CN113871626A - Bipolar current collector of secondary battery and manufacturing process thereof - Google Patents
Bipolar current collector of secondary battery and manufacturing process thereof Download PDFInfo
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- CN113871626A CN113871626A CN202111038806.6A CN202111038806A CN113871626A CN 113871626 A CN113871626 A CN 113871626A CN 202111038806 A CN202111038806 A CN 202111038806A CN 113871626 A CN113871626 A CN 113871626A
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
- 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
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/029—Bipolar electrodes
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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
Abstract
The invention belongs to the technical field of new energy battery manufacturing, and particularly relates to a secondary battery bipolar current collector and a manufacturing process thereof. Because the auxiliary ion layer is very thin, the electron conduction efficiency at the position cannot be greatly influenced, the thickness of the composite bipolar current collector cannot be excessively increased, and the low-resistance and ultrathin composite bipolar current collector can be obtained. According to the invention, the nano-scale auxiliary ion layer is added, so that the purposes of small contact resistance inside the current collector and ultrathin preparation are achieved, and the energy density of the new energy battery can be improved.
Description
Technical Field
The invention belongs to the technical field of new energy battery manufacturing, and particularly relates to a secondary battery bipolar current collector and a manufacturing process thereof.
Background
The power battery used by the existing electric automobile realizes high voltage through external series connection between single battery cores, the method often weakens power output at the contact position of a lead because of overhigh resistance, and meanwhile, the complex wire harness increases the technical cost and reduces the space utilization rate. The bipolar battery realizes the internal series connection of the battery cores by respectively coating the positive electrode and the negative electrode on the two sides of the bipolar current collector, the method can easily realize the high-voltage output of the battery, and the prepared battery has the advantages of high energy density and high output power.
In the bipolar battery, the two sides of the current collector are coated with the positive electrode and the negative electrode at the same time, so that the positive electrode surface and the negative electrode surface of the current collector need to be resistant to oxidation and reduction, and the current collector needs to have enough strength to resist possible holes, because the fine holes of the bipolar current collector can cause internal ion short circuit. The current ideal bipolar current collector is a copper-aluminum composite current collector, the prior disclosed technology mainly focuses on finding a suitable method for integrating an aluminum foil and a copper foil, such as CN111725519A, the inventor places a tin layer between the aluminum foil and the copper foil, and the tin layer is melted by hot pressing so as to realize the bonding of the aluminum foil and the copper foil, the tin layer used by the method is 10-50 μm and is far larger than the thickness of the copper and the aluminum foil which are normally used at present, the energy density of the prepared battery cell is inevitably greatly weakened, the uniformity of the thickness of the composite current collector can be influenced by the uneven thickness of the tin layer, such as CN108390068A, the inventor uses a polymer to bond the copper-aluminum material together, and the electronic transmission in the current collector is greatly hindered due to the insulating property of the polymer.
Disclosure of Invention
In view of the above, the present invention provides a bipolar current collector for a secondary battery and a manufacturing process thereof, which are used for manufacturing an ultra-thin composite bipolar current collector with low resistance by surface ion modification.
In order to achieve the technical purpose, the invention adopts the following specific technical scheme:
a bipolar current collector for secondary batteries, comprising:
the supporting foil is one of an oxidation-resistant layer or a reduction-resistant layer of the current collector;
an additional layer which is the other one of the oxidation-resistant layer or the reduction-resistant layer of the current collector;
the auxiliary ion layer is arranged between the supporting foil and the adding layer and used for reducing the reaction activation energy of the adding layer and the supporting foil.
Further, the auxiliary ion layer comprises an evaporation affinity element or a deposition affinity element of the additional layer; the additive layer is combined on the supporting foil through an evaporation process or a deposition process.
Further, the auxiliary ion layer is injected or sputtered onto the support foil.
Further, the oxidation-resistant layer is aluminum or aluminum alloy; the reduction-resistant layer is copper, copper alloy, nickel or nickel alloy; the thickness of the supporting foil is 7-16 μm; the thickness of the auxiliary ion layer is 5-510 nm.
