CN111138661A - Preparation method and application of graphene/carbon nanotube/polyaniline composite material - Google Patents
Preparation method and application of graphene/carbon nanotube/polyaniline composite material Download PDFInfo
- Publication number
- CN111138661A CN111138661A CN202010060641.1A CN202010060641A CN111138661A CN 111138661 A CN111138661 A CN 111138661A CN 202010060641 A CN202010060641 A CN 202010060641A CN 111138661 A CN111138661 A CN 111138661A
- Authority
- CN
- China
- Prior art keywords
- graphene
- composite material
- polyaniline composite
- carbon nanotube
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method and application of a graphene/carbon nano tube/polyaniline composite material, which comprises the following steps: carrying out oxalic acid modification on graphene oxide to obtain modified graphene oxide; then dispersing the modified graphene oxide in water to obtain a modified graphene oxide suspension, and adding concentrated hydrochloric acid; adding aniline monomer, and ultrasonically dispersing uniformlyCarrying out pre-reaction to obtain aniline modified graphene; adding carbon nano tube and active MnO into aniline modified graphene2And ammonium persulfate to carry out oxidative polymerization; carrying out solid-liquid separation, washing and drying on the reacted materials to obtain an HCl-doped composite material; and adding ammonia water and hydrazine hydrate into the HCl-doped composite material for dedoping and reduction treatment to obtain the graphene/carbon nano tube/polyaniline composite material. Compared with the prior art, the lithium ion battery anode provided by the invention has excellent electrochemical performance, and has the advantages of simple process, mild conditions, low cost and the like.
Description
Technical Field
The invention belongs to the technical field of material science and electrochemistry, and particularly relates to a preparation method and application of a graphene/carbon nano tube/polyaniline composite material.
Background
With the increasingly prominent energy and environmental problems, new energy industries have gained more and more attention. The development of portable electronic equipment, electric automobiles and other industries is very rapid, and the lithium ion battery is widely applied to energy storage equipment due to the advantages of high energy density, good cycle performance, no memory effect and the like.
Lithium ion batteries are energy storage devices composed of a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein electrode materials are key factors determining the performance of the lithium ion batteries. A commonly used positive electrode material is a lithium ion intercalation compound or the like. However, the conventional positive electrode material has a disadvantage of volume expansion during lithiation, thereby causing pulverization of the material, resulting in breakage and loss of electrical contact. In order to search for new electrode materials, researchers have conducted research on organic electrode materials. Compared with inorganic electrode materials, the electrode materials are expected to have the advantages of variable structure, oxidation-reduction stability, low cost, environmental protection and the like. For this reason, organic electrode materials are generally designed to improve their electrochemical performance.
Chinese patent CN 108440753 a discloses a carbon nanotube/polyaniline/graphene composite flexible film and a preparation method thereof. The method comprises the following steps: step 1, adding an acidified carbon nano tube into an acid solution containing aniline, adding an oxidant after ultrasonic treatment, and reacting at 0-25 ℃ for 12-36 hours to obtain a polyaniline-coated carbon nano tube, wherein the mass ratio of the carbon nano tube to the aniline to the oxidant is 0.01-1: 0.1-1: 0.5 to 2; and 2, adding the polyaniline-coated carbon nano tube into the graphene dispersion liquid, performing ultrasonic treatment at 5-20 ℃, and performing suction filtration to obtain the carbon nano tube/polyaniline/graphene composite flexible film. However, due to the influence of surface oxidation groups, Graphene Oxide (GO) prepared from layered graphite is seriously agglomerated, the specific surface area is greatly reduced, the adsorption capacity is weakened, and the graphene oxide is difficult to uniformly disperse in an aqueous solution, so that an expected composite effect cannot be achieved in the polymerization process of the graphene oxide and aniline, and the capacity and the cycle performance of a battery cannot meet requirements
Disclosure of Invention
The invention aims to overcome the defect of poor electrical property in the prior art and provide a preparation method and application of a graphene/carbon nanotube/polyaniline composite material.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a graphene/carbon nanotube/polyaniline composite material comprises the following steps:
(1) carrying out oxalic acid modification on graphene oxide to obtain modified graphene oxide; then dispersing the modified graphene oxide in water to obtain a modified graphene oxide suspension, and adding concentrated hydrochloric acid;
(2) controlling the temperature of the mixed material obtained in the step (1) to be below 10 ℃, adding an aniline monomer, performing ultrasonic dispersion uniformly, and performing pre-reaction at the reaction temperature of 0-5 ℃ to obtain aniline modified graphene;
(3) maintaining the temperature of the mixed material below 5 ℃, and uniformly mixing the aniline modified graphene obtained in the step (2) with the carbon nano tube; then adding active MnO2And ammonium persulfate, controlling the temperature of the mixed materials to be 5-8 ℃, and carrying out oxidative polymerization reaction;
(4) carrying out solid-liquid separation, washing and drying on the reacted materials to obtain the HCl-doped graphene/carbon nano tube/polyaniline composite material;
(5) and adding ammonia water and hydrazine hydrate into the HCl-doped graphene/carbon nano tube/polyaniline composite material for dedoping and reduction treatment to obtain the graphene/carbon nano tube/polyaniline composite material.
