CN106883456A - 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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- CN106883456A CN106883456A CN201710071475.3A CN201710071475A CN106883456A CN 106883456 A CN106883456 A CN 106883456A CN 201710071475 A CN201710071475 A CN 201710071475A CN 106883456 A CN106883456 A CN 106883456A
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- nickel
- polyaminopropylsilsesquioxane
- preparation
- nickel coated
- coated graphene
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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 96
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 69
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 36
- 239000010439 graphite Substances 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000005119 centrifugation Methods 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 238000001291 vacuum drying Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- KXIFSSCKBFYNMX-UHFFFAOYSA-N hydrazine;nickel;hydrate Chemical compound O.[Ni].NN KXIFSSCKBFYNMX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 14
- 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 13
- 229910001868 water Inorganic materials 0.000 claims description 13
- -1 Aminopropyl Chemical group 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 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
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 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
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims 9
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims 1
- 238000000527 sonication Methods 0.000 claims 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims 1
- 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
- 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
- 239000003643 water by type Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005259 measurement 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
- 239000013078 crystal Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 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
- 238000001556 precipitation Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [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
- 238000005253 cladding Methods 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
- 238000005034 decoration Methods 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
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 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 a kind of preparation method of polyaminopropylsilsesquioxane doping nickel coated Graphene；The method first mixes graphite oxide and absolute ethyl alcohol, add polyaminopropylsilsesquioxane solution, stirred 3~5 hours at 50~70 DEG C, then go to ultrasonic cleaner carry out it is ultrasonically treated, it is ultrasonically treated, stand, 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, centrifugation, washing, vacuum drying obtains polyaminopropylsilsesquioxane doping nickel coated Graphene.The present invention provides a kind of preparation method without palladium, and polyaminopropylsilsesquioxane doping nickel coated Graphene resistivity is less than 0.1 Ω .cm, and saturation magnetization is more than 3.5A.m2/ kg, magnetic conductivity is more than 0.3mH/m.
Description
Technical field
The present invention relates to a kind of method of metal-coated graphite alkene, more particularly to nickel is coated in graphenic surface without palladium
Method, and in particular to a kind of polyaminopropylsilsesquioxane adulterates the preparation method of nickel coated Graphene, belongs to inorganic material
Technical field of modification.
Background technology
Graphene is the only one layer of atomic thickness being made up of carbon atomTwo dimensional crystal, with density is small, conductive and heat-conductive,
The advantages of good stability, but its magnetic loss consumption is weak, and magnetic conductivity is low.Metallic nickel electrical conductivity is high, and magnetic conductivity is high, effectiveness
It is good, metallic nickel is coated in graphenic surface 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 the method is led to
Cross and Graphene be roughened, be sensitized, activated, reduced, nickel coating is added to Graphene using the technique of chemical plating；Li Shumei etc.
[preparation of nickel coated reduced graphene composite 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, obtains reducing stone as reducing agent reduction-oxidation graphite with hydrazine hydrate
Black alkene, and to reduced graphene by the amorphous nickel-phosphor alloy of Surface coating after alkaline chemical nickel-plating treatment, resistivity reaches
To 4.5m Ω m, hence it is evident that better than the electric conductivity of reduced graphene (40.6m Ω m).
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 to environment, runs counter to the development side without palladium nickel plating
To；Additionally, having used sodium hypophosphite in reducing agent, the phosphorus of high level is contained in gained coating, so gained Graphene electricity
Resistance rate is still higher.Thus, using significant without palladium nickel plating process and the further resistivity for reducing nickel coated Graphene.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of polyaminopropylsilsesquioxane doping nickel coated stone without palladium
The preparation method of black alkene, obtains resistivity less than 0.1 Ω .cm, and saturation magnetization is more than 3.5A.m2/ kg, magnetic conductivity is more than
0.3mH/m, the polyaminopropylsilsesquioxane doping nickel coated Graphene with excellent conductive and permeance property.
