CN107501612B - 3D printing graphene oxide/cellulose composite material and preparation method and application thereof - Google Patents
3D printing graphene oxide/cellulose composite material and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The invention discloses a 3D printing graphene oxide/cellulose composite material and a preparation method and application thereof. The method comprises the following steps: (1) dissolving sodium hydroxide and urea into water to obtain a sodium hydroxide/urea aqueous solution; (2) precooling the sodium hydroxide/urea aqueous solution obtained in the step (1) to-8-15 ℃, adding the slurry, and stirring for dissolving to obtain a cellulose solution; (3) dispersing graphene oxide into the cellulose solution obtained in the step (2), and adding an adhesive to obtain a mixed solution; (4) and (4) performing 3D printing on the mixed solution obtained in the step (3) to obtain a 3D printed graphene oxide/cellulose composite material. The composite material prepared by the method has the characteristics of high flexibility, high heat resistance, high conductivity and the like, and can be applied to the fields of high-performance electronic devices, sensors, semiconductors and the like.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a 3D printing graphene oxide/cellulose composite material, and a preparation method and application thereof.
Background
With the rapid development of society, various electronic devices are being introduced into people's daily life, and the people's life is constantly facilitated. However, some potential problems are also caused. Electronic devices used at present are mainly constructed on silicon wafers, glass and plastic films, and the substrates can be degraded only after hundreds of years or even thousands of years under natural conditions, which does not meet the sustainable development target of human society. Cellulose has attracted attention as the most abundant natural renewable polymer material in nature. Various environment-friendly composite materials can be prepared by using cellulose. Direct processing of cellulose becomes extremely difficult due to the complex network of hydrogen bonds in the cellulose molecule. Professor Zhang Li Na of Wuhan university develops a set of alkali/urea system for quickly and effectively dissolving cellulose at low temperature, and therefore, the alkali/urea system has great significance for reprocessing cellulose solution to prepare various advanced composite materials. The three-dimensional materials of various ideal models are manufactured by 3D printing by utilizing the characteristics of cellulose dissolution and solidification, and the application field of cellulose is greatly widened.
However, the simple production of various three-dimensional model materials from cellulose is difficult to meet the requirements of modern high-performance products, and the search for reinforcement with excellent performance to prepare cellulose-based composite materials is very important. In recent years, research results of graphene oxide and graphene composite materials are continuously emerging, and the graphene oxide composite materials have great application potential in the fields of electrochemistry, catalysis, energy storage and the like. The rich oxygen-containing functional groups endow the graphene oxide with good hydrophilicity and chemical modification, and are beneficial to preparing various functionalized composite materials. However, no report is found on the preparation of a composite material having strong thermal stability and electrical conductivity by mixing graphene oxide with cellulose and using a 3D printing technique.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a 3D printing graphene oxide/cellulose composite material.
The invention also aims to provide the 3D printing graphene oxide/cellulose composite material prepared by the method.
The invention further aims to provide application of the 3D printing graphene oxide/cellulose composite material.
The purpose of the invention is realized by the following technical scheme: a preparation method of a 3D printing graphene oxide/cellulose composite material comprises the following steps:
(1) dissolving sodium hydroxide and urea into water to obtain a sodium hydroxide/urea aqueous solution;
(2) precooling the sodium hydroxide/urea aqueous solution obtained in the step (1) to-8-15 ℃, adding the slurry, and stirring for dissolving to obtain a cellulose solution;
(3) dispersing graphene oxide into the cellulose solution obtained in the step (2), and adding an adhesive to obtain a mixed solution;
(4) and (4) performing 3D printing on the mixed solution obtained in the step (3) to obtain a 3D printed graphene oxide/cellulose composite material.
The water in the step (1) is preferably deionized water.
The mass fraction of the sodium hydroxide in the sodium hydroxide/urea aqueous solution in the step (1) is 6-10%, and the mass fraction of the urea is 10-15%.