The modified graphene oxide, aniline, carbon nano tube and active MnO2And ammonium persulfate in a mass ratio of 1: 50-75: 0.2-0.6: 4-6: 70 to 215.
Adding concentrated hydrochloric acid in the step (1), stirring, further adding triton, and reacting for 0.5-1.5 hours to obtain a mixed material; the mass ratio of the modified graphene oxide to the triton is 1: 0.3 to 0.4.
The reaction time of the pre-reaction is 15-25 minutes, and preferably 20 minutes; the reaction time of the oxidative polymerization reaction is 3.5 to 4.5 hours, preferably 4 hours.
In the step (3), the mixing time of the aniline modified graphene and the carbon nano tube is 25-35 minutes, and the ammonium persulfate is added into the reaction system in batches.
The active MnO2Slowly adding the mixture into a reaction system, and finishing adding the mixture for 8-12 min. The preparation method of the modified graphene oxide comprises the steps of adding an HBr solution into a graphene oxide suspension; stirring and reacting for 10-20 hours under the water bath condition of 70-80 ℃, adding oxalic acid, continuously stirring and reacting for 3-7 hours, and after the reaction is finished, carrying out suction filtration, water washing and drying on the obtained mixed material to obtain modified graphene oxide; the mass ratio of the graphene oxide to the oxalic acid is 1: 20 to 30.
The active MnO2The preparation method comprises the following steps:
dissolving manganese sulfate in water, and dripping one drop of H into the solution2SO4Obtaining manganese sulfate solution;
dissolving potassium permanganate in water, and dripping one drop of HClO4Obtaining potassium permanganate solution;
dropwise adding a manganese sulfate solution into a potassium permanganate solution, and reacting for 1.5-2.5 hours at 40-60 ℃;
and (3) filtering the reacted mixed material, washing the obtained filter cake with deionized water until the filtrate is neutral, dispersing the solid material in water, and refrigerating for later use.
Throughout the preparation process, the temperature of the mixed material was controlled by adding deionized ice to the mixed material.
The invention also provides an application of the graphene/carbon nano tube/polyaniline composite material obtained by the preparation method, and the graphene/carbon nano tube/polyaniline composite material and the binder are uniformly mixed, coated on an aluminum foil, and dried to obtain the lithium ion battery anode material.
The mass ratio of the graphene/carbon nanotube/polyaniline composite material to the binder is 4:1, and the binder is PVDF.
In the preparation process, firstly, the graphene oxide needs to be modified by oxalic acid, the functionalized graphene material is compounded with aniline to obtain a layered structure of polyaniline-coated graphene, the agglomeration phenomenon of the functionalized graphene material is improved, aniline can be better adsorbed, and meanwhile, some functional groups on the surface of the graphene can chemically react with aniline to form the polyaniline composite material with chemical bonding. The composite material has the advantages that the agglomeration phenomenon of polyaniline can be improved, the utilization rate of the interior of the polyaniline is improved, the doping and de-doping of ions are more complete, the binding force of polyaniline and graphene is strong, the decomposition and falling-off phenomena of the material serving as a battery anode material in the charging and discharging processes can be inhibited, and the capacity and the cycle performance of the battery are improved.
In the preparation process, compared with the conventional scientific research data, the amount of the graphene, the carbon nano tube and the aniline participating in the reaction is determined within the range of the invention, if the amount of the graphene is too much, the load rate of an active substance aniline monomer is too much, the utilization efficiency of the material is influenced, and if the amount of the graphene is too little, the amount of the active substance is too little, and the electrochemical performance is lower.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, graphene oxide is modified and then mixed with the carbon nano tube to synthesize the polyaniline composite material, so that polyaniline can uniformly cover the graphene and the carbon nano tube in the reaction process, the process is simple, the conditions are mild, and industrial expanded production is easy to realize.
(2) The invention takes graphene and carbon nano tubes as carbon sources and polyaniline as a composite material, and has the advantages of designability of raw materials and low cost;
(3) the modified graphene/carbon nanotube/polyaniline composite material prepared by the invention has excellent electrochemical performance as a lithium ion battery anode, has high specific discharge capacity and rate capability, has the characteristics of no toxicity, environmental protection, reproducibility, low cost and the like, conforms to the green development trend of lithium ion batteries, and has a very good application prospect in the fields of portable electronic equipment, automobile batteries, novel material batteries and the like.
