CN106883456B - A kind of preparation method of polyaminopropylsilsesquioxane doping nickel coated graphene - Google Patents
A kind of preparation method of polyaminopropylsilsesquioxane doping nickel coated graphene Download PDFInfo
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- CN106883456B CN106883456B CN201710071475.3A CN201710071475A CN106883456B CN 106883456 B CN106883456 B CN 106883456B CN 201710071475 A CN201710071475 A CN 201710071475A CN 106883456 B CN106883456 B CN 106883456B
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- polyaminopropylsilsesquioxane
- nickel
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 147
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 69
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 39
- 239000010439 graphite Substances 0.000 claims abstract description 39
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- KXIFSSCKBFYNMX-UHFFFAOYSA-N hydrazine;nickel;hydrate Chemical compound O.[Ni].NN KXIFSSCKBFYNMX-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- 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 15
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 11
- -1 Aminopropyl Chemical group 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 239000003643 water by type Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- SRKJGPDOXJNQBU-UHFFFAOYSA-L O.NN.C(C)(=O)[O-].[Ni+2].C(C)(=O)[O-] Chemical compound O.NN.C(C)(=O)[O-].[Ni+2].C(C)(=O)[O-] SRKJGPDOXJNQBU-UHFFFAOYSA-L 0.000 claims 2
- 238000000527 sonication Methods 0.000 claims 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 18
- 229910052763 palladium Inorganic materials 0.000 abstract description 13
- 230000005415 magnetization Effects 0.000 abstract description 8
- 238000005406 washing Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 14
- 238000007747 plating Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229910001453 nickel ion Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000976924 Inca Species 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
Abstract
The invention discloses the preparation methods that a kind of polyaminopropylsilsesquioxane adulterates nickel coated graphene；This method first mixes graphite oxide and absolute ethyl alcohol, add polyaminopropylsilsesquioxane solution, it is stirred 3~5 hours at 50~70 DEG C, then ultrasonic cleaner is gone to be ultrasonically treated, it is ultrasonically treated, it stands, filtering obtains polyaminopropylsilsesquioxane modified graphene oxide suspension；Then inorganic nickel-hydrazine hydrate complex solution is added in gained polyaminopropylsilsesquioxane modified graphene oxide suspension, stirring is reacted at 60~80 DEG C, it centrifuges, washing, vacuum drying adulterate nickel coated graphene to get to polyaminopropylsilsesquioxane.The present invention provides a kind of preparation method of no palladium, and polyaminopropylsilsesquioxane adulterates nickel coated graphene resistivity and is less than 0.1 Ω .cm, and saturation magnetization is more than 3.5A.m2/ kg, magnetic conductivity are more than 0.3mH/m.
Description
Technical field
The present invention relates to a kind of methods of metal-coated graphite alkene, more particularly to the cladding nickel on the surface of graphene of no palladium
Method, and in particular to a kind of preparation method of polyaminopropylsilsesquioxane doping nickel coated graphene belongs to inorganic material
Technical field of modification.
Background technology
Graphene is the only one layer of atomic thickness being made of carbon atomTwo dimensional crystal, have density is small, conductive and heat-conductive,
The advantages that stability is good, but its magnetic loss consumption is weak, and magnetic conductivity is low.Metallic nickel conductivity is high, and magnetic conductivity is high, effectiveness
It is good, it coats metallic nickel on the surface of graphene using chemical plating method, can assign graphene certain magnetic conductance.Central-South forestry section
The patent of invention (CN201310296080.5) of skill university discloses a kind of preparation method of chemical nickel plating graphene, and this method is logical
It crosses and graphene is roughened, is sensitized, is activated, is restored, nickel coating is added to graphene using the technique of chemical plating；Li Shumei etc.
[preparation of nickel coated reduced graphene composite material and performance study, plating and finish, 2015,37.9,12-14,18] is used
Natural flake graphite is oxidized to graphite oxide by Hummers methods, and reduction stone is obtained by reducing agent reduction-oxidation graphite of hydrazine hydrate
Black alkene, and amorphous nickel-phosphor alloy has been coated by alkaline chemical nickel-plating processing rear surface to reduced graphene, resistivity reaches
To 4.5m Ω m, hence it is evident that be better than the electric conductivity of reduced graphene (40.6m Ω m).