During the present invention in graphite oxide ultrasound by peeling off into Graphene, polyaminopropylsilsesquioxane is added,
Its surface is set to connect the amino for being formed with nickel ion and relatively stablizing coordinate bond；So nickel ion is gone back in addition to being coordinated with hydrazine hydrate
It is coordinated with the amino on graphenic surface polyaminopropylsilsesquioxane, in 60 DEG C~80 DEG C, under alkaline environment, the divalence of complexing
Nickel ion is gradually reduced by hydrazine hydrate, and tiny nickel particle is reduced into graphenic surface, and the nickel particle for initially forming is played into
Core is acted on, and is catalyzed more nickel ions and is constantly reduced in graphenic surface, and is grown in graphenic surface well, is so existed
Without having coated uniform, fine and close, a small amount of polyaminopropylsilsesquioxane in graphenic surface using chemical plating method under conditions of palladium
The metallic nickel of doping, the Graphene for obtaining has excellent conduction and capability of electromagnetic shielding；And high for filling-modified, imparting
During 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, comprises the following steps：
(1) graphite oxide and absolute ethyl alcohol are pressed 1：60~80 mass ratio mixing, adds the matter of graphite oxide 10~20
The polyaminopropylsilsesquioxane solution of amount times, stirs 3~5 hours at 50~70 DEG C, then goes to ultrasonic cleaner and enters
Row is ultrasonically treated, and ultrasonic power is 60W~150W, and ultrasonic time is 10~30 minutes, is stood, and is filtered to remove solids of sedimentation, is obtained
To polyaminopropylsilsesquioxane modified graphene oxide suspension；
(2) inorganic nickel-hydrazine hydrate complex solution is added to step (1) the modified oxygen of gained polyaminopropylsilsesquioxane
In graphite alkene suspension, it is 1~3 times of graphite oxide to control the quality of inorganic nickel, and stirring reacts 1 at 60~80 DEG C
~3 hours, centrifugation was washed with absolute ethyl alcohol and deionized water, and vacuum drying obtains polyaminopropylsilsesquioxane and mix
Miscellaneous nickel coated Graphene.
Further to 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
55~65 DEG C are warming up to after 1~4 hour, are reacted 8~12 hours, be subsequently poured into 200~300 portions of frozen water, add 5~10 parts of matter
Amount concentration is 30% hydroperoxidation 1~3 hour, and bottom solid is collected in centrifugation；Washed with hydrochloric acid solution, then spent
Ion water washing, by the vacuum drying of gained filter cake, obtains graphite oxide to neutrality.
Preferably, the mass concentration of the concentrated sulfuric acid is 98%；The phosphoric acid quality concentration is 85%.
Preferably, described washing with hydrochloric acid solution is washed twice with the hydrochloric acid solution that mass concentration is 4~8%.
Preferably, described is that gained filter cake is placed in 50~60 DEG C of vacuum drying chamber to do by the vacuum drying of gained filter cake
It is dry.
Preferably, in terms of mass fraction, the consumption of the frozen water is 200~300 parts.
Preferably, step (1) the polyaminopropylsilsesquioxane solution manufacturing method is：In terms of mass fraction, add
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, stirring reaction 3~5 hours under normal temperature obtain polyaminopropylsilsesquioxane solution.
Preferably, step (2) inorganic nickel-hydrazine hydrate complex solution preparation method is：Under normal temperature, by inorganic nickel
With 50% hydrazine hydrate in mass ratio 1：4~6 are added in reactor, are subsequently adding the deionization that quality is 5~8 times of inorganic nickel
Water, it is well mixed to obtain 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.
The present invention compared with prior art, has the following effects that：
(1) the inventive method realizes nickel coated Graphene under conditions of without palladium, and process is simple is environment-friendly, overcomes
Prior art is required to use palladium bichloride, not only complex process, and processing cost is higher, and serious precious metal palladium is caused to environment
Pollution.
(2) nickel coated Graphene resistivity prepared by the inventive method is less than 0.1 Ω .cm, lower than prior art nearly one
The order of magnitude, electric conductivity is higher.
(3) nickel coated Graphene saturation magnetization prepared by the inventive method is more than 3.5A.m2/ kg, magnetic conductivity is more than
0.3mH/m, its saturation magnetization and magnetic conductivity distinguish high by 79% and 67% than prior art, and magnetic conductance is stronger, than existing skill
Art product has obvious advantage.
(4) the technology of the present invention is adulterated polyaminopropylsilsesquioxane in nickel coated Graphene, and a small amount of organic group is deposited
Adhesion and compatibility with polymer resin matrix will largely increased, it is not necessary to be surface-treated and be capable of achieving
In the base dispersed.
Brief description of the drawings
Fig. 1 is the X-ray diffraction of the gained polyaminopropylsilsesquioxane of the embodiment of the present invention 1 doping nickel coated Graphene
Figure.
Fig. 2 is the SEM-EDS figures of the gained polyaminopropylsilsesquioxane of the embodiment of the present invention 1 doping nickel coated Graphene.
Specific embodiment
Content for a better understanding 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：Add the 10g gamma-aminopropyl-triethoxy-silane (trades mark：CG-
550, Nanjing Chen Gong organosilicon materials Co., Ltd), 100g absolute ethyl alcohols (analysis pure) and 5g deionized waters burn for tri- mouthfuls in 250ml
In bottle, stirring reaction 5 hours under normal temperature obtain polyaminopropylsilsesquioxane solution；
(2) inorganic nickel-hydrazine hydrate complex solution is prepared：Under normal temperature, 1g nickel sulfates (analysis is pure), 4g are sequentially added
50% hydrazine hydrate (analysis pure) and 8g deionized waters are well mixed and obtain final product in 50ml beakers；
(3) graphite oxide is prepared：Under condition of ice bath, sequentially adding 1g graphite, 6g potassium permanganate, 25g mass concentrations is
98% concentrated sulfuric acid and the phosphoric acid that 6g mass concentrations are 85%, stirring are warming up to 55 DEG C after 1 hour, react 8 hours, are subsequently poured into
In 300g frozen water, the hydroperoxidation 1 hour that 10g mass concentrations are 30% is added, bottom solid is collected in centrifugation；With
Mass concentration is that 8% hydrochloric acid solution is washed twice, then is washed with deionized to neutrality, and gained filter cake is placed in into 60 DEG C true
Dried 10 hours in empty drying box, obtain 0.255g Tan solid shape graphite oxides；Graphite (GR) used is Alfa Aesar
Co., Ltd's product, other are AR；
(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 then going to ultrasonic cleaner is carried out
Ultrasonically treated, ultrasonic power is 60W, and ultrasonic time is 30 minutes, is then stood, and is filtered to remove a small amount of solids of sedimentation, is obtained
Polyaminopropylsilsesquioxane modified graphene oxide suspension；The inorganic nickel that addition 3.9g is prepared in the suspension-
Hydrazine hydrate complex solution, mechanical agitation, mixing speed is 15r/min, is warmed up to 80 DEG C, and nickel ion is hydrated in graphenic surface
Hydrazine is reduced into the precipitation of nickel simple substance, and room temperature is down to after 1 hour, and centrifugation is washed, at 55 DEG C with absolute ethyl alcohol and deionized water
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 is copper target λ=0.15418nm, 10 °~85 ° of the angle of diffraction) test, acquired results are such as
Accompanying drawing 1, on spectrogram 2 θ be 44.5 °, 51.8 °, 76.4 ° place occur three diffraction maximums, and diffraction peak intensity greatly, half-peak breadth is smaller,
(111), (200), (220) three crystal faces of nickel are corresponded to respectively, are the polygonal nickel simple substance of Emission in Cubic.
Using ESEM-electron spectrometer (Britain INCA 250) to polyaminopropylsilsesquioxane doping nickel coated
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, its mass fraction is 93.12%, also contains a small amount of carbon, oxygen and element silicon, and mass fraction is respectively
4.98%th, 1.27% and 0.63%.
Test above shows that the present embodiment realizes the cladding of the nickel on Graphene, and poly- aminopropyl times is doped with coating
Half siloxanes.