Drawings
Fig. 1 is an SEM photograph of the graphene/carbon nanotube/polyaniline composite material obtained in example 1;
fig. 2 is a cycle performance diagram of the graphene/carbon nanotube/polyaniline composite material obtained in example 1 as a lithium ion battery positive electrode material;
fig. 3 is a rate performance graph of the graphene/carbon nanotube/polyaniline composite material obtained in example 1 as a lithium ion battery cathode material.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
Preparation of a graphene/carbon nanotube/polyaniline composite material and electrochemical performance test of the composite material used as a lithium ion battery anode material;
(1) the preparation method comprises the following steps:
step one, preparing a oxalated graphene solution:
and (3) putting 50mL of 5mg/mL graphene oxide solution into a beaker, adding 19mL of HBr solution, reacting in a water bath at 75 ℃ for 15 hours under strong stirring, adding 6.25g of oxalic acid, continuing to react for 5 hours under stirring, after the reaction is finished, performing suction filtration, washing with water for three times, and performing vacuum drying at 60 ℃ for 24 hours to obtain the oxalated graphene.
Second step, active MnO2And (4) preparing.
Taking 10.14g of MnSO4·H2O was dissolved in 50mL of deionized water and one drop of H was added dropwise2SO4(ii) a Taking 6.32g of KMnO4Dissolving in 200mL of deionized water, and adding one drop of HClO dropwise4(ii) a Mixing MnSO4The solution was slowly added dropwise to KMnO4And (3) dripping the solution for 30 minutes, reacting in a water bath at 50 ℃ for 2 hours, carrying out suction filtration, washing the obtained filter cake with deionized water until the filtrate is neutral, dissolving the filter cake in 50mL of deionized water, and refrigerating for later use.
Step three, preparing the modified graphene/carbon nano tube/polyaniline composite material
Taking 2g of ultrasonically uniformly dispersed oxalated graphene solution, adding 150mL of deionized water into a 1L reaction kettle, then ultrasonically dispersing for 45 minutes, adding 200g of concentrated hydrochloric acid, stirring, adding 0.72g of triton, and reacting for 1h for later use. 100g of deionized ice is added into a reaction kettle, the internal temperature of the reaction kettle is reduced to below 10 ℃, then 100g of aniline monomer is added, the temperature in the kettle is controlled at 0 ℃, and the reaction is carried out for 20 min. Then 0.8g of carbon nanotubes was slowly added to the reaction kettle. After the graphene modified by aniline and the carbon nano tube are uniformly mixed, slowly adding 10g of the prepared active MnO2And 8min is finished. After 30 minutes of reaction, 1.43g of Ammonium Persulfate (APS) is added every 1 minute for 100 times, the total is 143g of APS, ice is added into the reaction kettle in the period, the temperature is kept below 5 ℃, and after the addition is finished, the temperature in the reaction kettle is kept at 5-8 ℃ for 4 hours of reaction. After the reaction is finished, filtering to obtain filterAnd (3) washing the cake with water for 3 times, and washing the cake with ethanol for one time to obtain the HCl-doped polyaniline/graphene/carbon nanotube ternary composite material. And taking out some of the wet powder, adding a proper amount of ammonia water and hydrazine hydrate for dedoping and reduction to obtain a reduced modified graphene/carbon nano tube/polyaniline composite material, which is marked as PANI/RGO/CNTs-1. The SEM photograph of the composite material is shown in fig. 1, and it can be found from fig. 1 that there are many small polyaniline polymer particles on the graphene skeleton, which indicates that polyaniline is successfully grown in situ on the graphene skeleton during the reaction process.
(2) The obtained composite material is used as a positive electrode material of the lithium ion battery to assemble a lithium ion button type half battery, and a pure lithium sheet is used as a counter electrode. 1M LiTFSI is dissolved in a mixed solution of 1, 3-Dioxolane (DOL)/ethylene glycol dimethyl ether (DME) (volume ratio is 1:1) to be prepared into an electrolyte, electrochemical tests are carried out by utilizing a button type half cell, and the cycle performance diagram and the rate performance diagram are respectively shown in figures 2 and 3.
Example 2
Preparation of a graphene/carbon nanotube/polyaniline composite material and electrochemical performance test of the composite material used as a lithium ion battery anode material;
(1) the preparation method comprises the following steps:
step one, preparing a oxalated graphene solution:
and (3) putting 50mL of 5mg/mL graphene oxide solution into a beaker, adding 19mL of HBr solution, reacting in a water bath at 75 ℃ for 15 hours under strong stirring, adding 6.25g of oxalic acid, continuing to react for 5 hours under stirring, after the reaction is finished, performing suction filtration, washing with water for three times, and performing vacuum drying at 60 ℃ for 24 hours to obtain the oxalated graphene.
Second step, active MnO2And (4) preparing.
Taking 10.14g of MnSO4·H2O was dissolved in 50m L DI water and one drop H was added2SO4(ii) a Taking 6.32g of KMnO4Dissolving in 200mL of deionized water, and adding one drop of HClO dropwise4(ii) a Mixing MnSO4The solution was slowly added dropwise to KMnO4Dripping the solution for 30 minutes, reacting in water bath at 50 ℃ for 2 hours, filtering, washing the obtained filter cake with deionized water until the filtrate is neutral, and dissolving the filter cakeIn 50mL deionized water, and refrigerated for later use.
