CN107899551B - Polypyrrole-containing amino graphene oxide/cellulose acetate composite material and application thereof - Google Patents
Polypyrrole-containing amino graphene oxide/cellulose acetate composite material and application thereof Download PDFInfo
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Abstract
The invention discloses an amino graphene oxide/cellulose acetate composite material containing polypyrrole and an application thereof. The amino graphene oxide/cellulose acetate composite material containing polypyrrole, which is prepared by the invention, has the properties of cellulose acetate, graphene oxide and polypyrrole; the paper, the film or the textile made of the composite material is expected to be widely applied to a plurality of fields such as water purification, metal ion enrichment, super capacitors, lithium ion batteries, antistatic or shielding materials, conductive films and the like.
Description
Technical Field
The invention belongs to the technical field of material science, and particularly relates to an amino graphene oxide/cellulose acetate composite material containing polypyrrole and application thereof.
Background
The cellulose is a natural biological material, is rich in reserves in the nature, has excellent mechanical properties and can be biodegraded. However, natural cellulose has many hydroxyl groups in its main chain, and a large number of hydrogen bonds are formed between and in molecules, which makes cellulose difficult to dissolve or melt. A large number of cellulose derivatives have been developed, including cellulose acetate, cellulose ethers, cellulose graft copolymers and cellulose esters.
The cellulose diacetate fiber serving as a derivative of natural polymer cellulose is non-toxic and tasteless, can selectively absorb surrounding toxic substances, has good antibacterial and bacteriostatic effects, has good biocompatibility and biodegradability, and is an environment-friendly material. The cellulose diacetate tow produced in industry has Y-shaped section, large specific surface area, strong adsorption capacity, small absorption resistance, obvious filtration effect, no toxicity and no smell, can adsorb peculiar smell and can selectively adsorb surrounding toxic substances.
Graphene Oxide (GO) is an oxide of graphene, and is brown yellow in color, and common products in the market are in powder, flake and solution states. After oxidation, the oxygen-containing functional groups on the graphene are increased, so that the graphene is more active than graphene in property, and the properties of the graphene can be improved through various reactions with the oxygen-containing functional groups. Graphene oxide can be considered a non-traditional soft material with properties of polymers, colloids, films, and amphiphilic molecules. Graphene oxide has long been considered as a hydrophilic substance because of its superior dispersibility in water, but related experimental results show that graphene oxide is actually amphiphilic, exhibiting a distribution of hydrophilic to hydrophobic properties from the edge to the center of a graphene sheet.
Oxygen-containing groups on the surface of the graphene oxide mainly comprise oxygen-containing groups such as-OH, C-O-C, COO-and the like, hydrogen bonds are easily formed between the oxygen-containing groups and hydroxyl groups of cellulose molecules, and meanwhile, abundant hydroxyl groups and C-H on the surface of the cellulose can form CH-pi interaction and electrostatic interaction with the graphene. Therefore, the graphene is compounded with the cellulose, so that the tensile property, the conductive property, the thermal property and the like of the cellulose can be improved. In addition, the steric effect of cellulose can also promote the stable dispersion of graphene oxide in a solution. Researchers use Graphene Oxide Sheets (GOS) as a cross-linking agent for cellulose to prepare aerogels, and the compressive strength is improved by 30% and the modulus is improved by 90%, indicating that there is an interaction between graphene oxide and cellulose.
The amination modification of graphene is considered to be one of the most effective modification methods, and amino groups are introduced to the surface of graphene oxide, so that the hydrophilicity and polarity of the surface of graphene can be improved, the dispersibility of graphene in a polymer is further improved, and hydrogen bonds or chemical bonds are formed between graphene and the polymer; meanwhile, the amino group has high reactivity and can react with a plurality of other compounds, so that the dispersibility of the aminated graphene in epoxy resin, polyamide and other resins is improved, and the reinforcing effect of the composite material is improved, so that the amino group is widely regarded. Currently, there are two main methods for performing amination modification on graphene: one method is to perform acyl chlorination modification on graphene oxide, and then further utilize the activity of acyl chloride groups to react with amino groups of amides to prepare amination modified graphene; in another method, a condensing agent is used to perform a condensation reaction between carboxyl groups on graphene oxide and amino groups of an amide compound to prepare each aminated modified graphene.
