CN104003380A - Preparation method of ultra-thin graphite paper and graphene oxide composited film - Google Patents
Preparation method of ultra-thin graphite paper and graphene oxide composited film Download PDFInfo
- Publication number
- CN104003380A CN104003380A CN201410252396.9A CN201410252396A CN104003380A CN 104003380 A CN104003380 A CN 104003380A CN 201410252396 A CN201410252396 A CN 201410252396A CN 104003380 A CN104003380 A CN 104003380A
- Authority
- CN
- China
- Prior art keywords
- graphite
- graphene oxide
- acid
- ultra
- purity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a graphite material. A preparation method of an ultra-thin graphite paper and graphene oxide composited film comprises the following steps: uniformly mixing graphite with an oxidizing agent, an acid solvent and a protective agent, carrying out oxidation reaction on the obtained mixture at certain temperature, carrying out ultrasonic stirring on the obtained product so as to obtain graphene oxide, repeatedly carrying out centrifugal washing on the graphene oxide by using a hydrochloric acid and deionized water until the graphene oxide is close to neutral, and drying the obtained product so as to obtain graphene oxide; mixing another part of graphite with a nitric acid and hydrogen peroxide, adding a hydrofluoric acid, carrying out oxidation reaction on the obtained mixture under the condition that the temperature is controlled at 70-80 DEG C so as to obtain expandable graphite expanded by 200-300 times, and dehydrating, deacidifying and drying the expandable graphite so as to obtain high-purity expandable graphite; and adding the graphene oxide and the expandable graphite into a ball mill in a rate of 1-4:1 to carry out ball-milling and mixing, feeding the obtained mixture into an expansion furnace at a temperature of greater than 950 DEG C through a cyclone, feeding expanded vermicular graphite into a bunker, and calendaring the vermicular graphite for multiple times, in accordance with thickness requirements, so that an ultra-thin graphite composited film with a minimum thickness of 0.01 mm is obtained. The composited film prepared according to the invention is thin in thickness, and the highest thermal conductivity can reach over 613 W/m.k.
Description
Technical field
The present invention relates to graphite material, relate in particular to a kind of preparation method of the laminated film based on graphite material.
Background technology
Along with scientific and technological development, graphite paper is widely used in sealing material as graphite deep processed product, military affairs, space flight, national defence, the fields such as nuclear industry, played beyond thought good effect, the problem cann't be solved with other material before preferably resolving, as being used as sealing material, can replace asbestos to solve poorly sealed, the problem such as be not durable that the time is short.It is the thing that smart mobile phone grows up in recent years that graphite paper is used in the portable type electronic products such as mobile phone, notebook, has played good radiating effect, can extend continuous duration of service and not generate heat, and has improved the work-ing life of mobile phone.But along with people are more and more higher to the service requirements of product, the aspect such as producer researches and develops to lighter, thinner, more attractive in appearance, more durable development, has thinner thickness with regard to requiring as the graphite paper of radiating protective film, lighter quality, rate of heat transfer is faster.Through scientific research personnel's effort its thickness is the thinnest reach 0.04mm more than; Although but its thermal conductivity is 300W/m.k. such performance index, can apply, can't reach research staff's desired outstanding effect.Ultra-thin composite graphite film prepared by the present invention has further solved above-mentioned problem better, and the thinnest 0.01mm that reaches of its ultra-thin composite graphite film, more than its thermal conductivity can reach 613W/m.k.
Walk environment amity, the road of resource-conserving sustainable development is total purport of global development of all countries economy.Therefore electromobile replaces traditional fuel-engined vehicle greatly to improve atmospheric pollution, saves valuable petroleum resources, and according to statistics, power truck in 2013 and the total owning amount of hybrid electric vehicle surpass 1,500,000, saves oil more than 7,700,000 tons, reduces CO
2discharge 2,330 ten thousand tons.Wherein in power truck over half with ultracapacitor as power supply power, ultracapacitor is a kind of novel energy storing device, there is the advantages such as high power density (for the more than 10 times of common batteries), high cycle life (cycle index can reach more than 100,000 times), fast charging and discharging performance are good, be widely used in the AC-battery power source of military field, device for mobile communication, computer and electromobile etc.Conventionally ultracapacitor is mainly assembled by electrode active material layer, ionogen, barrier film, collector, shell etc.The energy density of existing ultracapacitor is generally lower, the factor that affects energy density mainly contains the electric capacity of electrode materials, the voltage of system, electrode materials accounts for proportion of the gross weight that electrode active material layer, collector, sheating material form etc., therefore, wherein, the quality of reduction collector is a method that effectively improves energy density.Collector is a kind of structure or part that collects electric current, and major function is that the electric current that cell active materials is produced collects, and electron channel is provided, and accelerates charge transfer, improves and discharges and recharges coulombic efficiency.As collector, need to meet the features such as specific conductivity is high, good mechanical property, quality is light, internal resistance is little.At present, in most document or in industry, anodal aluminium foil, the negative pole of adopting of general collector adopts Copper Foil, because the density of metal collector is larger, quality is heavier, the weight of general collector accounts for the 20-25% of whole battery, and the proportion that electrode materials accounts for whole battery greatly reduces, and finally causes the energy density of ultracapacitor lower.