Step three, preparing the modified graphene/carbon nano tube/polyaniline composite material
Taking 2g of ultrasonically uniformly dispersed oxalated graphene solution, adding 150mL of deionized water into a 1L reaction kettle, then ultrasonically dispersing for 45 minutes, adding 200g of concentrated hydrochloric acid, stirring, adding 0.72g of triton, and reacting for 1h for later use. 100g of deionized ice is added into a reaction kettle, the internal temperature of the reaction kettle is reduced to below 10 ℃, then 150g of aniline monomer is added, the temperature in the kettle is controlled at 0 ℃, and the reaction is carried out for 20 min. Then 0.8g of carbon nanotubes was slowly added to the reaction kettle. After the graphene modified by aniline and the carbon nano tube are uniformly mixed, slowly adding 10g of the prepared active MnO2And finishing adding 12 min. After 30 minutes of reaction, 2.86g of APS is added every 1 minute for 100 times in total, wherein the total amount of the APS is 286g, ice can be added into the reaction kettle in the period, the temperature is kept below 5 ℃, and after the addition is finished, the temperature in the reaction kettle is kept at 5-8 ℃ for 4 hours of reaction. And after the reaction is finished, carrying out suction filtration to obtain a filter cake, washing with water for 3 times, and washing with ethanol for one time to obtain the HCl-doped polyaniline/graphene/carbon nanotube ternary composite material. And taking out some of the wet powder, adding a proper amount of ammonia water and hydrazine hydrate for dedoping and reduction to obtain a reduced modified graphene/carbon nano tube/polyaniline composite material, which is marked as PANI/RGO/CNTs-2.
(2) The obtained composite material is used as a positive electrode material of the lithium ion battery to assemble a lithium ion button type half battery, and a pure lithium sheet is used as a counter electrode. 1M LiTFSI is dissolved in a mixed solution of 1, 3-Dioxolane (DOL)/ethylene glycol dimethyl ether (DME) (volume ratio is 1:1) to be prepared into an electrolyte, electrochemical tests are carried out by utilizing a button type half cell, and the cycle performance diagram and the rate performance diagram are respectively shown in figures 2 and 3.
Example 3
Preparation of a graphene/carbon nanotube/polyaniline composite material and electrochemical performance test of the composite material used as a lithium ion battery anode material;
(1) the preparation method comprises the following steps:
step one, preparing a oxalated graphene solution:
and (3) putting 50mL of 5mg/mL graphene oxide solution into a beaker, adding 19mL of HBr solution, reacting in a water bath at 75 ℃ for 15 hours under strong stirring, adding 6.25g of oxalic acid, continuing to react for 5 hours under stirring, after the reaction is finished, performing suction filtration, washing with water for three times, and performing vacuum drying at 60 ℃ for 24 hours to obtain the oxalated graphene.
Second step, active MnO2And (4) preparing.
Taking 10.14g of MnSO4·H2O was dissolved in 50m L DI water and one drop H was added2SO4(ii) a Taking 6.32g KMn O4Dissolving in 200mL of deionized water, and adding one drop of HClO dropwise4(ii) a Mixing MnSO4The solution was slowly added dropwise to KMnO4And (3) dripping the solution for 30 minutes, reacting in a water bath at 50 ℃ for 2 hours, carrying out suction filtration, washing the obtained filter cake with deionized water until the filtrate is neutral, dissolving the filter cake in 50mL of deionized water, and refrigerating for later use.
Step three, preparing the modified graphene/carbon nano tube/polyaniline composite material
Taking 2g of ultrasonically uniformly dispersed oxalated graphene solution, adding 150mL of deionized water into a 1L reaction kettle, then ultrasonically dispersing for 45 minutes, adding 200g of concentrated hydrochloric acid, stirring, adding 0.72g of triton, and reacting for 1h for later use. 100g of deionized ice is added into a reaction kettle, the internal temperature of the reaction kettle is reduced to below 10 ℃, then 150g of aniline monomer is added, the temperature in the kettle is controlled at 5 ℃, and the reaction is carried out for 20 min. Then 0.8g of carbon nanotubes was slowly added to the reaction kettle. After the graphene modified by aniline and the carbon nano tube are uniformly mixed, slowly adding 10g of the prepared active MnO2And 8min is finished. After 30 minutes of reaction, 4.29g of APS was added every 1 minute for a total of 100 times, totaling 429g of APS, during which time ice was added to the reaction vessel to maintain the temperature below 5 ℃ and, after the addition, the temperature in the reaction vessel was maintained at 5 to 8 ℃ for 4 hours. And after the reaction is finished, carrying out suction filtration to obtain a filter cake, washing with water for 3 times, and washing with ethanol for one time to obtain the HCl-doped polyaniline/graphene/carbon nanotube ternary composite material. And taking out some of the wet powder, adding a proper amount of ammonia water and hydrazine hydrate for dedoping and reduction to obtain a reduced modified graphene/carbon nano tube/polyaniline composite material, which is marked as PANI/RGO/CNTs-3.
(2) The obtained composite material is used as a positive electrode material of the lithium ion battery to assemble a lithium ion button type half battery, and a pure lithium sheet is used as a counter electrode. 1M LiTFSI is dissolved in a mixed solution of 1, 3-Dioxolane (DOL)/ethylene glycol dimethyl ether (DME) (volume ratio is 1:1) to be prepared into an electrolyte, electrochemical tests are carried out by utilizing a button type half cell, and the cycle performance diagram and the rate performance diagram are respectively shown in figures 2 and 3.