The above-mentioned prior art has obtained nickel coated graphene using the method for chemical plating, but has used palladium bichloride, not only
Complex process, processing cost is higher, and causes serious precious metal palladium to pollute environment, runs counter to the development side of no palladium nickel plating
To；In addition, having used sodium hypophosphite in reducing agent, the phosphorus of high level is contained in gained coating, in this way gained graphene electricity
Resistance rate is still higher.As a result, using no palladium nickel plating process and further decrease nickel coated graphene resistivity it is significant.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of polyaminopropylsilsesquioxane doping nickel coated stone of no palladium
The preparation method of black alkene obtains resistivity and is less than 0.1 Ω .cm, and saturation magnetization is more than 3.5A.m2/ kg, magnetic conductivity are more than
0.3mH/m, the polyaminopropylsilsesquioxane with excellent conductive and permeance property adulterate nickel coated graphene.
The present invention by graphite oxide ultrasound remove at graphene during, be added polyaminopropylsilsesquioxane,
Its surface is set to connect the amino for forming more stable coordinate bond with nickel ion；Nickel ion in this way with hydrazine hydrate other than being coordinated, also
It is coordinated with the amino on graphene surface polyaminopropylsilsesquioxane, in 60 DEG C~80 DEG C, under alkaline environment, the divalent of complexing
Nickel ion is gradually restored by hydrazine hydrate, is reduced into tiny nickel particle on the surface of graphene, and the nickel particle initially formed is played into
Core acts on, and is catalyzed more nickel ions and constantly restores on the surface of graphene, and grow well on the surface of graphene, exists in this way
Uniform, fine and close, a small amount of polyaminopropylsilsesquioxane has been coated on the surface of graphene using chemical plating method under conditions of no palladium
The metallic nickel of doping, obtained graphene have excellent conduction and capability of electromagnetic shielding；And for filling-modified, imparting to be high
When molecular material capability of electromagnetic shielding, organic aminopropyl can also effectively increase between nickel coated graphene and macromolecule matrix
Bonding force and compatibility, promote fine dispersion in the base.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of polyaminopropylsilsesquioxane doping nickel coated graphene, includes the following steps：
(1) graphite oxide and absolute ethyl alcohol are pressed 1：60~80 mass ratio mixing, adds 10~20 matter of graphite oxide
Amount times polyaminopropylsilsesquioxane solution, stirred 3~5 hours at 50~70 DEG C, then go to ultrasonic cleaner into
Row is ultrasonically treated, and ultrasonic power is 60W~150W, and ultrasonic time is 10~30 minutes, is stood, and is filtered to remove solid precipitation, obtains
To polyaminopropylsilsesquioxane modified graphene oxide suspension；
(2) inorganic nickel-hydrazine hydrate complex solution is added to polyaminopropylsilsesquioxane obtained by step (1) and is modified oxygen
In graphite alkene suspension, the quality for controlling inorganic nickel is 1~3 times of graphite oxide, and stirring reacts 1 at 60~80 DEG C
It~3 hours, centrifuges, is washed with absolute ethyl alcohol and deionized water, vacuum drying is mixed to get to polyaminopropylsilsesquioxane
Miscellaneous nickel coated graphene.
To further realize the object of the invention, it is preferable that step (1) the graphite oxide preparation method is：Under ice bath, with
Mass fraction meter sequentially adds 1 part of graphite, 4~6 parts of potassium permanganate, 15~25 parts of the concentrated sulfuric acid and 4~6 parts of phosphoric acid, stirring
It is warming up to 55~65 DEG C after 1~4 hour, reacts 8~12 hours, is subsequently poured into 200~300 portions of ice water, 5~10 parts of matter are added
It measures a concentration of 30% hydroperoxidation 1~3 hour, centrifuges, collect bottom solid；It is washed, then spent with hydrochloric acid solution
Gained filter cake is dried in vacuo to neutrality, obtains graphite oxide by ion water washing.
Preferably, the mass concentration of the concentrated sulfuric acid is 98%；The phosphoric acid quality a concentration of 85%.
