CN111584864A - Carbon nano tube fullerene battery and preparation method thereof - Google Patents

Carbon nano tube fullerene battery and preparation method thereof Download PDF

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Publication number
CN111584864A
CN111584864A CN201910134214.0A CN201910134214A CN111584864A CN 111584864 A CN111584864 A CN 111584864A CN 201910134214 A CN201910134214 A CN 201910134214A CN 111584864 A CN111584864 A CN 111584864A
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fullerene
parts
slurry
carbon nanotube
battery
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叶小剑
平松雄二
牛尾顺一
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Priority to CN201910134214.0A priority Critical patent/CN111584864A/en
Priority to PCT/CN2020/075051 priority patent/WO2020168973A1/en
Priority to JP2021547313A priority patent/JP2022527688A/en
Priority to KR1020217030180A priority patent/KR20210145145A/en
Publication of CN111584864A publication Critical patent/CN111584864A/en
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H—ELECTRICITY
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
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    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
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    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • 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
    • H—ELECTRICITY
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    • 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
    • H01M4/621—Binders
    • H—ELECTRICITY
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    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
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    • 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
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a carbon nano tube fullerene battery, wherein a positive electrode material of the carbon nano tube fullerene battery comprises the following components: lithium cobaltate, a conductive agent, a binder, a collective fluid, carbon nanotube slurry or graphene; the anode material comprises the following components: graphite carbon black, conductive agent, adhesive, collective fluid and fullerene. Adding carbon nano tubes or graphene into coating slurry of a positive electrode material of a battery; the fullerene is added into the coating slurry of the cathode material, so that the capacity of the carbon nano tube fullerene battery is increased by 1.2-2.7 times compared with the common battery, the current density is increased, the internal resistance is reduced, the battery is not easy to generate heat and burn, is not easy to short circuit when being pierced or damaged, and the cycle period is increased by more than 1 time.

