CN113903883A - Electrode plate and preparation method and application thereof - Google Patents
Electrode plate and preparation method and application thereof Download PDFInfo
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- CN113903883A CN113903883A CN202111162071.8A CN202111162071A CN113903883A CN 113903883 A CN113903883 A CN 113903883A CN 202111162071 A CN202111162071 A CN 202111162071A CN 113903883 A CN113903883 A CN 113903883A
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- electrode
- binder
- active material
- additive
- current collector
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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
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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
- H01M10/052—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
- 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
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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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an electrode piece and a preparation method and application thereof, wherein the electrode piece comprises an electrode active material, a conductive agent, a binder and an additive, the binder is a carboxyl modified binder, the additive is 4, 4' -trihydroxy triphenylamine, and the binder and the additive can give consideration to crosslinking, melting and ion transmission performances and improve the performance of the electrode piece.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to an electrode plate and a preparation method and application thereof.
Background
The lithium ion battery has high energy density, high working voltage, no memory effect and long cycle life, and is widely applied to the fields of intelligent wearable equipment, new energy automobiles and the like.
The binder is an important component of the electrode, and its main function is to connect the electrode active material, the conductive agent, and the current collector. The choice of binder can significantly affect the electrochemical performance of the electrode. PVDF is the most widely used oily binder, has good chemical stability, thermal stability, mechanical properties, processability and dispersibility, and can show good electrochemical properties in the conventional carbon material electrode. However, with the development of silicon-based materials, PVDF has not been able to meet the current application needs.
CN110350196A discloses a composite binder, a silicon-based negative plate and a preparation method thereof. The preparation method of the silicon-based negative plate comprises the following steps: mixing polyvinylidene fluoride with different molecular weights by a ball mill to obtain a composite binder; dissolving the composite binder in an organic solvent to obtain a binder glue solution; dispersing a conductive agent in a binder glue solution to obtain a conductive glue solution; adding silicon-carbon composite material powder and an organic solvent into the conductive glue solution to prepare electrode slurry; coating the electrode slurry on a negative current collector, and carrying out vacuum high-temperature solvent removal treatment on the obtained current collector coated with the electrode slurry; and rolling the obtained negative pole piece to obtain the silicon-based negative pole piece.
CN112310399A discloses a lithium ion battery silicon negative electrode binder and a preparation method and application of an electrode thereof. The lithium ion battery silicon cathode binder is prepared from the following components in a mass ratio of 10-1: 1-10 of polyvinylidene fluoride and polyvinyl alcohol.
The electrode plate prepared by the scheme has the problems of poor crosslinking capability of the adhesive, difficulty in forming a net structure, low peeling force of the electrode plate, electrode falling and large expansion of the electrode plate, so that the development of the electrode plate which has crosslinking, melting and ion transmission performances and can improve the performance of the electrode plate is necessary.
Disclosure of Invention
The invention aims to provide an electrode pole piece and a preparation method and application thereof, wherein the electrode pole piece comprises a carboxyl modified binder and a 4, 4' -trihydroxy triphenylamine additive, and the binder and the additive can give consideration to cross-linking, melting and ion transmission performances and improve the performance of the pole piece.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an electrode piece, wherein the electrode piece is prepared from raw materials including an electrode active material, a conductive agent, an adhesive and an additive, wherein the adhesive is a carboxyl-modified adhesive, and the additive is 4, 4' -trihydroxy triphenylamine (the molecular formula is shown in formula I):
formula I.
The invention adopts 4,4 '-trihydroxy triphenylamine as an additive, and 1, a compound with a triphenylamine structure type is used as an electrode additive, so that the melting temperature is reduced, and the wettability of a pole piece is improved, in addition, the 4, 4' -trihydroxy triphenylamine is combined with a carboxyl modified adhesive for use, N atoms in 4,4 '-trihydroxy triphenylamine molecules are good electron acceptors, and have good affinity with electrolyte, so that the wettability of the pole piece electrolyte can be improved, the power performance is improved, and-OH groups in the 4, 4' -trihydroxy triphenylamine molecules and-COOH on a modified adhesive molecular chain are subjected to condensation reaction at high temperature to remove water molecules and form a net structure after crosslinking, so that the stripping force of the pole piece is improved, the powder drop is improved, and the expansion of the pole piece is reduced.
Preferably, the mass ratio of the additive to the binder is 1 (2-5), such as: 1:2, 1:3, 1:4, 1:4.5 or 1:5, etc.
Preferably, the electrode active material includes a positive electrode active material or a negative electrode active material.
Preferably, the positive electrode active material includes any one of NCM, NCMA, NCA, LMO, or LNO or a combination of at least two thereof.
Preferably, the negative active material includes any one of graphite, hard carbon, soft carbon, LTO, Si, a silicon oxygen material, or Sn, or a combination of at least two thereof.
Preferably, the conductive agent includes any one or a combination of at least two of conductive carbon black, carbon nanotubes, flake graphite, graphene, carbon fibers, or ketjen black.
Preferably, the binder comprises a carboxy-modified PVDF and/or a carboxy-modified PTFE.
In a second aspect, the present invention provides a method of preparing an electrode according to the first aspect, the method comprising the steps of:
(1) modifying the binder to obtain a carboxyl modified binder;
(2) mixing a carboxyl modified binder, an additive, a conductive agent and an electrode active material to obtain electrode slurry;
(3) and coating the electrode slurry on the surface of a current collector, and drying and rolling to obtain the electrode piece.
According to the invention, the adhesive is modified in advance, so that a molecular chain of the adhesive contains carboxyl groups-COOH, and the carboxyl groups can be subjected to condensation reaction with hydroxyl groups-OH on additive 4, 4' -trihydroxy triphenylamine to remove water molecules and form a network structure through crosslinking, thereby improving the stripping force of the pole piece, improving the powder falling problem, reducing the expansion of the pole piece, and solving the problems of difficult melting of the adhesive, low stripping force of the pole piece, easy powder falling and poor power performance in the preparation process of a dry electrode.
Preferably, the modification treatment in step (1) comprises mixing a binder, acrylic acid and an initiator, and obtaining the carboxyl modified binder after reaction.
Preferably, the binder comprises PVDF and/or PTFE.
Preferably, the ratio of acrylic acid monomer in the binder is 0.1-10%, for example: 0.1%, 1%, 3%, 5%, 10%, etc.
Preferably, the initiator comprises any one of or a combination of at least two of a peroxide, a persulfate, an alkyl peroxide or diisopropyl peroxydicarbonate.
Preferably, the mass ratio of the electrode active material, the carboxyl modified binder, the additive and the conductive agent in the step (2) is (95-97): 1-2.5): 0.5: (1-2), for example: 95:1:0.5:1, 96:1.5:0.5:1.8, 96:2.0:0.5:1.5, 96.5:2.2:0.5:1.8 or 97:2.5:0.5:2, etc.
Preferably, the method of obtaining the electrode slurry includes melting the mixed material or mixing the mixed material with a solvent, preferably melting the mixed material.
Preferably, the current collector of step (3) includes a positive electrode current collector or a negative electrode current collector.
Preferably, the positive electrode current collector includes an aluminum foil.
Preferably, the negative electrode current collector includes a copper foil.
In a third aspect, the invention provides a lithium ion battery, which includes the electrode sheet according to the first aspect or the electrode sheet prepared by the preparation method according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, 4,4 ' -trihydroxy triphenylamine is used as an additive (the molecular formula is shown in formula I), the additive is combined with a carboxyl modified binder for use, N atoms in 4,4 ' -trihydroxy triphenylamine molecules are good electron acceptors, the good affinity with electrolyte is provided, the wettability of the pole piece electrolyte can be improved, the power performance is improved, and-OH groups in the 4,4 ' -trihydroxy triphenylamine molecules and-COOH on a modified binder molecular chain are subjected to condensation reaction at high temperature, water molecules are removed, and a network structure is formed after crosslinking, so that the pole piece stripping force is improved, the powder falling is improved, and the expansion of the pole piece is reduced.
(2) The 4, 4' -trihydroxy triphenylamine used in the invention has a low melting point of about 130 ℃, is applied to a preparation process of a lithium battery dry electrode, can reduce the melting temperature, is easy to form a film, and forms good coating on an active material.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a positive pole piece, which is prepared by the following method:
(1) modifying PVDF to obtain carboxyl modified PVDF;
(2) mixing carboxyl modified PVDF, 4' -trihydroxy triphenylamine, conductive carbon black and NCM811 according to the mass ratio of 2:0.5:1.5:96, and then melting at high temperature to obtain electrode slurry;
(3) and coating the electrode slurry on the surface of an aluminum foil, and cooling and rolling to obtain the positive pole piece.
Example 2
The embodiment provides a negative pole piece, which is prepared by the following method:
(1) performing modification treatment on PTFE to obtain carboxyl modified PTFE;
(2) mixing carboxyl modified PTFE, 4' -trihydroxy triphenylamine, a carbon nano tube and a silica material according to a mass ratio of 1.25:0.5:1.75:96.5, and then melting at high temperature to obtain electrode slurry;
(3) and coating the electrode slurry on the surface of copper foil, and cooling and rolling to obtain the negative pole piece.
Example 3
This example differs from example 1 only in that the mass ratio of the carboxyl-modified PVDF to 4, 4' -trihydroxytriphenylamine is 1:1, and the other conditions and parameters are exactly the same as those in example 1.
Example 4
This example differs from example 1 only in that the mass ratio of the carboxyl-modified PVDF to 4, 4' -trihydroxytriphenylamine is 6:1, and the other conditions and parameters are exactly the same as those in example 1.
Comparative example 1
This comparative example differs from example 1 only in that no 4, 4', 4 "-trihydroxytriphenylamine is added, the other conditions and parameters being exactly the same as in example 1.
Comparative example 2
This comparative example differs from example 2 only in that no 4, 4', 4 "-trihydroxytriphenylamine is added, the other conditions and parameters being exactly the same as in example 2.
Comparative example 3
This comparative example differs from example 1 only in that the PVDF was not modified and the other conditions and parameters were exactly the same as in example 1.
And (3) performance testing:
the electrode pieces obtained in examples 1 to 4 and comparative examples 1 to 3 were taken, and electrode melting temperature, electrode piece peeling force, full electrode piece expansion, electrolyte absorption and DCR were measured, and the test results are shown in table 1:
TABLE 1
As can be seen from table 1, the electrode melting temperature of the electrode plate of the present invention can be up to 250 ℃, the peel strength of the electrode plate can be up to 9.4N/m or more, the expansion of the full electrode plate can be up to 21.5% or less, the absorption rate of the electrolyte can be up to 5.1% or more, and the DCR can be up to 22.1m Ω or less, by adjusting the type of the binder and the mass ratio of 4, 4', 4 ″ -trihydroxytriphenylamine to the carboxyl-modified binder, the electrode melting temperature of the electrode plate can be up to 140 ℃, the peel strength of the electrode plate can be up to 10.2N/m, the expansion of the full electrode plate can be up to 19.8%, the absorption rate of the electrolyte can be up to 5.6%, and the DCR can be up to 21.3m Ω, as can be obtained in examples 1-4. .
Compared with the embodiment 1 and the embodiment 4, the invention has the advantages that the quality ratio of the 4,4 ' -trihydroxy triphenylamine to the carboxyl modified binder added into the electrode slurry influences the performance of the prepared pole piece, the quality ratio of the 4,4 ' -trihydroxy triphenylamine to the carboxyl modified binder is controlled to be 1 (2-5), the electrode pole piece with excellent performance can be prepared, if the quality ratio of the 4,4 ' -trihydroxy triphenylamine is too high, the melting temperature of the material can be further reduced, but the dosage of PVDF is too low, the crosslinking effect is poor, the stripping force of the pole piece is low, the expansion is large, the liquid absorption performance is reduced, and the DCR is increased; if the mass ratio of the 4, 4' -trihydroxy triphenylamine is too low, the melting temperature of the pole piece is increased, the initiation sites of the cross-linking reaction are insufficient, and the stripping force of the pole piece is also reduced, the expansion is increased, the liquid absorption performance is reduced, and the DCR is increased.
Compared with the embodiment 1 and the comparative example 1, and the embodiment 2 and the comparative example 2, the invention has the advantages that the 4,4 '-trihydroxy triphenylamine is added into the electrode slurry, N atoms in molecules of the 4, 4' -trihydroxy triphenylamine are good electron acceptors, the N atoms have good affinity with electrolyte, the wettability of the pole piece electrolyte can be improved, and the power performance can be improved.
Compared with the embodiment 1 and the comparative example 3, the-OH group in the 4, 4' -trihydroxy triphenylamine molecule and-COOH on the carboxyl modified adhesive molecular chain are subjected to condensation reaction at high temperature, water molecules are removed, and a net structure is formed after crosslinking, so that the stripping force of the pole piece is improved, the powder falling is improved, and the expansion of the pole piece is reduced.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The electrode plate is characterized in that raw materials for preparing the electrode plate comprise an electrode active material, a conductive agent, an adhesive and an additive, wherein the adhesive is a carboxyl modified adhesive, and the additive is 4, 4' -trihydroxy triphenylamine.
2. The electrode piece according to claim 1, wherein the mass ratio of the additive to the binder is 1 (2-5).
3. The electrode sheet according to claim 1 or 2, wherein the binder comprises a carboxy-modified PVDF and/or a carboxy-modified PTFE.
4. The electrode pad of any one of claims 1-3, wherein the electrode active material comprises a positive electrode active material or a negative electrode active material;
preferably, the positive electrode active material includes any one or a combination of at least two of NCM, NCMA, NCA, LMO, or LNO;
preferably, the negative active material includes any one of graphite, hard carbon, soft carbon, LTO, Si, a silicon oxygen material, or Sn, or a combination of at least two thereof.
5. The electrode sheet according to any one of claims 1 to 4, wherein the conductive agent comprises any one or a combination of at least two of conductive carbon black, carbon nanotubes, flake graphite, graphene, carbon fibers or Ketjen black.
6. A preparation method of the electrode plate according to any one of claims 1 to 5, wherein the preparation method comprises the following steps:
(1) modifying the binder to obtain a carboxyl modified binder;
(2) mixing a carboxyl modified binder, an additive, a conductive agent and an electrode active material to obtain electrode slurry;
(3) and coating the electrode slurry on the surface of a current collector, and drying and rolling to obtain the electrode piece.
7. The method according to claim 6, wherein the modification treatment in the step (1) comprises mixing a binder, acrylic acid and an initiator to obtain the carboxyl-modified binder after the reaction;
preferably, the binder comprises PVDF and/or PTFE;
preferably, the acrylic acid monomer proportion in the binder is 0.1-10%;
preferably, the initiator comprises any one of or a combination of at least two of a peroxide, a persulfate, an alkyl peroxide or diisopropyl peroxydicarbonate.
8. The preparation method according to claim 6 or 7, wherein the mass ratio of the electrode active material, the carboxyl-modified binder, the additive and the conductive agent in the step (2) is (95-97): 1-2.5): 0.5: (1-2);
preferably, the method of obtaining the electrode slurry includes melting the mixed material or mixing the mixed material with a solvent, preferably melting the mixed material.
9. The production method according to any one of claims 6 to 8, wherein the current collector of step (3) includes a positive electrode current collector or a negative electrode current collector;
preferably, the positive electrode current collector includes an aluminum foil;
preferably, the negative electrode current collector includes a copper foil.
10. A lithium ion battery, characterized in that the lithium ion battery comprises the electrode sheet according to any one of claims 1 to 5 or the electrode sheet prepared by the preparation method according to any one of claims 6 to 9.
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| CN202111162071.8A CN113903883B (en) | 2021-09-30 | 2021-09-30 | Electrode plate and preparation method and application thereof |
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| CN202111162071.8A CN113903883B (en) | 2021-09-30 | 2021-09-30 | Electrode plate and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08236155A (en) * | 1995-02-27 | 1996-09-13 | Sanyo Electric Co Ltd | Lithium secondary battery |
| CN102484239A (en) * | 2009-10-02 | 2012-05-30 | 丰田自动车株式会社 | Lithium secondary battery and positive electrode for said battery |
| CN108370026A (en) * | 2015-12-10 | 2018-08-03 | 株式会社钟化 | Nonaqueous electrolytic solution secondary battery |
-
2021
- 2021-09-30 CN CN202111162071.8A patent/CN113903883B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08236155A (en) * | 1995-02-27 | 1996-09-13 | Sanyo Electric Co Ltd | Lithium secondary battery |
| CN102484239A (en) * | 2009-10-02 | 2012-05-30 | 丰田自动车株式会社 | Lithium secondary battery and positive electrode for said battery |
| US20120189914A1 (en) * | 2009-10-02 | 2012-07-26 | Tomitaro Hara | Lithium secondary battery and positive electrode for said battery |
| CN108370026A (en) * | 2015-12-10 | 2018-08-03 | 株式会社钟化 | Nonaqueous electrolytic solution secondary battery |
Non-Patent Citations (1)
| Title |
|---|
| 姜姗姗: "锂离子电池正极材料聚三苯胺的制备与性能研究", 《世界有色金属》 * |
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