Preferably, described washed with hydrochloric acid solution is that the hydrochloric acid solution for being 4~8% with mass concentration washes twice.
Preferably, described be dried in vacuo gained filter cake is that gained filter cake is placed in 50~60 DEG C of vacuum drying chamber to do
It is dry.
Preferably, in terms of mass fraction, the dosage of the ice water is 200~300 parts.
Preferably, step (1) the polyaminopropylsilsesquioxane solution manufacturing method is：In terms of mass fraction, it is added
10 parts of gamma-aminopropyl-triethoxy-silanes or N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, 80~100 parts of anhydrous second
Alcohol and 5~10 parts of deionized waters are stirred to react 3~5 hours under room temperature, obtain polyaminopropylsilsesquioxane solution.
Preferably, step (2) inorganic nickel-hydrazine hydrate complex solution preparation method is：Under room temperature, by inorganic nickel
With 50% hydrazine hydrate in mass ratio 1：4~6 are added in reactor, and the deionization that quality is 5~8 times of inorganic nickel is then added
Water is uniformly mixed to obtain the final product；The inorganic nickel is nickel sulfate, nickel chloride or nickel acetate；The molecular formula of the hydrazine hydrate is N2H4·
H2O。
Preferably, step (2) stirring is mechanical agitation, and the rotating speed of stirring is 15~30r/min.
Preferably, step (2) the vacuum drying time is 4~8 hours.
Compared with prior art, the present invention having the following effects that：
(1) the method for the present invention realizes nickel coated graphene under conditions of no palladium, simple for process, environmental-friendly, overcomes
The prior art is required to use palladium bichloride, not only complex process, and processing cost is higher, and cause serious precious metal palladium to environment
Pollution.
(2) the method for the present invention prepare nickel coated graphene resistivity be less than 0.1 Ω .cm, nearly one lower than the prior art
The order of magnitude, electric conductivity higher.
(3) nickel coated graphene saturation magnetization prepared by the method for the present invention is more than 3.5A.m2/ kg, magnetic conductivity are more than
0.3mH/m, saturation magnetization and magnetic conductivity ratio prior art difference high 79% and 67%, magnetic conductance is stronger, than existing skill
Art product has apparent advantage.
(4) the technology of the present invention adulterates polyaminopropylsilsesquioxane in nickel coated graphene, and a small amount of organic group is deposited
Will largely increase with the binding force and compatibility of polymer resin matrix, surface treatment need not be carried out and can be realized
In the base evenly dispersed.
Description of the drawings
Fig. 1 is the X-ray diffraction that 1 gained polyaminopropylsilsesquioxane of the embodiment of the present invention adulterates nickel coated graphene
Figure.
Fig. 2 is the SEM-EDS figures that 1 gained polyaminopropylsilsesquioxane of the embodiment of the present invention adulterates nickel coated graphene.
Specific implementation mode
In order to better understand the content of the present invention, with reference to embodiment, the invention will be further described, but implements
Example is not intended to limit the scope of the present invention..
