CN114914451A - Preparation method of conductive material for lithium battery anode - Google Patents
Preparation method of conductive material for lithium battery anode Download PDFInfo
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Abstract
The invention discloses a preparation method of a conductive material for a lithium battery anode, belonging to the field of electrochemical material preparation, and comprising the following steps: 1) preparing a graphene porous microtube; 2) preparing a primary modified graphene porous microtube; 3) preparing a modified graphene porous microtube; 4) and preparing the conductive material for the lithium battery anode. According to the invention, graphene is used as a substrate, amino-terminated polyamidoamine dendrimer is synthesized in a sheet layer and a porous hole of a graphene porous microtube, the graphene porous microtube is subjected to non-covalent bond modification, the modified graphene porous microtube is then blended with silver nitrate, the amino-terminated polyamidoamine is used as a template agent and a reducing agent, a silver precursor and the amino-terminated polyamidoamine are subjected to complexation and thermal reduction to prepare nano silver particles, compared with the traditional graphene sheet, the content of hybridized nano silver particles is remarkably improved by enlarging the specific surface area and increasing the hybridization sites, and the technical problem that the conductivity of the graphene which is actually exerted is lower is solved.
Description
Technical Field
The invention belongs to the field of electrochemical material preparation, and particularly relates to a preparation method of a conductive material for a lithium battery anode.
Background
The lithium ion battery is used as a new generation of green and environment-friendly power supply, has the advantages of high energy density, high voltage, small self-discharge, no memory effect and the like, and is widely applied to products such as mobile phones, cameras, notebook computers, electric tools, electric bicycles, electric automobiles and the like. With the rapid development of electronic products, the requirements on the energy and power of a lithium ion battery are higher and higher, and the anode material of the lithium ion battery is an important component of the lithium ion battery and is a main influence factor on the performance of the lithium ion battery.
Graphene is a material consisting of carbon atoms in sp 2 The honeycomb planar film formed by the hybridization mode is a quasi-two-dimensional material with the thickness of only one atomic layer, so the film is called monoatomic layer graphite, and is a novel nano material which is the thinnest, the highest in strength and the strongest in electric conduction and heat conduction performance and is discovered at present.
The theoretical conductivity of the graphene can reach 10 6 S/cm, far exceeding that of common carbon materials. However, in practical applications, the electrical conductivity actually exhibited by graphene is 10 due to the contact resistance between graphene sheets and the internal defects thereof 3 The level below S/cm is equivalent to the related performances of materials such as carbon nanotubes, vapor grown carbon nanofibers and the like, so the application of the carbon nanotubes in the electrochemical field is limited.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a conductive material for a lithium battery anode.
The technical scheme adopted for achieving the purpose of the invention is as follows: a preparation method of a conductive material for a lithium battery anode comprises the following steps:
1) preparation of graphene porous microtubes
Soaking the polyester fiber coated with the graphene oxide solution prepared by an electrostatic method into a calcium chloride solution, taking out the polyester fiber after soaking, washing the polyester fiber in deionized water to remove calcium chloride, drying the polyester fiber, and calcining the polyester fiber at high temperature under the protection of argon to prepare the graphene porous microtube;
2) preparation of primarily modified graphene porous microtubes
Adding the graphene porous microtube prepared in the step 1) into deionized water to prepare a suspension, adding ethylenediamine, performing ultrasonic dispersion to prepare a mixed solution, adding methanol, continuously stirring, slowly dropwise adding methyl acrylate, introducing nitrogen, discharging air, reacting while stirring, heating, and removing methanol and methyl acrylate to prepare a primary modified graphene porous microtube;
3) preparation of modified graphene porous microtubes
Adding the primarily modified graphene porous micro-tube prepared in the step 2) into methanol, slowly dropwise adding ethylenediamine, continuously reacting at room temperature, and removing redundant methanol and ethylenediamine to obtain a modified graphene porous micro-tube;
4) preparation of conductive material for lithium battery anode
Adding the modified graphene porous microtube prepared in the step 3) into methanol, stirring at a constant speed, adding silver acetate, slowly stirring, then distilling under reduced pressure to remove the methanol to prepare a compound, and then carrying out heat treatment to prepare the conductive material for the lithium battery anode.