Further, the supporting foil is aluminum or an alloy thereof, the addition layer is copper or an alloy thereof, and the auxiliary ion layer comprises sulfur ions, oxygen ions or nitrogen ions.
Further, the supporting foil is copper or an alloy thereof, the addition layer is aluminum or an alloy thereof, and the auxiliary ion layer comprises chloride ions, oxygen ions or fluoride ions.
Further, the supporting foil is nickel or an alloy thereof, the addition layer is aluminum or an alloy thereof, and the auxiliary ion layer comprises chloride ions.
Further, the invention also provides a manufacturing process of the bipolar current collector of the secondary battery based on the bipolar current collector of the secondary battery, which comprises the following steps:
1) polishing the surface of the supporting foil;
2) degreasing the surface;
3) washing and drying the surface with deionized water;
4) performing auxiliary ion layer injection or sputtering on the surface;
5) and depositing or evaporating the addition layer on the surface.
Further, during the deposition or evaporation process of 5), the surface is in a local gasification state.
Further, the 4) and the 5) are both performed in a vacuum environment.
By adopting the technical scheme, the invention can bring the following beneficial effects:
because the auxiliary ion layer is very thin, the electron conduction efficiency at the position cannot be greatly influenced, the thickness of the composite bipolar current collector cannot be excessively increased, and the low-resistance and ultrathin composite bipolar current collector can be obtained. According to the invention, the nano-scale auxiliary ion layer is added, so that the purposes of small contact resistance inside the current collector and ultrathin preparation are achieved, and the energy density of the new energy battery can be improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings needed to be used in the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present disclosure, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a bipolar current collector of a secondary battery according to an embodiment of the present invention;
FIG. 2 is a schematic flow chart of a process for manufacturing a bipolar current collector for a secondary battery according to an embodiment of the present invention;
wherein: 1. supporting the foil; 2. adding a layer; 3. an auxiliary ion layer.
Detailed Description
The embodiments of the present disclosure are described in detail below with reference to the accompanying drawings.
The embodiments of the present disclosure are described below with specific examples, and other advantages and effects of the present disclosure will be readily apparent to those skilled in the art from the disclosure in the specification. It is to be understood that the described embodiments are merely illustrative of some, and not restrictive, of the embodiments of the disclosure. The disclosure may be embodied or carried out in various other specific embodiments, and various modifications and changes may be made in the details within the description without departing from the spirit of the disclosure. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict. All other embodiments, which can be derived by a person skilled in the art from the embodiments disclosed herein without making any creative effort, shall fall within the protection scope of the present disclosure.
It is noted that various aspects of the embodiments are described below within the scope of the appended claims. It should be apparent that the aspects described herein may be embodied in a wide variety of forms and that any specific structure and/or function described herein is merely illustrative. Based on the disclosure, one skilled in the art should appreciate that one aspect described herein may be implemented independently of any other aspects and that two or more of these aspects may be combined in various ways. For example, an apparatus may be implemented and/or a method practiced using any number of the aspects set forth herein. Additionally, such an apparatus may be implemented and/or such a method may be practiced using other structure and/or functionality in addition to one or more of the aspects set forth herein.
It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present disclosure, and the drawings only show the components related to the present disclosure rather than the number, shape and size of the components in actual implementation, and the type, amount and ratio of the components in actual implementation may be changed arbitrarily, and the layout of the components may be more complicated.
In addition, in the following description, specific details are provided to facilitate a thorough understanding of the examples. However, it will be understood by those skilled in the art that the aspects may be practiced without these specific details.
In one embodiment of the present invention, a bipolar current collector for a secondary battery is provided, as shown in fig. 1, including:
the supporting foil 1 is one of an oxidation-resistant layer or a reduction-resistant layer of the current collector;
an additional layer 2, which is the other of the oxidation-resistant layer or the reduction-resistant layer of the current collector;
and the auxiliary ion layer 3 is arranged between the supporting foil 1 and the adding layer 2 and is used for reducing the reaction activation energy of the combination of the adding layer 2 and the supporting foil 1.
In the present embodiment, the auxiliary ion layer 3 is composed of the evaporation affinity element or the deposition affinity element of the additive layer 2; the additional layer 2 is bonded to the support foil 1 by an evaporation process or a deposition process.
In this embodiment, the auxiliary ion layer 3 is injected or sputtered onto the support foil 1.
In the present embodiment, the oxidation resistant layer is aluminum or an aluminum alloy; the reduction-resistant layer is copper, copper alloy, nickel or nickel alloy; the thickness of the supporting foil 1 is 7-16 μm; the thickness of the auxiliary ion layer 3 is 5-510 nm.
In one embodiment the support foil 1 is aluminium or an alloy thereof, the additive layer 2 is copper or an alloy thereof and the auxiliary ionic layer 3 comprises sulphur ions, oxygen ions or nitrogen ions.
In one embodiment the support foil 1 is copper or an alloy thereof, the additive layer 2 is aluminum or an alloy thereof, and the auxiliary ionic layer 3 comprises chloride, oxygen or fluoride ions.
In one embodiment the support foil 1 is nickel or an alloy thereof, the additive layer 2 is aluminum or an alloy thereof and the auxiliary ionic layer 3 comprises chloride ions.
In an embodiment, the present invention also provides a manufacturing process of a bipolar current collector of a secondary battery based on the bipolar current collector of a secondary battery, as shown in fig. 2, including the following steps:
1) polishing the surface of the supporting foil;
2) removing oil from the surface;
3) cleaning the surface with deionized water and drying;
4) injecting or sputtering an auxiliary ion layer 3 on the surface;
5) deposition or evaporation of the additional layer 2 is performed on the surface.
In the present embodiment, during the deposition or evaporation of 5), the surface is in a partially vaporized state.
In this example, 4) and 5) were both performed in a vacuum atmosphere.
Several current collector combinations and methods of making are listed below
List 1
Preparation of a bipolar current collector, comprising the steps of:
1) pretreatment of the base support foil 1: selecting an aluminum foil with the thickness of 12 mu M as a basic supporting foil material 1, grinding and polishing the surface of the aluminum foil by using 400-mesh sand paper, then soaking the aluminum foil in 0.1M NaOH solution for 1h, then ultrasonically cleaning the aluminum foil by using deionized water for three times, then drying and drying the aluminum foil in vacuum, and injecting a layer of sulfur ions with the thickness of 50nm into the surface of the aluminum foil by using an ion injection machine under the vacuum environment to form an auxiliary ion layer;
2) preparation of additive layer 2: by using an evaporation method, under the vacuum environment, copper is used as a metal target material, pulse laser is used as a heating source, under the instantaneous high temperature, the sublimed sulfide ions on the surface of the aluminum have strong affinity with copper atoms, the rapid deposition of the copper on the surface of the aluminum can be realized, the evaporation time is set to 0.5h, and after the evaporation is finished, a sample is placed at 0 ℃ for cooling for 8h, so that the aluminum-copper composite bipolar current collector is obtained.
Preparation of a bipolar current collector, comprising the steps of:
1) pretreatment of the base support foil 1: selecting an aluminum foil with the thickness of 15 mu M as a basic supporting foil material 1, grinding and polishing the surface of the aluminum foil by using 400-mesh sand paper, then soaking the aluminum foil in 0.1M NaOH solution for 1h, then ultrasonically cleaning the aluminum foil by using deionized water for three times, then drying and drying the aluminum foil in vacuum, and injecting a layer of oxygen ions with the thickness of 100nm into the surface of the aluminum foil by using an ion injection machine under the vacuum environment to form an auxiliary ion layer;
2) preparation of additive layer 2: by utilizing an evaporation method, under the vacuum environment, copper is used as a metal target material, an electron beam is used as a heating source, oxygen ions in a sublimation state on the surface of aluminum have strong affinity with copper atoms at the instantaneous high temperature, the rapid deposition of the copper on the surface of the aluminum can be realized, the evaporation time is set to be 1h, and a sample is placed at 0 ℃ for cooling for 8h after the evaporation is finished, so that the aluminum-copper composite bipolar current collector is obtained.
Preparation of a bipolar current collector, comprising the steps of:
1) pretreatment of the base support foil 1: selecting a copper foil with the thickness of 8 microns as a basic supporting foil material 1, grinding and polishing the surface of the copper foil by using 600-mesh sand paper, soaking the copper foil in 0.1M NaOH solution for 1h, ultrasonically cleaning the copper foil by using deionized water for three times, drying and drying the copper foil in vacuum, and sputtering a layer of chloride ions with the thickness of 200nm on the surface of the copper foil by using an ion sputtering instrument in a vacuum environment to form an auxiliary ion layer;
2) preparation of additive layer 2: by utilizing a magnetron sputtering method, under the vacuum environment, aluminum is used as a metal target material, an electron beam is used as a heating source, chloride ions in a sublimation state on the surface of the aluminum have strong affinity with aluminum atoms at a high temperature in the moment, rapid deposition of the aluminum on the surface of copper can be realized, the sputtering time is set to be 0.5h, and after the sputtering is finished, a sample is placed at 0 ℃ for cooling for 8h to obtain the copper-aluminum composite bipolar current collector.
List 4
Preparation of a bipolar current collector, comprising the steps of:
1) pretreatment of the base support foil 1: selecting a copper foil with the thickness of 8 microns as a basic supporting foil material 1, grinding and polishing the surface of the copper foil by using 800-mesh sand paper, soaking the copper foil in 0.1M NaOH solution for 1h, ultrasonically cleaning the copper foil by using deionized water for three times, drying and drying the copper foil in vacuum, and injecting a layer of 400nm fluorine ions into the surface of the copper foil by using an ion sputtering instrument under a vacuum environment to form an auxiliary ion layer;
2) preparation of additive layer 2: by utilizing a magnetron sputtering method, under the vacuum environment, aluminum is used as a metal target material, pulse laser is used as a heating source, under the instantaneous high temperature, fluoride ions in a sublimation state on the surface of copper have strong affinity with aluminum atoms, the rapid deposition of the aluminum on the surface of the copper can be realized, the sputtering time is set to be 0.5h, and after the sputtering is finished, a sample is placed at 0 ℃ for cooling for 8h to obtain the copper-aluminum composite bipolar current collector.
List 5
Preparation of a bipolar current collector, comprising the steps of:
1) pretreatment of the base support foil 1: selecting a 10-micron nickel foil as the basic support foil 1, grinding and polishing the surface of the nickel foil by using 800-mesh abrasive paper, soaking the nickel foil in 0.1M NaOH solution for 1h, ultrasonically cleaning the nickel foil for three times by using deionized water, drying and drying the nickel foil in vacuum, and sputtering a layer of 400nm chloride ions on the surface of the nickel foil by using an ion sputtering instrument in a vacuum environment to form an auxiliary ion layer;
2) preparation of additive layer 2: by utilizing a magnetron sputtering method, under the vacuum environment, aluminum is used as a metal target material, pulse laser is used as a heating source, chloride ions in a sublimation state on the surface of nickel have strong affinity with aluminum atoms at an instant high temperature, rapid deposition of aluminum on the surface of nickel can be realized, the sputtering time is set to be 1h, and a sample is placed at 0 ℃ to be cooled for 8h after sputtering is finished, so that the nickel-aluminum composite bipolar current collector is obtained.
Comparative example 1
In the traditional process, the preparation of the bipolar current collector comprises the following steps:
1) preparing conductive glue solution: 100w of PVDF with molecular weight and conductive carbon black are mixed in a mass ratio of 1: 1 is mixed into NMP, the concentration of PVDF in the NMP is 8 percent, and the mixture is stirred strongly for 24 hours;
2) adhesion of two metals: and selecting a 12-micron aluminum foil and a 8-micron copper foil, coating the prepared conductive glue solution on the aluminum foil by using a scraper, then pasting the copper foil on the conductive glue solution, and baking the copper foil in a vacuum box at 80 ℃ for 12 hours to obtain the bipolar current collector bonded by the conductive adhesive.
The resistivity and overall thickness of all current collectors in the conventional process and enumeration were measured and compared as follows:
table 1: several examples of this embodiment compare resistivity and thickness with conventional processes.
The above description is only for the specific embodiments of the present disclosure, but the scope of the present disclosure is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present disclosure should be covered within the scope of the present disclosure. Therefore, the protection scope of the present disclosure shall be subject to the protection scope of the claims.
Claims (10)
1. A bipolar current collector for a secondary battery, comprising:
the supporting foil is one of an oxidation-resistant layer or a reduction-resistant layer of the current collector;
an additional layer which is the other one of the oxidation-resistant layer or the reduction-resistant layer of the current collector;
the auxiliary ion layer is arranged between the supporting foil and the adding layer and used for reducing the reaction activation energy of the adding layer and the supporting foil.
2. The bipolar current collector of claim 1, wherein the auxiliary ionic layer comprises an evaporated or deposited affinity element of the additional layer; the additive layer is combined on the supporting foil through an evaporation process or a deposition process.
3. The bipolar current collector of claim 2 wherein said auxiliary ion layer is injected or sputtered onto said supporting foil.
4. The bipolar current collector of claim 3, wherein said oxidation resistant layer is aluminum or an aluminum alloy; the reduction-resistant layer is copper, copper alloy, nickel or nickel alloy; the thickness of the supporting foil is 7-16 μm; the thickness of the auxiliary ion layer is 5-510 nm.
5. The bipolar current collector of claim 4, wherein the support foil is aluminum or an alloy thereof, the additional layer is copper or an alloy thereof, and the auxiliary ionic layer comprises sulfur, oxygen, or nitrogen ions.
6. The bipolar current collector of claim 4, wherein the support foil is copper or an alloy thereof, the additional layer is aluminum or an alloy thereof, and the auxiliary ion layer comprises chloride, oxygen, or fluoride ions.
7. The bipolar current collector of claim 4, wherein the support foil is nickel or an alloy thereof, the additional layer is aluminum or an alloy thereof, and the auxiliary ionic layer comprises chloride ions.
8. The secondary battery bipolar current collector manufacturing process of a secondary battery bipolar current collector according to any one of claims 1-7, characterized by comprising the steps of:
1) polishing the surface of the supporting foil;
2) degreasing the surface;
3) washing and drying the surface with deionized water;
4) performing auxiliary ion layer injection or sputtering on the surface;
5) and depositing or evaporating the addition layer on the surface.
9. The bipolar current collector manufacturing process for secondary batteries according to claim 8, wherein during said deposition or evaporation of 5), said surface is in a partially vaporized state.
10. The secondary battery bipolar current collector manufacturing process according to claim 9, characterized in that said 4) and 5) are both performed in a vacuum environment.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114597420A (en) * | 2022-03-04 | 2022-06-07 | 蔚来动力科技(合肥)有限公司 | Lithium ion battery, bipolar current collector and preparation method thereof |
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| CN112103512A (en) * | 2020-10-09 | 2020-12-18 | 中国科学院物理研究所 | Negative current collector, and preparation method and application thereof |
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| CN113113612A (en) * | 2021-04-08 | 2021-07-13 | 福州大学 | Cationic group carbon cloth current collector and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114597420A (en) * | 2022-03-04 | 2022-06-07 | 蔚来动力科技(合肥)有限公司 | Lithium ion battery, bipolar current collector and preparation method thereof |
| CN114597420B (en) * | 2022-03-04 | 2024-01-12 | 蔚来动力科技(合肥)有限公司 | Lithium ion battery, bipolar current collector and preparation method thereof |
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