Summary of the invention
The present invention is intended to overcome the defect of prior art, and the preparation method of the laminated film of a kind of ultrathin graphite paper and graphene oxide is provided.Laminated film specific conductivity of the present invention is high, good mechanical property, and the feature such as quality is light, and internal resistance is little, as collector, can reach very good effect for ultracapacitor.
In order to solve the problems of the technologies described above, a kind of method of high-purity expanded graphite and the ultra-thin composite graphite film of the compound preparation of graphene oxide, it comprises following step:
The preparation process of graphene oxide: at the temperature of 20 ℃, high purity graphite is mixed by 20～120:1:3～9 with oxygenant, sour solvent and a kind of protective material, be slightly heated to 35-40 ℃; Then in mixture, slowly add part pure water and stir 30 minutes, making material heat release; Opening heating unit again and elevate the temperature to 98 ℃, keep 15 minutes, add part pure water cooling mixture 10 minutes, then add pure water and 30%H2O2 heat release be cooled to room temperature again, is 5～350W ultrasonic agitation 5min～5h at power; With hydrochloric acid and pure water, repeatedly carry out centrifuge washing and approach neutrality, the dry graphene oxide powder that obtains;
High-purity expansible black lead powder preparation process: high purity graphite, concentrated nitric acid and hydrogen peroxide are added in retort in the ratio of 1:0.75:0.25, temperature remains on 16 ℃ of stirring reactions 2 hours, again through centrifuge dehydration washing to neutral, in temperature, be less than under the condition of 80 ℃ and dry and obtain high-purity expansible black lead powder;
Composite steps: above-mentioned graphene oxide and high-purity expansible black lead add and carry out ball milling in ball mill and mix in 1:1～4 ratio, again mixture is entered in the expansion furnace that temperature is greater than 950 ℃ by swirler, worm graphite after expansion enters feed bin, according to thickness requirement, worm graphite is carried out at least eight calenderings, finally obtain the ultra-thin graphite laminated film that thickness is minimal to 0.02mm.
The method of described a kind of high-purity expanded graphite and the ultra-thin composite graphite film of the compound preparation of graphene oxide, described oxygenant is a kind of of potassium permanganate, concentrated nitric acid, potassium bichromate.
The method of described a kind of high-purity expanded graphite and the ultra-thin composite graphite film of the compound preparation of graphene oxide, described sour solvent is one or more the combination being selected from chlorsulfonic acid, fluosulfonic acid, trifluoromethanesulfonic acid.
The method of described a kind of high-purity expanded graphite and the ultra-thin composite graphite film of the compound preparation of graphene oxide, described protective material is selected from trifluoroacetic acid; Phosphoric acid; Ortho-phosphoric acid; Metaphosphoric acid; Tripyrophosphoric acid; Boric acid; Trifluoroacetic anhydride; Phosphoric anhydride; Ortho-phosphoric acid acid anhydride; Metaphosphoric acid acid anhydride; Tripyrophosphoric acid acid anhydride; The combination of one or more in boron trioxide.
The method of described a kind of high-purity expanded graphite and the ultra-thin composite graphite film of the compound preparation of graphene oxide, in the preparation process of described graphene oxide, the ratio of front its consumption of the pure water adding for twice and sour solvent is suitable; The ratio of the pure water adding for the third time and hydrogen peroxide and graphite is 100:1:1.
The method of described a kind of high-purity expanded graphite and the ultra-thin composite graphite film of the compound preparation of graphene oxide, its purity of pure water is at 1～10us/cm.
