CN110217781A - The preparation method of graphene - Google Patents
The preparation method of graphene Download PDFInfo
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- CN110217781A CN110217781A CN201910567843.2A CN201910567843A CN110217781A CN 110217781 A CN110217781 A CN 110217781A CN 201910567843 A CN201910567843 A CN 201910567843A CN 110217781 A CN110217781 A CN 110217781A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 140
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 46
- 239000000017 hydrogel Substances 0.000 claims abstract description 23
- 239000004094 surface-active agent Substances 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical compound [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 claims description 8
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 8
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 235000004515 gallic acid Nutrition 0.000 claims description 4
- 229940074391 gallic acid Drugs 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 108010082495 Dietary Plant Proteins Proteins 0.000 claims description 3
- 235000021120 animal protein Nutrition 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims 2
- 229960005070 ascorbic acid Drugs 0.000 claims 1
- 235000010323 ascorbic acid Nutrition 0.000 claims 1
- 239000011668 ascorbic acid Substances 0.000 claims 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical group CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims 1
- 238000007906 compression Methods 0.000 abstract description 19
- 230000006835 compression Effects 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 15
- 229910021538 borax Inorganic materials 0.000 description 10
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000004328 sodium tetraborate Substances 0.000 description 10
- 235000010339 sodium tetraborate Nutrition 0.000 description 10
- 239000004964 aerogel Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 235000010378 sodium ascorbate Nutrition 0.000 description 6
- 229960005055 sodium ascorbate Drugs 0.000 description 6
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 6
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000005187 foaming Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 229940012017 ethylenediamine Drugs 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- -1 Graphite alkene Chemical class 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/26—Mechanical properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of graphene, includes the following steps: that (1) mixes the mixed solution of crosslinking agent and surfactant with graphene oxide solution, obtain frothing solution；(2) frothing solution is mixed with reducing agent, obtains graphene hydrogel；(3) graphene hydrogel is freezed and is thawed, obtain graphene.The graphene compression strength with higher being prepared by this method.
Description
Technical field
The present invention relates to a kind of preparation methods of graphene.
Background technique
Graphene aerogel refers to exist between graphene sheet layer or with other organic or inorganic molecules based on graphene
The three-dimensional porous network structure being interconnected to form under certain condition.Comprising many micro- in the three-dimensional structure of graphene aerogel
Hole, mesoporous, macropore, micropore and it is mesoporous provide great specific surface area for graphene aerogel, also reduce graphene airsetting
The density of glue.Graphene aerogel unique three-dimensional macrostructure, the physics and chemistry that single-layer graphene can not only be made full use of intrinsic
Property solves the problems, such as that graphene film interlayer is easy to reunite, also imparts the porosity of its even compact, can greatly improve suction
Attached effect, and graphene macrostructure is easily recycled after use in water phase, and reducing it may be to the secondary dirt of environment bring
Dye, is a kind of ideal adsorbent material.But since graphene raw material itself is brittle and the high feature of flexibility, so that preparation
The mechanical performance of obtained graphene aerogel is also poor, limits application of the graphene aerogel in adsorbent material.
CN106517160A discloses a kind of preparation method of isotropic super-elasticity graphene aerogel: (1) restoring
In the presence of agent, graphene oxide aqueous dispersions are stirred at low speed with lauryl sodium sulfate aqueous solution after mixing, then high-speed stirred
Foaming, graphene oxide layer is restored to form tridimensional network；(2) freezing reinforcing graphene sheet layer is formed by hole wall,
Last normal heating is dry, obtains the graphene aerogel of isotropic.The graphene aerogel that this method is prepared does not have
By crosslinking, compression strength is not high.
CN109232013A discloses a kind of preparation method of big size graphene cystosepiment: (1) to graphene oxide water
Reducing agent is added in solution and adds surfactant after to be restored dose is completely dissolved, stirs the gas into graphene oxide solution
Bubble, obtains the foaming graphene oxide solution with micron order uniform liquid crystal phase；(2) by the foaming oxygen of micron order uniform liquid crystal phase
Graphite alkene solution, which is transferred in mold, heats reduction, obtains big size graphene hydrogel；(3) large scale hydrogel is cold
Freeze, then melt, obtains the big size graphene hydrogel of freeze thaw processing；(4) by the large scale stone of freeze thaw processing
Black alkene hydrogel naturally dry or 30~It is dry at 60 DEG C, obtain big size graphene cystosepiment.The stone that this method is prepared
Black alkene cystosepiment elasticity is higher, but compression strength is bad.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of preparation methods of graphene.What this method was prepared
Graphene compression strength with higher.
The present invention provides a kind of preparation method of graphene, includes the following steps:
(1) mixed solution of crosslinking agent and surfactant is mixed with graphene oxide solution, obtains frothing solution；
(2) frothing solution is mixed with reducing agent, obtains graphene hydrogel；
(3) graphene hydrogel is freezed and is thawed, obtain graphene.
Preparation method according to the present invention, it is preferable that crosslinking agent is the tetraborate or boric acid of alkali metal.
Preparation method according to the present invention, it is preferable that the mass ratio of graphene oxide and crosslinking agent is 1:0.005~0.2.
Preparation method according to the present invention, it is preferable that surfactant is selected from lauryl sodium sulfate, cetyl front three
One of base ammonium bromide, neopelex, animal protein or vegetable protein.
Preparation method according to the present invention, it is preferable that the mass ratio of graphene oxide and surfactant is 1:0.1~1.
Preparation method according to the present invention, it is preferable that reducing agent is selected from ethylenediamine, sodium ascorbate, gallic acid, hydration
One of hydrazine, sodium borohydride, vulcanized sodium, sodium dithionite or ferrous sulfate.
Preparation method according to the present invention, it is preferable that the mass ratio of graphene oxide and reducing agent is 1:2~10.
Preparation method according to the present invention, it is preferable that in step (1), the mixed solution of crosslinking agent and surfactant with
Graphene oxide solution mixes under stirring conditions, and revolving speed is 5000~20000rpm.
Preparation method according to the present invention, it is preferable that in graphene oxide solution the concentration of graphene oxide be 2~
10mg/ml。
Preparation method according to the present invention, it is preferable that the purity of graphene oxide is 95% or more in graphene oxide, piece
Diameter≤50 μm, lamellar spacing≤30nm, oxygen carbon molar ratio are 0.15~0.65.
First the mixed liquor of crosslinking agent and surfactant is mixed with graphene oxide solution in the present invention, then with reducing agent
Mixing, can make the graphene the being prepared degree of cross linking with higher, and the pore structure homogeneity in graphene is high, effectively mention
The high compression strength of graphene.In a preferred embodiment of the invention, using the tetraborate of alkali metal or boric acid as crosslinking agent,
Make the graphene being prepared that there is higher compression strength.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, but protection scope of the present invention is not limited to
This.
The preparation method of graphene of the invention, includes the following steps:
(1) the step of preparing frothing solution；(2) the step of preparing graphene hydrogel；(3) the step of preparing graphene.
<the step of preparing frothing solution>
The mixed liquor of crosslinking agent and surfactant is mixed with graphene oxide solution, obtains frothing solution.
Graphene oxide in the present invention can be obtained using conventional method.Including but not limited to by Hummers method,
The methods of Brodie method, Staudenmaier method are prepared.A specific embodiment according to the present invention, graphite oxide
Alkene is prepared by Hummers method.
In the present invention, the purity of graphene oxide is 95% or more, piece diameter≤50 μm, lamellar spacing≤30nm, oxygen carbon
Molar ratio is 0.15~0.65.Preferably, the purity of graphene oxide is 96% or more.It is highly preferred that graphene oxide is pure
Degree is 98% or more.For example, can be 99%.Preferably, the piece diameter of graphene oxide is 2~45 μm.It is highly preferred that oxidation ink
The piece diameter of alkene is 20~30 μm.Preferably, the lamellar spacing of graphene oxide is 1~10nm.It is highly preferred that graphene oxide
Lamellar spacing is 5~10nm.Preferably, the oxygen carbon molar ratio of graphene oxide is 0.2~0.5.It is highly preferred that graphene oxide
Oxygen carbon molar ratio be 0.3~0.5.It can make the graphene being prepared that there is higher compression strength in this way.
In the present invention, the concentration of graphene oxide is 2~10mg/ml in graphene oxide water solution.Preferably, it aoxidizes
The concentration of graphene is 3~8mg/ml.It is highly preferred that the concentration of graphene oxide is 4~6mg/ml.
In the present invention, crosslinking agent can be the tetraborate or boric acid of alkali metal.One according to the present invention specific real
Mode is applied, crosslinking agent is the tetraborate of alkali metal.The example of the tetraborate of alkali metal includes but is not limited to sodium tetraborate.This
Sample can make graphene reach better cross-linking effect, higher compression strength.
In the present invention, the mass ratio of graphene oxide and crosslinking agent is 1:0.005~0.2.Preferably, graphene oxide
Mass ratio with crosslinking agent is 1:0.01~0.1.It is highly preferred that the mass ratio of graphene oxide and crosslinking agent be 1:0.03~
0.08.Graphene can be made to reach better cross-linking effect, higher compression strength in this way.
In the present invention, surfactant can be selected from lauryl sodium sulfate, cetyl trimethylammonium bromide, 12
One of sodium alkyl benzene sulfonate, animal protein or vegetable protein.Preferably, surfactant can be selected from dodecyl sulphate
Sodium or neopelex.It is highly preferred that surfactant is lauryl sodium sulfate.Graphene can be made to have in this way
Higher compression strength.
In the present invention, the mass ratio of graphene oxide and surfactant is 1:0.1~1.Preferably, graphene oxide
Mass ratio with surfactant is 1:0.3~1.It is highly preferred that the mass ratio of graphene oxide and surfactant is 1:0.5
~0.8.It can make graphene that there is higher compression strength in this way.
In the present invention, the mixed liquor of crosslinking agent and surfactant can be prepared by the method for ultrasound.Ultrasound
Time is 10~30min.Preferably, ultrasonic time is 10~20min.It is highly preferred that ultrasonic time is 10~15min.
In the present invention, the mixed solution of crosslinking agent and surfactant and graphene oxide solution be under stirring conditions
Mixing, revolving speed are 5000~20000rpm.Preferably, revolving speed is 8000~15000rpm.It is highly preferred that revolving speed be 10000~
13000rpm。
In the present invention, the reaction temperature of the mixed solution and graphene oxide solution of crosslinking agent and surfactant is 50
~150 DEG C.Preferably, reaction temperature is 70~120 DEG C.It is highly preferred that reaction temperature is 70~100 DEG C.Reaction time is 30
~120min.Preferably, the reaction time is 40~100min.It is highly preferred that the reaction time is 50~80min.It can reach in this way
To better cross-linking effect and foaming effect, make the graphene being prepared that there is higher compression strength.
<the step of preparing graphene hydrogel>
Frothing solution is mixed with reducing agent, obtains graphene hydrogel.
In the present invention, reducing agent is selected from ethylenediamine, sodium ascorbate, gallic acid, hydrazine hydrate, sodium borohydride, vulcanization
One of sodium, sodium dithionite or ferrous sulfate.Preferably, reducing agent is ethylenediamine, sodium ascorbate or gallic acid.
It is highly preferred that reducing agent is ethylenediamine.
In the present invention, the mass ratio of graphene oxide and reducing agent is 1:2~10.Preferably, graphene oxide with also
The mass ratio of former agent is 1:2~7.It is highly preferred that the mass ratio of graphene oxide and reducing agent is 1:3~6.It can make to make in this way
Standby obtained graphene has higher compression strength.
In the present invention, the reaction temperature of frothing solution and reducing agent is 50~150 DEG C.Preferably, reaction temperature 70
~120 DEG C.It is highly preferred that reaction temperature is 70~100 DEG C.Reaction time is 5~20h.Preferably, the reaction time be 5~
15h.It is highly preferred that the reaction time is 8~12h.It can make the graphene being prepared that there is higher compression strength in this way.
In the present invention, can also include the steps that washing graphene hydrogel.It is washed used in washing step
Liquid can be water or the aqueous solution of ethyl alcohol.Preferably, washing lotion is the aqueous solution of ethyl alcohol.It is highly preferred that second in the aqueous solution of ethyl alcohol
The content of alcohol is 1~10vol%.
<the step of preparing graphene>
Graphene hydrogel is freezed and thawed, graphene is obtained.
In the present invention, the time of freezing is 10~35h.Preferably, cooling time is 15~30h.It is highly preferred that freezing
Time is 18~25h.
In the present invention, drying can also be included the steps that after defrosting step.Drying temperature is 40~100 DEG C.It is preferred that
Ground, drying temperature are 50~90 DEG C.It is highly preferred that drying temperature is 60~80 DEG C.Drying time is 12~36h.Preferably, it does
The dry time is 15~30h.It is highly preferred that drying time is 20~25h.The graphene being prepared can in this way had higher
Compression strength.
Embodiment 1
300mg graphene oxide (purity 98%, piece diameter are 20 μm, lamellar spacing 4nm) is weighed, water is dissolved in
In, ultrasonic disperse, preparation obtains the graphene oxide water solution of 5mg/ml.
3mg sodium tetraborate and 150mg lauryl sodium sulfate are weighed respectively, are dissolved in water, ultrasonic disperse
10min obtains the mixed solution of sodium tetraborate and lauryl sodium sulfate.
By the mixed solution of graphene oxide water solution and sodium tetraborate and lauryl sodium sulfate, in revolving speed 10000rpm
Under the conditions of be stirred, then react 1h under the conditions of 80 DEG C, obtain frothing solution.
1500mg sodium ascorbate and frothing solution are weighed, is stirred, mixing.10h is reacted at 80 DEG C, then uses 1vol%
Ethanol water washing, obtain graphene hydrogel.
Graphene hydrogel is freezed into 20h under cryogenic, thaws and arrives room temperature, drying for 24 hours, obtains graphite at 65 DEG C
Alkene.
Embodiment 2
Weighing 300mg graphene oxide, (purity 99%, piece diameter are 30 μm, lamellar spacing 10nm, and oxygen carbon molar ratio is
0.4) it, is dissolved in water, ultrasonic disperse, preparation obtains the graphene oxide water solution of 5mg/ml.
15mg sodium tetraborate and 210mg lauryl sodium sulfate are weighed respectively, are dissolved in water, ultrasonic disperse
10min obtains the mixed solution of sodium tetraborate and lauryl sodium sulfate.
By the mixed solution of graphene oxide water solution and sodium tetraborate and lauryl sodium sulfate, in revolving speed 12000rpm
Under the conditions of be stirred, then react 1h under the conditions of 80 DEG C, obtain frothing solution.
1500mg ethylenediamine and frothing solution are weighed, is stirred, mixing.10h is reacted at 80 DEG C, then uses the second of 1vol%
Alcohol solution washing, obtains graphene hydrogel.
Graphene hydrogel is freezed into 20h under cryogenic, thaws and arrives room temperature, drying for 24 hours, obtains graphite at 65 DEG C
Alkene.
Embodiment 3
Weighing 300mg graphene oxide, (purity 96%, piece diameter are 10 μm, lamellar spacing 15nm, and oxygen carbon molar ratio is
0.2) it, is dissolved in water, ultrasonic disperse, preparation obtains the graphene oxide water solution of 5mg/ml.
30mg sodium tetraborate and 240mg lauryl sodium sulfate are weighed respectively, are dissolved in water, ultrasonic disperse
10min obtains the mixed solution of sodium tetraborate and lauryl sodium sulfate.
By the mixed solution of graphene oxide water solution and sodium tetraborate and lauryl sodium sulfate, in revolving speed 13000rpm
Under the conditions of be stirred, then react 1h under the conditions of 80 DEG C, obtain frothing solution.
1500mg sodium ascorbate and frothing solution are weighed, is stirred, mixing.10h is reacted at 80 DEG C, then uses 1vol%
Ethanol water washing, obtain graphene hydrogel.
Graphene hydrogel is freezed into 20h under cryogenic, thaws and arrives room temperature, drying for 24 hours, obtains graphite at 65 DEG C
Alkene.
Comparative example 1
Weighing 300mg graphene oxide, (purity 99%, piece diameter are 30 μm, lamellar spacing 10nm, and oxygen carbon molar ratio is
0.4) it, is dissolved in water, ultrasonic disperse, preparation obtains the graphene oxide water solution of 5mg/ml.
210mg lauryl sodium sulfate is weighed, is dissolved in water, ultrasonic disperse 10min obtains dodecyl sulphate
Sodium water solution.
By graphene oxide water solution and lauryl sodium sulfate aqueous solution, stirred under the conditions of revolving speed 12000rpm mixed
It closes, then reacts 1h under the conditions of 80 DEG C, obtain frothing solution.
1500mg sodium ascorbate and frothing solution are weighed, is stirred, mixing.10h is reacted at 80 DEG C, then uses 1vol%
Ethanol water washing, obtain graphene hydrogel.
Graphene hydrogel is freezed into 20h under cryogenic, thaws and arrives room temperature, drying for 24 hours, obtains graphite at 65 DEG C
Alkene aeroge.
Experimental example
The density and compression strength for the graphene sample that Examples 1 to 3 and comparative example 1 are prepared are tested.
Density measurement: signified density is the bulk density of graphene sample in this test method.Keep graphene sample logical
It crosses funnel quantitatively freely to fall, after loose filling, with the graphene sample quality fallen divided by packing volume to get graphene sample
The freely settled density of product.Each graphene sample at least measures three times, is averaged.
Intensity test: graphene sample is put into universal testing machine testboard, records graphene sample compressive deformation
Load at 10%.The compression strength measured every time is accurate to 0.1kPa, and each graphene sample is at least measured three times, made even
Mean value.
Table 1
| Test sample | Density (mg/ml) | Compression strength (compression 10%)/kPa |
| Embodiment 1 | 5.2 | 1.8 |
| Embodiment 2 | 4.9 | 2.0 |
| Embodiment 3 | 5.3 | 1.7 |
| Comparative example 1 | 5.3 | 1.5 |
Present invention is not limited to the embodiments described above, without departing from the essence of the present invention, this field skill
Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.
Claims (10)
1. a kind of preparation method of graphene, which comprises the steps of:
(1) mixed solution of crosslinking agent and surfactant is mixed with graphene oxide solution, obtains frothing solution；
(2) frothing solution is mixed with reducing agent, obtains graphene hydrogel；
(3) graphene hydrogel is freezed and is thawed, obtain graphene.
2. preparation method according to claim 1, which is characterized in that the crosslinking agent is selected from the tetraborate of alkali metal
Or boric acid.
3. preparation method according to claim 1, which is characterized in that the mass ratio of graphene oxide and crosslinking agent is 1:
0.005~0.2.
4. preparation method according to claim 1, which is characterized in that the surfactant is selected from dodecyl sulphate
One of sodium, cetyl trimethylammonium bromide, neopelex, animal protein or vegetable protein.
5. preparation method according to claim 1, which is characterized in that the mass ratio of graphene oxide and surfactant is
1:0.1~1.
6. preparation method according to claim 1, which is characterized in that the reducing agent is selected from ethylenediamine, ascorbic acid
One of sodium, gallic acid, hydrazine hydrate, sodium borohydride, vulcanized sodium, sodium dithionite or ferrous sulfate.
7. preparation method according to claim 1, which is characterized in that the mass ratio of graphene oxide and reducing agent is 1:2
~10.
8. preparation method according to claim 1, which is characterized in that in step (1), crosslinking agent and surfactant it is mixed
It closes solution to mix under stirring conditions with graphene oxide solution, revolving speed is 5000~20000rpm.
9. preparation method according to claim 1, which is characterized in that graphene oxide in the graphene oxide solution
Concentration is 2~10mg/ml.
10. preparation method according to claim 1, which is characterized in that graphene oxide in the graphene oxide
Purity is 95% or more, and piece diameter≤50 μm, lamellar spacing≤30nm, oxygen carbon molar ratio is 0.15~0.65.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517160A (en) * | 2016-11-22 | 2017-03-22 | 青岛科技大学 | Method for preparing isotropic superelastic graphene aerogel |
| CN108695010A (en) * | 2018-05-07 | 2018-10-23 | 北京航空航天大学 | A kind of preparation method of imitative kiss clam worm high-strength conductive graphene composite material |
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2019
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517160A (en) * | 2016-11-22 | 2017-03-22 | 青岛科技大学 | Method for preparing isotropic superelastic graphene aerogel |
| CN108695010A (en) * | 2018-05-07 | 2018-10-23 | 北京航空航天大学 | A kind of preparation method of imitative kiss clam worm high-strength conductive graphene composite material |
Non-Patent Citations (1)
| Title |
|---|
| ZHI AN等: "Bio-Inspired Borate Cross-Linking in Ultra-Stiff Graphene Oxide Thin Films", 《ADV. MATER》 * |
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