CN111933897B - Composite material, preparation method and application thereof - Google Patents

Composite material, preparation method and application thereof Download PDF

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CN111933897B
CN111933897B CN201910395845.8A CN201910395845A CN111933897B CN 111933897 B CN111933897 B CN 111933897B CN 201910395845 A CN201910395845 A CN 201910395845A CN 111933897 B CN111933897 B CN 111933897B
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nano tube
carbon nano
composite material
molybdenum
metal oxide
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CN111933897A (en
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胡君
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Beijing Electric Vehicle Co Ltd
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Beijing Electric Vehicle Co Ltd
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 the field of batteries, in particular to a composite material, and a preparation method and application thereof. The composite material comprises a carbon nano tube and a molybdenum-based metal oxide embedded in a tube cavity of the carbon nano tube. The preparation method comprises the following steps: dispersing the purified carbon nano tube in water, adding sodium molybdate and phosphoric acid with the mass concentration of 85%, and infiltrating the carbon nano tube; separating the infiltrated carbon nano tube, and washing with a polar organic solvent to obtain a wet carbon nano tube; and mixing the wet carbon nano tube with concentrated hydrochloric acid, fully reacting, separating and precipitating, and removing redundant concentrated hydrochloric acid and molybdenum-based metal oxide on the surface of the precipitate to obtain the composite material. The carbon nano tube effectively protects the integrity of the molybdenum-based metal oxide; meanwhile, the carbon nano tube has good conductivity, and the composite material formed by the carbon nano tube and the carbon nano tube is beneficial to the transmission of lithium ions. The composite material is used as a negative electrode of a lithium ion battery, and can improve the cycle life and stability of the battery.

Description

Composite material, preparation method and application thereof
Technical Field
The invention relates to the field of batteries, in particular to a composite material, and a preparation method and application thereof.
Background
A lithium ion battery is a type of secondary battery that mainly operates by movement of lithium ions between a positive electrode and a negative electrode. During charging and discharging, Li+Intercalation and deintercalation to and from two electrodes: upon charging, Li+The lithium ion battery is extracted from the positive electrode and is inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true during discharge. Lithium ion batteries have the outstanding advantages of high energy, long cycle life, no pollution, etc., have become the mainstream of the battery market, and are beginning to be applied to driving electric batteries.
The energy density, the service life and other properties of the lithium ion battery are mainly determined by the electrode material. Therefore, the development of high-performance electrode materials has become a hot spot in battery research. In the aspect of the negative electrode material, the carbon material or the metal oxide material can be applied as the negative electrode material. Currently, commercial graphite anode materials have low capacity and are prone to side reactions during cycling, which can cause safety problems. It has been difficult to meet the demand.
Disclosure of Invention
The invention aims to solve the technical problem of providing a composite material, a preparation method and application thereof.
The invention provides a composite material, which comprises a carbon nano tube and molybdenum-based metal oxide embedded in a tube cavity of the carbon nano tube.
Preferably, the carbon nanotubes are single-walled carbon nanotubes.
Preferably, the mass ratio of the molybdenum-based metal oxide to the carbon nanotube is 1 (4-20).
The invention provides a preparation method of a composite material, which comprises the following steps:
(A) dispersing the purified carbon nano tube in water, adding sodium molybdate and phosphoric acid with the mass concentration of 85%, and infiltrating the carbon nano tube;
(B) separating the infiltrated carbon nano tube, and washing with a polar organic solvent to obtain a wet carbon nano tube;
(C) and mixing the wet carbon nano tube with concentrated hydrochloric acid, fully reacting, separating and precipitating, and removing redundant concentrated hydrochloric acid and molybdenum-based metal oxide on the surface of the precipitate to obtain the composite material.
Preferably, the purification treatment method comprises the following steps:
mixing the single-walled carbon nanotube with sulfuric acid, carrying out ultrasonic treatment, washing the mixture to be neutral by using a sodium bicarbonate solution, washing the mixture by using deionized water, and drying the mixture in vacuum to obtain the purified carbon nanotube.
Preferably, the mass ratio of the carbon nano tube, the sodium molybdate and the phosphoric acid is (1-1.15): 242: 115.
Preferably, the molar ratio of the sodium molybdate to the phosphoric acid to the concentrated hydrochloric acid is 12:1 (0.05-0.10).
Preferably, the polar organic solution is an alcohol.