The polyaminopropylsilsesquioxane of diameter 1cm manufactured in the present embodiment is adulterated nickel coated using four-point probe
Graphene film carries out the test of resistivity, and 5 average values of measurement are taken during test, obtains resistivity for 0.07 Ω .cm；Using
Polyaminopropylsilsesquioxane of the U.S. Lake-Shore7410 types vibrating specimen magnetometer to diameter 1cm manufactured in the present embodiment
Doping nickel coated graphene film carries out magnetic property analysis, and its saturation magnetization Ms is 4.81A.m2/ kg, magnetic conductivity is
0.33mH/m。
Embodiment 2
(1) polyaminopropylsilsesquioxane solution is prepared：Add 10gN-(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 there-necked flasks, stirring reaction 3 hours under normal temperature obtain polyaminopropylsilsesquioxane solution；
(2) inorganic nickel-hydrazine hydrate complex solution is prepared：Under normal temperature, 1g nickel chlorides (analysis is pure), 6g are sequentially added
50% hydrazine hydrate (analysis pure) and 5g deionized waters are well mixed and obtain final product in 50ml beakers；
(3) graphite oxide is prepared：Under condition of ice bath, sequentially adding 1g graphite, 5g potassium permanganate, 15g mass concentrations is
98% concentrated sulfuric acid and the phosphoric acid that 5g mass concentrations are 85%, stirring are warming up to 65 DEG C after 2 hours, react 10 hours, then fall
In entering 250g frozen water, the hydroperoxidation 2 hours that 5g mass concentrations are 30% is added, bottom solid is collected in centrifugation；With
Mass concentration is that 4% hydrochloric acid solution is washed twice, then is washed with deionized to neutrality, and gained filter cake is placed in into 50 DEG C true
Dried 14 hours in empty drying box, obtain 0.213g Tan solid shape graphite oxides；Graphite (GR) used is Alfa Aesar
Co., Ltd's product, other are AR；
(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 then going to ultrasonic cleaner is carried out
Ultrasonically treated, ultrasonic power is 100W, and ultrasonic time is 10 minutes, is stood, and is filtered to remove a small amount of solids of sedimentation, obtains poly- ammonia
Propylsilsesquioxane modified graphene oxide suspension；Inorganic nickel-the hydration for adding 1.2g to be prepared in the suspension
Hydrazine complex solution, mechanical agitation, mixing speed is 30r/min, is warmed up to 60 DEG C, nickel ion graphenic surface by hydrazine hydrate also
It is former to be separated out into nickel simple substance, room temperature is down to after 3 hours, centrifugation is washed, the vacuum at 50 DEG C with absolute ethyl alcohol and deionized water
Dry 8 hours, obtain polyaminopropylsilsesquioxane doping nickel coated Graphene；Using four-point probe to diameter 1cm's
Polyaminopropylsilsesquioxane doping nickel coated graphene film carries out the test of resistivity, takes 5 average values of measurement, obtains
Resistivity is 0.06 Ω .cm；Using U.S. Lake-Shore7410 type vibrating specimen magnetometer analyzing magnetic energy, its saturated magnetization
Intensity Ms is 5.48A.m2/ kg, magnetic conductivity is 0.37mH/m.
Embodiment 3
(1) polyaminopropylsilsesquioxane solution is prepared：Add 10gN-Aminoethyl-γ-Aminopropyl trimethoxysilane,
In 250ml there-necked flasks, stirring reaction 4 hours under normal temperature obtain poly- ammonia for 90g absolute ethyl alcohols (analysis is pure) and 8g deionized waters
Propylsilsesquioxane solution；
(2) inorganic nickel-hydrazine hydrate complex solution is prepared：Under normal temperature, 1g nickel acetates (analysis is pure), 5g are sequentially added
50% hydrazine hydrate (analysis pure) and 6g deionized waters are well mixed and obtain final product in 50ml beakers；
(3) graphite oxide is prepared：Under condition of ice bath, sequentially adding 1g graphite, 4g potassium permanganate, 20g mass concentrations is
98% concentrated sulfuric acid and the phosphoric acid that 4g mass concentrations are 85%, stirring are warming up to 60 DEG C after 4 hours, react 12 hours, then fall
In entering 200g frozen water, the hydroperoxidation 3 hours that 7g mass concentrations are 30% is added, bottom solid is collected in centrifugation；With
Mass concentration is that 6% hydrochloric acid solution is washed twice, then is washed with deionized to neutrality, and gained filter cake is placed in into 55 DEG C true
Dried 12 hours in empty drying box, obtain 0.192g Tan solid shape graphite oxides；Graphite (GR) used is Alfa Aesar
Co., Ltd's product, other are AR；
(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, is then gone to ultrasonic cleaner and is entered
Row is ultrasonically treated, and ultrasonic power is 150W, and ultrasonic time is 20 minutes, is stood, and is filtered to remove a small amount of solids of sedimentation, is gathered
Aminopropyl silsesquioxane modified graphene oxide suspension；Inorganic nickel-the water for adding 2.4g to be prepared in the suspension
Hydrazine complex solution is closed, mechanical agitation, mixing speed is 20r/min, is warming up to 70 DEG C, and nickel ion is in graphenic surface by hydrazine hydrate
The precipitation of nickel simple substance is reduced into, room temperature is down to after 2 hours, centrifugation is washed with absolute ethyl alcohol and deionized water, true at 60 DEG C
Sky is dried 6 hours, obtains polyaminopropylsilsesquioxane doping nickel coated Graphene；Using four-point probe to diameter 1cm
Polyaminopropylsilsesquioxane doping nickel coated graphene film carry out the test of resistivity, take 5 average values of measurement, obtain
It is 0.08 Ω .cm to resistivity；Using U.S. Lake-Shore7410 type vibrating specimen magnetometer analyzing magnetic energy, its saturation magnetic
It is 3.59A.m to change intensity Ms2/ kg, magnetic conductivity is 0.32mH/m.