And (3) precooling in the step (2) is carried out in a low-temperature cooling circulating pump.
The pulp in the step (2) is bleached linseed pulp.
And (3) calculating the addition amount of the slurry in the step (2) according to the absolute dry weight of the slurry which is 2-5% of the mass of the sodium hydroxide/urea aqueous solution.
The stirring in the step (2) is preferably performed in a high-speed dispersion homogenizer.
The stirring speed in the step (2) is preferably 2000-10000 r/min.
The stirring time in the step (2) is preferably 4-8 min.
The addition amount of the graphene oxide in the step (3) is that the mass ratio of the graphene oxide to the sodium hydroxide/urea aqueous solution is 0-0.03: 1, calculating the mixture ratio; preferably, the mass ratio of the graphene oxide to the sodium hydroxide/urea aqueous solution is 0.01-0.03: 1, calculating the mixture ratio.
The adhesive in the step (3) is preferably guar gum, and the liquid viscosity reaches 2000-6500 mPa & s after the adhesive is added.
The addition amount of the adhesive in the step (3) is that the mass ratio of the adhesive to the sodium hydroxide/urea aqueous solution is 0.001-0.005: 1, calculating the mixture ratio.
And (3) dispersing in a stirring mode.
The stirring speed is 1000-5000 r/min.
And (4) printing in the step (3) is performed by adopting a 3D printer.
The 3D printer is a double-nozzle 3D printer, and the coagulating liquid is 5% (v/v) dilute sulfuric acid.
The parameters of 3D printing described in step (3) are preferably: the diameter of the nozzle is 0.2mm, the printing precision is 0.1mm, the printing speed is 30mm/s, and the working temperature of the bottom plate is 120 ℃.
The graphene oxide in the step (3) is preferably prepared by the following method:
(a) stirring and adding natural graphite powder and sodium nitrate into concentrated sulfuric acid under the condition of ice-water bath, adding potassium permanganate, transferring a reaction system into an oil bath, and reacting at 35 +/-5 ℃ to obtain a reaction system I;
(b) adding water into the reaction system I obtained in the step (a), reacting at 90 +/-5 ℃, sequentially adding water and hydrogen peroxide, filtering and cleaning to obtain the graphene oxide.
The temperature of adding potassium permanganate in the step (a) is not more than 2 ℃.
The concentration of the concentrated sulfuric acid in the step (a) is preferably 98% by mass.
The mass ratio of the natural graphite powder, the sodium nitrate and the potassium permanganate in the step (a) is preferably 2: 1: 6.
the reaction time in step (a) is preferably 30 min.
The water in step (b) is preferably ionized water.
The reaction time in step (b) is preferably 15 min.
The concentration of the hydrogen peroxide in the step (b) is 30 percent by mass.
The cleaning in the step (b) is carried out by adopting hydrochloric acid aqueous solution; preferably, hydrochloric acid and water are adopted according to the volume ratio of 1: 10 and washing with an aqueous hydrochloric acid solution.
The graphene oxide obtained in the step (b) further comprises the steps of removing residual acid and metal ions, purifying, and freeze-drying.
The removal of residual acid and metal ions is preferably achieved by: adding deionized water into the graphene oxide, and performing suction filtration to remove residual acid; and adding deionized water for dilution, dialyzing and removing residual metal ions.
The dialysis time is 5-8 days, preferably 7 days.
The purification is preferably achieved by: and dispersing the graphene oxide with the residual acid and metal ions removed into water, centrifuging, then taking the lower-layer solid to disperse into the water, centrifuging, taking the upper-layer liquid to centrifuge, and obtaining the purified graphene oxide.
The dispersion mode is stirring or ultrasonic treatment.
The conditions of the first centrifugation are as follows: centrifuging at 10000rpm for 20 min.
The conditions of the second and third centrifugation are: centrifuging at 4000rpm for 30 min.
A3D printing graphene oxide/cellulose composite material is prepared by any one of the methods.
The 3D printing graphene oxide/cellulose composite material is applied to conductive materials, high-performance electronic devices, sensors or semiconductors.
Compared with the prior art, the invention has the following advantages and effects:
1. the method has simple process and can quickly obtain the preset ideal three-dimensional model material. The obtained material is convenient to apply and can meet the requirements on various sizes.
2. The composite material prepared by the method has the characteristics of high flexibility, high heat resistance, high conductivity and the like, and can be applied to the fields of high-performance electronic devices, sensors, semiconductors and the like.
3. The graphene oxide has rich oxygen-containing functional groups and good hydrophilicity and chemical modification, and is favorable for preparing various functionalized composite materials. And adding a proper amount of guar gum solution to perform rheological control on the cellulose solution so as to meet the requirement of 3D printing, and manufacturing the composite material of the preset model through a 3D printer.
Drawings
FIG. 1 is a thermogravimetric analysis (TG plot) of the graphene oxide/cellulose composite and regenerated cellulose in examples 1-4 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The graphene oxide used in the invention is prepared by the following steps:
stirring a beaker filled with concentrated sulfuric acid (70mL, 98 wt%) in an ice-water bath, adding natural graphite powder (3g) and sodium nitrate (1.5g) into the beaker respectively, stirring for a period of time, and slowly adding potassium permanganate (9.0g) into the beaker, wherein the temperature is kept to be not more than 2 ℃. The reaction system was transferred to an oil bath and reacted at 35. + -. 5 ℃ for 30 min. Then 150ml of deionized water was slowly added to maintain the temperature at 90. + -. 5 ℃ for 15 minutes. After 500ml of water is added, 15ml of hydrogen peroxide with the concentration of 30 percent by mass is added, and the color of the solution is changed from black brown to bright yellow. The product was filtered and purified by a volume ratio of 1: after washing with 10 ml of aqueous hydrochloric acid (250ml), 250ml of deionized water was added and the residual acid was removed by suction filtration. After the filtration, 500ml deionized water is added for dilution, and the solution is dialyzed for 7 days to remove residual metal ions, treated in ultrasonic waves and centrifuged. And after dialysis, transferring the sample into a beaker, stirring to completely disperse the sample in water (if dispersion cannot be carried out by adopting short-time ultrasonic treatment), carrying out centrifugal purification after complete dispersion, firstly centrifuging at 10000rpm for 20min to remove upper-layer liquid, reserving a lower-layer sample, after centrifugation is finished, completely dispersing with 300ml of deionized water, centrifuging at 4000rpm for 30min, reserving upper-layer liquid, removing residual graphite and graphite oxide on the lower layer, and centrifuging at 4000rpm for 30min again to reserve upper-layer liquid, thus obtaining the graphene oxide. And (4) freeze-drying the solution to obtain a graphene oxide solid.
Example 1
A preparation method of a graphene oxide/cellulose composite material for 3D printing comprises the following steps:
(1) adding sodium hydroxide, urea and deionized water into a 500ml beaker to form 300g of sodium hydroxide/urea aqueous solution as a solvent, wherein the mass fraction of the sodium hydroxide in the obtained sodium hydroxide/urea aqueous solution (solvent) is 6%, and the mass fraction of the urea is 10%;
(2) the sodium hydroxide/urea aqueous solution obtained above is placed in a low-temperature cooling circulating pump to be pre-cooled to-8 ℃, and 2 percent of oven-dried bleached flax pulp (percentage of oven-dried amount of pulp relative to the mass of solvent) is added into the solution. Stirring for 4min at 4000r/min by using a high-speed dispersion homogenizer to form a transparent cellulose solution;
(3) adding 3g of graphene oxide (accounting for 1% of the solvent by mass) into the cellulose solution for a plurality of times in a small amount, dispersing the graphene oxide in the cellulose solution under the stirring condition of 2000r/min, adding 0.1% of guar gum (relative to the solvent by mass) to obtain a mixed solution, and measuring the viscosity of the liquid;
(4) and (3) manufacturing a preset three-dimensional model material by the mixed solution through a 3D printer. Wherein the printing mode is double-nozzle printing, and the solidification liquid is 5% (v/v) dilute sulfuric acid. The printing parameters are as follows: the diameter of the nozzle is 0.2mm, the printing precision is 0.1mm, the printing speed is 30mm/s, and the working temperature of the bottom plate is 120 ℃.
Example 2
A preparation method of a graphene oxide/cellulose composite material for 3D printing comprises the following steps:
(1) adding sodium hydroxide, urea and deionized water into a 500ml beaker to form 300g of sodium hydroxide/urea aqueous solution as a solvent, wherein the mass fraction of the sodium hydroxide in the sodium hydroxide/urea aqueous solution is 7%, and the mass fraction of the urea is 11%;
(2) placing the obtained sodium hydroxide/urea aqueous solution in a low-temperature cooling circulating pump for precooling to-10 ℃, and adding 3% (weight of pulp relative to the mass of the agent) of oven-dried bleached flax pulp into the solution. Stirring for 5min at 6000r/min by using a high-speed dispersion homogenizer to form a transparent cellulose solution;
(3) adding 6g of graphene oxide (accounting for 2% of the mass of the solution) into the cellulose solution for a plurality of times in a small amount, dispersing the graphene oxide in the cellulose solution under the stirring condition of 3000r/min, simultaneously adding 0.2% of guar gum (relative to the mass of the solvent) to obtain a mixed solution, and measuring the viscosity of the liquid;
(4) and (3) manufacturing a preset three-dimensional model material by the mixed solution through a 3D printer. Wherein the printing mode is double-nozzle printing, and the solidification liquid is 5% (v/v) dilute sulfuric acid. The printing parameters are as follows: the diameter of the nozzle is 0.2mm, the printing precision is 0.1mm, the printing speed is 30mm/s, and the working temperature of the bottom plate is 120 ℃.
Example 3
A preparation method of a graphene oxide/cellulose composite material for 3D printing comprises the following steps:
(1) adding sodium hydroxide, urea and deionized water into a 500ml beaker to form 300g of sodium hydroxide/urea aqueous solution as a solvent, wherein the mass fraction of the sodium hydroxide in the sodium hydroxide/urea aqueous solution is 8%, and the mass fraction of the urea is 12%;
(2) placing the obtained sodium hydroxide/urea aqueous solution in a low-temperature cooling circulating pump for precooling to-12 ℃, and adding 4% (percentage of absolute dry amount of pulp to mass of solution) of absolute dry bleached flax pulp into the solution. Stirring for 6min at 8000r/min by using a high-speed dispersion homogenizer to form a transparent cellulose solution;
(3) adding 7.5g of graphene oxide (accounting for 2.5 percent of the mass of the solution) into the cellulose solution for a plurality of times in a small amount, dispersing the graphene oxide in the cellulose solution under the stirring condition of 4000r/min, adding 0.3 percent of guar gum (relative to the mass of the solvent) to obtain a mixed solution, and measuring the viscosity of the liquid;
(4) and (3) manufacturing a preset three-dimensional model material by the mixed solution through a 3D printer. Wherein the printing mode is double-nozzle printing, and the solidification liquid is 5% (v/v) dilute sulfuric acid. The printing parameters are as follows: the diameter of the nozzle is 0.2mm, the printing precision is 0.1mm, the printing speed is 30mm/s, and the working temperature of the bottom plate is 120 ℃.
Example 4
A preparation method of a graphene oxide/cellulose composite material for 3D printing comprises the following steps:
(1) adding sodium hydroxide, urea and deionized water into a 500ml beaker to form 300g of sodium hydroxide/urea aqueous solution as a solvent, wherein the mass fraction of the sodium hydroxide in the sodium hydroxide/urea aqueous solution is 10%, and the mass fraction of the urea is 15%;
(2) placing the obtained sodium hydroxide/urea aqueous solution in a low-temperature cooling circulating pump for precooling to-15 ℃, and adding 5% (weight percentage of absolute dry amount of pulp to mass of solution) of absolute dry bleached flax pulp into the solution. Stirring for 8min at 10000r/min by using a high-speed dispersion homogenizer to form a transparent cellulose solution;
(3) adding 9g of graphene oxide (accounting for 3% of the solvent by mass) into the cellulose solution for a plurality of times in a small amount, dispersing the graphene oxide in the cellulose solution under the stirring condition of 5000r/min, adding 0.5% of guar gum (relative to the solvent by mass) to obtain a mixed solution, and measuring the viscosity of the liquid;
(4) and (3) manufacturing a preset three-dimensional model material by the mixed solution through a 3D printer. Wherein the printing mode is double-nozzle printing, and the solidification liquid is 5% (v/v) dilute sulfuric acid. The printing parameters are as follows: the diameter of the nozzle is 0.2mm, the printing precision is 0.1mm, the printing speed is 30mm/s, and the working temperature of the bottom plate is 120 ℃.
Comparative example 1
The preparation method of the flax regenerated cellulose material without adding graphene oxide comprises the following steps:
(1) adding sodium hydroxide, urea and deionized water into a 500ml beaker to form 300g of sodium hydroxide/urea aqueous solution as a solvent, wherein the mass fraction of the sodium hydroxide in the sodium hydroxide/urea aqueous solution is 8%, and the mass fraction of the urea is 12%;
(2) placing the obtained sodium hydroxide/urea aqueous solution in a low-temperature cooling circulating pump for precooling to-12 ℃, and adding 4% (percentage of absolute dry amount of pulp to mass of solution) of absolute dry bleached flax pulp into the solution. Stirring for 6min at 8000r/min by using a high-speed dispersion homogenizer to form a transparent cellulose solution;
(3) adding 0.3% of guar gum (relative to the mass of the solvent) into the cellulose solution to obtain a mixed solution, and measuring the viscosity of the liquid;
(4) and (3) manufacturing a preset three-dimensional model material by the mixed solution through a 3D printer. Wherein the printing mode is double-nozzle printing, and the solidification liquid is 5% (v/v) dilute sulfuric acid. The printing parameters are as follows: the diameter of the nozzle is 0.2mm, the printing precision is 0.1mm, the printing speed is 30mm/s, and the working temperature of the bottom plate is 120 ℃.
Effects of the embodiment
The graphene oxide/cellulose composite material can be used for testing the thermal stability and the conductivity of the 3D printing graphene oxide/cellulose composite material: the thermal stability and conductivity of the graphene oxide/cellulose composite material prepared in examples 1 to 4 and the flax regenerated cellulose (without graphene oxide) prepared in comparative example 1 were tested, and the viscosity of the mixed solution before 3D printing was also determined.
(1) And (3) measuring the viscosity: the viscosity measuring instrument is a Brookfield DV-II + viscometer, a No. 1 rotor (rotating disc) and 300 r/min. To ensure repeatability of results, the torque output by the rotor during testing should be greater than 10% span. The measurement temperatures were all 35 ℃ and the results are shown in Table 1.
(2) Measurement of conductivity: a sample of the composite material obtained in the above example was selected, sufficiently ground, pressed at 15MPa into a circular sheet having a thickness of 1mm and a diameter of 12mm, and tested for electrical conductivity, the results of which are shown in Table 1.
(3) TG analysis: thermogravimetric analysis was performed on the sample using a thermogravimetric analyzer (TA Q500, usa), and 5g of the sample was accurately weighed and placed in a loading crucible for thermogravimetric analysis. And (3) testing conditions are as follows: the carrier gas is high-purity nitrogen, the flow rate is 20mL/min, the test temperature is 30-600 ℃, and the heating rate is 10K/min. The TG analysis curve is shown in FIG. 1.
TABLE 1 viscosity and conductivity measurements of graphene oxide/cellulose composites and regenerated cellulose prepared in examples 1-4 above
| Sample (I) | Viscosity (mPa. s) | Conductivity S/cm |
| Example 1 | 2597.8 | 7.2×10-3 |
| Example 2 | 3864.9 | 8.9×10-2 |
| Example 3 | 6121.5 | 3.2×10-1 |
| Example 4 | 6457.2 | 5.4×10-1 |
| Comparative example 1 | 1888.5 | 5.6×10-12 |
From table 1, it can be seen that the addition of graphene to the cellulose-based material greatly improves the electrical conductivity of the cellulose-based composite material. The conductivity gradually increases with the increase of the addition amount of graphene oxide. Additionally, as the amount of slurry was increased, the viscosity of the entire mixed liquor system increased, with example 3 being closer to the requirements of the 3D printer.
As can be seen from fig. 1, the addition of graphene to cellulose greatly improves the thermal stability of the cellulose-based material. With the increase of the addition amount of the graphene oxide, the thermal stability of the cellulose-based composite material is also improved, so that the application range of the cellulose material is greatly expanded.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. A preparation method of a 3D printing graphene oxide/cellulose composite material is characterized by comprising the following steps:
(1) dissolving sodium hydroxide and urea into water to obtain a sodium hydroxide/urea aqueous solution;
(2) precooling the sodium hydroxide/urea aqueous solution obtained in the step (1) to-8-15 ℃, adding the slurry, and stirring for dissolving to obtain a cellulose solution;
(3) dispersing graphene oxide into the cellulose solution obtained in the step (2), and adding an adhesive to obtain a mixed solution;
(4) 3D printing is carried out on the mixed solution obtained in the step (3), and a 3D printed graphene oxide/cellulose composite material is obtained;
the mass fraction of sodium hydroxide in the sodium hydroxide/urea aqueous solution in the step (1) is 6-10%, and the mass fraction of urea is 10-15%;
the pulp in the step (2) is bleached linseed pulp;
the addition amount of the slurry in the step (2) is calculated according to the absolute dry weight of the slurry which is 2-5% of the mass of the sodium hydroxide/urea aqueous solution;
the adhesive in the step (3) is guar gum;
the addition amount of the graphene oxide in the step (3) is 0.01-0.03 by mass of the graphene oxide and the sodium hydroxide/urea aqueous solution: 1, calculating the mixture ratio;
the addition amount of the adhesive in the step (3) is 0.001-0.005 in terms of the mass ratio of the adhesive to the sodium hydroxide/urea aqueous solution: 1, calculating the mixture ratio;
the solidification liquid used for 3D printing in the step (3) is 5% (v/v) dilute sulfuric acid.
2. The preparation method of the 3D printed graphene oxide/cellulose composite material according to claim 1, wherein:
the printing in the step (3) is performed by adopting a 3D printer; the 3D printer be dual spray 3D printer.
3. The preparation method of the 3D printed graphene oxide/cellulose composite material according to claim 1, wherein:
the parameters of 3D printing in the step (3) are as follows: the diameter of the nozzle is 0.2mm, the printing precision is 0.1mm, the printing speed is 30mm/s, and the working temperature of the bottom plate is 120 ℃.
4. The preparation method of the 3D printed graphene oxide/cellulose composite material according to claim 1, wherein:
the water in the step (1) is deionized water;
the precooling in the step (2) is carried out in a low-temperature cooling circulating pump;
the stirring in the step (2) is carried out in a high-speed dispersion homogenizer; the stirring speed is 2000-10000 r/min, and the stirring time is 4-8 min;
the dispersion in the step (3) is performed in a stirring manner; the stirring speed is 1000-5000 r/min.
5. The utility model provides a 3D prints graphene oxide/cellulose combined material which characterized in that: prepared by the method of any one of claims 1 to 4.
6. Use of the 3D printed graphene oxide/cellulose composite material according to claim 5 in conductive materials, high performance electronics, sensors or semiconductors.
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