Preferably, the polyester fiber coated with the graphene oxide solution prepared by the electrostatic method in step 1) is prepared by the following steps: and (2) spraying the graphene oxide aqueous solution from the needle head through a propulsion pump, arranging a substrate under the needle head, placing a rectangular frame on the substrate, and uniformly winding polyester fibers on the frame to prepare the polyester fibers coated with the graphene oxide solution.
Preferably, the mass fraction of the calcium chloride solution is 5-10%, and the drying temperature is 45-60 ℃; the reaction conditions of the high-temperature calcination are as follows: heating to 800-850 ℃ at the heating rate of 5-10 ℃/min, and carrying out heat preservation treatment for 2-3 h.
Preferably, the mass fraction of the graphene oxide aqueous solution is 2-3%, the ejection speed of a needle is 10-12 muL/min, and the ejection time is controlled to be 25-35 min; a substrate is arranged 2.5-3.5cm under the needle head, a high voltage of 7-8kV is applied between the needle head and the substrate, and the rectangular frame is turned over once every 10-15 min.
Preferably, the dosage ratio of the graphene porous microtube, the deionized water, the ethylenediamine, the methanol and the methyl acrylate in the step 2) is 1-1.5g, 50mL, 1.5-2g, 60-65mL, 17.0-17.2 g.
Preferably, the dosage ratio of the primarily modified graphene porous microtube, methanol and ethylenediamine in step 3) of the invention is 22.5-23.2g, 150mL, 18.5-19.2 g.
Preferably, the dosage ratio of the modified graphene porous microtube, methanol and silver acetate in the step 4) of the invention is 2 g: 15-20 mL: 1 g.
Preferably, the temperature of the heat treatment in the step 4) of the invention is controlled at 130-150 ℃ and the heat treatment time is 3-5 h.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the conductive material for the lithium battery anode takes graphene as a substrate, graphene oxide aqueous solution is sprayed on the surface of polyester fiber by an electrostatic spraying method, the polyester fiber is taken as a base material to prepare the polyester fiber coated with the graphene oxide solution, then the polyester fiber is placed in calcium chloride solution to improve the fiber strength, the polyester fiber is added into a tube furnace to be calcined, through thermal reduction, on one hand, graphene nanosheets on the surface of the fiber are reduced, on the other hand, the polyester fiber is removed at high temperature to prepare the graphene porous microtube, because of the interaction between amino-containing molecules and a conjugated pi structure, a Michael addition reaction is carried out between ethylenediamine and methyl acrylate to generate an intermediate product, then, excessive ethylenediamine and the intermediate product are subjected to an amidation reaction completely to generate an amino-terminated polyamidoamine dendrimer, and through the synthesis of the amino-terminated polyamidoamine dendrimer in the lamella and the porous holes of the graphene porous microtube, the preparation method comprises the steps of modifying a graphene porous microtube in a non-covalent bond mode to prepare a modified graphene porous microtube, then blending the modified graphene porous microtube with silver nitrate, using amino-terminated polyamide amine as a template agent and a reducing agent, complexing a silver precursor with the amino-terminated polyamide amine, and performing thermal reduction to prepare nano silver particles.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. Other embodiments, which can be derived by one of ordinary skill in the art from the embodiments given herein without any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a preparation method of a conductive material for a lithium battery anode, which comprises the following steps:
1) preparing a graphene porous microtube: and (3) immersing the polyester fiber coated with the graphene oxide solution prepared by the electrostatic method into a calcium chloride solution, taking out after immersion, placing in deionized water for washing to remove calcium chloride, drying, and then calcining at high temperature under the protection of argon to prepare the graphene porous microtube.
According to the invention, a graphene oxide aqueous solution is sprayed on the surface of a polyester fiber by an electrostatic spraying method, the polyester fiber is used as a base material to prepare the polyester fiber coated with the graphene oxide solution, then the polyester fiber is placed in a calcium chloride solution to improve the fiber strength, and thermal reduction is carried out by high-temperature calcination, so that graphene nanosheets on the surface of the fiber are reduced, the polyester fiber is removed at high temperature, and the graphene porous microtube is prepared.
2) Preparing a primary modified graphene porous microtube: adding the graphene porous microtube into deionized water to prepare a suspension, adding ethylenediamine, performing ultrasonic dispersion to prepare a mixed solution, then adding methanol, continuing stirring, slowly dropwise adding methyl acrylate, introducing nitrogen, discharging air, reacting while stirring, then heating, and removing methanol and methyl acrylate to prepare the primary modified graphene porous microtube.
3) Preparing a modified graphene porous microtube: and adding the prepared primary modified graphene porous microtube into methanol, slowly dropwise adding ethylenediamine, continuously reacting at room temperature, and removing redundant methanol and ethylenediamine to obtain the modified graphene porous microtube.
4) Preparing a conductive material for a lithium battery anode: adding the prepared modified graphene porous microtube into methanol, stirring at a constant speed, adding silver acetate, slowly stirring, then distilling under reduced pressure to remove the methanol to obtain a compound, and then carrying out heat treatment to obtain the conductive material for the lithium battery anode.
According to the invention, a Michael addition reaction is carried out between ethylenediamine and methyl acrylate to generate an intermediate product, then excessive ethylenediamine and the intermediate product are subjected to an amidation reaction completely to generate an amino-terminated polyamidoamine dendrimer, the amino-terminated polyamidoamine dendrimer is synthesized in sheets and porous holes of the graphene porous microtube to carry out non-covalent bond modification on the graphene porous microtube to prepare a modified graphene porous microtube, then the modified graphene porous microtube is blended with silver nitrate, the amino-terminated polyamidoamine is used as a template and a reducing agent, a silver precursor is complexed with the amino-terminated polyamidoamine, nano silver particles are prepared by thermal reduction, and a large amount of nano silver particles can be hybridized by preparing the porous graphene microtube.
Example 1
1) Preparation of graphene porous microtubes
Spraying a graphene oxide aqueous solution with the mass fraction of 2.5% prepared by a Hummers method from a needle head at the speed of 10 muL/min by a propulsion pump, arranging a substrate 3.5cm below the needle head, placing a rectangular frame on the substrate, wherein the size of the frame is 30 multiplied by 20cm, uniformly winding polyester fibers on the frame, applying 7kV high-voltage electricity between the needle head and the substrate, overturning the rectangular frame once every 15min to prepare the polyester fibers coated with the graphene oxide solution, and controlling the spraying time to be 25 min;
soaking the polyester fiber coated with the graphene oxide solution into a calcium chloride solution with the mass fraction of 5%, taking out after soaking for 30min, placing in deionized water for washing to remove calcium chloride, drying at 45 ℃, then placing in a tubular furnace, introducing argon, heating to 800 ℃ at the heating rate of 5 ℃, and carrying out heat preservation treatment for 3h to obtain the graphene porous microtube;
2) preparation of primarily modified graphene porous microtubes
Adding 10g of graphene porous microtube into 500mL of deionized water to prepare a suspension, adding 15g of ethylenediamine, performing ultrasonic dispersion for 20min to prepare a mixed solution, then adding 600mL of methanol, continuing stirring for 3min, slowly dropwise adding 170g of methyl acrylate, introducing nitrogen, discharging air, performing magnetic stirring, reacting for 4h, then heating to 60 ℃, and removing solvents such as methanol and the like and methyl acrylate under 0.15kPa to prepare a primary modified graphene porous microtube;
3) preparation of modified graphene porous microtubes
Adding 9g of the primarily modified graphene porous micro-tube into 60mL of methanol, slowly dropwise adding 7.4g of ethylenediamine, continuously reacting for 10 hours at room temperature, and removing redundant monomer ethylenediamine and solvent methanol to obtain a modified graphene porous micro-tube;
4) preparation of conductive material for lithium battery anode
Adding 10g of modified graphene porous microtube into 75mL of methanol, stirring at a constant speed for 10min, adding 5g of silver acetate, slowly stirring for 4h, then distilling under reduced pressure to remove the methanol to obtain a compound, and then carrying out heat treatment at 130 ℃ for 5h to obtain the conductive material for the lithium battery anode.
Example 2
1) Preparation of graphene porous microtubes
Spraying a graphene oxide aqueous solution with the mass fraction of 2% prepared by a Hummers method from a needle head at the speed of 10 muL/min by a propulsion pump, arranging a substrate 2.5cm below the needle head, placing a rectangular frame on the substrate, wherein the size of the frame is 30 multiplied by 20cm, uniformly winding polyester fibers on the frame, applying 8kV high voltage between the needle head and the substrate, overturning the rectangular frame once every 10min to prepare the polyester fibers coated with the graphene oxide solution, and controlling the spraying time to be 35 min;
soaking the polyester fiber coated with the graphene oxide solution into a calcium chloride solution with the mass fraction of 8%, taking out the polyester fiber after soaking for 30min, placing the polyester fiber in deionized water for washing to remove calcium chloride, drying the polyester fiber at 55 ℃, then placing the polyester fiber in a tubular furnace, introducing argon, heating to 850 ℃ at the heating rate of 6 ℃, and carrying out heat preservation treatment for 2h to obtain the graphene porous microtube;
2) preparation of primarily modified graphene porous microtubes
Adding 12g of graphene porous microtube into 500mL of deionized water to prepare a suspension, adding 16g of ethylenediamine, performing ultrasonic dispersion for 25min to prepare a mixed solution, then adding 620mL of methanol, continuing stirring for 4min, slowly dropwise adding 170g of methyl acrylate, introducing nitrogen, discharging air, performing magnetic stirring, reacting for 6h, then heating to 65 ℃, and removing solvents such as methanol and the like and methyl acrylate under 0.3kPa to prepare a primary modified graphene porous microtube;
3) preparation of modified graphene porous microtubes
Adding 9.12g of the primarily modified graphene porous micro-tube into 60mL of methanol, slowly dropwise adding 7.52g of ethylenediamine, continuously reacting for 12 hours at room temperature, and removing redundant monomer ethylenediamine and solvent methanol to obtain a modified graphene porous micro-tube;
4) preparation of conductive material for lithium battery anode
Adding 10g of modified graphene porous microtube into 90mL of methanol, stirring at a constant speed for 12min, adding 5g of silver acetate, slowly stirring for 5h, then distilling under reduced pressure to remove the methanol to obtain a compound, and then carrying out heat treatment at 140 ℃ for 4h to obtain the conductive material for the lithium battery anode.
Example 3
1) Preparation of graphene porous microtubes
Spraying a graphene oxide aqueous solution with the mass fraction of 2.5% prepared by a Hummers method from a needle head at the speed of 12 muL/min by a propulsion pump, arranging a substrate 3cm below the needle head, placing a rectangular frame on the substrate, wherein the size of the frame is 30 multiplied by 20cm, uniformly winding polyester fibers on the frame, applying 8kV high voltage between the needle head and the substrate, overturning the rectangular frame once every 12min to prepare the polyester fibers coated with the graphene oxide solution, and controlling the spraying time to be 28 min;
soaking the polyester fiber coated with the graphene oxide solution into a calcium chloride solution with the mass fraction of 10%, taking out after soaking for 30min, placing in deionized water for washing to remove calcium chloride, drying at 60 ℃, then placing in a tubular furnace, introducing argon, heating to 820 ℃ at the heating rate of 8 ℃, and carrying out heat preservation treatment for 3h to obtain the graphene porous microtube;
2) preparation of primarily modified graphene porous microtubes
Adding 14g of graphene porous microtube into 500mL of deionized water to prepare a suspension, adding 18g of ethylenediamine, performing ultrasonic dispersion for 28min to prepare a mixed solution, then adding 640mL of methanol, continuing stirring for 4min, slowly dropwise adding 171g of methyl acrylate, introducing nitrogen, discharging air, performing magnetic stirring, reacting for 5h, then heating to 60 ℃, and removing solvents such as methanol and the like and methyl acrylate under 0.5kPa to prepare a primary modified graphene porous microtube;
3) preparation of modified graphene porous microtubes
Adding 9.2g of the primarily modified graphene porous micro-tube into 60mL of methanol, slowly dropwise adding 7.6g of ethylenediamine, continuously reacting for 12 hours at room temperature, and removing redundant monomer ethylenediamine and solvent methanol to obtain a modified graphene porous micro-tube;
4) preparation of conductive material for lithium battery anode
Adding 10g of modified graphene porous microtube into 90mL of methanol, stirring at a constant speed for 15min, adding 5g of silver acetate, slowly stirring for 6h, then distilling under reduced pressure to remove the methanol to obtain a compound, and then carrying out heat treatment at 150 ℃ for 3h to obtain the conductive material for the lithium battery anode.
Example 4
1) Preparation of graphene porous microtubes
Spraying a graphene oxide aqueous solution with the mass fraction of 3% prepared by a Hummers method from a needle head at the speed of 11 muL/min by a propulsion pump, arranging a substrate 3cm below the needle head, placing a rectangular frame on the substrate, wherein the size of the frame is 30 multiplied by 20cm, uniformly winding polyester fibers on the frame, applying 7kV high voltage between the needle head and the substrate, overturning the rectangular frame once every 15min to prepare the polyester fibers coated with the graphene oxide solution, and controlling the spraying time to be 30 min;
soaking the polyester fiber coated with the graphene oxide solution into a calcium chloride solution with the mass fraction of 5%, taking out after soaking for 30min, placing in deionized water for washing to remove calcium chloride, drying at 60 ℃, then placing in a tubular furnace, introducing argon, heating to 840 ℃ at the heating rate of 10 ℃, and carrying out heat preservation treatment for 2h to obtain the graphene porous microtube;
2) preparation of primarily modified graphene porous microtubes
Adding 15g of graphene porous microtube into 500mL of deionized water to prepare a suspension, adding 20g of ethylenediamine, performing ultrasonic dispersion for 30min to prepare a mixed solution, then adding 650mL of methanol, continuing stirring for 5min, slowly dropwise adding 172g of methyl acrylate, introducing nitrogen, discharging air, performing magnetic stirring, reacting for 4h, then heating to 65 ℃, removing solvents such as methanol and the like and the methyl acrylate under 0.60kPa, and preparing a primary modified graphene porous microtube;
3) preparation of modified graphene porous microtubes
Adding 9.28g of the primarily modified graphene porous micro-tube into 60mL of methanol, slowly dropwise adding 7.68 of ethylenediamine, continuously reacting for 12 hours at room temperature, and removing redundant monomer ethylenediamine and solvent methanol to obtain a modified graphene porous micro-tube;
4) preparation of conductive material for lithium battery anode
Adding 10g of modified graphene porous microtube into 100mL of methanol, stirring at a constant speed for 15min, adding 5g of silver acetate, slowly stirring for 5h, then distilling under reduced pressure to remove the methanol to obtain a compound, and then carrying out heat treatment at 150 ℃ for 3h to obtain the conductive material for the lithium battery anode.
Comparative example 1
The preparation method of the graphene conductive material prepared in the patent CN201810251698.2 is as follows:
mixing graphene and a dispersing agent according to a mass ratio of 8:92, and performing ball milling dispersion to obtain a graphene dispersion system; wherein the average number of layers of the graphene is 8, and the average sheet diameter is 2 mu m; the dispersing agent is a mixed solution of glycol and water, and the volume ratio of the glycol to the water is 1: 1;
dissolving cobalt nitrate in a mixed solvent of water and isopropanol in a volume ratio of 1:2 to obtain 0.5mol/L metal salt solution;
ultrasonically dispersing the metal salt solution and the graphene dispersion system, and adding citric acid to obtain a mixed solution; wherein the citric acid accounts for 3% of the total mass of the metal salt and the graphene;
heating the mixed solution by 800W microwave for 2min, filtering, washing with ethanol, and vacuum drying to obtain mixed powder;
sintering the mixed powder for 5 hours at 600 ℃ in a mixed atmosphere of argon and hydrogen with a molar ratio of 9:1, and crushing and ball-milling to obtain a nano metal modified graphene conductive material;
the nano metal modified graphene conductive material comprises the following components in percentage by mass: nano metal particles: 30 percent, and the average grain diameter of the nano metal particles is 20 nm; graphene: 70 percent.
Comparative example 2
The preparation method of the graphene conductive material prepared in the patent CN201811051018.9 is as follows:
weighing 0.5g of aramid chopped fiber and 0.005g of sodium dodecyl sulfate, placing the aramid chopped fiber and the sodium dodecyl sulfate in a beaker, adding 240g of warm water with the temperature of 45 ℃, standing and soaking for 20min, filtering and cleaning for a plurality of times, and pulping by a pulping machine for later use;
weighing 0.5g of aramid pulp fiber and 0.005g of polyethylene oxide, placing the aramid pulp fiber and the polyethylene oxide in a beaker, adding 240g of warm water (40 ℃), standing and soaking for 20min, and pulping by a pulping machine for later use;
respectively weighing 0.5g of carbon nano tube and 0.3g of graphene, placing the carbon nano tube and the graphene in a beaker, uniformly dispersing the carbon nano tube and the graphene in 350g of ethanol, uniformly mixing the aramid chopped fiber dispersion liquid and the aramid pulp fiber dispersion liquid through a stainless steel fluid mixer, and shearing the mixture through a high-speed shearing machine to prepare mixed slurry;
freeze-drying the mixed slurry by a freeze dryer, and rolling and forming to prepare the carbon nanotube-graphene-aramid conductive material;
and sequentially laminating the porous metal foil, the waterproof breathable film and the carbon nanotube-graphene-aramid fiber conductive material, and then pressing into the lithium-air battery positive electrode material.
The average conductivity of the graphene conductive materials prepared in examples 1 to 4 and comparative examples 1 to 2 was measured, and the results are shown in the following table:
the test method comprises the following steps: and testing the resistance by adopting a two-probe method, and further calculating to obtain the average conductivity.
As can be seen from the above table, the conductive materials prepared in the embodiments 1-4 of the present invention have excellent conductive performance, which reaches 2.2 × 10 3 The level of S/cm is higher than that of the graphene, so that the technical problem that the conductivity of the graphene is actually low is well solved.
Claims (8)
1. A preparation method of a conductive material for a lithium battery anode is characterized by comprising the following steps: the method comprises the following steps:
1) preparation of graphene porous microtubes
Soaking the polyester fiber coated with the graphene oxide solution prepared by an electrostatic method into a calcium chloride solution, taking out the polyester fiber after soaking, washing the polyester fiber in deionized water to remove calcium chloride, drying the polyester fiber, and then calcining the polyester fiber at high temperature under the protection of argon to prepare the graphene porous microtube;
2) preparation of primarily modified graphene porous microtubes
Adding the graphene porous microtube prepared in the step 1) into deionized water to prepare a suspension, adding ethylenediamine, performing ultrasonic dispersion to prepare a mixed solution, adding methanol, continuously stirring, slowly dropwise adding methyl acrylate, introducing nitrogen, discharging air, reacting while stirring, heating, and removing methanol and methyl acrylate to prepare a primary modified graphene porous microtube;
3) preparation of modified graphene porous microtubes
Adding the primarily modified graphene porous micro-tube prepared in the step 2) into methanol, slowly dropwise adding ethylenediamine, continuously reacting at room temperature, and removing redundant methanol and ethylenediamine to obtain a modified graphene porous micro-tube;
4) preparation of conductive material for lithium battery anode
Adding the modified graphene porous microtube prepared in the step 3) into methanol, stirring at a constant speed, adding silver acetate, slowly stirring, then distilling under reduced pressure to remove the methanol to prepare a compound, and then carrying out heat treatment to prepare the conductive material for the lithium battery anode.
2. The method of claim 1, wherein the conductive material for a positive electrode of a lithium battery comprises: the preparation method of the polyester fiber coated with the graphene oxide solution prepared by the electrostatic method in the step 1) comprises the following steps: and (2) spraying the graphene oxide aqueous solution from the needle head through a propulsion pump, arranging a substrate under the needle head, placing a rectangular frame on the substrate, and uniformly winding polyester fibers on the frame to prepare the polyester fibers coated with the graphene oxide solution.
3. The method of claim 1, wherein the conductive material for a positive electrode of a lithium battery comprises: the mass fraction of the calcium chloride solution in the step 1) is 5-10%, and the drying temperature is 45-60 ℃; the reaction conditions of the high-temperature calcination are as follows: heating to 800-850 ℃ at the heating rate of 5-10 ℃/min, and carrying out heat preservation treatment for 2-3 h.
4. The method of claim 2, wherein the conductive material for a lithium battery positive electrode comprises: the mass fraction of the graphene oxide aqueous solution is 2-3%, the ejection speed of a needle is 10-12 mu L/min, and the ejection time is controlled to be 25-35 min; a substrate is arranged 2.5-3.5cm under the needle head, a high voltage of 7-8kV is applied between the needle head and the substrate, and the rectangular frame is turned over once every 10-15 min.
5. The method of claim 1, wherein the conductive material for a positive electrode of a lithium battery comprises: the dosage ratio of the graphene porous microtube, the deionized water, the ethylenediamine, the methanol and the methyl acrylate in the step 2) is 1-1.5 g: 50 mL: 1.5-2 g: 60-65 mL: 17.0-17.2 g.
6. The method of claim 1, wherein the conductive material for a positive electrode of a lithium battery comprises: the dosage ratio of the primary modified graphene porous microtube, methanol and ethylenediamine in the step 3) is 22.5-23.2g, 150mL, 18.5-19.2 g.
7. The method of claim 1 for preparing a conductive material for a positive electrode of a lithium battery, wherein: the dosage ratio of the modified graphene porous microtube, the methanol and the silver acetate in the step 4) is 2 g: 15-20 mL: 1 g.
8. The method of claim 1, wherein the conductive material for a positive electrode of a lithium battery comprises: the temperature of the heat treatment in the step 4) is controlled at 130 ℃ and 150 ℃, and the heat treatment time is 3-5 h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102390830A (en) * | 2011-08-23 | 2012-03-28 | 华南理工大学 | Method for preparing polyamide-amine in-situ intercalation graphene composite material |
| CN102671710A (en) * | 2011-03-07 | 2012-09-19 | 河南科技大学 | Noble metal nanocatalyst loaded on dendritic macromolecule functionalized graphene and preparation method thereof |
| CN102828267A (en) * | 2012-09-10 | 2012-12-19 | 浙江大学 | Preparation method of conductive high-strength graphene-reinforced polymer fiber |
| US20180267049A1 (en) * | 2017-03-15 | 2018-09-20 | King Fahd University Of Petroleum And Minerals | Method for detecting methimazole by surface-enhanced raman scattering |
| CN110224121A (en) * | 2019-06-10 | 2019-09-10 | 合肥众禾动力新能源科技有限公司 | A kind of preparation method of anode sizing agent |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671710A (en) * | 2011-03-07 | 2012-09-19 | 河南科技大学 | Noble metal nanocatalyst loaded on dendritic macromolecule functionalized graphene and preparation method thereof |
| CN102390830A (en) * | 2011-08-23 | 2012-03-28 | 华南理工大学 | Method for preparing polyamide-amine in-situ intercalation graphene composite material |
| CN102828267A (en) * | 2012-09-10 | 2012-12-19 | 浙江大学 | Preparation method of conductive high-strength graphene-reinforced polymer fiber |
| US20180267049A1 (en) * | 2017-03-15 | 2018-09-20 | King Fahd University Of Petroleum And Minerals | Method for detecting methimazole by surface-enhanced raman scattering |
| CN110224121A (en) * | 2019-06-10 | 2019-09-10 | 合肥众禾动力新能源科技有限公司 | A kind of preparation method of anode sizing agent |
Non-Patent Citations (1)
| Title |
|---|
| 刘孔华: ""石墨烯/纳米银杂化物的制备及在环氧树脂导电胶中的应用基础研究"", 《中国优秀博硕士学位论文全文数据库（博士） 工程科技Ⅰ辑》 * |
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