Embodiment 1
(1) polyaminopropylsilsesquioxane solution is prepared：10g gamma-aminopropyl-triethoxy-silane (the trades mark are added：CG-
550, Nanjing Chen Gong organosilicon materials Co., Ltd), 100g absolute ethyl alcohols (analysis is pure) and 5g deionized waters burn for tri- mouthfuls in 250ml
In bottle, it is stirred to react under room temperature 5 hours, obtains polyaminopropylsilsesquioxane solution；
(2) inorganic nickel-hydrazine hydrate complex solution is prepared：Under room temperature, 1g nickel sulfates (analysis is pure), 4g are sequentially added
In 50% hydrazine hydrate (analysis is pure) and 8g deionized waters to 50ml beakers, it is uniformly mixed to obtain the final product；
(3) graphite oxide is prepared：Under condition of ice bath, sequentially adding 1g graphite, 6g potassium permanganate, 25g mass concentrations is
The phosphoric acid that 98% concentrated sulfuric acid and 6g mass concentrations is 85%, stirring are warming up to 55 DEG C after 1 hour, react 8 hours, be subsequently poured into
In 300g ice water, the hydroperoxidation that addition 10g mass concentrations are 30% 1 hour centrifuges, collects bottom solid；With
The hydrochloric acid solution that mass concentration is 8% washes twice, then is washed with deionized to neutrality, and gained filter cake is placed in 60 DEG C true
It is 10 hours dry in empty drying box, obtain 0.255g Tan solid shape graphite oxides；Graphite (GR) used is Alfa Aesar
Co., Ltd's product, other is analytical reagents；
(4) by the poly- ammonia obtained by the made Tan solid shape graphite oxides of 0.1g, 6g absolute ethyl alcohols (analysis is pure) and 2g
Propylsilsesquioxane solution is added sequentially in flask, is stirred 5 hours at 50 DEG C, and ultrasonic cleaner progress is then gone to
It is ultrasonically treated, ultrasonic power 60W, ultrasonic time is 30 minutes, is then allowed to stand, and is filtered to remove a small amount of solid precipitation, obtains
Polyaminopropylsilsesquioxane modified graphene oxide suspension；The prepared inorganic nickels-of 3.9g are added in the suspension
Hydrazine hydrate complex solution, mechanical agitation, mixing speed 15r/min are warming up to 80 DEG C, and nickel ion is hydrated on the surface of graphene
Hydrazine is reduced into the precipitation of nickel simple substance, and room temperature is down to after 1 hour, centrifuges, and is washed with absolute ethyl alcohol and deionized water, at 55 DEG C
Vacuum drying 7 hours obtains polyaminopropylsilsesquioxane doping nickel coated graphene.
X-ray diffraction (Japanese Rigaku D/ are carried out to polyaminopropylsilsesquioxane doping nickel coated graphene
MAX2200PC X-ray diffractometers, diffraction source are copper target λ=0.15418nm, 10 °~85 ° of the angle of diffraction) test, acquired results are such as
Attached drawing 1,2 θ are 44.5 °, 51.8 °, 76.4 ° place's appearance, three diffraction maximums on spectrogram, and diffraction peak intensity is big, and half-peak breadth is smaller,
(111), (200), (220) three crystal faces of nickel are corresponded to respectively, are the polygonal nickel simple substance of cubic phase.
Nickel coated is adulterated to the polyaminopropylsilsesquioxane using scanning electron microscope-electron spectrometer (Britain INCA 250)
The micro-area composition element species and content analysis of graphene, the attached such as Fig. 2 of gained SEM-EDS spectrograms, as shown in Figure 2 in coating mainly
Containing nickel element, mass fraction 93.12% also contains a small amount of carbon, oxygen and element silicon, and mass fraction is respectively
4.98%, 1.27% and 0.63%.
Test shows that the present embodiment realizes the cladding of the nickel on graphene above, and poly- aminopropyl times is doped in coating
Half siloxanes.
Nickel coated is adulterated to the polyaminopropylsilsesquioxane of diameter 1cm manufactured in the present embodiment using four-point probe
Graphene film carries out the test of resistivity, and when test takes the average values of 5 measurements, and it is 0.07 Ω .cm to obtain resistivity；Using
Polyaminopropylsilsesquioxane of the U.S. Lake-Shore7410 types vibrating specimen magnetometer to diameter 1cm manufactured in the present embodiment
It adulterates nickel coated graphene film and carries out magnetic property analysis, saturation magnetization Ms is 4.81A.m2/ kg, magnetic conductivity are
0.33mH/m。
Embodiment 2
(1) polyaminopropylsilsesquioxane solution is prepared：10g is addedN-(β-Aminoethyl)-γ-Aminopropyl trimethoxy
Silane (the trade mark：CG-792, Nanjing Chen Gong organosilicon materials Co., Ltd), 80g absolute ethyl alcohols (analysis pure) and 10g deionized waters
In 250ml three-necked flasks, it is stirred to react under room temperature 3 hours, obtains polyaminopropylsilsesquioxane solution；
(2) inorganic nickel-hydrazine hydrate complex solution is prepared：Under room temperature, 1g nickel chlorides (analysis is pure), 6g are sequentially added
In 50% hydrazine hydrate (analysis is pure) and 5g deionized waters to 50ml beakers, it is uniformly mixed to obtain the final product；
(3) graphite oxide is prepared：Under condition of ice bath, sequentially adding 1g graphite, 5g potassium permanganate, 15g mass concentrations is
The phosphoric acid that 98% concentrated sulfuric acid and 5g mass concentrations is 85%, stirring are warming up to 65 DEG C after 2 hours, react 10 hours, then fall
Enter in 250g ice water, the hydroperoxidation that addition 5g mass concentrations are 30% 2 hours centrifuges, collects bottom solid；With
The hydrochloric acid solution that mass concentration is 4% washes twice, then is washed with deionized to neutrality, and gained filter cake is placed in 50 DEG C true
It is 14 hours dry in empty drying box, obtain 0.213g Tan solid shape graphite oxides；Graphite (GR) used is Alfa Aesar
Co., Ltd's product, other is analytical reagents；
(4) by the poly- ammonia obtained by the made Tan solid shape graphite oxides of 0.1g, 8g absolute ethyl alcohols (analysis is pure) and 1g
Propylsilsesquioxane solution is added sequentially in flask, is stirred 3 hours at 70 DEG C, and ultrasonic cleaner progress is then gone to
It is ultrasonically treated, ultrasonic power 100W, ultrasonic time is 10 minutes, is stood, and is filtered to remove a small amount of solid precipitation, obtains poly- ammonia
Propylsilsesquioxane modified graphene oxide suspension；Prepared inorganic nickel-the hydrations of 1.2g are added in the suspension
Hydrazine complex solution, mechanical agitation, mixing speed 30r/min are warming up to 60 DEG C, nickel ion on the surface of graphene by hydrazine hydrate also
Original is precipitated at nickel simple substance, and room temperature is down to after 3 hours, centrifuges, and is washed with absolute ethyl alcohol and deionized water, the vacuum at 50 DEG C
It is 8 hours dry, obtain polyaminopropylsilsesquioxane doping nickel coated graphene；Using four-point probe to diameter 1cm's
Polyaminopropylsilsesquioxane adulterates the test that nickel coated graphene film carries out resistivity, takes the average value of 5 measurements, obtains
Resistivity is 0.06 Ω .cm；Using U.S. Lake-Shore7410 type vibrating specimen magnetometer analyzing magnetic energy, saturated magnetization
Intensity Ms is 5.48A.m2/ kg, magnetic conductivity 0.37mH/m.
Embodiment 3
(1) polyaminopropylsilsesquioxane solution is prepared：10g is addedN-Aminoethyl-γ-Aminopropyl trimethoxysilane,
90g absolute ethyl alcohols (analysis is pure) and 8g deionized waters are stirred to react 4 hours under room temperature in 250ml three-necked flasks, obtain poly- ammonia
Propylsilsesquioxane solution；
(2) inorganic nickel-hydrazine hydrate complex solution is prepared：Under room temperature, 1g nickel acetates (analysis is pure), 5g are sequentially added
In 50% hydrazine hydrate (analysis is pure) and 6g deionized waters to 50ml beakers, it is uniformly mixed to obtain the final product；
(3) graphite oxide is prepared：Under condition of ice bath, sequentially adding 1g graphite, 4g potassium permanganate, 20g mass concentrations is
The phosphoric acid that 98% concentrated sulfuric acid and 4g mass concentrations is 85%, stirring are warming up to 60 DEG C after 4 hours, react 12 hours, then fall
Enter in 200g ice water, the hydroperoxidation that addition 7g mass concentrations are 30% 3 hours centrifuges, collects bottom solid；With
The hydrochloric acid solution that mass concentration is 6% washes twice, then is washed with deionized to neutrality, and gained filter cake is placed in 55 DEG C true
It is 12 hours dry in empty drying box, obtain 0.192g Tan solid shape graphite oxides；Graphite (GR) used is Alfa Aesar
Co., Ltd's product, other is analytical reagents；
It (4) will be poly- obtained by the made Tan solid shape graphite oxides of 0.1g, 7g absolute ethyl alcohols (analysis is pure) and 1.5g
Aminopropyl silsesquioxane solution is added sequentially in flask, is stirred 4 hours at 60 DEG C, then go to ultrasonic cleaner into
Row is ultrasonically treated, ultrasonic power 150W, and ultrasonic time is 20 minutes, is stood, and is filtered to remove a small amount of solid precipitation, is gathered
Aminopropyl silsesquioxane modified graphene oxide suspension；Prepared inorganic nickel-the water of 2.4g is added in the suspension
Hydrazine complex solution, mechanical agitation are closed, mixing speed 20r/min is warming up to 70 DEG C, and nickel ion is on the surface of graphene by hydrazine hydrate
It is reduced into the precipitation of nickel simple substance, room temperature is down to after 2 hours, is centrifuged, is washed with absolute ethyl alcohol and deionized water, it is true at 60 DEG C
Sky is 6 hours dry, obtains polyaminopropylsilsesquioxane doping nickel coated graphene；Using four-point probe to diameter 1cm
Polyaminopropylsilsesquioxane doping nickel coated graphene film carry out resistivity test, take 5 times measurement average values, obtain
It is 0.08 Ω .cm to resistivity；Using U.S. Lake-Shore7410 type vibrating specimen magnetometer analyzing magnetic energy, it is saturated magnetic
It is 3.59A.m to change intensity Ms2/ kg, magnetic conductivity 0.32mH/m.
