CN104629275A - Preparation method of high-conductive-stability graphene composite material - Google Patents
Preparation method of high-conductive-stability graphene composite material Download PDFInfo
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- CN104629275A CN104629275A CN201310544741.1A CN201310544741A CN104629275A CN 104629275 A CN104629275 A CN 104629275A CN 201310544741 A CN201310544741 A CN 201310544741A CN 104629275 A CN104629275 A CN 104629275A
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Abstract
The invention discloses a preparation method of a high-conductive-stability graphene composite material, and is characterized in that the preparation method comprises the following steps: (1) obtaining graphene oxide; (2) dispersing graphene oxide in N-methyl pyrrolidone, and carrying out ultrasonic treatment to obtain an evenly-dispersed graphite oxide suspension; (3) adding a copper sulfate solution, while stirring, adding vitamin C, and refluxing; (4) adding a polylactic acid solution, and thus obtaining a master batch; and (5) adding a mixture composed of a titanium powder and asphalt into the master batch, drying, and grinding to obtain the graphene composite material. An agglomeration phenomenon cannot happen, graphitization plays a catalytic role, and the thermal conductivity of the material is greatly improved. The element titanium improves mechanical strength and oxidation resistance of the material. Nano Cu particles have excellent electrical conductivity and heat stability, and the preparation method has the advantages of simple process, convenient operation, high production efficiency and good industrialized production prospects.
Description
Technical field
The invention belongs to technical field of composite materials, particularly relate to a kind of preparation method of high connductivity stability graphene composite material.
Background technology
Graphite-base composite material is as matrix or reinforcement by materials such as graphite, by the material that recombining process combines, belong to inorganic non-metallic based composites, it is the material that heatproof is the highest, its intensity raises along with temperature and increases, be about 2500 DEG C in temperature and reach maximum value, there is good corrosion resistance and thermal shock resistance simultaneously.
Poly(lactic acid) is a kind of novel biodegradable material, and the starch material using reproducible plant resources to propose is made.Starch material obtains glucose via saccharification, then makes highly purified lactic acid by glucose and certain strain fermentation, then synthesizes the poly(lactic acid) of certain molecular weight by chemical synthesis process.It has good biodegradability, can be degradable by occurring in nature microorganism after using, and final generation carbonic acid gas and water, free from environmental pollution, this is highly beneficial to protection of the environment, is generally acknowledged environment-friendly material.
Poly(lactic acid) has the best tensile strength and extensibility, poly(lactic acid) also can various common process mode be produced, such as: fusing extrusion moulding, ejection formation, blowfilm shaping, foaming and vacuum forming, have similar molding condition with widely used polymkeric substance, and it also has the printing performance identical with conventional films in addition.So, poly(lactic acid) just can answer the demand of variant industry, makes application product miscellaneous.
Graphene is the monatomic carbon-coating be combined into sp2 hydridization by carbon atom, and structure is highly stable, has excellent mechanical property, peculiar electrical properties and good thermal property.The present inventor consider, by Graphene and poly-lactic acid material blended, impelling strength and the resistance toheat of poly-lactic acid material can be improved simultaneously.
The specific surface area of copper nanoparticle is large, Active sites number is many, is excellent catalyzer in metallurgy and petrochemical complex.In the application of structural timber, Nanometer Copper crystalline material has good tensile property and resistance to impact shock, and its mechanical property has lifting clearly compared with traditional copper material.Therefore the development of copper nanoparticle and the matrix material relevant with it has important theory significance and practical value.
Summary of the invention
The technical problem to be solved in the present invention is to provide kind of a preparation method for high connductivity stability graphene composite material, and the matrix material that the present invention obtains has good toughness, intensity and resistance toheat.
The technical scheme that the present invention takes is:
A preparation method for high connductivity stability graphene composite material, is characterized in that, comprise the steps:
(1) with oxygenant, the graphite after preoxidation is oxidized, obtains graphene oxide;
(2) graphene oxide is scattered in N-methyl-2-pyrrolidone ultrasonic, obtains finely dispersed graphite oxide suspension;
(3) by graphite oxide suspension sodium hydrate regulator solution pH=9-10, add the copper-bath that concentration is 1.5-2.5g/L, under agitation, add the vitamins C of 3 times of graphite oxide quality, at 85-95 DEG C of back flow reaction 2.5-3h;
(4) be 0.6-0.8% by mass percent, molecular weight is that more than 50000 equally distributed PLA solution join in above-mentioned phegma, and the volume ratio of PLA solution and phegma is 1:5, and control temperature is 65-70 DEG C will stir 5-6h, stratification, obtains masterbatch after filtration;
(5) in masterbatch, add size range is 300-400 u m, and mass ratio is the titanium valve of 10:3: the mixture of pitch composition, and the mass ratio of masterbatch and mixture is 20:1, raised temperature is 150-180 DEG C and stirs 20-30min, drying, grinding, obtains graphene composite material.
In above-mentioned step (1), oxygenant is the one in the vitriol oil, potassium permanganate, Potassium Persulphate, Vanadium Pentoxide in FLAKES and hydrogen peroxide.
In above-mentioned steps (2), the concentration of graphene oxide dispersion is 0.3-0.6mg/mL;
In above-mentioned steps (3), the mass ratio of graphite oxide and copper sulfate is 1:1-1.5.
In above-mentioned step (4), PLA solution is the tetrahydrofuran solution of poly(lactic acid) or the chloroform soln of poly(lactic acid).
Above-mentioned steps (5) medium pitch is the petroleum pitch that softening temperature is positioned between 90-100 DEG C.
The beneficial effect of the invention:
Compared with prior art, graphene oxide is dispersed in poly(lactic acid) by method provided by the invention, and aggregation phenomenon can not occur, greying plays katalysis, and correspondingly, material conducts heat performance improves greatly.With the addition of other element titanium among material, thus the physical strength of material and antioxidant property are all increased.Be coated on the surface of graphene platelet nanometer Cu uniform particle, make it have excellent conductivity and thermal stability, present invention process is simple, and easy to operate, production efficiency is high, has good industrial production prospect.
Embodiment
Embodiment 1
A preparation method for high connductivity stability graphene composite material, is characterized in that, comprise the steps:
(1) with hydrogen peroxide, the graphite after preoxidation is oxidized, obtains graphene oxide;
(2) be scattered in N-methyl-2-pyrrolidone by graphene oxide ultrasonic, obtaining concentration is the finely dispersed graphite oxide suspension of 0.5mg/mL;
(3) by graphite oxide suspension sodium hydrate regulator solution pH=9-10, add the copper-bath that concentration is 2g/L, the mass ratio of graphite oxide and copper sulfate is 1:1.3, under agitation, add the vitamins C of 3 times of graphite oxide quality, at 90 DEG C of back flow reaction 3h;
(4) be 0.8% by mass percent, molecular weight is that the chloroform soln of more than 50000 equally distributed poly(lactic acid) joins in above-mentioned phegma, and the volume ratio of PLA solution and phegma is 1:5, and control temperature is 70 DEG C will stir 5h, stratification, obtains masterbatch after filtration;
(5) in masterbatch, add size range is 300-400 u m, mass ratio is the titanium valve of 10:3: softening temperature is positioned at the mixture of the petroleum pitch composition between 90-100 DEG C, the mass ratio of masterbatch and mixture is 20:1, raised temperature is 170 DEG C and stirs 25min, dry, grinding, obtains graphene composite material.
Embodiment 2
A preparation method for high connductivity stability graphene composite material, is characterized in that, comprise the steps:
(1) with the vitriol oil, the graphite after preoxidation is oxidized, obtains graphene oxide;
(2) be scattered in N-methyl-2-pyrrolidone by graphene oxide ultrasonic, obtaining concentration is the finely dispersed graphite oxide suspension of 0.5mg/mL;
(3) by graphite oxide suspension sodium hydrate regulator solution pH=9-10, add the copper-bath that concentration is 2g/L, the mass ratio of graphite oxide and copper sulfate is 1:1.2, under agitation, add the vitamins C of 3 times of graphite oxide quality, at 85 DEG C of back flow reaction 3h;
(4) be 0.6% by mass percent, molecular weight is that the chloroform soln of more than 50000 equally distributed poly(lactic acid) joins in above-mentioned phegma, and the volume ratio of PLA solution and phegma is 1:5, and control temperature is 65 DEG C will stir 6h, stratification, obtains masterbatch after filtration;
(5) in masterbatch, add size range is 300-400 u m, mass ratio is the titanium valve of 10:3: softening temperature is positioned at the mixture of the petroleum pitch composition between 90-100 DEG C, the mass ratio of masterbatch and mixture is 20:1, raised temperature is 150 DEG C and stirs 30min, dry, grinding, obtains graphene composite material.
Embodiment 3
A preparation method for high connductivity stability graphene composite material, is characterized in that, comprise the steps:
(1) with potassium permanganate, the graphite after preoxidation is oxidized, obtains graphene oxide;
(2) be scattered in N-methyl-2-pyrrolidone by graphene oxide ultrasonic, obtaining concentration is the finely dispersed graphite oxide suspension of 0.5mg/mL;
(3) by graphite oxide suspension sodium hydrate regulator solution pH=9-10, add the copper-bath that concentration is 2.5g/L, the mass ratio of graphite oxide and copper sulfate is 1:1.5, under agitation, add the vitamins C of 3 times of graphite oxide quality, at 95 DEG C of back flow reaction 2.5h;
(4) be 0.8% by mass percent, molecular weight is that the chloroform soln of more than 50000 equally distributed poly(lactic acid) joins in above-mentioned phegma, and the volume ratio of PLA solution and phegma is 1:5, and control temperature is 70 DEG C will stir 5h, stratification, obtains masterbatch after filtration;
(5) in masterbatch, add size range is 300-400 u m, mass ratio is the titanium valve of 10:3: softening temperature is positioned at the mixture of the petroleum pitch composition between 90-100 DEG C, the mass ratio of masterbatch and mixture is 20:1, raised temperature is 180 DEG C and stirs 20min, dry, grinding, obtains graphene composite material.
Claims (5)
1. a preparation method for high connductivity stability graphene composite material, is characterized in that, comprises the steps:
(1) with oxygenant, the graphite after preoxidation is oxidized, obtains graphene oxide;
(2) graphene oxide is scattered in N-methyl-2-pyrrolidone ultrasonic, obtains finely dispersed graphite oxide suspension;
(3) by graphite oxide suspension sodium hydrate regulator solution pH=9-10, add the copper-bath that concentration is 1.5-2.5g/L, under agitation, add the vitamins C of 3 times of graphite oxide quality, at 85-95 DEG C of back flow reaction 2.5-3h;
(4) be 0.6-0.8% by mass percent, molecular weight is that more than 50000 equally distributed PLA solution join in above-mentioned phegma, and the volume ratio of PLA solution and phegma is 1:5, and control temperature is 65-70 DEG C will stir 5-6h, stratification, obtains masterbatch after filtration;
(5) in masterbatch, add size range is 300-400 u m, and mass ratio is the titanium valve of 10:3: the mixture of pitch composition, and the mass ratio of masterbatch and mixture is 20:1, raised temperature is 150-180 DEG C and stirs 20-30min, drying, grinding, obtains graphene composite material.
2. the preparation method of a kind of high connductivity stability graphene composite material according to claim 1, is characterized in that, in described step (1), oxygenant is the one in the vitriol oil, potassium permanganate, Potassium Persulphate, Vanadium Pentoxide in FLAKES and hydrogen peroxide.
3. the preparation method of a kind of high connductivity stability graphene composite material according to claim 1, is characterized in that, in described step (2), the concentration of graphene oxide dispersion is 0.3-0.6mg/mL;
The preparation method of a kind of high connductivity stability graphene composite material according to claim 1, is characterized in that, in described step (3), the mass ratio of graphite oxide and copper sulfate is 1:1-1.5.
4. the preparation method of a kind of high connductivity stability graphene composite material according to claim 1, is characterized in that, in described step (4), PLA solution is the tetrahydrofuran solution of poly(lactic acid) or the chloroform soln of poly(lactic acid).
5. the preparation method of a kind of high connductivity stability graphene composite material according to claim 1, it is characterized in that, described step (5) medium pitch is the petroleum pitch that softening temperature is positioned between 90-100 DEG C.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105885906A (en) * | 2016-04-12 | 2016-08-24 | 方大炭素新材料科技股份有限公司 | Preparation method of oxidized graphene modified medium-temperature coal tar pitch |
| CN106189297A (en) * | 2016-08-17 | 2016-12-07 | 河南师范大学 | A kind of conductive asphalt and preparation method thereof |
| CN106280506A (en) * | 2016-08-17 | 2017-01-04 | 河南师范大学 | A kind of novel modified asphalt with antistrip performance and preparation method thereof |
| CN106280508A (en) * | 2016-08-17 | 2017-01-04 | 河南师范大学 | A kind of novel conductive Colophonium and preparation method thereof |
| CN106906028A (en) * | 2017-03-16 | 2017-06-30 | 柯鹏 | A kind of Graphene antiwear composite agent and preparation method thereof |
| CN109148887A (en) * | 2018-08-30 | 2019-01-04 | 上海力信能源科技有限责任公司 | A kind of production method of graphene-carbon nano-fiber conductive agent |
| CN110358314A (en) * | 2019-07-05 | 2019-10-22 | 广西清鹿新材料科技有限责任公司 | A kind of preparation method of graphene composite asphalt |
| CN115611264A (en) * | 2022-11-10 | 2023-01-17 | 泰安市法拉第能源科技有限公司 | Asphalt-based hard carbon negative electrode material, preparation method thereof and sodium ion battery |
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- 2013-11-07 CN CN201310544741.1A patent/CN104629275A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105885906A (en) * | 2016-04-12 | 2016-08-24 | 方大炭素新材料科技股份有限公司 | Preparation method of oxidized graphene modified medium-temperature coal tar pitch |
| CN106189297A (en) * | 2016-08-17 | 2016-12-07 | 河南师范大学 | A kind of conductive asphalt and preparation method thereof |
| CN106280506A (en) * | 2016-08-17 | 2017-01-04 | 河南师范大学 | A kind of novel modified asphalt with antistrip performance and preparation method thereof |
| CN106280508A (en) * | 2016-08-17 | 2017-01-04 | 河南师范大学 | A kind of novel conductive Colophonium and preparation method thereof |
| CN106189297B (en) * | 2016-08-17 | 2018-10-19 | 河南师范大学 | A kind of conductive asphalt and preparation method thereof |
| CN106280508B (en) * | 2016-08-17 | 2018-12-14 | 河南师范大学 | A kind of conductive asphalt and preparation method thereof |
| CN106280506B (en) * | 2016-08-17 | 2019-04-30 | 河南师范大学 | A kind of modified pitch and preparation method thereof with antistrip performance |
| CN106906028A (en) * | 2017-03-16 | 2017-06-30 | 柯鹏 | A kind of Graphene antiwear composite agent and preparation method thereof |
| CN106906028B (en) * | 2017-03-16 | 2019-07-30 | 深圳市百顺源节能科技有限公司 | A kind of graphene antiwear composite agent and preparation method thereof |
| CN109148887A (en) * | 2018-08-30 | 2019-01-04 | 上海力信能源科技有限责任公司 | A kind of production method of graphene-carbon nano-fiber conductive agent |
| CN110358314A (en) * | 2019-07-05 | 2019-10-22 | 广西清鹿新材料科技有限责任公司 | A kind of preparation method of graphene composite asphalt |
| CN115611264A (en) * | 2022-11-10 | 2023-01-17 | 泰安市法拉第能源科技有限公司 | Asphalt-based hard carbon negative electrode material, preparation method thereof and sodium ion battery |
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