The invention provides a lithium ion battery cathode, which comprises the composite material, a conductive agent and a binder in the technical scheme;
the mass ratio of the composite material, the conductive agent and the binder is (70-85): (5-20): 5-15).
The invention also provides a lithium ion battery, which comprises the lithium ion battery cathode in the technical scheme.
Compared with the prior art, the composite material is characterized in that the active molybdenum-based metal oxide is embedded in the cavity of the carbon nano tube. The molybdenum-based metal oxide has higher theoretical capacity, and exists in the carbon nano tube in a monomolecular mode, so that the integrity of the molybdenum-based metal oxide is effectively protected by the carbon nano tube; meanwhile, the carbon nano tube has good conductivity, and the composite material formed by the carbon nano tube and the carbon nano tube is beneficial to the transmission of lithium ions. Especially, when the carbon nano tube is a single-wall carbon nano tube, the performance stability of the composite material can be effectively improved. When the composite material is used as the negative electrode of the lithium ion battery, the molybdenum-based metal oxide cannot be broken and lose efficacy due to volume expansion in the process of lithium ion intercalation and deintercalation because of the protection of the carbon nano tube, so that the cycle life and the stability of the battery can be improved.
Drawings
FIG. 1 shows a micrograph of a composite prepared according to the present invention;
fig. 2 shows a rate test chart of a lithium ion battery produced using the composite material of example 1 as a negative electrode.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention in conjunction with the following examples, but it will be understood that the description is intended to illustrate the features and advantages of the invention further, and not to limit the invention.
The embodiment of the invention discloses a composite material, which comprises a carbon nano tube and a molybdenum-based metal oxide embedded in a tube cavity of the carbon nano tube.
In the present invention, the molybdenum-based metal oxide exists in a monomolecular form and is embedded in the cavity of the carbon nanotube. The carbon nanotubes are preferably single-walled carbon nanotubes. Because the unimolecule of the molybdenum-based metal oxide is matched with the pipe cavity size of the single-walled carbon nanotube, the stability is strong after the molybdenum-based metal oxide is embedded, and the performance stability of the composite material can be improved.
The molybdenum-based metal oxide is preferably H3PMo12O40。
Preferably, the mass ratio of the molybdenum-based metal oxide to the carbon nanotubes is 1 (4-20), and more preferably 3: 17.
The embodiment of the invention discloses a preparation method of a composite material, which comprises the following steps:
(A) dispersing the purified carbon nano tube in water, adding sodium molybdate and phosphoric acid with the mass concentration of 85%, and infiltrating the carbon nano tube;
(B) separating the infiltrated carbon nano tube, and washing with a polar organic solvent to obtain a wet carbon nano tube;
(C) and mixing the wet carbon nano tube with concentrated hydrochloric acid, fully reacting, centrifugally separating and precipitating, and removing redundant concentrated hydrochloric acid and molybdenum-based metal oxide on the surface of the precipitate to obtain the composite material.
According to the invention, the preparation of the composite material is described in detail below in terms of the individual steps:
(A) dispersing the purified carbon nano tube in water, adding sodium molybdate and phosphoric acid with the mass concentration of 85%, and infiltrating the carbon nano tube.
The purification treatment method is preferably:
mixing the single-walled carbon nanotube with sulfuric acid, carrying out ultrasonic treatment, washing the mixture to be neutral by using a sodium bicarbonate solution, then washing the mixture by using deionized water, and carrying out vacuum drying to obtain the purified carbon nanotube.
The concentration of the sulfuric acid is preferably 4-10M, and more preferably 5-8M. The concentration of the sodium bicarbonate is preferably 0.05-2M. The temperature of the vacuum drying is preferably 50-70 ℃. Under the condition, the purified carbon nano tube can be obtained, and the oxidation of the carbon nano tube is avoided as much as possible.
After purification treatment, impurities on the surface of the carbon nano tube, such as metal catalyst, can be removed.
(B) Separating the soaked carbon nano tube, and washing with a polar organic solvent to obtain the wet carbon nano tube.
The carbon nano tube after being separated and infiltrated can adopt the modes of centrifugal separation, filtration and the like.
The polar organic solvent is preferably an alcohol, more preferably ethanol. The number of times of washing is preferably 3-10 times. After the carbon nano tube is washed by the polar organic solvent, sodium molybdate and phosphoric acid are arranged in the inner tube cavity of the carbon nano tube, and the outside is a polar organic environment.
The mass ratio of the carbon nano tube to the sodium molybdate to the phosphoric acid is preferably (1-1.15): 242:115, and more preferably 1:242:115, so that the sodium molybdate and the phosphoric acid are fully filled in the carbon nano tube to facilitate the subsequent reaction with concentrated hydrochloric acid.
(C) And mixing the wet carbon nano tube with concentrated hydrochloric acid, fully reacting, centrifugally separating and precipitating, and removing redundant concentrated hydrochloric acid and molybdenum-based metal oxide on the surface of the precipitate to obtain the composite material.
The wet carbon nanotube is mixed with concentrated hydrochloric acid, and the concentrated hydrochloric acid reacts with sodium molybdate and phosphoric acid in the tube cavity of the wet carbon nanotube to generate molybdenum-based metal oxide inside the wet carbon nanotube.
The molar ratio of the sodium molybdate to the phosphoric acid to the concentrated hydrochloric acid is preferably 12:1 (0.05-0.10), and more preferably 12:1:0.05, so that the sodium molybdate, the phosphoric acid and the concentrated hydrochloric acid react better to form the optimal molybdenum-based metal oxide.
The molybdenum-based metal oxide is preferably H3PMo12O40。
The invention also discloses a lithium ion battery cathode, which comprises the composite material, the conductive agent and the binder in the technical scheme;
the mass ratio of the composite material, the conductive agent and the binder is (70-85): (5-20): 5-15).
The mass ratio of the composite material, the conductive agent and the binder is preferably 80:10:10, 70:20:10 or 85:5: 10. The lithium ion battery cathode prepared according to the mass ratio has good stability, is suitable for the desorption/intercalation of lithium ions, and has good volume stability.
The conductive agent is preferably carbon black, and the binder is preferably polyvinylidene fluoride (PVDF). The source of the conductive agent and the binder in the present invention is not particularly limited and may be selected conventionally by those skilled in the art.
The composite material realizes the in-situ synthesis of the molybdenum-based metal oxide and has good structure and appearance. When the composite material is used for the cathode of the lithium ion battery, the carbon nano tube has good conductivity and is suitable for the desorption/intercalation of lithium ions; the molybdenum-based metal oxide has stable performance, good conductivity and high theoretical capacity, so that the molybdenum-based metal oxide cannot be broken and failed due to volume expansion under the synergistic action of the carbon nanotubes and the molybdenum-based metal oxide, and the cycle life and the stability of the battery can be improved.
The preparation method of the lithium ion battery cathode preferably comprises the following steps:
after the composite material is dried, the composite material, a conductive agent and a binder are uniformly mixed according to the mass ratio of 70-85: 5-20: 5-15, the mixture is coated on a battery-grade copper foil, and the lithium ion battery cathode is obtained after drying.
In the preparation method of the lithium ion battery cathode, the drying temperature of the material is preferably 100-150 ℃, and the drying time is preferably 20-30 hours.
The invention also discloses a lithium ion battery, which comprises the lithium ion battery cathode in the technical scheme.
The lithium ion battery also comprises a lithium sheet as a positive electrode, LiF6As an electrolyte, a battery separator.
For further understanding of the present invention, the following examples are given to illustrate the composite material, the preparation method and the application thereof, and the scope of the present invention is not limited by the following examples.
Example 1
1) Using single-walled carbon nanotubes as the substrate, 6M H2SO4Sonicate for 6h to remove metal catalyst, then use 0.1M NaHCO3Washing the solution toWashing with deionized water for 3 times, and vacuum drying at 60 deg.C;
2) weighing 100mg of the single-walled carbon nanotube in the step 1), dispersing the single-walled carbon nanotube in 100mL of water, then adding 5g of sodium molybdate and 0.5mL of 85% phosphoric acid, fully and uniformly stirring, fully infiltrating the carbon nanotube overnight, then carrying out centrifugal separation, and washing with ethanol for 3 times to obtain a wet carbon nanotube, wherein the inside of the carbon nanotube is an acidic solution, and the outside of the carbon nanotube is an ethanol environment;
adding the obtained wet carbon nano tube into a small beaker, dripping 5mL of concentrated hydrochloric acid, stirring, fully reacting for 6h, then performing centrifugal separation, washing with deionized water for 3 times to remove redundant hydrochloric acid and molybdenum-based oxide generated on the surface, only keeping the embedded molybdenum-based metal oxide-carbon nano tube composite material, then washing with ethanol for 3 times, and transferring to a 60-DEG oven for vacuum drying;
3) and verifying the physicochemical property and the electrochemical property of the embedded molybdenum-based oxide-carbon nanotube composite material.
In fig. 1, the black shaded portions are molybdenum-based metal oxide particles having a size of about 0.8nm, and the striped background is single-walled carbon nanotubes, and it is considered that the molybdenum-based metal oxide is successfully embedded in the single-walled carbon nanotubes and thus is not easily lost during electrochemical cycling.
Example 2
1) Drying the composite material prepared in the embodiment 1 at 120 ℃ for 24 hours, uniformly mixing the dried composite material with conductive agent carbon black and binder PVDF according to the mass ratio of 80:10:10, coating the mixture on a battery-grade copper foil, drying the mixture at 120 ℃ for 24 hours, and cutting the mixture into electrode slices with the diameter of 11mm by using a battery slice cutting machine for later use;
2) placing the prepared electrode slice in a Braun glove box, taking a lithium slice as a counter electrode, and 1M LiF6The electrolyte is taken as a diaphragm of the celegard battery diaphragm, and the celegard battery diaphragm is assembled into a C2032 type button battery;
3) and (3) placing the prepared C2032 button cell in a test room, standing overnight, and testing, wherein the test item is CV test.
For the button cell type C2032 cell using the composite material prepared in example 1 as the negative electrode, the test item is the cycle life test. The specific capacity of the composite material was maintained at 1000mAh/g after 100 cycles at a current density of 100mA/g, see in particular FIG. 2.
Comparative example 1
1) Drying the molybdenum-based metal oxide at 120 ℃ for 24 hours, uniformly mixing the molybdenum-based metal oxide with conductive agent carbon black and binder PVDF according to the mass ratio of 80:10:10, coating the mixture on a battery-grade copper foil, drying the mixture at 120 ℃ for 24 hours, and cutting the mixture into electrode slices with the diameter of 11mm by using a battery slice cutting machine for later use;
2) placing the prepared electrode slice in a Braun glove box, taking a lithium slice as a counter electrode, and 1M LiF6The electrolyte is taken as a diaphragm of the celegard battery diaphragm, and the celegard battery diaphragm is assembled into a C2032 type button battery;
3) and (3) placing the prepared C2032 button cell in a test room, standing overnight, and testing, wherein the test item is CV test.
For the C2032 button cell with molybdenum-based metal oxide as the cathode, the test item is the cycle life test. The specific capacity of the molybdenum-based metal oxide is kept at 500mAh/g after 100 cycles under the current density of 100 mA/g.
Comparative example 2
1) Using single-walled carbon nanotubes as the substrate, 6M H2SO4Sonicate for 6h to remove metal catalyst, then use 0.1M NaHCO3Washing the solution to be neutral, then washing the solution for 3 times by using deionized water, and drying the solution in vacuum at 60 ℃;
2) weighing 50mg of the single-walled carbon nanotube in the step 1) and dispersing the single-walled carbon nanotube in 100mL of water, then adding 1g of sodium molybdate and 0.5mL of 85% phosphoric acid, fully and uniformly stirring, fully infiltrating the carbon nanotube overnight, then carrying out centrifugal separation, and washing with ethanol for 3 times to obtain a wet carbon nanotube, wherein the inside of the carbon nanotube is an acidic solution, and the outside of the carbon nanotube is an ethanol environment;
adding the obtained wet carbon nano tube into a small beaker, dripping 10mL of concentrated hydrochloric acid, stirring, fully reacting for 6h, then carrying out centrifugal separation, washing with deionized water for 3 times to remove redundant hydrochloric acid and molybdenum-based oxide generated on the surface, only keeping the embedded molybdenum-based metal oxide-carbon nano tube composite material, then washing with ethanol for 3 times, and transferring to a 60-DEG oven for vacuum drying;
3) and verifying the physicochemical property and the electrochemical property of the embedded molybdenum-based oxide-carbon nanotube composite material.
4) Drying the prepared composite material at 120 ℃ for 24 hours, uniformly mixing the dried composite material with conductive agent carbon black and binder PVDF according to the mass ratio of 80:10:10, coating the mixture on a battery-grade copper foil, drying the mixture for 24 hours at 120 ℃, and cutting the mixture into electrode slices with the diameter of 11mm by using a battery slice cutting machine for later use;
2) placing the prepared electrode slice in a Braun glove box, taking a lithium slice as a counter electrode, and 1M LiF6The electrolyte is taken as a diaphragm of the celegard battery diaphragm, and the celegard battery diaphragm is assembled into a C2032 type button battery;
3) and (3) placing the prepared C2032 button cell in a test room, standing overnight, and testing, wherein the test item is CV test.
For the C2032 button cell using the prepared composite material as the cathode, the test item is the cycle life test. The specific capacity of the composite material is kept at 550mAh/g after 100 cycles under the current density of 100 mA/g.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (8)

1. The composite material is characterized by comprising a carbon nano tube and a molybdenum-based metal oxide embedded in a tube cavity of the carbon nano tube; the carbon nano tube is a single-wall carbon nano tube;
the preparation method of the composite material comprises the following steps: (A) dispersing the purified carbon nano tube in water, adding sodium molybdate and phosphoric acid with the mass concentration of 85%, and infiltrating the carbon nano tube;
(B) separating the infiltrated carbon nano tube, and washing with a polar organic solvent to obtain a wet carbon nano tube;
(C) and mixing the wet carbon nano tube with concentrated hydrochloric acid, fully reacting, separating and precipitating, and removing redundant concentrated hydrochloric acid and molybdenum-based metal oxide on the surface of the precipitate to obtain the composite material.
2. The composite material of claim 1, wherein the mass ratio of the molybdenum-based metal oxide to the carbon nanotubes is 1 (4-20).
3. The composite material according to claim 1, wherein the purification treatment is performed by:
mixing the single-walled carbon nanotube with sulfuric acid, carrying out ultrasonic treatment, washing the mixture to be neutral by using a sodium bicarbonate solution, washing the mixture by using deionized water, and drying the mixture in vacuum to obtain the purified carbon nanotube.
4. The composite material of claim 1, wherein the mass ratio of the carbon nanotubes to the sodium molybdate to the phosphoric acid is (1-1.15): 242: 115.
5. The composite material of claim 1, wherein the molar ratio of the sodium molybdate to the phosphoric acid to the concentrated hydrochloric acid is 12:1 (0.05-0.10).
6. The composite material of claim 1, wherein the polar organic solution is an alcohol.
7. A lithium ion battery negative electrode, characterized by comprising the composite material of any one of claims 1 to 2, a conductive agent and a binder;
the mass ratio of the composite material, the conductive agent and the binder is (70-85): (5-20): 5-15).
8. A lithium ion battery comprising the lithium ion battery negative electrode of claim 7.
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CN113690416B (en) * 2021-08-08 2022-09-09 苏州大学 Layered metal oxide/amine composite material, preparation method thereof and application thereof in magnesium ion battery
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JP2004214116A (en) * 2003-01-08 2004-07-29 National Institute Of Advanced Industrial & Technology High power type secondary battery
CN104051734A (en) * 2014-06-16 2014-09-17 中国东方电气集团有限公司 Electrode material for polyoxometallate carbon nanotube lithium ion battery and preparation method of electrode material
CN104332597A (en) * 2014-10-20 2015-02-04 北京化工大学 Polyacid/polyaniline/carbon nano tube electrode material as well as preparation method and application thereof
CN104638245A (en) * 2015-02-13 2015-05-20 江苏科技大学 Keggin type phosphomolybdate-graphene composite material for lithium ion battery and preparation method thereof
CN105870435A (en) * 2016-04-19 2016-08-17 陕西科技大学 MoO2@CNTs composite material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
JP2004214116A (en) * 2003-01-08 2004-07-29 National Institute Of Advanced Industrial & Technology High power type secondary battery
CN104051734A (en) * 2014-06-16 2014-09-17 中国东方电气集团有限公司 Electrode material for polyoxometallate carbon nanotube lithium ion battery and preparation method of electrode material
CN104332597A (en) * 2014-10-20 2015-02-04 北京化工大学 Polyacid/polyaniline/carbon nano tube electrode material as well as preparation method and application thereof
CN104638245A (en) * 2015-02-13 2015-05-20 江苏科技大学 Keggin type phosphomolybdate-graphene composite material for lithium ion battery and preparation method thereof
CN105870435A (en) * 2016-04-19 2016-08-17 陕西科技大学 MoO2@CNTs composite material and preparation method thereof

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