CN111384363A - Positive pole piece and lithium ion battery - Google Patents
Positive pole piece and lithium ion battery Download PDFInfo
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- CN111384363A CN111384363A CN201811607171.5A CN201811607171A CN111384363A CN 111384363 A CN111384363 A CN 111384363A CN 201811607171 A CN201811607171 A CN 201811607171A CN 111384363 A CN111384363 A CN 111384363A
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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
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- 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
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
In order to solve the problem that the energy density and the electronic conductivity of the conventional lithium ion battery positive pole piece cannot be considered at the same time, the invention provides a positive pole piece which comprises a positive pole material layer, wherein the positive pole material layer comprises the following components in parts by weight: 96.5-98 parts of positive electrode active substance, 0.02-0.2 part of single-walled carbon nanotube, 0.98-1.3 parts of conductive carbon black and 1-2 parts of positive electrode binder. Meanwhile, the invention also discloses a lithium ion battery comprising the positive pole piece. The positive pole piece provided by the invention can greatly reduce the using amount of the conductive agent under the condition of ensuring that the positive pole piece has lower resistance, and the energy density of the lithium ion battery is improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a positive pole piece and a lithium ion battery.
Background
A lithium ion battery is a secondary battery that operates by migration of lithium ions between positive and negative electrodes. As an efficient energy storage device, a lithium ion battery is widely used in the fields of consumer electronics, new energy vehicles, energy storage, and the like.
With the rapid development of the terminal field, the requirements of various performances of the lithium ion battery, such as capacity, voltage, service life, etc., are also continuously improved. In particular, with the rapid development of the new energy automobile field, in order to meet the requirement of higher endurance mileage, various technical schemes have been proposed to improve the energy density of the lithium ion battery.
The selection of the high-capacity anode material is one of effective ways for improving the energy density of the lithium ion battery. In recent years, a layered ternary lithium nickel cobalt manganese oxide positive electrode material has gradually replaced a lithium iron phosphate material and is widely applied to the field of new energy passenger vehicles. However, as the gram volume of the material increases, there are disadvantages such as deterioration of thermal stability and poor cyclability. Meanwhile, the design and formula of the positive pole piece are optimized, the proportion of positive active substances is improved, and the method is also an effective means for improving the energy density of the battery.
Generally, the positive electrode plate is composed of a current collector, a positive active material, a conductive agent, and a binder. Among the commonly used conductive agents are conductive carbon black, conductive graphite, and the like. Conductive carbon black is the most widely used conductive agent at present, and has the disadvantages of low price, small particle size and large specific surface area, but the addition amount is large. The conductive graphite is often mixed with conductive carbon black for use, and has better compressibility and dispersibility, but poor conductivity.
Another conventional conductive agent is a carbon nanotube, which is a coaxial circular tube having several to tens of layers formed by carbon atoms arranged in a hexagonal pattern. The layers are maintained at a fixed distance of about 0.34nm, with a diameter of typically 2-20 nm. The P electrons of carbon atoms on the carbon nano tube form a large-range delocalized pi bond, the carbon nano tube has some special electrical properties due to the obvious conjugate effect, the carbon nano tube has good conductivity, the hollow structure is more favorable for the permeability of electrolyte in a pole piece, and the tensile strength can reach 100-150 Gpa. At present, the carbon nano-tube commonly used in the market is a multi-wall carbon nano-tube, and the number of the layers is between 10 and 15. The multi-walled carbon nanotube can replace the traditional conductive carbon black in the dosage ratio of 1:10, and can be applied to battery slurry to prepare a lithium ion battery.
The positive pole piece using the multi-walled carbon nanotube as the conductive agent can reduce the addition amount of the conductive agent to a certain extent, and realize the improvement of the proportion of positive active substances, thereby improving the energy density of the lithium ion battery. However, the improvement effect is limited, and the proportion of the positive electrode active material is usually 96.5% or less, and the requirements of the lithium ion battery for higher energy density, longer cycle and other performances cannot be met.
Disclosure of Invention
The invention provides a positive pole piece and a lithium ion battery, aiming at the problem that the energy density and the electronic conductivity of the conventional lithium ion battery positive pole piece cannot be considered at the same time.
The technical scheme adopted by the invention for solving the technical problems is as follows:
on one hand, the invention provides a positive pole piece, which comprises a positive pole material layer, wherein the positive pole material layer comprises the following components in parts by weight:
96.5-98 parts of positive electrode active substance, 0.02-0.2 part of single-walled carbon nanotube, 0.98-1.3 parts of conductive carbon black and 1-2 parts of positive electrode binder.
The inventor discovers through a large number of experiments that in the positive pole piece of the lithium ion battery, the single-walled carbon nanotube and the conductive carbon black have good synergistic effect, and the combination of the single-walled carbon nanotube and the conductive carbon black as a conductive agent can improve the migration rate of electrons in the lithium battery and reduce the polarization of the battery; the processability of the pole piece can be improved, the pole piece is promoted to be soaked by the electrolyte, and meanwhile, the adhesion among particles can be enhanced, so that the use of the positive electrode adhesive is reduced. Particularly, 0.02-0.2 part of single-walled carbon nanotube and 0.98-1.3 parts of conductive carbon black are added as conductive agents, so that the dosage of the conductive agents can be greatly reduced under the condition of ensuring that the positive pole piece has lower resistance, the proportion of positive active substances is improved, the maximum positive active substances can reach 98%, and the energy density of the lithium ion battery is improved.
Optionally, the diameter of the single-walled carbon nanotube is less than or equal to 3nm, and the length of the single-walled carbon nanotube is more than or equal to 5 μm.
Optionally, the mass fraction of the positive electrode active material is 96.5% to 98%, the mass fraction of the single-walled carbon nanotube is 0.02% to 0.2%, the mass fraction of the conductive carbon black is 0.98% to 1.3%, and the mass fraction of the positive electrode binder is 1% to 2%, based on 100% of the mass of the positive electrode material layer.
Optionally, the positive active material is selected from one or more of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium iron phosphate, and lithium manganese oxide.
Optionally, the positive electrode plate further includes a positive current collector, and the positive material layer covers on the positive current collector.
Optionally, the positive current collector is an aluminum foil.
Optionally, the positive binder includes one or more of polyvinyl alcohol, styrene butadiene rubber, polyvinylidene fluoride, sodium alginate, polyacrylic acid, polyimide, and lithium polyacrylate.
On the other hand, the invention also provides a lithium ion battery which comprises electrolyte, a negative pole piece and the positive pole piece.
Optionally, the lithium ion battery further includes a diaphragm, and the diaphragm is located between the negative electrode plate and the positive electrode plate.
Optionally, the negative electrode plate includes a negative current collector and a negative material layer, and the negative material layer covers on the negative current collector.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a positive pole piece, which comprises a positive pole material layer, wherein the positive pole material layer comprises the following components in parts by weight:
96.5-98 parts of positive electrode active substance, 0.02-0.2 part of single-walled carbon nanotube, 0.98-1.3 parts of conductive carbon black and 1-2 parts of positive electrode binder.
The inventor discovers through a large number of experiments that in the positive pole piece of the lithium ion battery, the single-walled carbon nanotube and the conductive carbon black have good synergistic effect, and the combination of the single-walled carbon nanotube and the conductive carbon black as a conductive agent can improve the migration rate of electrons in the lithium battery and reduce the polarization of the battery; the processability of the pole piece can be improved, the pole piece is promoted to be soaked by the electrolyte, and meanwhile, the adhesion among particles can be enhanced, so that the use of the positive electrode adhesive is reduced. Particularly, 0.02-0.2 part of single-walled carbon nanotube and 0.98-1.3 parts of conductive carbon black are added as conductive agents, so that the dosage of the conductive agents can be greatly reduced under the condition of ensuring that the positive pole piece has lower resistance, the proportion of positive active substances is improved, the maximum positive active substances can reach 98%, and the energy density of the lithium ion battery is improved.
The inventor finds that the use of a small amount of single-walled carbon nanotubes and a proper amount of conductive carbon black improves the conductivity of the positive electrode plate unexpectedly, 0.02-0.2 parts of single-walled carbon nanotubes and 0.98-1.3 parts of conductive carbon black are in a preferable range, and when the addition amount of the single-walled carbon nanotubes is too small, the electronic conductivity of the positive electrode plate is not improved obviously; when the addition amount of the single-walled carbon nanotube is too large, the energy density of the positive pole piece is adversely affected, and compared with 0.02-0.2 parts of single-walled carbon nanotube, the subsequent improvement effect of increasing the addition amount of the single-walled carbon nanotube on the electronic conductivity of the positive pole piece is not obvious.
On the other hand, experiments show that the lifting effect on the positive electrode plate only exists on the single-walled carbon nanotube, and the lifting effect on the positive electrode plate by another carbon nanotube (multi-walled carbon nanotube) is limited, so that the lifting effect is related to the single-walled structure of the carbon nanotube.
In some embodiments, the single-walled carbon nanotubes have a diameter of 3nm or less and a length of 5 μm or more.
When the diameter of the single-walled carbon nanotube is too large or the length of the single-walled carbon nanotube is too short, the lifting effect of the single-walled carbon nanotube on the positive pole piece is reduced to a certain extent.
In some embodiments, the mass fraction of the positive electrode active material is 96.5% to 98%, the mass fraction of the single-walled carbon nanotubes is 0.02% to 0.2%, the mass fraction of the conductive carbon black is 0.98% to 1.3%, and the mass fraction of the positive electrode binder is 1% to 2%, based on 100% by mass of the positive electrode material layer.
In some embodiments, the positive active material is selected from one or more of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium iron phosphate, lithium manganese oxide.
In some embodiments, the positive electrode plate further includes a positive electrode current collector, and the positive electrode material layer covers the positive electrode current collector.
The positive electrode material layer is obtained by coating and drying positive electrode slurry, the positive electrode slurry comprises components of the positive electrode material layer and a solvent for dispersing the components of the positive electrode material layer, the solvent can be an organic solvent, and specifically, the solvent can be N-methylpyrrolidone.
The positive current collector can adopt various metal materials with good conductivity.
In a more preferred embodiment, the positive electrode current collector is an aluminum foil.
In some embodiments, the positive electrode binder comprises one or more of polyvinyl alcohol, styrene butadiene rubber, polyvinylidene fluoride, sodium alginate, polyacrylic acid, polyimide, lithium polyacrylate.
Another embodiment of the present invention provides a lithium ion battery, which includes an electrolyte, a negative electrode plate, and the positive electrode plate described above.
In some embodiments, the lithium ion battery further comprises a separator between the negative pole piece and the positive pole piece.
The diaphragm can adopt various existing diaphragms, and the details are not repeated.
In some embodiments, the negative electrode sheet includes a negative electrode current collector and a negative electrode material layer overlying the negative electrode current collector.
The negative current collector can be made of various metal materials with good conductivity.
In a more preferred embodiment, the negative electrode current collector is a copper foil.
The negative electrode material layer includes a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder.
The negative active material may be made of one or more of a carbon material, a metal alloy, a lithium-containing oxide, and a silicon-containing material.
The negative electrode conductive agent comprises one or more of carbon black, graphite, carbon nanotubes and graphene.
The negative electrode binder comprises one or more of polyvinyl alcohol, styrene-butadiene rubber, polyvinylidene fluoride, sodium alginate, polyacrylic acid, polyimide and lithium polyacrylate.
The present invention will be further illustrated by the following examples.
Example 1
The embodiment is used for explaining the positive pole piece, the lithium ion battery and the preparation method thereof, and the preparation method comprises the following operation steps:
(1) preparation of positive pole piece
LiNi as positive electrode active material0.8Co0.1Mn0.1O2Mixing the conductive carbon black with conductive carbon black super-P, single-wall CNT (the diameter is less than or equal to 3nm and the length is more than or equal to 5 mu m), and a binder PVDF according to mass fraction of 97.97: 1.0: 0.03: 1.0, adding a proper amount of N-methyl pyrrolidone (NMP), and dispersing in a high-speed dispersion machine until the viscosity is 3000-6000 mPa.S to obtain the anode slurry. And uniformly coating the positive electrode slurry on an aluminum foil current collector with the thickness of 14 mu m, drying to obtain a positive electrode material layer, rolling and cutting to obtain the positive electrode piece.
(2) Preparation of negative pole piece
Uniformly mixing the anode active material artificial graphite, the conductive agent super-P, the adhesive Styrene Butadiene Rubber (SBR) and the sodium carboxymethyl cellulose (CMC) according to the mass ratio of 95.2:1.5:2.0:1.3, adding deionized water, and dispersing in a high-speed dispersion machine until the viscosity is 2500-. And uniformly coating the negative electrode slurry on a copper foil current collector with the thickness of 8 mu m, and drying, rolling and slitting to obtain a negative electrode plate.
(3) Preparation of lithium ion battery
Respectively placing the positive pole piece and the negative pole piece on a winding machine, isolating the positive pole piece and the negative pole piece by adopting an isolating film, preparing a naked electric core in a winding mode, manufacturing a packaging bag by using an aluminum plastic film composite material, placing the naked electric core in the packaging bag for packaging to obtain a dry electric core, and obtaining the lithium ion battery after the dry electric core is subjected to the working procedures of baking, liquid injection, sealing, standing, formation, degassing packaging, capacity grading and the like.
Examples 2 to 4
Embodiments 2 to 4 are used to illustrate the positive electrode plate, the lithium ion battery and the preparation method thereof disclosed in the present invention, including most of the operation steps in embodiment 1, and the differences are as follows:
in the preparation of the positive pole piece:
the positive electrode active materials shown in examples 2 to 4 in table 1 were used, and the components shown in examples 2 to 4 in table 1 were added to the positive electrode slurry in mass percentage based on 100% of the total mass of the positive electrode material layer.
Comparative examples 1 to 5
Comparative examples 1 to 5 are used to illustrate the positive electrode plate, the lithium ion battery and the preparation method thereof disclosed in the present invention, and include most of the operation steps in example 1, and the differences are as follows:
in the preparation of the positive pole piece:
the positive electrode active materials shown in comparative examples 1 to 5 in table 1 are adopted, and the components shown in comparative examples 1 to 5 in table 1 are added into the positive electrode slurry according to the mass percentage, wherein the total mass of the positive electrode material layer is 100%.
TABLE 1 composition and addition of positive electrode material layer for each example and comparative example
Performance testing
Resistance tests are carried out on the positive pole pieces prepared in the above examples 1-4 and comparative examples 1-5;
the lithium ion batteries prepared in the above examples 1 to 4 and comparative examples 1 to 5 were subjected to a 1000-week cycle capacity retention rate test and a first efficiency test:
the test results obtained are filled in table 2.
TABLE 2
From the test results in table 2, it can be seen that, compared with a lithium ion battery in which conductive carbon black is added alone or multi-walled carbon nanotubes are added in the conductive carbon black, the resistance of the positive electrode plate of the lithium ion battery adopting the technical scheme of the present invention is significantly reduced, and the battery capacity and the battery cycle performance are improved.
On the other hand, comparing examples 1 to 4 with comparative example 5 shows that when the addition amount of the single-walled carbon nanotube exceeds the range defined by the present invention, the resistance of the positive electrode sheet is not reduced significantly, and the battery capacity is reduced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The positive pole piece is characterized by comprising a positive pole material layer, wherein the positive pole material layer comprises the following components in parts by weight:
96.5-98 parts of positive electrode active substance, 0.02-0.2 part of single-walled carbon nanotube, 0.98-1.3 parts of conductive carbon black and 1-2 parts of positive electrode binder.
2. The positive electrode plate as claimed in claim 1, wherein the diameter of the single-walled carbon nanotube is less than or equal to 3nm, and the length of the single-walled carbon nanotube is greater than or equal to 5 μm.
3. The positive electrode sheet according to claim 1, wherein the positive electrode active material is present in an amount of 96.5 to 98% by mass, the single-walled carbon nanotubes are present in an amount of 0.02 to 0.2% by mass, the conductive carbon black is present in an amount of 0.98 to 1.3% by mass, and the positive electrode binder is present in an amount of 1 to 2% by mass, based on 100% by mass of the positive electrode material layer.
4. The positive electrode sheet according to claim 1, wherein the positive active material is selected from one or more of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium iron phosphate, and lithium manganese oxide.
5. The positive pole piece of claim 1, further comprising a positive current collector, wherein the positive material layer covers the positive current collector.
6. The positive electrode sheet according to claim 5, wherein the positive electrode current collector is an aluminum foil.
7. The positive electrode sheet according to claim 1, wherein the positive electrode binder comprises one or more of polyvinyl alcohol, styrene-butadiene rubber, polyvinylidene fluoride, sodium alginate, polyacrylic acid, polyimide and lithium polyacrylate.
8. A lithium ion battery, characterized by comprising an electrolyte, a negative electrode plate and the positive electrode plate of any one of claims 1 to 7.
9. The lithium ion battery of claim 8, further comprising a separator between the negative pole piece and the positive pole piece.
10. The lithium ion battery of claim 7, wherein the negative electrode tab comprises a negative electrode current collector and a negative electrode material layer, and the negative electrode material layer covers the negative electrode current collector.
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CN112510248A (en) * | 2020-12-25 | 2021-03-16 | 王书珍 | High-energy-density lithium ion battery and preparation method thereof |
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CN105406070A (en) * | 2015-12-18 | 2016-03-16 | 山东精工电子科技有限公司 | Preparation method of lithium ion battery positive pole size |
CN106252712A (en) * | 2016-08-20 | 2016-12-21 | 深圳市比克动力电池有限公司 | A kind of lithium rechargeable battery |
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