Polypyrrole (PPy) has high conductivity, no toxicity, good environmental stability, easy doping, and special optical, electrical, acoustic characteristics. The cellulose nanocrystalline is added into the composite material, so that the thermal stability, the mechanical strength, the hardness, the rigidity and the flexibility of the material can be obviously improved. The novel nano composite material can be used for a chemical sensor or a formula of an antistatic coating, and can improve the mechanical property of the conductive nano material. In recent years, researchers in make internal disorder or usurp found that polypyrrole and polyaniline have heavy metal ion adsorption performance, and polypyrrole and polyaniline are often immobilized on inorganic nanoparticles for adsorption of heavy metal ions, while those in make internal disorder or usurp, which are obtained by immobilizing polypyrrole on an aminated graphene oxide/cellulose acetate composite material, are less. Therefore, researches and developments on the aminated graphene oxide/cellulose acetate composite material containing polypyrrole are carried out, and the application of the aminated graphene oxide/cellulose acetate composite material in multiple fields such as electric conduction, adsorption, medicine carrying and the like is significant.
Disclosure of Invention
The invention aims to provide an amino graphene oxide/cellulose acetate composite material containing polypyrrole and an application thereof. The prepared composite material has the functions of cellulose acetate, graphene oxide and polypyrrole, is widely applied to multiple fields of electrochemistry, adsorption, medicine carrying and the like, and has good economic and social benefits.
The technical scheme adopted by the invention is as follows: a polypyrrole-containing amino graphene oxide/cellulose acetate composite material is prepared by the following steps:
firstly, preparing Graphene Oxide (GO) into a 1mg/ml solution, carrying out ultrasonic treatment on 50ml of the solution in a water bath, then weighing 15mg of N, N-dimethyl ethylenediamine or N, N-diethyl ethylenediamine, adding the N, N-dimethyl ethylenediamine into the GO solution, adding 12mg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC.HCl), 100 mg of N-hydroxysuccinimide (NHS) and 12mg of 4-Dimethylaminopyridine (DMAP), stirring at 25 ℃ for reaction for 24 hours, centrifuging the solution at 6000 rpm for 1 hour after the reaction is finished, discarding the supernatant, repeatedly washing the lower layer substance with deionized water for three times, and carrying out freeze drying for 12 hours to obtain an aminated graphene oxide solution;
then mixing the aminated graphene oxide suspension with an alkaline solution of cellulose diacetate, and stirring, mechanically shearing or ultrasonically treating the mixed solution to obtain an aminated graphene oxide/cellulose composite material, wherein the alkaline solution is as follows: fully mixing sodium carbonate or sodium hydroxide, urea, thiourea and deionized water according to the weight ratio of 1-10:4-10: 0-10: 70-95;
finally, dissolving the aminated graphene oxide/cellulose acetate composite material with deionized water and ultrasonically treating the mixture to form a suspension, adding pyrrole monomers, then respectively adding doping agents such as NaCl and DBSDA in equal amount, slowly adding an oxidizing agent FeCl3.6H2O while stirring, polymerizing the pyrrole monomers for 6-24h, centrifugally separating the obtained suspension, precipitating the suspension in deionized water, ultrasonically dispersing and washing until the upper layer liquid obtained by centrifugal separation is neutral, placing the product in a Buchner funnel, filtering by using a microporous filter membrane, freeze-drying the precipitate for 24h, and grinding to obtain black aminated graphene oxide/cellulose acetate composite material powder containing polypyrrole.
Preferably, the mixing ratio of the alkali solution of the cellulose diacetate to the aminated graphene oxide suspension is 1: 1-10: 1.
Preferably, the specific steps of mixing the aminated graphene oxide suspension and the alkaline solution of cellulose diacetate to obtain the aminated graphene oxide/cellulose acetate composite material are as follows:
1) dissolving aminated graphene oxide by using deionized water, and carrying out ultrasonic treatment in an ultrasonic device with the power of 300-1000W for 0.5-5h to obtain an uniformly dispersed aminated graphene oxide suspension;
2) fully mixing sodium carbonate or sodium hydroxide, urea, thiourea and deionized water according to the weight ratio of 1-10:4-10: 0-10: 70-95;
3) then adding a cellulose acetate suspension, stirring at-10 to 20 ℃, mechanically shearing or ultrasonically processing for 12 to 24 hours, and filtering and washing to obtain the aminated graphene oxide/cellulose acetate composite material.
Preferably, in the polymerization reaction of the pyrrole monomer, the mass of the pyrrole monomer is 10-100% of the mass of the cellulose diacetate.
Preferably, the graphene oxide is a single-layer graphene oxide, a multi-layer graphene oxide or a mixture of the two.
Preferably, in the preparation of the aminated graphene oxide solution, the selected amino moiety is N, N-dimethylethylenediamine or N, N-diethylethylenediamine, and the condensing agent is edc.hcl or NHS.
The composite material of the invention is applied to the adsorption and purification of waste gas and waste water containing organic matters and/or heavy metal ions.
The composite material is applied to conductive composite films, super capacitors, electrodes and electrocatalytic materials.
The invention has the beneficial effects that: the amino graphene oxide/cellulose acetate composite material containing polypyrrole, which is prepared by the invention, has the properties of cellulose acetate, graphene oxide and polypyrrole, such as better toughness, film forming property, spinnability and adsorbability of the cellulose acetate, high surface reaction activity, unique electric and magnetic properties, adsorption property and the like of the graphene oxide, and the polypyrrole has unique conductivity and heavy metal adsorption capacity; the paper, the film or the textile made of the composite material is expected to be widely applied to a plurality of fields such as water purification, metal ion enrichment, super capacitors, lithium ion batteries, antistatic or shielding materials, conductive films and the like; meanwhile, the invention adopts a simple water system process method, has mild reaction conditions, low equipment requirement and convenient large-scale production, and relates to the technical field of cheap and easily obtained raw materials and no pollution. The prepared composite material has the functions of cellulose acetate, graphene oxide and polypyrrole, is widely applied to multiple fields of electrochemistry, adsorption, medicine carrying and the like, and has good economic and social benefits.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
A polypyrrole-containing amino graphene oxide/cellulose acetate composite material is prepared by the following steps:
firstly, preparing 1mg/ml solution of Graphene Oxide (GO), wherein the graphene oxide is single-layer graphene oxide, multi-layer graphene oxide or a mixture of the single-layer graphene oxide and the multi-layer graphene oxide, taking 50ml of the solution to perform ultrasonic treatment in a water bath, then, 15mg of N, N-dimethylethylenediamine or N, N-diethylethylenediamine is weighed and added to the GO solution, 12mg of 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride (EDC. HCl), 100 mg of N-hydroxysuccinimide (NHS) and 12mg of 4-Dimethylaminopyridine (DMAP) are added, stirring and reacting at 25 ℃ for 24h, centrifuging the solution at 6000 revolutions for 1h after the reaction is finished, discarding the supernatant, repeatedly washing the lower layer substance with deionized water for three times, and freeze-drying for 12 hours to obtain an aminated graphene oxide solution; in the preparation of the aminated graphene oxide solution, the selected amino fragment is N, N-dimethylethylenediamine or N, N-diethylethylenediamine, and the condensing agent is EDC.HCl and NHS.
Then mixing the aminated graphene oxide suspension with an alkaline solution of cellulose diacetate in a mixing ratio of 1: 1-10: 1, stirring, mechanically shearing or ultrasonically treating the mixed solution to obtain the aminated graphene oxide/cellulose composite material, wherein the alkaline solution is as follows: fully mixing sodium carbonate or sodium hydroxide, urea, thiourea and deionized water according to the weight ratio of 1-10:4-10: 0-10: 70-95; the method comprises the following specific steps:
1) dissolving aminated graphene oxide by using deionized water, and carrying out ultrasonic treatment in an ultrasonic device with the power of 300-1000W for 0.5-5h to obtain an uniformly dispersed aminated graphene oxide suspension;
2) fully mixing sodium carbonate or sodium hydroxide, urea, thiourea and deionized water according to the weight ratio of 1-10:4-10: 0-10: 70-95;
3) then adding a cellulose acetate suspension, stirring at-10 to 20 ℃, mechanically shearing or ultrasonically processing for 12 to 24 hours, and filtering and washing to obtain the aminated graphene oxide/cellulose acetate composite material.
Finally, dissolving the aminated graphene oxide/cellulose acetate composite material with deionized water and ultrasonically treating the mixture to form a suspension, adding pyrrole monomer, wherein the mass of the pyrrole monomer is 10% -100% of that of cellulose diacetate, then adding doping agents such as NaCl and DBSDA in equal amount respectively, slowly adding an oxidizing agent FeCl3.6H2O while stirring, after polymerizing the pyrrole monomer for 6-24h, centrifugally separating the obtained suspension, precipitating the suspension in deionized water, ultrasonically dispersing and washing until the upper layer liquid obtained by centrifugal separation is neutral, placing the product in a Buchner funnel, filtering with a microporous filter membrane, freeze-drying the precipitate for 24h, and grinding to obtain black aminated graphene oxide/cellulose acetate composite material powder containing polypyrrole.
The composite material of the invention is applied to the adsorption and purification of waste gas and waste water containing organic matters and/or heavy metal ions.
The composite material is applied to conductive composite films, super capacitors, electrodes and electrocatalytic materials.
Example (b):
1. graphene Oxide (GO) was formulated as a 1mg/ml solution. Taking 50ml of the solution, carrying out ultrasonic treatment in a water bath, then weighing 15mg of N, N-dimethylethylenediamine, adding into GO solution, adding 12mg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC.HCl), 100 mg of N-hydroxysuccinimide (NHS) and 12mg of 4-Dimethylaminopyridine (DMAP), stirring and reacting at 25 ℃ for 24 hours, centrifuging the solution at 6000 revolutions for 1 hour after the reaction is finished, discarding the supernatant, repeatedly washing the lower layer with deionized water for three times, and freeze-drying for 12 hours to obtain the aminated graphene oxide.
2. Dissolving 0.5g of aminated graphene oxide in deionized water, and carrying out ultrasonic treatment in an ultrasonic device with the power of 300-1000W for 0.5-5h to obtain an evenly dispersed aminated graphene oxide suspension; fully mixing sodium carbonate, urea, thiourea and deionized water according to a weight ratio of 5: 8: 6: 81; 3) then adding 1.0g of cellulose acetate suspension, stirring at-10-20 ℃, mechanically shearing or ultrasonically processing for 12-24h, and filtering and washing to obtain the aminated graphene oxide/cellulose acetate composite material.
3. Dissolving the obtained aminated graphene oxide/cellulose acetate composite material with 15ml of deionized water, and performing ultrasonic treatment to obtain suspension. 0.5g pyrrole monomer is added, then the doping agents NaCl and DBSDA with the same amount of substances are respectively added, and then 0.3g oxidant FeCl3.6H2O is slowly added while stirring. And polymerizing the pyrrole monomer for 12h, centrifugally separating the obtained suspension, and then precipitating the suspension in deionized water for ultrasonic dispersion washing until the upper-layer liquid obtained by centrifugal separation is neutral. The product was placed in a buchner funnel and filtered using a microfiltration membrane. And (3) freeze-drying the precipitate for 24h, and grinding to obtain black aminated graphene oxide/cellulose acetate composite material powder containing polypyrrole.
4. Heavy metal adsorption test
An electronic analytical balance is used to take a proper amount of copper nitrate or potassium dichromate crystals, and the copper nitrate or potassium dichromate crystals are dissolved in a proper amount of deionized water to prepare about 100ppm of Cu (II) solution or 100ppm of Cr (VI) solution. The remaining concentrations of Cu (II), Cr (VI) solution required for the experiments were obtained by diluting the prepared 100ppm solution.
In order to test the adsorption effect of the adsorbent before and after modification, three adsorption materials, namely common cellulose acetate, graphene oxide and polypyrrole-containing amino graphene oxide/cellulose acetate, are respectively filled into conical flasks with 50m L Cu (II) ion concentration of 100ppm copper nitrate solution or 50m L Cr (VI) ion concentration of 100ppm potassium dichromate solution, and are continuously vibrated and adsorbed for 4h at room temperature, and the concentrations of Cu (II) ions in the solutions before and after adsorption are measured by a plasma atomic emission spectrometer (ICP-OES).
The experimental results show that the adsorption capacity of the adsorption materials of common cellulose acetate, graphene oxide and polypyrrole-containing aminographene oxide/cellulose acetate is greatly different from that of the adsorption materials of Cu (II) and Cr (VI) ions, the adsorption capacity of the adsorption materials of polypyrrole-containing aminographene oxide/cellulose acetate is greatly improved compared with that of the adsorption materials of Cu (II) and Cr (VI) ions in a solution of cellulose acetate and graphene oxide, and the adsorption capacity of the adsorption materials of polypyrrole-containing aminographene oxide/cellulose acetate is respectively 28.5 mg/g and 33.1 mg/g when the adsorption materials of polypyrrole-containing aminographene oxide/cellulose acetate adsorption materials of Cu (II) and Cr (VI) ions are respectively placed in a copper nitrate solution containing 50m L Cu ions and 88.7 mg/L or a potassium dichromate solution containing 50m L Cr ions and 96.6 mg/L, while the adsorption capacity of the adsorption materials of polypyrrole-containing aminographene oxide/cellulose acetate and Cr (VI) ions is respectively 1.7 mg/g and 3.8 mg/g, and the adsorption capacity of the adsorption materials of polypyrrole-containing aminographene oxide and Cr (II) ions is respectively good as the adsorption materials of polypyrrole-containing heavy metal.
5. Firstly, 5mg of an amino graphene oxide/cellulose acetate composite material containing polypyrrole is dissolved in 10 ml of distilled water, ultrasonic treatment is carried out for 1 hour to uniformly disperse, 10 mu L solution is dropped on the surface of a glassy carbon electrode, the glassy carbon electrode is taken as a working electrode after natural drying, 0.5N dilute sulfuric acid solution is taken as electrolyte, the glassy carbon electrode adhered with the composite material is taken as the working electrode, a platinum wire is taken as a counter electrode, an Ag/AgCl electrode is taken as a reference electrode to carry out charge-discharge test and cyclic voltammetry test, the test voltage range is-0.1-0.8V, and pure polypyrrole is taken as a comparison material.
According to the test result, the amino graphene oxide/cellulose acetate composite material containing polypyrrole has better electrochemical capacitance than pure polypyrrole. At 5-10 mV/S, the scan curve approximates a rectangle, with the CV curve gradually deviating from the "rectangle" as the scan rate increased, due to the reduced interaction between the ions and the electrode caused by the impedance inside the composite electrode. It can also be seen that the integrated area of the CV curve of the composite is significantly higher than the area of pure polypyrrole at the same scan rate, indicating that the polypyrrole-containing aminographene oxide/cellulose acetate composite has higher electrochemical activity.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents and modifications within the scope of the description.
Claims (7)
1. An amino graphene oxide/cellulose acetate composite material containing polypyrrole, which is characterized in that: the preparation method comprises the following steps:
firstly, preparing Graphene Oxide (GO) into a 1mg/ml solution, carrying out ultrasonic treatment on 50ml of the solution in a water bath, then weighing 15mg of N, N-dimethylethylenediamine or N, N-diethylethylenediamine, adding the N, N-dimethylethylenediamine into the GO solution, adding 12mg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC.HCl), 100 mg of N-hydroxysuccinimide (NHS) and 12mg of 4-Dimethylaminopyridine (DMAP), stirring at 25 ℃ for reaction for 24 hours, centrifuging the solution at 6000 revolutions for 1 hour after the reaction is finished, discarding the supernatant, repeatedly washing the lower-layer substance with deionized water for three times, and carrying out freeze drying for 12 hours to obtain an aminated graphene oxide solution;
then mixing the aminated graphene oxide suspension with an alkaline solution of cellulose diacetate, and stirring, mechanically shearing or ultrasonically treating the mixed solution to obtain an aminated graphene oxide/cellulose composite material, wherein the alkaline solution is as follows: fully mixing sodium carbonate or sodium hydroxide, urea, thiourea and deionized water according to the weight ratio of 1-10:4-10: 0-10: 70-95;
finally, dissolving the aminated graphene oxide/cellulose acetate composite material with deionized water and ultrasonically treating the mixture to form a suspension, adding pyrrole monomers, then respectively adding doping agents such as NaCl and DBSDA in equal amount, slowly adding an oxidizing agent FeCl3.6H2O while stirring, polymerizing the pyrrole monomers for 6-24 hours, centrifugally separating the obtained suspension, precipitating the suspension in deionized water, ultrasonically dispersing and washing until the upper layer liquid obtained by centrifugal separation is neutral, placing the product in a Buchner funnel, filtering by using a microporous filter membrane, freeze-drying the precipitate for 24 hours, and grinding to obtain black aminated graphene oxide/cellulose acetate composite material powder containing polypyrrole;
the method comprises the following specific steps of mixing the aminated graphene oxide suspension with an alkaline solution of cellulose diacetate to obtain the aminated graphene oxide/cellulose acetate composite material:
1) dissolving aminated graphene oxide by using deionized water, and carrying out ultrasonic treatment in an ultrasonic device with the power of 300-1000W for 0.5-5h to obtain an uniformly dispersed aminated graphene oxide suspension;
2) fully mixing sodium carbonate or sodium hydroxide, urea, thiourea and deionized water according to the weight ratio of 1-10:4-10: 0-10: 70-95;
3) then adding a cellulose acetate suspension, stirring at-10 to 20 ℃, mechanically shearing or ultrasonically processing for 12 to 24 hours, and filtering and washing to obtain the aminated graphene oxide/cellulose acetate composite material.
2. The polypyrrole-containing graphene oxide-amino/cellulose acetate composite material according to claim 1, wherein: the mixing and dissolving ratio of the alkali solution of the cellulose diacetate to the aminated graphene oxide suspension is 1: 1-10: 1.
3. The polypyrrole-containing graphene oxide-amino/cellulose acetate composite material according to claim 1, wherein: in the polymerization reaction of the pyrrole monomer, the mass of the pyrrole monomer is 10-100% of that of the cellulose diacetate.
4. The polypyrrole-containing graphene oxide-amino/cellulose acetate composite material according to claim 1, wherein: the graphene oxide is single-layer graphene oxide, multi-layer graphene oxide or a mixture of the two.
5. The polypyrrole-containing graphene oxide-amino/cellulose acetate composite material according to claim 1, wherein: in the preparation of the aminated graphene oxide solution, the selected amino fragment is N, N-dimethylethylenediamine or N, N-diethylethylenediamine, and the condensing agent is EDC.HCl and NHS.
6. The use of a polypyrrole-containing graphene oxide-amino/cellulose acetate composite material according to claim 1, wherein: the application of adsorbing and purifying waste gas and waste water containing organic matters and/or heavy metal ions.
7. The use of a polypyrrole-containing graphene oxide-amino/cellulose acetate composite material according to claim 1, wherein: the material is applied to conductive composite films, super capacitors, electrodes and electrocatalytic materials.
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| CN110564098B (en) * | 2019-07-29 | 2023-09-05 | 河北晨阳工贸集团有限公司 | Nano lignocellulose/graphite-like carbon nitride composite material, wood coating, preparation method and application |
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| CN114249916A (en) * | 2022-01-12 | 2022-03-29 | 华尔科技集团股份有限公司 | Polymer composite film and electrostatic generator using same |
| CN115715976A (en) * | 2022-11-29 | 2023-02-28 | 西安工业大学 | Method for selectively adsorbing lithium ions based on protein/inorganic nanoparticle composite membrane |
| CN116059980A (en) * | 2022-12-08 | 2023-05-05 | 华北电力大学（保定） | Halogen doped polypyrrole adsorbent, and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489259A (en) * | 2011-11-10 | 2012-06-13 | 河南大学 | Graphene oxide/cellulose compound material as well as preparation method and application of same |
| CN103346325A (en) * | 2013-06-28 | 2013-10-09 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery |
| CN105032488A (en) * | 2015-06-21 | 2015-11-11 | 苏州大学 | Manganese-Schiff base-graphene oxide compound and preparation method thereof |
| CN105355450A (en) * | 2015-12-25 | 2016-02-24 | 哈尔滨工业大学 | Preparation method and application of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacterial cellulose membrane material |
| CN105428080A (en) * | 2015-12-25 | 2016-03-23 | 哈尔滨工业大学 | Preparation method for bacterial cellulose based polypyrrole/graphene flexible electrode material and application thereof |
| CN105609326A (en) * | 2015-12-25 | 2016-05-25 | 哈尔滨工业大学 | Preparation method and application of polypyrrole/graphene/bacterial cellulose conducting film material |
| CN106057279A (en) * | 2016-05-27 | 2016-10-26 | 北京林业大学 | Novel polymer/graphene flexible conductive composite film and preparation method thereof |
| CN110449039A (en) * | 2019-08-16 | 2019-11-15 | 宁波石墨烯创新中心有限公司 | A kind of graphene/graphene oxide base seperation film and preparation method thereof |
-
2017
- 2017-10-11 CN CN201710941999.3A patent/CN107899551B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489259A (en) * | 2011-11-10 | 2012-06-13 | 河南大学 | Graphene oxide/cellulose compound material as well as preparation method and application of same |
| CN103346325A (en) * | 2013-06-28 | 2013-10-09 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery |
| CN105032488A (en) * | 2015-06-21 | 2015-11-11 | 苏州大学 | Manganese-Schiff base-graphene oxide compound and preparation method thereof |
| CN105355450A (en) * | 2015-12-25 | 2016-02-24 | 哈尔滨工业大学 | Preparation method and application of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacterial cellulose membrane material |
| CN105428080A (en) * | 2015-12-25 | 2016-03-23 | 哈尔滨工业大学 | Preparation method for bacterial cellulose based polypyrrole/graphene flexible electrode material and application thereof |
| CN105609326A (en) * | 2015-12-25 | 2016-05-25 | 哈尔滨工业大学 | Preparation method and application of polypyrrole/graphene/bacterial cellulose conducting film material |
| CN106057279A (en) * | 2016-05-27 | 2016-10-26 | 北京林业大学 | Novel polymer/graphene flexible conductive composite film and preparation method thereof |
| CN110449039A (en) * | 2019-08-16 | 2019-11-15 | 宁波石墨烯创新中心有限公司 | A kind of graphene/graphene oxide base seperation film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis and Electrochemical Characterization of Modified Graphene/Polypyrrole Nanocomposites;Sumanta Sahoo等;《Macromol. Symp.》;20121231;第315卷;第177–187页 * |
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