Description

Carbon nano tube fullerene battery and preparation method thereof
Technical Field
The invention relates to the field of batteries, in particular to a carbon nano tube fullerene battery and a preparation method thereof.
Background
Compared with the traditional secondary batteries such as lead-acid, nickel-cadmium, nickel-hydrogen and the like, the lithium ion battery has the advantages of high working voltage, small volume, light weight, high capacity density, no memory effect, no pollution, small self-discharge, long cycle life and the like. Lithium batteries are becoming more and more popular with people.
At present, cathode materials used in lithium ion batteries are all carbon materials, including natural graphite, artificial graphite, mesocarbon microbeads and the like. The carbon cathodes have the advantages of stable voltage, good cycle performance and the like in the charging and discharging processes. However, the theoretical capacity of the graphite material is only 372mAh/g, which is difficult to satisfy the pursuit of people for high capacity of lithium ion batteries, especially the demand of electric automobiles for high performance lithium batteries, and the development of a negative electrode material with high capacity density is urgently required; and the existing cathode material has poor wear resistance.
Disclosure of Invention
The present invention is directed to a carbon nanotube fullerene battery and a method for preparing the same, which can solve the above problems, and provide a carbon nanotube fullerene battery having a high wear resistance of a negative electrode material and an increased energy storage capacity by using the high capacity characteristics of fullerene and carbon nanotube.
The invention realizes the purpose through the following technical scheme: a carbon nano tube fullerene battery comprises the following components in percentage by weight in a coating slurry of a positive electrode material: lithium cobaltate, a conductive agent, a binder, carbon nanotube slurry or graphene; the anode material coating slurry contains the following components: graphite carbon black, a conductive agent, a binder and fullerene.
Preferably, the positive electrode material coating slurry comprises the following components in parts by weight: 2-10 parts of lithium cobaltate, 5-30 parts of a conductive agent, 1-15 parts of an adhesive and 2.5-30 parts of carbon nanotube slurry or graphene.
Preferably, the negative electrode material coating slurry comprises the following components in parts by weight: 1-20 parts of graphite carbon black, 5-30 parts of conductive agent, 1-15 parts of adhesive and 0.8-25 parts of fullerene.
Preferably, the cathode is an aluminum foil.
Preferably, the negative electrode is a copper foil.
Preferably, the conductive agent is acetylene black.
Preferably, the binder is polyvinylidene fluoride (PVDF).
The invention also provides a preparation method for preparing the carbon nano tube fullerene battery, which comprises the following steps:
(1) preparing materials: mixing lithium cobaltate, a conductive agent, an adhesive and carbon nanotube slurry to obtain mixed positive electrode slurry; mixing graphite carbon black, a conductive agent, an adhesive and fullerene to obtain mixed negative electrode slurry;
(2) coating: coating the positive electrode slurry on a positive electrode collective fluid through a coating machine; coating the negative electrode slurry on a negative electrode collective fluid through a coating machine;
(3) then rolling, slitting, flaking, winding, assembling, top side sealing, drying, injecting liquid, melting and finally packaging to obtain the battery of the invention.
Preferably, the fullerene is extracted before the step (1), and the extraction method comprises the following steps: and putting the carbon powder into an oxidation-reduction kettle, electrifying and burning, then extracting carbon gas black particles attached to the inner wall of the kettle, and then carrying out electrostatic processing to obtain the fullerene.
The invention has the beneficial effects that: adding carbon nano tubes or graphene into a positive electrode material of a battery; the addition of fullerene in the cathode material increases the capacity of the carbon nano tube fullerene battery by 1.2-2.7 times compared with the common battery, increases the current density, reduces the internal resistance, is not easy to generate heat and burn, is not easy to short circuit when being pierced or damaged, and increases the cycle period by more than 1 time.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
In the carbon nanotube fullerene battery of the embodiment, the cathode coating slurry material comprises the following components: 2 parts of lithium cobaltate, 5 parts of acetylene black, 1 part of polyvinylidene fluoride (PVDF) and 2.5 parts of carbon nanotube slurry; the negative electrode coating slurry material contains the following components: graphite carbon black 1 part, acetylene black 5 parts, polyvinylidene fluoride 1 part, fullerene 0.8 part, and further comprises a positive aluminum foil and a negative copper foil.
The preparation method of the carbon nano tube fullerene battery comprises the following steps:
(1) preparing materials: mixing the lithium cobaltate, the acetylene black, the polyvinylidene fluoride (PVDF) and the carbon nanotube slurry in parts by weight to obtain a mixed positive electrode slurry; mixing the graphite carbon black, the acetylene black, the polyvinylidene fluoride and the fullerene in parts by weight to obtain mixed negative electrode slurry;
(2) coating: coating the positive electrode slurry on an aluminum foil through a coating machine; coating the negative electrode slurry on a copper foil through a coating machine;
(3) then rolling, slitting, flaking, winding, assembling, top side sealing, drying, injecting liquid, forming and finally packaging to obtain the battery of the invention.
The following steps are adopted for extracting fullerene in the embodiment:
(1) about one ton of firewood (uncontaminated pine, cedar, Chinese juniper and the like) is put into a redox kiln for firing ceramics for combustion, and after 24 hours, 1100g of smoke attached to the inside wall of the redox kiln can be extracted;
(2) the 1100g of the ash was electrostatically processed in an electrostatic charger to obtain 110g of conductive fullerene.
Example 2
In the carbon nanotube fullerene battery of the embodiment, the positive coating slurry material comprises the following components: 10 parts of lithium cobaltate, 30 parts of acetylene black, 15 parts of polyvinylidene fluoride and 30 parts of carbon nanotube slurry; the negative electrode coating slurry material contains the following components: 20 parts of graphite carbon black, 30 parts of acetylene black, 5 parts of polyvinylidene fluoride, 25 parts of fullerene, and further comprises a positive aluminum foil and a negative copper foil
This example used the preparation of example 1.
Example 3
In the carbon nanotube fullerene battery of the embodiment, the positive coating slurry material comprises the following components: 5 parts of lithium cobaltate, 15 parts of acetylene black, 8 parts of polyvinylidene fluoride and 15 parts of carbon nanotube slurry; the negative electrode coating slurry material contains the following components: 10 parts of graphite carbon black, 15 parts of acetylene black, 5 parts of polyvinylidene fluoride, 13 parts of fullerene, and further comprises a positive aluminum foil and a negative copper foil
This example used the preparation of example 1.
Example 4
In the carbon nanotube fullerene battery of the embodiment, the positive coating slurry material comprises the following components: 5 parts of lithium cobaltate, 15 parts of acetylene black, 8 parts of polyvinylidene fluoride and 30 parts of graphene; the negative electrode coating slurry material contains the following components: 10 parts of graphite carbon black, 15 parts of acetylene black, 5 parts of polyvinylidene fluoride, 13 parts of fullerene, and further comprises a positive aluminum foil and a negative copper foil
This example used the preparation of example 1.
The carbon nanotube fullerene cells prepared in examples 1 to 4 above were subjected to the test
1. And (3) capacity test results: taking a lithium battery with the external dimension of 25 multiplied by 37 multiplied by 76mm as an example, the capacity of the non-carbon nano tube battery is 750mA, and the capacity of the carbon nano tube fullerene battery of the invention is 950 and 1050mA, which are improved by 26 percent to 30 percent compared with the prior art.
2. Destructive test results
The above test of 25X 37X 76mm carbon nanotube fullerene lithium battery
1) And (3) hammering test: a 10kg heavy steel hammer falls naturally at a height of 1 meter: the fire and explosion are avoided;
2) and (3) overcharging test: the heating and explosion can not occur;
3) and (3) nail penetration testing: directly nailing a 3 x 8.0mm iron nail through the battery without firing or explosion;
4) and (3) soaking test: soaking in water for 24 hours, and keeping the performance unchanged;
5) and (3) thermal shock resistance test: putting into a temperature test box, heating to 150 deg.C from 5 deg.C, and preventing fire and explosion;
6) vibration testing: placing in a vibration testing machine, and vibrating for 30 minutes until involved, wherein the appearance and the performance are unchanged;
7) and (3) extrusion testing: putting the mixture into an extruder, and applying a maximum pressure of 17MPa without firing or exploding;
8) the screwdriver penetration test: after the screwdriver penetrates through the battery, the voltage is not changed (the battery generally causes short circuit and is zero due to penetration), and the temperature is increased by 6-7 ℃ after 6-7 minutes;
9) drop test: the battery is placed on a 6m height and naturally falls down on the iron plate, and the voltage is unchanged.
The experiments prove that the capacity of the carbon nano tube fullerene battery is increased by 1.2-2.7 times compared with the common battery, the current density is increased, and the quality completely meets the safety certification requirements of PSE, GB, UC and the like.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (9)

1. The carbon nano tube fullerene battery is characterized in that the coating slurry of the positive electrode material comprises the following components: lithium cobaltate, a conductive agent, a binder, carbon nanotube slurry or graphene; the anode material coating slurry contains the following components: graphite carbon black, a conductive agent, a binder and fullerene.
2. The carbon nanotube fullerene battery according to claim 1, wherein the positive electrode material coating slurry comprises the following components in parts by weight: 2-10 parts of lithium cobaltate, 5-30 parts of a conductive agent, 1-15 parts of an adhesive and 2.5-30 parts of carbon nanotube slurry or graphene.
3. The carbon nanotube fullerene battery according to claim 1, wherein the negative electrode material coating slurry comprises the following components in parts by weight: 1-20 parts of graphite carbon black, 5-30 parts of conductive agent, 1-15 parts of adhesive and 0.8-25 parts of fullerene.
4. The carbon nanotube fullerene cell according to claim 1 or 2, wherein the positive electrode is an aluminum foil.
5. The carbon nanotube fullerene cell according to claim 1 or 3, wherein the negative electrode is a copper foil.
6. The carbon nanotube fullerene cell according to any one of claims 1 to 3, wherein the conductive agent is acetylene black.
7. The carbon nanotube fullerene cell according to any one of claims 1 to 3, wherein the binder is polyvinylidene fluoride.
8. A method of manufacturing a carbon nanotube fullerene cell according to any one of claims 1-7, comprising the steps of:
(1) preparing materials: mixing lithium cobaltate, a conductive agent, an adhesive and carbon nanotube slurry to obtain positive electrode slurry; mixing graphite carbon black, a conductive agent, an adhesive and fullerene to obtain negative electrode slurry;
(2) coating: coating the positive electrode slurry on a positive electrode collective fluid through a coating machine; coating the negative electrode slurry on a negative electrode collective fluid through a coating machine;
(3) then rolling, slitting, flaking, winding, assembling, top side sealing, drying, injecting liquid, forming and finally packaging to obtain the battery of the invention.
9. The method for manufacturing a carbon nanotube fullerene cell as claimed in claim 8, wherein the step (1) is preceded by a step of extracting fullerene, which comprises the steps of: and putting the carbon powder into an oxidation-reduction kettle, electrifying and burning, then extracting carbon gas black particles attached to the inner wall of the kettle, and then carrying out electrostatic processing to obtain the fullerene.
CN201910134214.0A 2019-02-22 2019-02-22 Carbon nano tube fullerene battery and preparation method thereof Pending CN111584864A (en)

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PCT/CN2020/075051 WO2020168973A1 (en) 2019-02-22 2020-02-13 Carbon nanotube fullerene battery and preparation method therefor
JP2021547313A JP2022527688A (en) 2019-02-22 2020-02-13 Carbon nanotube fullerene battery and its preparation method
KR1020217030180A KR20210145145A (en) 2019-02-22 2020-02-13 Carbon nanotube fullerene battery and manufacturing method thereof

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