Comparative example：Li Shumei etc. is in " preparation of nickel coated reduced graphene composite and performance study, plating and essence
Palladium active oxidation graphite is used in decorations, 2015,37 (9), 12-14, a 18 " text, hydrazine hydrate+sodium hypophosphite reduction is obtained nickel coated
Graphene composite material, with the composite as comparative example, the resistivity reported is 0.45 Ω cm, saturation magnetization Ms
It is 2.01A.m2/ kg, magnetic conductivity is 0.1916mH/m.
By obtained by embodiment 1,2 and 3 polyaminopropylsilsesquioxane doping nickel coated Graphene and comparative example it is each
Performance is compared and understands, polyaminopropylsilsesquioxane doping nickel coated Graphene resistivity ratio prepared by the inventive method shows
There is the low nearly an order of magnitude of technology, i.e. electric conductivity is higher；Saturation magnetization and magnetic conductivity distinguish high by 79% than prior art
With 67%, magnetic conductance is stronger.
From the foregoing, it will be observed that the technology of the present invention realizes nickel coated Graphene, process is simple, environment friend under conditions of without palladium
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 increased the adhesion and compatibility with polymer resin matrix, for the modified of macromolecular material
Disperse well by need not being surface-treated, using convenient.
Claims (10)
1. a kind of polyaminopropylsilsesquioxane adulterates the preparation method of 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 the mass of graphite oxide 10~20 times
Polyaminopropylsilsesquioxane solution, at 50~70 DEG C stir 3~5 hours, then go to ultrasonic cleaner and surpassed
Sonication, ultrasonic power is 60W~150W, and ultrasonic time is 10~30 minutes, is stood, and is filtered to remove solids of sedimentation, is gathered
Aminopropyl silsesquioxane modified graphene oxide suspension；
(2) inorganic nickel-hydrazine hydrate complex solution is added to step (1) the gained modified oxidized stone of polyaminopropylsilsesquioxane
In black alkene suspension, it is 1~3 times of graphite oxide to control the quality of inorganic nickel, and stirring reacts 1~3 small at 60~80 DEG C
When, centrifugation is washed, vacuum drying with absolute ethyl alcohol and deionized water, that is, obtain polyaminopropylsilsesquioxane doping nickel
Coated graphite alkene.
2. a kind of polysilsesquioxane according to claim 1 adulterates the preparation method of nickel coated Graphene, and its feature exists
In step (1) the graphite oxide preparation method is：Under ice bath, in terms of mass fraction, sequentially add 1 part of graphite, 4~6 parts high
Potassium manganate, 15~25 parts of the concentrated sulfuric acid and 4~6 parts of phosphoric acid, stirring are warming up to 55~65 DEG C, reaction 8~12 after 1~4 hour
Hour, it is subsequently poured into 200~300 portions of frozen water, add 5~10 parts of mass concentrations to be 30% hydroperoxidation 1~3 hour,
Centrifugation, collects bottom solid；Washed with hydrochloric acid solution, then be washed with deionized to neutrality, gained filter cake vacuum is done
It is dry, obtain graphite oxide.
3. a kind of polysilsesquioxane according to claim 2 adulterates the preparation method of nickel coated Graphene, and its feature exists
In the mass concentration of the concentrated sulfuric acid is 98%；The phosphoric acid quality concentration is 85%.
4. a kind of polysilsesquioxane according to claim 2 adulterates the preparation method of nickel coated Graphene, and its feature exists
In described washing with hydrochloric acid solution is washed twice with the hydrochloric acid solution that mass concentration is 4~8%.
5. a kind of polysilsesquioxane according to claim 2 adulterates the preparation method of nickel coated Graphene, and its feature exists
In described is that gained filter cake is placed in 50~60 DEG C of vacuum drying chamber to dry by the vacuum drying of gained filter cake.
6. a kind of polysilsesquioxane according to claim 2 adulterates the preparation method of nickel coated Graphene, and its feature exists
In in terms of mass fraction, the consumption of the frozen water is 200~300 parts.
7. a kind of polysilsesquioxane according to claim 1 adulterates the preparation method of nickel coated Graphene, and its feature exists
In step (1) the polyaminopropylsilsesquioxane solution manufacturing method is：In terms of mass fraction, 10 parts of γ-aminopropyls are added
Triethoxysilane or N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, 80~100 parts of absolute ethyl alcohols and 5~10 parts go
Ionized water, stirring reaction 3~5 hours under normal temperature, obtains polyaminopropylsilsesquioxane solution.
8. a kind of polysilsesquioxane according to claim 1 adulterates the preparation method of nickel coated Graphene, and its feature exists
In step (2) inorganic nickel-hydrazine hydrate complex solution preparation method is：Under normal temperature, by inorganic nickel and 50% hydrazine hydrate
In mass ratio 1：4~6 are added in reactor, are subsequently adding the deionized water that quality is 5~8 times of inorganic nickel, are well mixed
Obtain final product；The inorganic nickel is nickel sulfate, nickel chloride or nickel acetate；The molecular formula of the hydrazine hydrate is N2H4·H2O。
9. a kind of polysilsesquioxane according to claim 1 adulterates the preparation method of nickel coated Graphene, and its feature exists
In step (2) stirring is mechanical agitation, and the rotating speed of stirring is 15~30r/min.
10. a kind of polysilsesquioxane according to claim 1 adulterates the preparation method of nickel coated Graphene, and its feature exists
In step (2) the vacuum drying time is 4~8 hours.
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| CN109010014B (en) * | 2018-08-08 | 2020-09-22 | 武汉中投汉嘉科技有限公司 | Ear acupoint pressing pill and its preparing method |
| CN112592653A (en) * | 2020-12-02 | 2021-04-02 | 江苏四达特材科技有限公司 | Preparation method of high-temperature-resistant polyimide wire enamel |
| CN112680086A (en) * | 2020-12-02 | 2021-04-20 | 江苏四达特材科技有限公司 | Nano graphene oxide modified wire enamel and preparation method thereof |
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| CN105880614A (en) * | 2015-01-12 | 2016-08-24 | 冯云 | Mesoporous material with nano nickel loaded on graphene |
| CN106366409A (en) * | 2016-08-30 | 2017-02-01 | 中北大学 | Ultra-high molecular weight polyethylene-graphene-nickel composite material and preparation method |
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| CN105880614A (en) * | 2015-01-12 | 2016-08-24 | 冯云 | Mesoporous material with nano nickel loaded on graphene |
| CN106366409A (en) * | 2016-08-30 | 2017-02-01 | 中北大学 | Ultra-high molecular weight polyethylene-graphene-nickel composite material and preparation method |
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| CN109010014B (en) * | 2018-08-08 | 2020-09-22 | 武汉中投汉嘉科技有限公司 | Ear acupoint pressing pill and its preparing method |
| CN112592653A (en) * | 2020-12-02 | 2021-04-02 | 江苏四达特材科技有限公司 | Preparation method of high-temperature-resistant polyimide wire enamel |
| CN112680086A (en) * | 2020-12-02 | 2021-04-20 | 江苏四达特材科技有限公司 | Nano graphene oxide modified wire enamel and preparation method thereof |
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