As can be seen from FIG. 2, the electrochemical performance of the composite materials PANI/RGO/CNTs-1 and PANI/RGO/CNTs-2 is improved by increasing the amount of polyaniline, but when the amount ratio of graphene to polyaniline is increased to 1:75, the electrochemical performance of the composite material PANI/RGO/CNTs-3 is reduced, which indicates that excessive polyaniline causes particle accumulation and influences the effective contact and utilization rate of the active material. It can be seen from FIG. 3 that the electrochemical performance of the composites PANI/RGO/CNTs-1 and PANI/RGO/CNTs-2 is improved at different current densities. The composite material PANI/RGO/CNTs-2 has higher specific discharge capacity, better maintains the stability of the cycle, and the composite material PANI/RGO/CNTs-3 has poor cycle stability and lower electrochemical performance.
Example 4
Preparation of a graphene/carbon nanotube/polyaniline composite material and electrochemical performance test of the composite material used as a lithium ion battery anode material;
(1) the preparation method comprises the following steps:
step one, preparing a oxalated graphene solution:
and (3) putting 50mL of 5mg/mL graphene oxide solution into a beaker, adding 19mL of HBr solution, reacting in a water bath at 70 ℃ for 20 hours under strong stirring, then adding 6.25g of oxalic acid, continuing to react for 3 hours under stirring, after the reaction is finished, performing suction filtration, washing with water for three times, and performing vacuum drying at 60 ℃ for 24 hours to obtain the oxalated graphene.
Second step, active MnO2And (4) preparing.
Taking 10.14g of MnSO4·H2O was dissolved in 50mL of deionized water and one drop of H was added dropwise2SO4(ii) a Taking 6.32g of KMnO4Dissolving in 200mL of deionized water, and adding one drop of HClO dropwise4(ii) a Mixing MnSO4The solution was slowly added dropwise to KMnO4And (3) dripping the solution for 30 minutes, reacting in a water bath at 60 ℃ for 1.5 hours, carrying out suction filtration, washing the obtained filter cake with deionized water until the filtrate is neutral, dissolving the filter cake in 50mL of deionized water, and refrigerating for later use.
Step three, preparing the modified graphene/carbon nano tube/polyaniline composite material
And (2) putting 2g of the ultrasonically uniformly dispersed oxalated graphene solution into a 1L reaction kettle, adding 150mL of deionized water, then ultrasonically dispersing for 45 minutes, adding 200g of concentrated hydrochloric acid, stirring, adding 0.6g of triton, and reacting for 1.5 hours for later use. 100g of deionized ice is added into a reaction kettle, the internal temperature of the reaction kettle is reduced to below 10 ℃, then 100g of aniline monomer is added, the temperature in the kettle is controlled at 0 ℃, and the reaction is carried out for 25 min. Then 0.4g of carbon nanotubes was slowly added to the reaction kettle. After the graphene modified by aniline and the carbon nano tube are uniformly mixed, slowly adding 10g of the prepared active MnO2And 8min is finished. After 35 minutes of the reaction, 1.43g of APS was added every 1 minute for a total of 100 times, and the total amount of 143g of APS, ice was added to the reaction vessel during the reaction, and the temperature was maintained at 5 ℃ or lower, and after the addition, the temperature in the reaction vessel was maintained at 5 ℃ for 4.5 hours. And after the reaction is finished, carrying out suction filtration to obtain a filter cake, washing with water for 3 times, and washing with ethanol for one time to obtain the HCl-doped polyaniline/graphene/carbon nanotube ternary composite material. And taking out some of the wet powder, adding a proper amount of ammonia water and hydrazine hydrate for dedoping and reduction to obtain a reduced modified graphene/carbon nano tube/polyaniline composite material, which is marked as PANI/RGO/CNTs-1. The SEM photograph of the composite material is shown in fig. 1, and it can be found from fig. 1 that there are many small polyaniline polymer particles on the graphene skeleton, which indicates that polyaniline is successfully grown in situ on the graphene skeleton during the reaction process.
(2) The obtained composite material is used as a positive electrode material of the lithium ion battery to assemble a lithium ion button type half battery, and a pure lithium sheet is used as a counter electrode. 1M LiTFSI is dissolved in a mixed solution of 1, 3-Dioxolane (DOL)/ethylene glycol dimethyl ether (DME) (volume ratio is 1:1) to be prepared into an electrolyte, electrochemical tests are carried out by utilizing a button type half cell, and the cycle performance diagram and the rate performance diagram are respectively shown in figures 2 and 3.
Example 5
Preparation of a graphene/carbon nanotube/polyaniline composite material and electrochemical performance test of the composite material used as a lithium ion battery anode material;
(1) the preparation method comprises the following steps:
step one, preparing a oxalated graphene solution:
and (3) putting 50mL of 5mg/mL graphene oxide solution into a beaker, adding 19mL of HBr solution, reacting in a water bath at 75 ℃ for 15 hours under strong stirring, adding 6.25g of oxalic acid, continuing to react for 7 hours under stirring, after the reaction is finished, performing suction filtration, washing with water for three times, and performing vacuum drying at 60 ℃ for 24 hours to obtain the oxalated graphene.
Second step, active MnO2And (4) preparing.
Taking 10.14g of MnSO4·H2O was dissolved in 50mL of deionized water and one drop of H was added dropwise2SO4(ii) a Taking 6.32g of KMnO4Dissolving in 200mL of deionized water, and adding one drop of HClO dropwise4(ii) a Mixing MnSO4The solution was slowly added dropwise to KMnO4And (3) dripping the solution for 30 minutes, reacting in a water bath at 40 ℃ for 2.5 hours, carrying out suction filtration, washing the obtained filter cake with deionized water until the filtrate is neutral, dissolving the filter cake in 50mL of deionized water, and refrigerating for later use.
Step three, preparing the modified graphene/carbon nano tube/polyaniline composite material
And (2) putting 2g of the ultrasonically uniformly dispersed oxalated graphene solution into a 1L reaction kettle, adding 150mL of deionized water, then ultrasonically dispersing for 45 minutes, adding 200g of concentrated hydrochloric acid, stirring, adding 0.8g of triton, and reacting for 0.5h for later use. 100g of deionized ice is added into a reaction kettle, the internal temperature of the reaction kettle is reduced to below 10 ℃, then 100g of aniline monomer is added, the temperature in the reaction kettle is controlled at 5 ℃, and the reaction is carried out for 15 min. Then 1.2g of carbon nanotubes were slowly added to the reaction kettle. After the graphene modified by aniline and the carbon nano tube are uniformly mixed, slowly adding 12g of the prepared active MnO2And finishing adding 12 min. After 25 minutes of reaction, 1.43g of APS was added every 1 minute for a total of 100 times, and the total amount was 143g of APS, ice was added to the reaction vessel during which time the temperature was maintained at 5 ℃ or lower, and after the addition, the temperature in the reaction vessel was maintained at 8 ℃ for 3.5 hours. After the reaction is finishedAnd then, carrying out suction filtration to obtain a filter cake, washing with water for 3 times, and washing with ethanol for one time to obtain the HCl-doped polyaniline/graphene/carbon nanotube ternary composite material. And taking out some of the wet powder, adding a proper amount of ammonia water and hydrazine hydrate for dedoping and reduction to obtain a reduced modified graphene/carbon nano tube/polyaniline composite material, which is marked as PANI/RGO/CNTs-1. The SEM photograph of the composite material is shown in fig. 1, and it can be found from fig. 1 that there are many small polyaniline polymer particles on the graphene skeleton, which indicates that polyaniline is successfully grown in situ on the graphene skeleton during the reaction process.
(2) The obtained composite material is used as a positive electrode material of the lithium ion battery to assemble a lithium ion button type half battery, and a pure lithium sheet is used as a counter electrode. 1M LiTFSI is dissolved in a mixed solution of 1, 3-Dioxolane (DOL)/ethylene glycol dimethyl ether (DME) (volume ratio is 1:1) to be prepared into an electrolyte, electrochemical tests are carried out by utilizing a button type half cell, and the cycle performance diagram and the rate performance diagram are respectively shown in figures 2 and 3.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. A preparation method of a graphene/carbon nanotube/polyaniline composite material is characterized by comprising the following steps:
(1) carrying out oxalic acid modification on graphene oxide to obtain modified graphene oxide; then dispersing the modified graphene oxide in water to obtain a modified graphene oxide suspension, and adding concentrated hydrochloric acid;
(2) controlling the temperature of the mixed material obtained in the step (1) to be below 10 ℃, adding an aniline monomer, performing ultrasonic dispersion uniformly, and performing pre-reaction at the reaction temperature of 0-5 ℃ to obtain aniline modified graphene;
(3) maintaining the temperature of the mixed material below 5 ℃, and uniformly mixing the aniline modified graphene obtained in the step (2) with the carbon nano tube; then adding active MnO2And ammonium persulfate, controlled mixingCarrying out oxidative polymerization reaction at the temperature of 5-8 ℃;
(4) carrying out solid-liquid separation, washing and drying on the reacted materials to obtain the HCl-doped graphene/carbon nano tube/polyaniline composite material;
(5) and adding ammonia water and hydrazine hydrate into the HCl-doped graphene/carbon nano tube/polyaniline composite material for dedoping and reduction treatment to obtain the graphene/carbon nano tube/polyaniline composite material.
2. The method for preparing graphene/carbon nanotube/polyaniline composite material as claimed in claim 1, wherein the modified graphene oxide, aniline, carbon nanotube, active MnO are2And ammonium persulfate in a mass ratio of 1: 50-75: 0.2-0.6: 4-6: 70 to 215.
3. The preparation method of the graphene/carbon nanotube/polyaniline composite material according to claim 1, wherein in the step (1), concentrated hydrochloric acid is added, stirring is carried out, then triton is added, and the reaction is carried out for 0.5-1.5 hours to obtain a mixed material; the mass ratio of the modified graphene oxide to the triton is 1: 0.3 to 0.4.
4. The preparation method of the graphene/carbon nanotube/polyaniline composite material as claimed in claim 1, wherein the pre-reaction time is 15-25 minutes, preferably 20 minutes; the reaction time of the oxidative polymerization reaction is 3.5 to 4.5 hours, preferably 4 hours.
5. The method for preparing the graphene/carbon nanotube/polyaniline composite material according to claim 1, wherein in the step (3), the mixing time of the aniline-modified graphene and the carbon nanotube is 25-35 minutes, and the ammonium persulfate is added to the reaction system in batches.
6. The method according to claim 1, wherein the modified graphene oxide is prepared by adding an HBr solution to a graphene oxide suspension; stirring and reacting for 10-20 hours under the water bath condition of 70-80 ℃, adding oxalic acid, continuously stirring and reacting for 3-7 hours, and after the reaction is finished, carrying out suction filtration, water washing and drying on the obtained mixed material to obtain modified graphene oxide; the mass ratio of the graphene oxide to the oxalic acid is 1: 20 to 30.
7. The method for preparing graphene/carbon nanotube/polyaniline composite material as claimed in claim 1, wherein the active MnO is2The preparation method comprises the following steps:
dissolving manganese sulfate in water, and dripping one drop of H into the solution2SO4Obtaining manganese sulfate solution;
dissolving potassium permanganate in water, and dripping one drop of HClO4Obtaining potassium permanganate solution;
dropwise adding a manganese sulfate solution into a potassium permanganate solution, and reacting for 1.5-2.5 hours at 40-60 ℃;
and (3) filtering the reacted mixed material, washing the obtained filter cake with deionized water until the filtrate is neutral, dispersing the solid material in water, and refrigerating for later use.
8. The method for preparing the graphene/carbon nanotube/polyaniline composite material as claimed in claim 1, wherein the temperature of the mixture is controlled by adding deionized ice to the mixture during the whole preparation process.
9. The application of the graphene/carbon nanotube/polyaniline composite material obtained by the preparation method according to claim 1 is characterized in that the graphene/carbon nanotube/polyaniline composite material and a binder are uniformly mixed, coated on an aluminum foil, and dried to obtain the lithium ion battery anode material.
10. The application of the graphene/carbon nanotube/polyaniline composite material as claimed in claim 9, wherein the mass ratio of the graphene/carbon nanotube/polyaniline composite material to the binder is 4:1, and the binder is PVDF.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010060641.1A CN111138661B (en) | 2020-01-19 | 2020-01-19 | Preparation method and application of graphene/carbon nanotube/polyaniline composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010060641.1A CN111138661B (en) | 2020-01-19 | 2020-01-19 | Preparation method and application of graphene/carbon nanotube/polyaniline composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111138661A true CN111138661A (en) | 2020-05-12 |
| CN111138661B CN111138661B (en) | 2022-08-23 |
Family
ID=70526194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010060641.1A Active CN111138661B (en) | 2020-01-19 | 2020-01-19 | Preparation method and application of graphene/carbon nanotube/polyaniline composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111138661B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113174132A (en) * | 2021-04-19 | 2021-07-27 | 浙江优可丽新材料有限公司 | Composite electromagnetic shielding material |
| CN113444371A (en) * | 2021-06-21 | 2021-09-28 | 安徽理工大学 | Preparation method and application of metal organic framework/polyaniline composite material |
| CN113527673A (en) * | 2021-06-24 | 2021-10-22 | 安徽理工大学 | Preparation method and application of graphene oxide/polyaniline composite material |
| CN114318455A (en) * | 2022-03-10 | 2022-04-12 | 季华实验室 | High-conductivity corrosion-resistant polymer composite coating, preparation method thereof and bipolar plate |
| CN114634642A (en) * | 2022-02-23 | 2022-06-17 | 华中科技大学 | PCNT (prestressed concrete) and PGO (PGO) synergistically modified polymer hybrid proton exchange membrane and preparation method thereof |
| CN116254036A (en) * | 2023-05-15 | 2023-06-13 | 牛墨石墨烯应用科技有限公司 | Preparation method of graphene carbon nanotube heat conduction slurry |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103366971A (en) * | 2013-07-09 | 2013-10-23 | 武汉国墨新材料技术有限公司 | Preparation method of graphene-polyaniline-carbon nanotube stereo three-dimensional compounds |
| WO2015184815A1 (en) * | 2014-06-04 | 2015-12-10 | 福州大学 | Flocculent-polyaniline-coated graphene composite material, method for preparation thereof, and use thereof |
| CN105754094A (en) * | 2016-04-20 | 2016-07-13 | 桂林理工大学 | Method for preparing polyaniline nanotube/graphene composite material by using oxalic acid as template |
| CN108440753A (en) * | 2018-04-20 | 2018-08-24 | 武汉科技大学 | Carbon nano-tube/poly aniline/graphene composite and flexible film and preparation method thereof |
-
2020
- 2020-01-19 CN CN202010060641.1A patent/CN111138661B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103366971A (en) * | 2013-07-09 | 2013-10-23 | 武汉国墨新材料技术有限公司 | Preparation method of graphene-polyaniline-carbon nanotube stereo three-dimensional compounds |
| WO2015184815A1 (en) * | 2014-06-04 | 2015-12-10 | 福州大学 | Flocculent-polyaniline-coated graphene composite material, method for preparation thereof, and use thereof |
| CN105754094A (en) * | 2016-04-20 | 2016-07-13 | 桂林理工大学 | Method for preparing polyaniline nanotube/graphene composite material by using oxalic acid as template |
| CN108440753A (en) * | 2018-04-20 | 2018-08-24 | 武汉科技大学 | Carbon nano-tube/poly aniline/graphene composite and flexible film and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113174132A (en) * | 2021-04-19 | 2021-07-27 | 浙江优可丽新材料有限公司 | Composite electromagnetic shielding material |
| CN113444371A (en) * | 2021-06-21 | 2021-09-28 | 安徽理工大学 | Preparation method and application of metal organic framework/polyaniline composite material |
| CN113527673A (en) * | 2021-06-24 | 2021-10-22 | 安徽理工大学 | Preparation method and application of graphene oxide/polyaniline composite material |
| CN114634642A (en) * | 2022-02-23 | 2022-06-17 | 华中科技大学 | PCNT (prestressed concrete) and PGO (PGO) synergistically modified polymer hybrid proton exchange membrane and preparation method thereof |
| CN114634642B (en) * | 2022-02-23 | 2023-03-10 | 华中科技大学 | PCNT (prestressed concrete) and PGO (PGO) synergistically modified polymer hybrid proton exchange membrane and preparation method thereof |
| CN114318455A (en) * | 2022-03-10 | 2022-04-12 | 季华实验室 | High-conductivity corrosion-resistant polymer composite coating, preparation method thereof and bipolar plate |
| CN114318455B (en) * | 2022-03-10 | 2022-06-17 | 季华实验室 | High-conductivity corrosion-resistant polymer composite coating, preparation method thereof and bipolar plate |
| CN116254036A (en) * | 2023-05-15 | 2023-06-13 | 牛墨石墨烯应用科技有限公司 | Preparation method of graphene carbon nanotube heat conduction slurry |
| CN116254036B (en) * | 2023-05-15 | 2023-09-15 | 牛墨石墨烯应用科技有限公司 | Preparation method of graphene carbon nanotube heat conduction slurry |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111138661B (en) | 2022-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111138661B (en) | Preparation method and application of graphene/carbon nanotube/polyaniline composite material | |
| CN108461694B (en) | Double-effect composite diaphragm for lithium-sulfur battery and preparation method thereof | |
| CN111362254A (en) | Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material | |
| US8377546B2 (en) | Plastics electrode material and secondary cell using the material | |
| CN107221665A (en) | A kind of preparation method of Zinc ion battery barium oxide combination electrode material | |
| CN103545113B (en) | A kind of lithium ion hybrid super capacitor | |
| CN104300129A (en) | Battery, battery cathode, battery cathode material and preparation method thereof | |
| CN110265656A (en) | Aqueous zinc ion secondary battery using elemental sulfur or sulfide as anode | |
| CN111769265B (en) | Preparation method of modified high-nickel ternary cathode material | |
| EP2309572A1 (en) | Plastics electrode material and secondary cell using the material | |
| CN112038632A (en) | Carbon-oxazine composite water-based negative electrode material and application thereof | |
| CN113066964A (en) | Double-metal phosphide-inlaid carbon hollow nano cage and preparation method and application thereof | |
| CN110518212B (en) | Preparation method of positive plate for lithium-sulfur battery | |
| JP5818689B2 (en) | Lithium ion secondary battery | |
| CN111192997A (en) | Diaphragm for activated carbon-loaded tin oxide lithium-sulfur battery and preparation method and application thereof | |
| CN111987316A (en) | Lithium-rich manganese-based composite cathode material and preparation method and application thereof | |
| CN115571929B (en) | Nickel-manganese binary composite positive electrode material and preparation method thereof | |
| CN111193026A (en) | Preparation method of fusiform iron oxide single crystal nano material | |
| CN115259222B (en) | Intercalation vanadate composite nano material and preparation method and application thereof | |
| CN104091916B (en) | MoS2nanometer sheet with holes/Graphene electrochemistry storage sodium combination electrode and preparation method | |
| JP2000123825A (en) | High polymer electrode | |
| CN117317153A (en) | Interface-modified hard carbon anode material/anode of sodium ion battery, preparation method and application | |
| CN115385325A (en) | Nitrogen-doped carbon nanomaterial and preparation method and related application thereof | |
| CN114122394B (en) | Polyoxazine material and preparation method and application thereof | |
| CN113097643A (en) | Modified diaphragm for lithium-sulfur battery and preparation process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |