% hydrochloric acid washs again, suction filtration, promptly obtains graphene oxide at 60 ℃ of vacuum-drying 48h.
(3) Graphene: graphene oxide 100mg and deionized water 100mL join in the round-bottomed flask of 250mL, and this moment, solution was brown xanchromatic suspension liquid.Then the ultrasonic echography of suspension liquid with 150W disperseed.At last to wherein adding Hydrazine Hydrate 80 (1mL, 98%) and being heated to 100 ℃ of reaction 36h.Water 300mL and methyl alcohol 300mL washing successively after the gained Graphene filters, dry 48h in 80 ℃ of following vacuum drying ovens.
(4) fluorographite alkene: in (3) gained Graphene through with F
2Reaction obtains fluorographite alkene.Its concrete steps are packed into for the Graphene that drying has been got well and are fed exsiccant nitrogen 2h in the reactor drum, feed then that fluorine gas accounts for 20% fluorine gas and the mixed gas of nitrogen descends to react 60h at 250 ℃ with Graphene, promptly can obtain fluorographite alkene.
Gained fluorographite alkene is carried out following experiment:
XPS test experiments condition: sample is analyzed with VG Scientific ESCALab220i-XL type photoelectron spectrograph.Excitaton source is an AlK α X ray, the about 300W of power.Base vacuum during analysis is 3 * 10
-9Mbar.Electron binding energy is proofreaied and correct with the C1s peak (284.8eV) that pollutes carbon.
The element relative quantification calculates:
In the formula: I
iThe peak intensity of-i element (area)
S
iThe relative elemental sensitivity factor of-i element
The mass percent that can be drawn F by table 1 is 30%.
The XPS collection of illustrative plates of the C1s of the fluorographite alkene of present embodiment preparation as shown in Figure 3, as can be seen from the figure, the fluorographite alkene that makes has very strong peak value at the 284.8eV place, and carbon bond structure is C-C (284.8eV) in the corresponding fluorographite alkene.
The XPS collection of illustrative plates of the F1s of the fluorographite alkene of present embodiment preparation as shown in Figure 4, as can be seen from the figure, the fluorographite alkene that makes has very strong peak value at the 689.5eV place, and carbon bond structure is C-F (689.5eV) in the corresponding fluorographite alkene.
The SEM Electronic Speculum picture of the fluorographite alkene of present embodiment preparation as shown in Figure 5, as can be seen from the figure, the fluorographite alkene surface that makes has the corrugated structure, and this corrugated structure helps improving the specific surface area of material.
Embodiment 2
Present embodiment is following through the technical process that Graphene prepares fluorographite alkene:
Graphite → graphene oxide → Graphene → fluorographite alkene
(1) graphite: purity 99.5%.
(2) preparation graphene oxide such as embodiment 1 are said.
(3) preparation Graphene such as embodiment 1 are said.
(4) fluorographite alkene: in (3) gained Graphene through with F
2Reaction obtains fluorographite alkene.Its concrete steps are packed into for the Graphene that drying has been got well and are fed exsiccant nitrogen 4h in the reactor drum, feed then that fluorine gas accounts for 15% fluorine gas and the mixed gas of nitrogen descends to react 6h at 250 ℃ with Graphene, promptly can obtain fluorographite alkene.
The mass percent that can be drawn F by table 1 is 28.6%.
Embodiment 3
Present embodiment is following through the technical process that Graphene prepares fluorographite alkene:
Graphite → graphene oxide → Graphene → fluorographite alkene
(1) graphite: purity 99.5%.
(2) preparation graphene oxide such as embodiment 1 are said.
(3) preparation Graphene such as embodiment 1 are said.
(4) fluorographite alkene: in (3) gained Graphene through with F
2Reaction obtains fluorographite alkene.Its concrete steps are packed into for the Graphene that drying has been got well and are fed exsiccant nitrogen 0.5h in the reactor drum, feed then that fluorine gas accounts for 10% fluorine gas and the mixed gas of nitrogen descends to react 3h at 500 ℃ with Graphene, promptly can obtain fluorographite alkene.
The mass percent that can be drawn F by table 1 is 18.4%.
Present embodiment is following through the technical process that Graphene prepares fluorographite alkene:
Graphite → graphene oxide → Graphene → fluorographite alkene
(1) graphite: purity 99.5%.
(2) preparation graphene oxide such as embodiment 1 are said.
(3) preparation Graphene such as embodiment 1 are said.
(4) fluorographite alkene: in (3) gained Graphene through with F
2Reaction obtains fluorographite alkene.Its concrete steps are packed into for the Graphene that drying has been got well and are fed exsiccant nitrogen 2h in the reactor drum, feed then that fluorine gas accounts for 30% fluorine gas and the mixed gas of nitrogen descends to react 50h at 200 ℃ with Graphene, promptly can obtain fluorographite alkene.
The mass percent that can be drawn F by table 1 is 25.2%.
Embodiment 5
Present embodiment is following through the technical process that Graphene prepares fluorographite alkene:
Graphite → graphene oxide → Graphene → fluorographite alkene
(1) graphite: purity 99.5%.
(2) preparation graphene oxide such as embodiment 1 are said.
(3) preparation Graphene such as embodiment 1 are said.
(4) fluorographite alkene: in (3) gained Graphene through with F
2Reaction obtains fluorographite alkene.Its concrete steps are packed into for the Graphene that drying has been got well and are fed exsiccant nitrogen 2h in the reactor drum, feed then that fluorine gas accounts for 15% fluorine gas and the mixed gas of nitrogen descends to react 120h at 150 ℃ with Graphene, promptly can obtain fluorographite alkene.
The mass percent that can be drawn F by table 1 is 7.5%.
Embodiment 6
Graphite → graphene oxide → Graphene → fluorographite alkene
Present embodiment is following through the technical process that Graphene prepares fluorographite alkene:
(1) graphite: purity 99.5%.
(2) preparation graphene oxide such as embodiment 1 are said.
(3) preparation Graphene such as embodiment 1 are said.
(4) fluorographite alkene: in (3) gained Graphene through with F
2Reaction obtains fluorographite alkene.Its concrete steps are packed into for the Graphene that drying has been got well and are fed exsiccant nitrogen 2h in the reactor drum, feed then that fluorine gas accounts for 25% fluorine gas and the mixed gas of nitrogen descends to react 100h at 100 ℃ with Graphene, promptly can obtain fluorographite alkene.
The mass percent that can be drawn F by table 1 is 0.5%.
Embodiment 7
Present embodiment is following through the technical process that Graphene prepares fluorographite alkene:
Graphite → graphene oxide → Graphene → fluorographite alkene
(1) graphite: purity 99.5%.
(2) preparation graphene oxide such as embodiment 1 are said.
(3) preparation Graphene such as embodiment 1 are said.
(4) fluorographite alkene: in (3) gained Graphene through with F
2Reaction obtains fluorographite alkene.Its concrete steps are packed into for the Graphene that drying has been got well and are fed exsiccant nitrogen 2h in the reactor drum, feed then that fluorine gas accounts for 18% fluorine gas and the mixed gas of nitrogen descends to react 30h at 50 ℃ with Graphene, promptly can obtain fluorographite alkene.
The mass percent that can be drawn F by table 1 is 21%.
Embodiment 8
Present embodiment is following through the technical process that Graphene prepares fluorographite alkene:
Graphite → graphene oxide → Graphene → fluorographite alkene
(1) graphite: purity 99.5%.
(2) graphene oxide: be equipped with graphene oxide through improved Hummers legal system.Its concrete steps are that 20g 50 order Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in 95 ℃ the vitriol oil, stir, and more than the cooling 6h, washing is to neutral, drying.In the vitriol oil with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate again, the temperature of mixture remains on below 20 ℃, in 40 ℃ oil bath, behind the maintenance 1.5h, slowly adds the 920mL deionized water then.Behind the 15min; Add 2.8L deionized water (wherein contain 50mL concentration be 30% ydrogen peroxide 50) again; The mixture color becomes glassy yellow afterwards, and suction filtration while hot uses that 5L concentration is that 10% hydrochloric acid washs again, suction filtration, promptly obtains graphene oxide at 60 ℃ of vacuum-drying 48h.
(3) Graphene: graphene oxide 100mg and deionized water 100mL join in the round-bottomed flask of 250mL, and this moment, solution was brown xanchromatic suspension liquid.Then the ultrasonic echography of suspension liquid with 150W disperseed.At last to wherein adding Hydrazine Hydrate 80 (1mL, 98%) and being heated to 90 ℃ of reaction 48h.Water 300mL and methyl alcohol 300mL washing successively after the gained Graphene filters, dry 48h in 80 ℃ of following vacuum drying ovens.
(4) fluorographite alkene: prepare fluorographite alkene through solid phase method.Its concrete steps are according to certain mass ratio the Graphene of Sodium tetrafluoroborate and process thorough drying; Potassium fluoborate: in the reactor drum of packing into after Graphene=1: 1 mixes and weighs; Decomposition temperature according to inorganic fluorine source is set temperature of reaction, reacts 1h down at 1000 ℃.Reactant is taken out in the cooling back a little, after water and the washing with alcohol, obtains fluorographite alkene at 80 ℃ of vacuum-drying 24h successively.
The mass percent that can be drawn F by table 1 is 15%.
Embodiment 9
Present embodiment is following through the technical process that Graphene prepares fluorographite alkene:
Graphite → graphene oxide → Graphene → fluorographite alkene
(1) graphite: purity 99.5%.
(2) graphene oxide: be equipped with graphene oxide through improved Hummers legal system.Its concrete steps are that 20g 50 order Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in 75 ℃ the vitriol oil, stir, and more than the cooling 6h, washing is to neutral, drying.In the vitriol oil with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate again, the temperature of mixture remains on below 20 ℃, in 30 ℃ oil bath, behind the maintenance 2.5h, slowly adds the 920mL deionized water then.Behind the 15min; Add 2.8L deionized water (wherein contain 50mL concentration be 30% ydrogen peroxide 50) again; The mixture color becomes glassy yellow afterwards, and suction filtration while hot uses that 5L concentration is that 10% hydrochloric acid washs again, suction filtration, promptly obtains graphene oxide at 60 ℃ of vacuum-drying 48h.
(3) Graphene: graphene oxide 100mg and deionized water 100mL join in the round-bottomed flask of 250mL, and this moment, solution was brown xanchromatic suspension liquid.Then the ultrasonic echography of suspension liquid with 150W disperseed.At last to wherein adding Hydrazine Hydrate 80 (1mL, 98%) and being heated to 100 ℃ of reaction 24h.Water 300mL and methyl alcohol 300mL washing successively after the gained Graphene filters, dry 48h in 80 ℃ of following vacuum drying ovens.
(4) fluorographite alkene: prepare fluorographite alkene through solid phase method.Its concrete steps are according to certain mass ratio the Graphene of Neutral ammonium fluoride and process thorough drying; Neutral ammonium fluoride: in the reactor drum of packing into after Graphene=100: 1 mixes and weighs; Decomposition temperature according to inorganic fluorine source is set temperature of reaction, reacts 10h down at 200 ℃.Reactant is taken out in the cooling back a little, after water and the washing with alcohol, obtains fluorographite alkene at 80 ℃ of vacuum-drying 24h successively.
The mass percent that can be drawn F by table 1 is 23%.
Embodiment 10
Present embodiment is following through the technical process that Graphene prepares fluorographite alkene:
Graphite → graphene oxide → Graphene → fluorographite alkene
(1) graphite: purity 99.5%.
(2) graphene oxide: be equipped with graphene oxide through improved Hummers legal system.Its concrete steps are that 20g 50 order Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in 80 ℃ the vitriol oil, stir, and more than the cooling 6h, washing is to neutral, drying.In the vitriol oil with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate again, the temperature of mixture remains on below 20 ℃, in 35 ℃ oil bath, behind the maintenance 2h, slowly adds the 920mL deionized water then.Behind the 15min; Add 2.8L deionized water (wherein contain 50mL concentration be 30% ydrogen peroxide 50) again; The mixture color becomes glassy yellow afterwards, and suction filtration while hot uses that 5L concentration is that 10% hydrochloric acid washs again, suction filtration, promptly obtains graphene oxide at 60 ℃ of vacuum-drying 48h.
(3) Graphene: graphene oxide 100mg and deionized water 100mL join in the round-bottomed flask of 250mL, and this moment, solution was brown xanchromatic suspension liquid.Then the ultrasonic echography of suspension liquid with 150W disperseed.At last to wherein adding Hydrazine Hydrate 80 (1mL, 98%) and being heated to 100 ℃ of reaction 36h.Water 300mL and methyl alcohol 300mL washing successively after the gained Graphene filters, dry 48h in 80 ℃ of following vacuum drying ovens.
(4) fluorographite alkene: prepare fluorographite alkene through solid phase method.Its concrete steps are: in boiling water, boil 3h to process; Fluoropolymer tetrafluoroethylene after the oven dry is (tetrafluoroethylene: Graphene=1: 1) in organic solvent, mix according to a certain percentage; Put into baking oven then and about 150 ℃, dry, and then compressing tablet is put into the nickel boat.Put into the nickel boat silica tube and an amount of back of the logical nitrogen heated sealed of High Temperature Furnaces Heating Apparatus.Control for Kiln Temperature behind the reaction 1h, is taken out the silica tube cooling at 1000 ℃, can obtain fluorographite alkene.
The mass percent that can be drawn F by table 1 is 2.8%.
Embodiment 11
Present embodiment is following through the technical process that Graphene prepares fluorographite alkene:
Graphite → graphene oxide → Graphene → fluorographite alkene
(1) graphite: purity 99.5%.
(2) preparation graphene oxide such as embodiment 10 are said.
(3) preparation Graphene such as embodiment 10 are said.
(4) fluorographite alkene: prepare fluorographite alkene through solid phase method.Its concrete steps are: in boiling water, boil 3h to process; Polyhexafluoropropylene after the oven dry is in → fixed ratio (polyhexafluoropropylene: Graphene=100: 1) in organic solvent, mix; Put into baking oven then and about 150 ℃, dry, and then compressing tablet is put into the nickel boat.Put into the nickel boat silica tube and an amount of back of the logical nitrogen heated sealed of High Temperature Furnaces Heating Apparatus.Control for Kiln Temperature behind the reaction 10h, is taken out the silica tube cooling at 200 ℃, can obtain fluorographite alkene.
The mass percent that can be drawn F by table 1 is 3.5%.
Embodiment 12
Present embodiment is following through the technical process that Graphene prepares fluorographite alkene:
Graphite → graphene oxide → Graphene → fluorographite alkene
(1) graphite: purity 99.5%.
(2) preparation graphene oxide such as embodiment 10 are said.
(3) preparation Graphene such as embodiment 10 are said.
(4) fluorographite alkene: prepare fluorographite alkene through solid phase method.Its concrete steps are: in boiling water, boil 3h to process; Pvdf after the oven dry is (pvdf: Graphene=50: 1) in organic solvent, mix according to a certain percentage; Put into baking oven then and about 150 ℃, dry, and then compressing tablet is put into the nickel boat.Put into the nickel boat silica tube and an amount of back of the logical nitrogen heated sealed of High Temperature Furnaces Heating Apparatus.Control for Kiln Temperature behind the reaction 4h, is taken out the silica tube cooling at 500 ℃, can obtain fluorographite alkene.The mass percent that can be drawn F by table 1 is 4.5%.
The rare F content of table 1 fluorographite
| Numbering | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 |
| F content | 30％ | 28.6％ | 18.4％ | ?252％ | 7.5％ | 0.5％ | 21％ | 15％ | 23％ | 2.8％ | 3.5％ | 4.5％ |
The above embodiment has only expressed several kinds of embodiments of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with accompanying claims.
Claims (10)
1. the method for a fluorographite alkene is characterized in that, comprises the steps:
Graphite is provided;
Use said graphite to prepare graphene oxide;
The said graphene oxide of liquid-phase reduction makes Graphene;
Graphene and fluorine-containing material reaction make fluorographite alkene.
2. the preparation method of fluorographite alkene as claimed in claim 1 is characterized in that, said Graphene and fluorine-containing material reaction are for said Graphene and by N
2And F
2The mixed gas of forming is 50～500 ℃ in temperature, and the reaction times is to make said fluorographite alkene under the condition of 3～120h.
3. the preparation method of fluorographite alkene as claimed in claim 2 is characterized in that, F in the said mixed gas
2Volume(tric)fraction be 10%～30%.
4. the preparation method of fluorographite alkene as claimed in claim 3 is characterized in that, F in the said mixed gas
2Volume(tric)fraction be 20%.
5. the preparation method of fluorographite alkene as claimed in claim 1 is characterized in that, the step of using said graphite to prepare graphene oxide comprises:
Said graphite, Potassium Persulphate and Vanadium Pentoxide in FLAKES joined according to mass ratio at 2: 1: 1 in 75～95 ℃ the vitriol oil, the back naturally cooling that stirs, washing to neutral after drying obtains pretreated mixture;
Said pretreated mixture and potassium permanganate are joined temperature be lower than in 20 ℃ the vitriol oil,, add deionized water, add the ydrogen peroxide 50 reaction behind the 15min, suction filtration, collect solid then at 30～40 ℃ of following oil bath 1.5～2.5h;
Said solid washs with Hydrogen chloride, and drying obtains said graphene oxide.
6. fluorographite alkene preparation methods as claimed in claim 1 is characterized in that, the step that the said graphene oxide of liquid-phase reduction makes Graphene comprises:
Said graphene oxide is mixed with deionized water and is dispersed into suspension liquid;
In said suspension liquid, add reductive agent, 90～100 ℃ of thermal reduction 24～28h obtain the Graphene suspension;
Said Graphene suspension liquid filters the back and collects filter residue, and water, methanol wash after drying obtain said Graphene successively.
7. fluorographite alkene preparation methods as claimed in claim 6 is characterized in that said reductive agent is a Hydrazine Hydrate 80.
8. the preparation method of fluorographite alkene as claimed in claim 1; It is characterized in that; Said Graphene and fluorine-containing material reaction are that said Graphene and fluorochemicals are 1: 1～1: 100 processing 1～10h postcooling under 200～1000 ℃ with mass ratio; Water and washing with alcohol, drying obtain said fluorographite alkene successively.
9. the preparation method of fluorographite alkene as claimed in claim 8 is characterized in that, said fluorochemicals is at least a in Neutral ammonium fluoride, Sodium tetrafluoroborate, potassium fluoborate, potassium fluoroaluminate and the Sodium Silicofluoride 98min.
10. the preparation method of fluorographite alkene as claimed in claim 8 is characterized in that, said fluorochemicals is at least a in tetrafluoroethylene, polyhexafluoropropylene and the pvdf.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010600423.9A CN102530910B (en) | 2010-12-22 | 2010-12-22 | Method for preparing fluorinated graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010600423.9A CN102530910B (en) | 2010-12-22 | 2010-12-22 | Method for preparing fluorinated graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102530910A true CN102530910A (en) | 2012-07-04 |
| CN102530910B CN102530910B (en) | 2014-07-23 |
Family
ID=46339134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010600423.9A Active CN102530910B (en) | 2010-12-22 | 2010-12-22 | Method for preparing fluorinated graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102530910B (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086374A (en) * | 2013-02-22 | 2013-05-08 | 杭州格蓝丰纳米科技有限公司 | Method for preparing graphene fluoride by atomic layer deposition device |
| CN103086366A (en) * | 2013-01-16 | 2013-05-08 | 天津工业大学 | Preparation method of amphiphilic fluorinated-oxidized graphene |
| CN104944402A (en) * | 2014-03-24 | 2015-09-30 | 中国科学院兰州化学物理研究所 | Method for quickly and efficiently preparing adjustable-fluorine-content fluoridized graphene |
| CN104992987A (en) * | 2015-06-18 | 2015-10-21 | 西交利物浦大学 | Solar cell taking fluorinated graphene as high-resistance layer and preparing method thereof |
| CN105271199A (en) * | 2015-11-05 | 2016-01-27 | 湖北卓熙氟化股份有限公司 | Preparation method of fluorinated graphene |
| CN105621399A (en) * | 2015-12-25 | 2016-06-01 | 山东重山光电材料股份有限公司 | Method for preparing high-purity fluorinated graphene by taking nitrogen trifluoride as fluorine source |
| CN106086820A (en) * | 2016-07-26 | 2016-11-09 | 厦门烯成石墨烯科技有限公司 | A kind of preparation method of the fluorinated graphene composite being loaded with nanometer silver |
| WO2017041171A1 (en) * | 2015-09-08 | 2017-03-16 | Grafoid Inc. | Process for coating a substrate with a carbon-based material |
| CN107032343A (en) * | 2017-05-24 | 2017-08-11 | 北京服装学院 | The preparation method of wet spinning graphene oxide solution and graphene fiber |
| CN107500275A (en) * | 2017-10-20 | 2017-12-22 | 山东重山光电材料股份有限公司 | A kind of method for producing different Oil repellent fluorinated graphenes in enormous quantities |
| CN107501819A (en) * | 2017-09-15 | 2017-12-22 | 中国南方电网有限责任公司超高压输电公司贵阳局 | A kind of modified polytetrafluoroethylresin resin |
| CN108927191A (en) * | 2017-05-22 | 2018-12-04 | 天津大学 | Fluorine-containing graphite-phase nitrogen carbide photochemical catalyst and preparation method thereof |
| CN108963250A (en) * | 2017-05-19 | 2018-12-07 | 天津大学 | A kind of preparation method of the Fluorin doped graphene nanometer sheet based on-CF2 |
| CN108963251A (en) * | 2017-05-19 | 2018-12-07 | 天津大学 | Battery based on Fluorin doped graphene nanometer sheet |
| CN109179395A (en) * | 2018-10-23 | 2019-01-11 | 湖北工程学院 | A kind of fluorinated graphene and preparation method thereof, application |
| CN110877910A (en) * | 2018-09-06 | 2020-03-13 | 天津大学 | Preparation method of fluorine-nitrogen double-doped activated carbon used as supercapacitor electrode |
| CN110877906A (en) * | 2018-09-06 | 2020-03-13 | 天津大学 | Preparation method of fluorine-doped graphene |
| CN115818974A (en) * | 2022-12-26 | 2023-03-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for generating graphene coating on glass surface |
| CN116377710A (en) * | 2023-04-28 | 2023-07-04 | 广东墨睿科技有限公司 | Fluorinated graphene insulating heat-conducting film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4511493A (en) * | 1983-03-09 | 1985-04-16 | Nobuatsu Watanabe | Ternary intercalation compound of a graphite with a metal fluoride and fluorine, a process for producing the same, and an electrically conductive material comprising the ternary intercalation compound |
| CN101186808A (en) * | 2007-12-14 | 2008-05-28 | 华南理工大学 | Method for preparing graphite series nano fluid |
| CN101658786A (en) * | 2009-09-25 | 2010-03-03 | 上海大学 | Method for preparing graphene-based titanium dioxide composite photocatalyst by radiation of electron beams |
-
2010
- 2010-12-22 CN CN201010600423.9A patent/CN102530910B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4511493A (en) * | 1983-03-09 | 1985-04-16 | Nobuatsu Watanabe | Ternary intercalation compound of a graphite with a metal fluoride and fluorine, a process for producing the same, and an electrically conductive material comprising the ternary intercalation compound |
| CN101186808A (en) * | 2007-12-14 | 2008-05-28 | 华南理工大学 | Method for preparing graphite series nano fluid |
| CN101658786A (en) * | 2009-09-25 | 2010-03-03 | 上海大学 | Method for preparing graphene-based titanium dioxide composite photocatalyst by radiation of electron beams |
Non-Patent Citations (1)
| Title |
|---|
| S.-H. CHENG等: "Reversible Fluorination of Graphene: towards a Two-Dimensional Wide Bandgap Semiconductor", 《PHYS. REV. B 》 * |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086366A (en) * | 2013-01-16 | 2013-05-08 | 天津工业大学 | Preparation method of amphiphilic fluorinated-oxidized graphene |
| CN103086374B (en) * | 2013-02-22 | 2014-07-23 | 杭州格蓝丰纳米科技有限公司 | Method for preparing graphene fluoride by atomic layer deposition device |
| CN103086374A (en) * | 2013-02-22 | 2013-05-08 | 杭州格蓝丰纳米科技有限公司 | Method for preparing graphene fluoride by atomic layer deposition device |
| CN104944402A (en) * | 2014-03-24 | 2015-09-30 | 中国科学院兰州化学物理研究所 | Method for quickly and efficiently preparing adjustable-fluorine-content fluoridized graphene |
| CN104944402B (en) * | 2014-03-24 | 2017-04-26 | 中国科学院兰州化学物理研究所 | Method for quickly and efficiently preparing adjustable-fluorine-content fluoridized graphene |
| CN104992987B (en) * | 2015-06-18 | 2016-11-23 | 西交利物浦大学 | Fluorinated graphene is as the solar cell and preparation method thereof of resistive formation |
| CN104992987A (en) * | 2015-06-18 | 2015-10-21 | 西交利物浦大学 | Solar cell taking fluorinated graphene as high-resistance layer and preparing method thereof |
| WO2017041171A1 (en) * | 2015-09-08 | 2017-03-16 | Grafoid Inc. | Process for coating a substrate with a carbon-based material |
| US10710113B2 (en) | 2015-09-08 | 2020-07-14 | Grafoid, Inc. | Process for coating a substrate with a carbon-based material |
| CN105271199A (en) * | 2015-11-05 | 2016-01-27 | 湖北卓熙氟化股份有限公司 | Preparation method of fluorinated graphene |
| CN105621399A (en) * | 2015-12-25 | 2016-06-01 | 山东重山光电材料股份有限公司 | Method for preparing high-purity fluorinated graphene by taking nitrogen trifluoride as fluorine source |
| CN106086820A (en) * | 2016-07-26 | 2016-11-09 | 厦门烯成石墨烯科技有限公司 | A kind of preparation method of the fluorinated graphene composite being loaded with nanometer silver |
| CN106086820B (en) * | 2016-07-26 | 2019-01-11 | 厦门烯成石墨烯科技有限公司 | It is a kind of to load the preparation method for having the fluorinated graphene composite material of nano silver |
| CN108963250A (en) * | 2017-05-19 | 2018-12-07 | 天津大学 | A kind of preparation method of the Fluorin doped graphene nanometer sheet based on-CF2 |
| CN108963251A (en) * | 2017-05-19 | 2018-12-07 | 天津大学 | Battery based on Fluorin doped graphene nanometer sheet |
| CN108927191A (en) * | 2017-05-22 | 2018-12-04 | 天津大学 | Fluorine-containing graphite-phase nitrogen carbide photochemical catalyst and preparation method thereof |
| CN108927191B (en) * | 2017-05-22 | 2021-05-28 | 天津大学 | Fluorine-containing graphite phase nitrogen carbide photocatalyst and preparation method thereof |
| CN107032343A (en) * | 2017-05-24 | 2017-08-11 | 北京服装学院 | The preparation method of wet spinning graphene oxide solution and graphene fiber |
| CN107501819A (en) * | 2017-09-15 | 2017-12-22 | 中国南方电网有限责任公司超高压输电公司贵阳局 | A kind of modified polytetrafluoroethylresin resin |
| CN107501819B (en) * | 2017-09-15 | 2020-01-07 | 中国南方电网有限责任公司超高压输电公司贵阳局 | Modified polytetrafluoroethylene resin |
| CN107500275A (en) * | 2017-10-20 | 2017-12-22 | 山东重山光电材料股份有限公司 | A kind of method for producing different Oil repellent fluorinated graphenes in enormous quantities |
| CN110877910A (en) * | 2018-09-06 | 2020-03-13 | 天津大学 | Preparation method of fluorine-nitrogen double-doped activated carbon used as supercapacitor electrode |
| CN110877906A (en) * | 2018-09-06 | 2020-03-13 | 天津大学 | Preparation method of fluorine-doped graphene |
| CN110877910B (en) * | 2018-09-06 | 2022-04-05 | 天津大学 | Preparation method of fluorine-nitrogen double-doped activated carbon used as supercapacitor electrode |
| CN109179395A (en) * | 2018-10-23 | 2019-01-11 | 湖北工程学院 | A kind of fluorinated graphene and preparation method thereof, application |
| CN115818974A (en) * | 2022-12-26 | 2023-03-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for generating graphene coating on glass surface |
| CN115818974B (en) * | 2022-12-26 | 2024-04-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for generating graphene coating on glass surface |
| CN116377710A (en) * | 2023-04-28 | 2023-07-04 | 广东墨睿科技有限公司 | Fluorinated graphene insulating heat-conducting film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102530910B (en) | 2014-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102530910B (en) | Method for preparing fluorinated graphene | |
| CN103153848B (en) | Fluorographene and preparation method thereof | |
| CN103153851B (en) | Fluorinated graphene oxide and preparation method thereof | |
| Wang et al. | Cleanly synthesizing rotten potato-based activated carbon for supercapacitor by self-catalytic activation | |
| CN102530911B (en) | Graphene fluoride preparation method | |
| Cai et al. | Superhigh capacity and rate capability of high-level nitrogen-doped graphene sheets as anode materials for lithium-ion batteries | |
| Balaji et al. | Supercritical fluid processing of nitric acid treated nitrogen doped graphene with enhanced electrochemical supercapacitance | |
| WO2016138802A1 (en) | Method for preparing biomass graphene by using cellulose as raw material | |
| CN103854881B (en) | A kind of preparation method of graphene/carbon nano-tube combination electrode | |
| CN105645403A (en) | Preparation method of high-performance nitrogen-doped three-dimensional graphene | |
| CN104045077A (en) | Graphene three-dimensional hierarchical porous carbon material and preparation method thereof | |
| CN102569725B (en) | Fluorination grapheme-lithium vanadium phosphate composite material, as well as preparation method and application thereof | |
| CN109148843B (en) | Boron-doped negative electrode material with good high-temperature performance and solid-phase preparation method thereof | |
| CN103035881B (en) | Preparation method of graphene-silicon composite material | |
| CN107331838B (en) | Nano composite electrode material of chloride ion battery and preparation method thereof | |
| CN102532890B (en) | Fluorinated and oxidized grapheme/polyaniline composite material and preparation method thereof | |
| CN111276679A (en) | Double-carbon composite molybdenum sulfide composite material for sodium ion battery cathode material and preparation method thereof | |
| CN114604850B (en) | Preparation method and application of porous microsphere carbon anode material | |
| CN104078247B (en) | Composite electrode material vanadium trioxide or carbon for super capacitor and preparation method thereof | |
| CN106809827B (en) | The magnanimity preparation method of highly conductive iron chloride doped graphene nanometer sheet powder body material | |
| Ha et al. | Improved energy and power density of a Li/CFX primary battery through control of the CF bonds with thermobaric modifications | |
| CN102757643A (en) | Preparation method for nitrogen substituted graphene oxide/polypyrrole composite material | |
| CN102558770A (en) | Fluorinated graphene oxide/ polymer composite material, preparation method and application thereof | |
| EP3774652A2 (en) | Method for nitrogen-doped graphene production | |
| Gong et al. | CuS-based composite for high-performance magnesium storage with a clarified charge-discharge mechanism |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |