CN109411763B - Oil-based protective coating for cathode current collector - Google Patents
Oil-based protective coating for cathode current collector Download PDFInfo
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- CN109411763B CN109411763B CN201811250265.1A CN201811250265A CN109411763B CN 109411763 B CN109411763 B CN 109411763B CN 201811250265 A CN201811250265 A CN 201811250265A CN 109411763 B CN109411763 B CN 109411763B
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- protective coating
- current collector
- cathode current
- coating
- lithium ion
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- 239000011253 protective coating Substances 0.000 title claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 18
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 18
- 239000004642 Polyimide Substances 0.000 claims abstract description 16
- 150000002148 esters Chemical class 0.000 claims abstract description 16
- 229920001721 polyimide Polymers 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 239000011268 mixed slurry Substances 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000007646 gravure printing Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000006182 cathode active material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005187 foaming Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000011076 safety test Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a cathode current collector oil-based protective coating for a lithium ion battery, and belongs to the technical field of lithium batteries. The invention discloses a cathode current collector oil-based protective coating, which is coated on the surface of a cathode current collector and comprises the following components in parts by weight: 9-12 parts of carbon nano tube and 8-10 parts of polyimide ester. According to the invention, through the arrangement of the protective coating, the high energy density of the lithium ion battery cell is ensured, and the safety performance of the lithium ion battery cell is improved.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and relates to a cathode current collector oil-based protective coating for a lithium ion battery.
Background
With the exhaustion of fossil energy and the increasing severity of environmental pollution, the search for clean and sustainable energy is an urgent need. At present, a lithium ion battery as a clean energy source has the advantages of high energy density, good cycle performance, environmental protection and the like, and is widely applied to various fields of life, such as mobile phones, computers, automobiles and the like. The lithium ion battery is a secondary battery (rechargeable battery), and with the development of the society, the application of the lithium ion battery is increasingly wide, and the requirements on the performance of the lithium ion battery are higher and higher. Along with the continuous promotion of lithium ion battery energy density, its security performance worsens to some extent, leads to the phenomenon that electric core explosion burning can appear in the use, seriously threatens user's personal safety, consequently need keep electric core high energy density the time, improves the security performance of electric core.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a cathode current collector oil-based protective coating which improves the safety performance of a lithium ion battery cell while ensuring high energy density of the lithium ion battery cell.
The purpose of the invention can be realized by the following technical scheme:
the oil-based protective coating of the cathode current collector is coated on the surface of the cathode current collector and comprises the following components in parts by weight:
9-12 parts of carbon nano tube
8-10 parts of polyimide ester.
According to the invention, the oil-based protective coating is arranged on the lithium ion battery cathode current collector, and then the cathode active material is coated on the protective coating, so that the energy density of the lithium ion battery is ensured, and the safety performance of the lithium ion battery is effectively improved. The protective coating has good bonding property, is not easy to fall off, can firmly cover the surface of the cathode current collector, and greatly reduces the probability of direct contact of the cathode current collector and the anode current collector. Meanwhile, the diaphragm resistance value of the cathode pole piece is improved, a large amount of joule heat generated when the short circuit occurs in the battery cell is prevented, and the risk of thermal runaway of the battery cell is reduced. The protective coating also improves the passing capability of safety performance tests such as needling and impacting.
The binder system adopts polyimide ester (PI) which has good bonding effect and excellent high temperature resistance and electrolyte corrosion resistance, and can be firmly attached to an aluminum foil after Baking at 135 ℃, so that the polyimide ester is prevented from being dissolved again by NMP in cathode slurry during coating.
The carbon nano tube is in line contact with the active material layer and the current collector layer, an effective conductive network can be formed in the protective coating by using less usage amount, and the conductive coating has good conductive performance.
Preferably, the diameter of the carbon nano tube is 8-20 nm, and the length-diameter ratio is (300-700): 1.
The invention can ensure the uniformity and stability of the prepared protective coating slurry and better coating performance while ensuring the conductivity by controlling the diameter and the length-diameter ratio of the carbon nano tube, thereby forming a uniform and smooth protective coating surface, having good bonding performance with a cathode active material, and being not easy to cause the phenomena of delamination, foaming and the like due to the difference of materials of each layer.
Preferably, the thickness of the protective coating is 1-2 μm.
According to the invention, the thickness of the protective coating is set to be 1-2 μm, and the protective coating is thinner, so that the electron transfer path can be reduced, the contact resistance between the aluminum foil of the cathode current collector and the cathode active material is reduced, and the direct current internal resistance (DCR) of the battery cell is reduced. The thickness of the protective coating cannot be too thick (> 2 μm) because the protective coating has no cathode active material and cannot provide energy, too thick a coating easily causes a large reduction in energy density (ED Loss), and too thick a protective coating reduces the adhesion of the protective coating to the aluminum foil and does not function to protect the aluminum foil. Too thick coating can also greatly increase the diaphragm resistance of the cathode pole piece, further influence the alternating current resistance (IMP) value of the battery core and influence the final electrical property of the lithium ion battery.
Another object of the present invention is to provide a method for preparing an oil-based protective coating of a cathode current collector, comprising the steps of:
s1, preparing raw materials according to the formula of the components in the claim 1, adding the polyimide ester into NMP, stirring uniformly to form a polyimide ester solution, adding the carbon nano tube, and stirring uniformly to form uniform and stable mixed slurry;
and S2, coating the slurry on the surface of the cathode current collector to form a protective coating.
The invention takes NMP as solvent, and a binder and conductive agent system to prepare uniform and stable slurry according to proportion, the slurry is coated on the cathode current collector of the lithium ion battery to form an oil-based protective coating, and then cathode active substances are coated on the protective coating, and the existence of the protective coating effectively improves the safety performance of the lithium ion battery.
Preferably, the solid content of the mixed slurry formed in the step S1 is 13-17%, and the viscosity is 300-800 mpa.s.
Preferably, the thickness of the protective coating formed in step S2 is 1 to 2 μm.
Preferably, in step S2, the slurry is applied to the surface of the cathode current collector by gravure printing.
Preferably, the gravure printing is carried out by using a gravure bouncing machine, and the tape-moving speed is 4.6-5.3 m/min.
Preferably, the gravure printing mode comprises a coating process and a drying process, wherein the drying process adopts a three-stage oven heating method, and the oven temperature is set to be 100 ℃, 105 ℃ and 100 ℃ in sequence.
The invention adopts a three-stage heating mode in the gravure printing process, optimizes the heating temperature of each stage, ensures that the protective coating is tightly attached to the cathode current collector, has a uniform and smooth surface and a compact internal structure, and does not generate the phenomenon of layer formation and foaming in the long-term use process. The heating temperature cannot be too high, otherwise, the protective coating is easy to layer, the electrical property of the cathode current collector is influenced, and the protective coating cannot play a good protection role.
The protective coating prepared by the method is uniform and smooth, the membrane resistance value of the cathode pole piece prepared by the method is 0.6-0.8 m omega measured by adopting a four-probe membrane resistance test method, and is slightly higher than that of the conventional cathode pole piece, so that the danger of thermal runaway when a cell is in short circuit is prevented, and the safety performance of the lithium ion battery is effectively improved while the high energy density of the lithium ion battery is ensured.
Because the anode active substance of the lithium ion battery can adopt a water-based or oil-based binder, and the PI adhesive is easy to agglomerate and lose efficacy when meeting water, when the anode active substance adopts the water-based binder, the protective coating is not suitable for an anode current collector.
Compared with the prior art, the invention has the following beneficial effects:
the specific protective layer is coated on the cathode current collector, so that the cell performance, particularly the energy density, of the lithium ion battery is ensured, and the safety performance of the cell is effectively improved.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1
The preparation method of the lithium ion battery cathode current collector oil-based protective coating in the embodiment comprises the following steps:
(1) adding 9 parts of polyimide ester into NMP (N-methyl pyrrolidone), uniformly stirring to form a polyimide ester solution, adding 10 parts of carbon nano tubes, uniformly stirring to form uniform and stable mixed slurry, wherein the solid content of the mixed slurry is 13%, the viscosity of the mixed slurry is 300mpa.s, the diameter of each carbon nano tube is 13-20 nm, and the length-diameter ratio is (580-700): 1;
(2) and coating the mixed slurry on the surface of the aluminum foil of the cathode current collector by using a gravure bouncing machine in a gravure printing mode to form a protective coating with the thickness of 1 mu m, wherein the tape travelling speed of the gravure bouncing machine is 4.6m/min, and after coating, drying is carried out by adopting a three-stage oven heating method, and the oven temperature is set to 100 ℃, 105 ℃ and 100 ℃ in sequence.
Example 2
The preparation method of the lithium ion battery cathode current collector oil-based protective coating in the embodiment comprises the following steps:
(1) adding 10 parts of polyimide ester into NMP (N-methyl pyrrolidone), uniformly stirring to form a polyimide ester solution, adding 9 parts of carbon nano tubes, uniformly stirring to form uniform and stable mixed slurry, wherein the solid content of the mixed slurry is 15%, the viscosity of the mixed slurry is 560mpa.s, the diameter of each carbon nano tube is 10-17 nm, and the length-diameter ratio of each carbon nano tube is (460-570): 1;
(2) and coating the mixed slurry on the surface of the cathode current collector aluminum foil by using a gravure bouncing machine in a gravure printing mode to form a protective coating with the thickness of 1.5 mu m, wherein the tape-moving speed of the gravure bouncing machine is 5.0m/min, and drying by adopting a three-stage oven heating method after coating, wherein the oven temperature is set to be 100 ℃, 105 ℃ and 100 ℃ in sequence.
Example 3
The preparation method of the lithium ion battery cathode current collector oil-based protective coating in the embodiment comprises the following steps:
(1) adding 12 parts of polyimide ester into NMP (N-methyl pyrrolidone), uniformly stirring to form a polyimide ester solution, adding 8 parts of carbon nano tubes, uniformly stirring to form uniform and stable mixed slurry, wherein the solid content of the mixed slurry is 17%, the viscosity of the mixed slurry is 800mpa.s, the diameter of each carbon nano tube is 8-15 nm, and the length-diameter ratio of the carbon nano tubes is (300-450): 1;
(2) and coating the mixed slurry on the surface of the aluminum foil of the cathode current collector by using a gravure bouncing machine in a gravure printing mode to form a protective coating with the thickness of 2 mu m, wherein the tape travelling speed of the gravure bouncing machine is 5.3m/min, and after coating, drying is carried out by adopting a three-stage oven heating method, and the oven temperature is set to be 100 ℃, 105 ℃ and 100 ℃ in sequence.
Comparative example 1
PVDF was used as a binder instead of the polyimide ester, and the other was the same as in example 2.
Comparative example 2
The aspect ratio of the carbon nanotubes was (750-800) 1, and the rest was the same as in example 2.
Comparative example 3
The thickness of the protective coating was 0.9 μm, and the rest was the same as in example 2.
Comparative example 4
The thickness of the protective coating was 2.1 μm, and the rest was the same as in example 2.
Example 5
The oven temperature was set to 105 deg.C, and 105 deg.C in this order.
Comparative example 6
No protective coating was provided.
The lithium ion batteries manufactured by using the cathode current collectors coated with the protective coatings in the embodiments 1 to 3 and the comparative examples 1 to 6 of the present invention were subjected to impact and needle punching safety tests, each sample of the impact tests was subjected to 10 tests, each sample of the needle punching tests was subjected to 5 tests, 2 samples of each embodiment/comparative example were selected for the tests, the average number of passes is shown in table 1, and the manufactured battery performance is shown in table 2 below.
Table 1: comparison of safety Performance of batteries fabricated using the cathode Current collectors of examples 1-3 and comparative examples 1-6
Table 2: comparison of Battery Performance Using the cathode Current collectors of examples 1-3 and comparative examples 1-6
Through performance tests, the lithium ion batteries of the embodiments 1 to 3 have the performance similar to that of the comparative example 6 in terms of capacity, energy density, cycle life and the like, and have no obvious change, and it can be seen that the protective coating is arranged on the surface of the cathode current collector of the lithium ion battery, and the formula and the preparation method of the protective coating are reasonably compatible and optimized, so that the electrical performance of the lithium ion battery is ensured, and the safety performance of the lithium ion battery is effectively improved.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (1)
1. The preparation method of the oil-based protective coating of the cathode current collector is characterized in that the protective coating is coated on the surface of the cathode current collector and comprises the following components in parts by weight:
9-12 parts of carbon nano tube
8-10 parts of polyimide ester;
the preparation method of the coating comprises the following steps:
s1, preparing raw materials according to the formula of the components, adding polyimide ester into NMP, uniformly stirring to form a polyimide ester solution, adding carbon nano tubes, and uniformly stirring to form uniform and stable mixed slurry;
s2, coating the slurry on the surface of the cathode current collector to form a protective coating;
the solid content of the mixed slurry formed in the step S1 is 13-17%, and the viscosity is 300-800 mpa.s;
in the step S2, the paste is coated on the surface of the cathode current collector by gravure printing; the gravure printing mode comprises a coating process and a drying process, wherein the drying process adopts a three-level oven heating method, and the oven temperature is set to be 100 ℃, 105 ℃ and 100 ℃ in sequence;
the thickness of the protective coating is 1-2 mu m;
the diameter of the carbon nano tube is 8-20 nm, and the length-diameter ratio is (300-700): 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811250265.1A CN109411763B (en) | 2018-10-25 | 2018-10-25 | Oil-based protective coating for cathode current collector |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811250265.1A CN109411763B (en) | 2018-10-25 | 2018-10-25 | Oil-based protective coating for cathode current collector |
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| Publication Number | Publication Date |
|---|---|
| CN109411763A CN109411763A (en) | 2019-03-01 |
| CN109411763B true CN109411763B (en) | 2021-10-22 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104823314A (en) * | 2012-11-22 | 2015-08-05 | 株式会社钟化 | Collector for bipolar lithium ion secondary batteries, and bipolar lithium ion secondary battery |
| KR20160062617A (en) * | 2014-11-25 | 2016-06-02 | 울산과학기술원 | Three-dimensional porous-structured current colletor, method of manufacturing the same, electrode including the same, method of manufacturing the same electrode, and electrochemical device including the same current colletor |
| CN106654358A (en) * | 2016-12-15 | 2017-05-10 | 东莞力朗电池科技有限公司 | High-safety lithium ion power battery |
| CN107437625A (en) * | 2016-05-25 | 2017-12-05 | 中国科学院物理研究所 | A kind of two-sided heterogeneous collector and preparation method thereof, lithium battery |
| CN108493455A (en) * | 2017-12-29 | 2018-09-04 | 上海其鸿新材料科技有限公司 | A kind of multifunctional lithium battery collector and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2993098B1 (en) * | 2012-07-09 | 2019-11-01 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | CURRENT COLLECTOR FOR LITHIUM BATTERY |
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2018
- 2018-10-25 CN CN201811250265.1A patent/CN109411763B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104823314A (en) * | 2012-11-22 | 2015-08-05 | 株式会社钟化 | Collector for bipolar lithium ion secondary batteries, and bipolar lithium ion secondary battery |
| KR20160062617A (en) * | 2014-11-25 | 2016-06-02 | 울산과학기술원 | Three-dimensional porous-structured current colletor, method of manufacturing the same, electrode including the same, method of manufacturing the same electrode, and electrochemical device including the same current colletor |
| CN107437625A (en) * | 2016-05-25 | 2017-12-05 | 中国科学院物理研究所 | A kind of two-sided heterogeneous collector and preparation method thereof, lithium battery |
| CN106654358A (en) * | 2016-12-15 | 2017-05-10 | 东莞力朗电池科技有限公司 | High-safety lithium ion power battery |
| CN108493455A (en) * | 2017-12-29 | 2018-09-04 | 上海其鸿新材料科技有限公司 | A kind of multifunctional lithium battery collector and preparation method thereof |
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Effective date of registration: 20240412 Address after: No. 14 Longxing Road, Anliang Community, Yuanshan Street, Longgang District, Shenzhen City, Guangdong Province, 518115 Patentee after: Shenzhen Daxing Nickel Cobalt Technology Co.,Ltd. Country or region after: China Address before: 317599 No. 169 Jinping Avenue, Chengdong Street, Wenling City, Taizhou City, Zhejiang Province Patentee before: TAIZHOU QIANJIANG NEW ENERGY RESEARCH INSTITUTE Co.,Ltd. Country or region before: China |