The method of described a kind of high-purity expanded graphite and the ultra-thin composite graphite film of the compound preparation of graphene oxide, graphite used is high purity graphite-be 100 orders to any in 80 orders, described concentration of nitric acid is more than 65% concentrated nitric acid, and described hydrogen peroxide concentration is 30%.
The method of described a kind of high-purity expanded graphite and the ultra-thin composite graphite film of the compound preparation of graphene oxide, described binding agent is the organism such as pitch, tar or resin.
The method of described a kind of high-purity expanded graphite and the ultra-thin composite graphite film of the compound preparation of graphene oxide, described ultra-thin its sulfur-bearing of graphite laminated film is less than 1000ppm.
Ball mill Main Function of the present invention is by the monolithic layer of adhesive particle and graphene oxide or the micro-graphite flake of multi-disc layer and worm graphite uniform contact, is dispersed in worm graphite.
Heating unit temperature of the present invention is more than 200 ℃, the main carboniogenesis that rises, binding agent at high temperature first melts and recarbonizes, make graphene oxide monolithic layer or multi-disc layer (being less than 5 layers) particulate be embedded in graphite rete or be attached to graphite film surface, in any case roll, can not cause it to come off.Binding agent add the thorough problem that Graphene monolithic layer or multi-disc pull-up fall that solved,
Synthesis mechanism:
Through long ball milling, graphene oxide monolithic layer or multi-disc layer (being less than 5 layers) particulate is embedded in graphite rete or is attached to graphite film surface, because single-layer graphene thickness only has 0.35nm, multi-disc layer thickness (5 layers) also only has 3.094nm, and graphite film layer thickness is finally 0.01mm, can very easily embed or be attached to graphite film surface.Because Graphene has high conductivity and thermal conductivity, high carrier mobility, the characteristic such as electronics mobile space, high strength and hardness freely, and Graphene microplate layer is dispersed in graphite rete, has improved greatly the heat transfer of graphite rete and the speed of transmission electronic.At the graphite paper that do not have expanded graphite that Graphene adds to roll to form, there is acid group as NO because of its inside
3 -, SO
4 2-, PO
4 3-residual, its internal resistance increases, and its specific conductivity and thermal conductivity are relatively low, and the ultrathin graphite paper of the 0.04mm of existing ultrathin graphite paper thickness minimum on market of take is example, adopt double bridge method LDW-1 type carbon-graphite product resistivity tester to measure, its resistivity 4 * 10
-4s/m, adopt the laser method that shines to survey its thermal conductivity with laser heat conducting instrument and be about 306W/mK, and its thickness of ultra-thin graphite composite film of the present invention can reach 0.01mm, and resistivity can reach 10
4s/m; Thermal conductivity is 3 * 10
3w/mK, far above the traditional product on market.
It is low that the present invention compared with prior art has sulphur content, higher thermal conductivity, and specific conductivity is high, good mechanical property, quality is light, and internal resistance is little, and energy density is high; Whole production process is without sulfuric acid, and raw material is used high purity graphite, in graphite, containing S, Cl, Fe, Cu, Al, Mg, is all less than 500ppm, so the controlled sulphur content of final product is lower, is less than 600ppm.
Embodiment
A method for the ultra-thin composite graphite film of the compound preparation of high-purity expanded graphite and graphene oxide, it comprises following step:
The preparation process of graphene oxide: at the temperature of 20 ℃, high purity graphite is mixed by 20～120:1:3～9 with oxygenant, sour solvent and a kind of protective material, be slightly heated to 35-40 ℃; Then in mixture, slowly add part pure water and stir 30 minutes, making material heat release; Opening heating unit again and elevate the temperature to 98 ℃, keep 15 minutes, add part pure water cooling mixture 10 minutes, then add pure water and 30%H2O2 heat release be cooled to room temperature again, is 5～350W ultrasonic agitation 5min～5h at power; With hydrochloric acid and pure water, repeatedly carry out centrifuge washing and approach neutrality, the dry graphene oxide powder that obtains;
High-purity expansible black lead powder preparation process: high purity graphite, concentrated nitric acid and hydrogen peroxide are added in retort in the ratio of 1:0.75:0.25, temperature remains on 16 ℃ of stirring reactions 2 hours, again through centrifuge dehydration washing to neutral, in temperature, be less than under the condition of 80 ℃ and dry and obtain high-purity expansible black lead powder;
Composite steps: above-mentioned graphene oxide and high-purity expansible black lead in mass ratio ratio of 1:1～4 add and carry out ball milling in ball mill and mix, again mixture is entered in the expansion furnace that temperature is greater than 950 ℃ by swirler, worm graphite after expansion enters feed bin, according to thickness requirement, worm graphite is carried out at least eight calenderings, finally obtain the ultra-thin graphite laminated film that thickness is minimal to 0.02mm.