Comparative example：Li Shumei etc. is in " preparation of nickel coated reduced graphene composite material and performance study, plating and essence
It adorns, 2015,37 (9), 12-14, uses palladium active oxidation graphite, hydrazine hydrate+sodium hypophosphite reduction that nickel coated is made in 18 " one texts
Graphene composite material, using the composite material as comparative example, the resistivity reported is 0.45 Ω cm, saturation magnetization Ms
For 2.01A.m2/ kg, magnetic conductivity 0.1916mH/m.
By each of the obtained polyaminopropylsilsesquioxane in embodiment 1,2 and 3 doping nickel coated graphene and comparative example
Performance is compared it is found that polyaminopropylsilsesquioxane doping nickel coated graphene resistivity ratio prepared by the method for the present invention shows
There are the low nearly an order of magnitude of technology, i.e. electric conductivity higher；Saturation magnetization and magnetic conductivity ratio prior art difference are high by 79%
With 67%, magnetic conductance is stronger.
From the foregoing, it will be observed that the technology of the present invention realizes nickel coated graphene under conditions of no palladium, simple for process, environment friend
Good, prepared nickel coated graphene conductive performance is good, and magnetic conductance is strong, and contains polyaminopropylsilsesquioxane in clad,
The presence of a small amount of organic group increases binding force and compatibility with polymer resin matrix, is used for the modification of high molecular material
Need not carry out surface treatment can disperse well, using convenient.
Claims (10)
1. a kind of preparation method of polyaminopropylsilsesquioxane doping nickel coated graphene, it is characterised in that including following step
Suddenly：
(1) graphite oxide and absolute ethyl alcohol are pressed 1：60~80 mass ratio mixing, adds graphite oxide 10~20 mass times
Polyaminopropylsilsesquioxane solution, stirred 3~5 hours at 50~70 DEG C, then go to ultrasonic cleaner and surpassed
Sonication, ultrasonic power are 60W~150W, and ultrasonic time is 10~30 minutes, is stood, and is filtered to remove solid precipitation, is gathered
Aminopropyl silsesquioxane modified graphene oxide suspension；
(2) inorganic nickel-hydrazine hydrate complex solution is added to the modified oxidized stone of polyaminopropylsilsesquioxane obtained by step (1)
In black alkene suspension, the quality for controlling inorganic nickel is 1~3 times of graphite oxide, and it is small to react 1~3 at 60~80 DEG C for stirring
When, it centrifuges, is washed with absolute ethyl alcohol and deionized water, vacuum drying adulterates nickel to get to polyaminopropylsilsesquioxane
Coated graphite alkene.
2. a kind of preparation method of polyaminopropylsilsesquioxane doping nickel coated graphene according to claim 1,
It is characterized in that, step (1) the graphite oxide preparation method is：Under ice bath, in terms of mass fraction, 1 part of graphite, 4 are sequentially added
~6 parts of potassium permanganate, 15~25 parts of the concentrated sulfuric acid and 4~6 parts of phosphoric acid, stirring are warming up to 55~65 DEG C after 1~4 hour, instead
Answer 8~12 hours, be subsequently poured into 200~300 portions of ice water, be added 5~10 parts of mass concentrations be 30% hydroperoxidation 1~
It 3 hours, centrifuges, collects bottom solid；It is washed, then is washed with deionized to neutrality with hydrochloric acid solution, by gained filter cake
Vacuum drying, obtains graphite oxide.
3. a kind of preparation method of polyaminopropylsilsesquioxane doping nickel coated graphene according to claim 2,
It is characterized in that, the mass concentration of the concentrated sulfuric acid is 98%；The phosphoric acid quality a concentration of 85%.
4. a kind of preparation method of polyaminopropylsilsesquioxane doping nickel coated graphene according to claim 2,
It is characterized in that, described washed with hydrochloric acid solution is that the hydrochloric acid solution for being 4~8% with mass concentration washes twice.
5. a kind of preparation method of polyaminopropylsilsesquioxane doping nickel coated graphene according to claim 2,
It is characterized in that, described be dried in vacuo gained filter cake is that gained filter cake is placed in drying in 50~60 DEG C of vacuum drying chamber.
6. a kind of preparation method of polyaminopropylsilsesquioxane doping nickel coated graphene according to claim 1,
It is characterized in that, step (1) the polyaminopropylsilsesquioxane solution manufacturing method is：In terms of mass fraction, 10 parts of γ-are added
Aminopropyl triethoxysilane or N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, 80~100 parts of absolute ethyl alcohols and 5~
10 parts of deionized waters are stirred to react 3~5 hours under room temperature, obtain polyaminopropylsilsesquioxane solution.
7. a kind of preparation method of polyaminopropylsilsesquioxane doping nickel coated graphene according to claim 1,
It is characterized in that, step (2) inorganic nickel-hydrazine hydrate complex solution preparation method is：Under room temperature, by inorganic nickel and 50%
Hydrazine hydrate in mass ratio 1：4~6 are added in reactor, and the deionized water that quality is 5~8 times of inorganic nickel is then added, mixes
It closes uniformly to obtain the final product；The inorganic nickel is nickel sulfate or nickel chloride；The molecular formula of the hydrazine hydrate is N2H4·H2O。
8. a kind of preparation method of polyaminopropylsilsesquioxane doping nickel coated graphene according to claim 1,
It is characterized in that, step (2) stirring is mechanical agitation, and the rotating speed of stirring is 15~30r/min.
9. a kind of preparation method of polyaminopropylsilsesquioxane doping nickel coated graphene according to claim 1,
It is characterized in that, step (2) the vacuum drying time is 4~8 hours.
10. a kind of preparation method of polyaminopropylsilsesquioxane doping nickel coated graphene, it is characterised in that including following step
Suddenly：
(1) graphite oxide and absolute ethyl alcohol are pressed 1：60~80 mass ratio mixing, adds graphite oxide 10~20 mass times
Polyaminopropylsilsesquioxane solution, stirred 3~5 hours at 50~70 DEG C, then go to ultrasonic cleaner and surpassed
Sonication, ultrasonic power are 60W~150W, and ultrasonic time is 10~30 minutes, is stood, and is filtered to remove solid precipitation, is gathered
Aminopropyl silsesquioxane modified graphene oxide suspension；
(2) nickel acetate-hydrazine hydrate complex solution is added to polyaminopropylsilsesquioxane modified graphite oxide obtained by step (1)
In alkene suspension, the quality for controlling nickel acetate is 1~3 times of graphite oxide, and stirring is reacted 1~3 hour at 60~80 DEG C,
It centrifuges, is washed with absolute ethyl alcohol and deionized water, vacuum drying adulterates nickel coated to get to polyaminopropylsilsesquioxane
Graphene；
The nickel acetate-hydrazine hydrate complex solution preparation method is：Under room temperature, by nickel acetate and 50% hydrazine hydrate in mass ratio 1：
4~6 are added in reactor, and the deionized water that quality is 5~8 times of nickel acetate is then added, is uniformly mixed to obtain the final product；The hydration
The molecular formula of hydrazine is N2H4·H2O。
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