Example one;
At the temperature of 20 ℃, LC150-99.9 high purity graphite 20 weight parts and concentrated nitric acid 1 weight part, fluosulfonic acid 3 weight parts and phosphatase 11 weight part are added in retort, unlatching is uniformly mixed, and is slightly heated to 35-40 ℃.Then in mixture, slowly add a small amount of pure water and stir 30 minutes, making material heat release; Open again heating unit and elevate the temperature to 98 ℃, keep 15 minutes, add a small amount of pure water cooling mixture 10 minutes, then add a large amount of pure water and 30%H
2o
2heat release be cooled to room temperature is again 300W ultrasonic agitation 1h in frequency.With hydrochloric acid and pure water, repeatedly carry out centrifuge washing to approaching neutrality, the dry graphene oxide powder that obtains.Another part of high purity graphite LC150-99.9 high purity graphite 100 weight parts and concentrated nitric acid 75 weight parts and hydrogen peroxide 0.25 weight part are added in retort, add again hydrofluoric acid 10 weight parts, temperature remains on 16 ℃ of stirring reactions 2 hours, again through centrifuge dehydration washing to neutral, in temperature, be less than under the condition of 80 ℃ and dry and obtain high purity expansible black lead powder.In ratio mixture 100 weight parts of 1:2, adding temperature to be greater than in the expansion furnace of 950 ℃ in above-mentioned graphene oxide powder and high purity expansible black lead powder expands, worm admixed graphite after expansion enters feed bin, add binding agent 10 weight parts, enter ball mill ball milling more than 3 hours, again mixture is sent into feed bin, by feed bin, through evenly paving, being entered individual layer plane rolling machine rolls through one-level, enter again warming mill and roll, remove liquid remaining in graphite and make unexpanded graphite continue to expand; Through secondary, roll, enter again carbonization in secondary heating unit, enter afterwards three grades of milling rollers and prolong the thickness of pressing adjustment graphite film, the fourth stage is further adjusted according to the thickness of graphite paper that the third stage goes out, the samely roll above adjustment thickness through 8 grades, obtain the ultra-thin graphite laminated film that minimum thickness can reach 0.01mm.
Adopt double bridge method LDW-1 type carbon-graphite product resistivity tester to measure, one of the ultra-thin graphite laminated film of sample thief,, with two, estimate nib and put at sample surfaces respectively.Two tip spacings are about 20mm, turn on the power switch and read its resistivity 4.8 * 10
-4s/m; Adopt the laser method that shines to survey its thermal conductivity step with laser heat conducting instrument as follows: 1. one of ultra-thin graphite laminated film is got in the preparation of sample, is cut to the circle that diameter is 20mm, and measures its thickness record with screw micrometer.
The installation of sample and mensuration
Sample is put into instrument and test, first set the test conditions of sample to be tested, comprise heating-up time, test temperature and experimental atmosphere.Reach after design temperature and temperature-stable, select mode manually or automatically to open laser generator, instrument records sample upper surface temperature rise temporal evolution curve automatically
3. the data analysis system software in instrument carries out Automatic analysis to data, obtains for half heating-up time, thereby show that thermal diffusivity is 316W/mK, and ultra-thin graphite composite film of the present invention is measured its thickness with screw micrometer and can be reached 0.02mm.
Embodiment bis-:
Under normal temperature, LC100-99.9 high purity graphite 100 weight parts and potassium permanganate 5 weight parts, chlorsulfonic acid 15 weight parts and phosphoric acid 5 weight parts are added in retort, unlatching is uniformly mixed, and is slightly heated to 35-40 ℃.Then in mixture, slowly add a small amount of pure water and stir 30 minutes, making material heat release; Open again heating unit and elevate the temperature to 98 ℃, keep 15 minutes, add a small amount of pure water cooling mixture 10 minutes, then add a large amount of pure water and 30%H
2o
2heat release be cooled to room temperature is again 200W ultrasonic agitation 2h in frequency.With hydrochloric acid and pure water, repeatedly carry out centrifuge washing to approaching neutrality, the dry graphene oxide powder that obtains.Another part of high purity graphite LC100-99.9 high purity graphite 100 weight parts and concentrated nitric acid 75 weight parts and hydrogen peroxide 0.25 weight part are added in retort, add again hydrofluoric acid 10 weight parts, temperature remains on 16 ℃ of stirring reactions 2 hours, again through centrifuge dehydration washing to neutral, in temperature, be less than under the condition of 80 ℃ and dry and obtain high purity expansible black lead powder.In ratio mixture 100 weight parts of 1:2, adding temperature to be greater than in the expansion furnace of 950 ℃ in above-mentioned graphene oxide powder and high purity expansible black lead powder expands, worm admixed graphite after expansion enters feed bin, add binding agent 10 weight parts, enter ball mill ball milling more than 3 hours, again mixture is sent into feed bin, by feed bin, through evenly paving, being entered individual layer plane rolling machine rolls through one-level, enter again warming mill and roll, remove liquid remaining in graphite and make unexpanded graphite continue to expand; Through secondary, roll, enter again carbonization in secondary heating unit, enter afterwards three grades of milling rollers and prolong the thickness of pressing adjustment graphite film, the fourth stage is further adjusted according to the thickness of graphite paper that the third stage goes out, the samely roll above adjustment thickness through 8 grades, obtain the ultra-thin graphite laminated film that minimum thickness can reach 0.01mm.
Adopt double bridge method LDW-1 type carbon-graphite product resistivity tester to measure, its resistivity 5.67 * 10
-4s/m, adopts the laser method that shines to survey its thermal conductivity with laser heat conducting instrument and is about 336W/mK, and ultra-thin graphite composite film of the present invention is measured its thickness with screw micrometer and can be reached 0.01mm.
Claims (9)
1. the method for a high-purity expanded graphite and the ultra-thin composite graphite film of the compound preparation of graphene oxide is characterized in that following step:
The preparation process of graphene oxide: at the temperature of 20 ℃, high purity graphite is mixed by 20～120:1:3～9 with oxygenant, sour solvent and a kind of protective material, be slightly heated to 35-40 ℃; Then in mixture, slowly add part pure water and stir 30 minutes, making material heat release; Open again heating unit and elevate the temperature to 98 ℃, keep 15 minutes, add part pure water cooling mixture 10 minutes, then add pure water and 30%H
2o
2heat release be cooled to room temperature is again 5～350W ultrasonic agitation 5min～5h at power; With hydrochloric acid and pure water, repeatedly carry out centrifuge washing and approach neutrality, the dry graphene oxide powder that obtains;
High-purity expansible black lead powder preparation process: high purity graphite, concentrated nitric acid and hydrogen peroxide are added in retort in the ratio of 1:0.75:0.25, temperature remains on 16 ℃ of stirring reactions 2 hours, again through centrifuge dehydration washing to neutral, in temperature, be less than under the condition of 80 ℃ and dry and obtain high-purity expansible black lead powder;
Composite steps: above-mentioned graphene oxide and high-purity expansible black lead in mass ratio 1:1～4 ratio add and carry out ball milling in ball mill and mix, again mixture is entered in the expansion furnace that temperature is greater than 950 ℃ by swirler, worm graphite after expansion enters feed bin, according to thickness requirement, worm graphite is carried out at least eight calenderings, finally obtain the ultra-thin graphite laminated film that thickness is minimal to 0.02mm.
2. the method for a kind of high-purity expanded graphite as claimed in claim 1 and the ultra-thin composite graphite film of the compound preparation of graphene oxide, is characterized in that, described oxygenant is a kind of of potassium permanganate, concentrated nitric acid, potassium bichromate.
3. the method for a kind of high-purity expanded graphite as claimed in claim 1 and the ultra-thin composite graphite film of the compound preparation of graphene oxide, is characterized in that, described sour solvent is one or more the combination being selected from chlorsulfonic acid, fluosulfonic acid, trifluoromethanesulfonic acid.
4. the method for a kind of high-purity expanded graphite as claimed in claim 1 and the ultra-thin composite graphite film of the compound preparation of graphene oxide, is characterized in that, described protective material is selected from trifluoroacetic acid; Phosphoric acid; Ortho-phosphoric acid; Metaphosphoric acid; Tripyrophosphoric acid; Boric acid; Trifluoroacetic anhydride; Phosphoric anhydride; Ortho-phosphoric acid acid anhydride; Metaphosphoric acid acid anhydride; Tripyrophosphoric acid acid anhydride; The combination of one or more in boron trioxide.
5. the method for a kind of high-purity expanded graphite as claimed in claim 1 and the ultra-thin composite graphite film of the compound preparation of graphene oxide, is characterized in that, in the preparation process of described graphene oxide, the ratio of front its consumption of the pure water adding for twice and sour solvent is suitable; The mass ratio of the pure water adding for the third time and hydrogen peroxide and graphite is 100:1:1.
6. a kind of method of high-purity expanded graphite and the ultra-thin composite graphite film of the compound preparation of graphene oxide as described in claim 1, is characterized in that, its purity of pure water is at 1～10us/cm.
7. a kind of method of high-purity expanded graphite and the ultra-thin composite graphite film of the compound preparation of graphene oxide as described in claim 1, it is characterized in that, graphite used is high purity graphite-be 100 orders to any in 80 orders, described concentration of nitric acid is more than 65% concentrated nitric acid, and described hydrogen peroxide concentration is 30%.
8. a kind of method of high-purity expanded graphite and the ultra-thin composite graphite film of the compound preparation of graphene oxide as described in claim 1, is characterized in that, described binding agent is the organism such as pitch, tar or resin.
9. a kind of method of high-purity expanded graphite and the ultra-thin composite graphite film of the compound preparation of graphene oxide as described in claim 1, is characterized in that, described ultra-thin its sulfur-bearing of graphite laminated film is less than 600ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410252396.9A CN104003380B (en) | 2014-06-09 | 2014-06-09 | The preparation method of the laminated film of a kind of ultrathin graphite paper and graphene oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410252396.9A CN104003380B (en) | 2014-06-09 | 2014-06-09 | The preparation method of the laminated film of a kind of ultrathin graphite paper and graphene oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104003380A true CN104003380A (en) | 2014-08-27 |
| CN104003380B CN104003380B (en) | 2016-06-08 |
Family
ID=51364325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410252396.9A Active CN104003380B (en) | 2014-06-09 | 2014-06-09 | The preparation method of the laminated film of a kind of ultrathin graphite paper and graphene oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104003380B (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104355306A (en) * | 2014-10-17 | 2015-02-18 | 浙江碳谷上希材料科技有限公司 | Method for rapidly preparing monolayer graphene oxide through one-pot method |
| CN104445162A (en) * | 2014-11-12 | 2015-03-25 | 东莞市青麦田数码科技有限公司 | Graphene oxide aqueous solution and graphene oxide thin film as well as preparation method of graphene oxide thin film |
| CN105016731A (en) * | 2015-07-09 | 2015-11-04 | 天津大学 | Expanded graphite and graphene composite material and preparation method therefor |
| CN105271170A (en) * | 2015-11-03 | 2016-01-27 | 山西中兴环能科技有限公司 | Preparation method of nano carbon and composite material of nano carbon |
| CN105803587A (en) * | 2015-01-02 | 2016-07-27 | 中原工学院 | Tape casting method for preparing graphene fibers |
| CN105803602A (en) * | 2015-01-02 | 2016-07-27 | 中原工学院 | Method for preparing graphene fiber through graphene film twisting forming method |
| CN105803601A (en) * | 2015-01-02 | 2016-07-27 | 中原工学院 | Method for preparing graphene composite fibers through coating method |
| CN105885804A (en) * | 2016-05-26 | 2016-08-24 | 哈尔滨工程大学 | Method for preparing graphene all-carbon composite thermal interface material |
| CN106185904A (en) * | 2016-07-15 | 2016-12-07 | 浙江大学 | A kind of high fold graphene paper |
| CN107754786A (en) * | 2017-10-16 | 2018-03-06 | 广西大学 | One kind utilizes KMnO4The method that electrocatalytic oxidation is improved on direct oxidation graphite paper |
| CN107777683A (en) * | 2017-11-20 | 2018-03-09 | 浙江海虹控股集团有限公司 | A kind of new method for producing graphene oxide |
| CN109133923A (en) * | 2018-08-21 | 2019-01-04 | 大同新成新材料股份有限公司 | A kind of method that graphene oxide-special graphite powder prepares special graphite paper |
| CN110875477A (en) * | 2018-08-31 | 2020-03-10 | 湖南科技大学 | Nitrogen-doped expanded graphite paper current collector and preparation and application thereof |
| CN111233515A (en) * | 2020-03-19 | 2020-06-05 | 北京晶龙特碳科技有限公司 | Method for preparing nano-graphite coating on surface of graphite product |
| CN114408908A (en) * | 2021-12-31 | 2022-04-29 | 厦门凯纳石墨烯技术股份有限公司 | Graphene heat dissipation film and preparation method thereof |
| WO2022261912A1 (en) * | 2021-06-17 | 2022-12-22 | 泰兴挚富显示技术有限公司 | Graphene composite heat dissipation thin film and preparation method therefor |
| CN116355469A (en) * | 2022-12-05 | 2023-06-30 | 中车青岛四方机车车辆股份有限公司 | Intumescent fire retardant coating for railway vehicle and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1472833A (en) * | 2003-05-22 | 2004-02-04 | 上海交通大学 | High-per formance carbon material preparing method by water-base curtain coating technology |
| CN102509642A (en) * | 2011-11-21 | 2012-06-20 | 余泉茂 | Method for preparing supercapacitor with expanded graphite, grapheme and activated carbon |
| CN103456520A (en) * | 2012-05-31 | 2013-12-18 | 海洋王照明科技股份有限公司 | Manufacturing method and application for graphene/carbon nano-tube composite film |
-
2014
- 2014-06-09 CN CN201410252396.9A patent/CN104003380B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1472833A (en) * | 2003-05-22 | 2004-02-04 | 上海交通大学 | High-per formance carbon material preparing method by water-base curtain coating technology |
| CN102509642A (en) * | 2011-11-21 | 2012-06-20 | 余泉茂 | Method for preparing supercapacitor with expanded graphite, grapheme and activated carbon |
| CN103456520A (en) * | 2012-05-31 | 2013-12-18 | 海洋王照明科技股份有限公司 | Manufacturing method and application for graphene/carbon nano-tube composite film |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104355306A (en) * | 2014-10-17 | 2015-02-18 | 浙江碳谷上希材料科技有限公司 | Method for rapidly preparing monolayer graphene oxide through one-pot method |
| CN104445162A (en) * | 2014-11-12 | 2015-03-25 | 东莞市青麦田数码科技有限公司 | Graphene oxide aqueous solution and graphene oxide thin film as well as preparation method of graphene oxide thin film |
| CN105803602B (en) * | 2015-01-02 | 2018-03-09 | 中原工学院 | The method that the graphene film twisting method of forming prepares graphene fiber |
| CN105803587A (en) * | 2015-01-02 | 2016-07-27 | 中原工学院 | Tape casting method for preparing graphene fibers |
| CN105803602A (en) * | 2015-01-02 | 2016-07-27 | 中原工学院 | Method for preparing graphene fiber through graphene film twisting forming method |
| CN105803601A (en) * | 2015-01-02 | 2016-07-27 | 中原工学院 | Method for preparing graphene composite fibers through coating method |
| CN105016731A (en) * | 2015-07-09 | 2015-11-04 | 天津大学 | Expanded graphite and graphene composite material and preparation method therefor |
| CN105271170A (en) * | 2015-11-03 | 2016-01-27 | 山西中兴环能科技有限公司 | Preparation method of nano carbon and composite material of nano carbon |
| CN105271170B (en) * | 2015-11-03 | 2017-04-19 | 山西中兴环能科技有限公司 | Preparation method of nano carbon and composite material of nano carbon |
| CN105885804A (en) * | 2016-05-26 | 2016-08-24 | 哈尔滨工程大学 | Method for preparing graphene all-carbon composite thermal interface material |
| CN105885804B (en) * | 2016-05-26 | 2019-02-26 | 哈尔滨工程大学 | A kind of preparation method of graphene all-carbon composite heat interfacial material |
| CN106185904A (en) * | 2016-07-15 | 2016-12-07 | 浙江大学 | A kind of high fold graphene paper |
| CN107754786A (en) * | 2017-10-16 | 2018-03-06 | 广西大学 | One kind utilizes KMnO4The method that electrocatalytic oxidation is improved on direct oxidation graphite paper |
| CN107754786B (en) * | 2017-10-16 | 2020-06-16 | 广西大学 | By using KMnO4Method for improving electrocatalytic oxidation on direct oxidized graphite paper |
| CN107777683A (en) * | 2017-11-20 | 2018-03-09 | 浙江海虹控股集团有限公司 | A kind of new method for producing graphene oxide |
| CN109133923A (en) * | 2018-08-21 | 2019-01-04 | 大同新成新材料股份有限公司 | A kind of method that graphene oxide-special graphite powder prepares special graphite paper |
| CN109133923B (en) * | 2018-08-21 | 2020-10-30 | 大同新成新材料股份有限公司 | Method for preparing special graphite paper from graphene oxide-special graphite powder |
| CN110875477A (en) * | 2018-08-31 | 2020-03-10 | 湖南科技大学 | Nitrogen-doped expanded graphite paper current collector and preparation and application thereof |
| CN110875477B (en) * | 2018-08-31 | 2021-02-09 | 湖南科技大学 | Nitrogen-doped expanded graphite paper current collector and preparation and application thereof |
| CN111233515A (en) * | 2020-03-19 | 2020-06-05 | 北京晶龙特碳科技有限公司 | Method for preparing nano-graphite coating on surface of graphite product |
| WO2022261912A1 (en) * | 2021-06-17 | 2022-12-22 | 泰兴挚富显示技术有限公司 | Graphene composite heat dissipation thin film and preparation method therefor |
| CN114408908A (en) * | 2021-12-31 | 2022-04-29 | 厦门凯纳石墨烯技术股份有限公司 | Graphene heat dissipation film and preparation method thereof |
| CN116355469A (en) * | 2022-12-05 | 2023-06-30 | 中车青岛四方机车车辆股份有限公司 | Intumescent fire retardant coating for railway vehicle and preparation method thereof |
| CN116355469B (en) * | 2022-12-05 | 2024-01-16 | 中车青岛四方机车车辆股份有限公司 | Intumescent fire retardant coating for railway vehicle and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104003380B (en) | 2016-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104003380B (en) | The preparation method of the laminated film of a kind of ultrathin graphite paper and graphene oxide | |
| Wang et al. | Fundamentals of electrolytes for solid-state batteries: challenges and perspectives | |
| Seino et al. | Synthesis of phosphorous sulfide solid electrolyte and all-solid-state lithium batteries with graphite electrode | |
| CN105428615B (en) | A kind of modified artificial graphite cathode material production method | |
| CN102868006A (en) | Method for preparing graphene through waste lithium batteries | |
| CN102485648B (en) | Modified graphite, composite graphite material containing the modified graphite and their preparation methods and application | |
| Abdollahifar et al. | Graphite recycling from end‐of‐life lithium‐ion batteries: processes and applications | |
| CN104993147B (en) | A kind of preparation method of multilevel hierarchy copper nitrate negative material | |
| CN103943377A (en) | Preparation method of porous electrode | |
| CN104993134A (en) | Preparation method of lithium ion battery copper nitrate composite negative electrode material | |
| CN105810919A (en) | Preparation method of modified graphite cathode material for lithium ion batteries | |
| JPWO2016136524A1 (en) | Carbon material, its production method and its use | |
| CN106169582A (en) | A kind of natural pin Jiao's composite graphite negative electrode material production method | |
| Jiang et al. | Li2S–Li3PS4 (LPS) Composite Synthesized by Liquid‐Phase Shaking for All‐Solid‐State Lithium–Sulfur Batteries with High Performance | |
| CN105742636A (en) | Graphite negative electrode material for lithium-ion battery and preparation method of graphite negative electrode material | |
| CN103996823B (en) | A kind of rapid microwave reaction method for preparing of power lithium-ion battery ternary polyanion phosphate/carbon positive electrode | |
| CN114394590A (en) | Graphitized negative electrode material prepared from graphitized waste and preparation method thereof | |
| CN103545492A (en) | Preparation method of multiple composite anode material of lithium ion battery | |
| Boparai et al. | On characterization of rechargeable, flexible electrochemical energy storage device | |
| CN105244502A (en) | Method for preparing anode material of lithium ion battery by high-temperature reaction of expansible graphite and zinc powder | |
| Lang et al. | Study on titanium foil coated with partial reduction titanium dioxide as bipolar lead-acid battery's substrate | |
| CN104779396B (en) | Production method of lithium ion composite graphite cathode material | |
| Salunkhe et al. | Exploring inexpensive electrodes for safer and evolved dual-ion batteries using modified electrolytes for enhanced energy density | |
| WO2017024898A1 (en) | Preparation method for high capacity tin-carbon negative electrode material | |
| CN105347333A (en) | Preparation method of low-cost negative electrode material of power lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |