CN114430026A - Electrode, alkaline storage battery using same and preparation method of electrode - Google Patents
Electrode, alkaline storage battery using same and preparation method of electrode Download PDFInfo
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- CN114430026A CN114430026A CN202210220028.0A CN202210220028A CN114430026A CN 114430026 A CN114430026 A CN 114430026A CN 202210220028 A CN202210220028 A CN 202210220028A CN 114430026 A CN114430026 A CN 114430026A
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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
- H01M4/24—Electrodes for alkaline accumulators
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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
- H01M10/24—Alkaline accumulators
- H01M10/28—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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/26—Processes of 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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/78—Shapes other than plane or cylindrical, e.g. helical
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention relates to an electrode, an alkaline storage battery using the electrode and a preparation method of the electrode, belonging to the technical field of batteries, aiming at the problems that the existing electrode is deformed due to charging and discharging to cause uneven distribution of electrolyte, further the internal resistance of the battery is increased, the internal consumption of the battery is increased and the service life is reduced, the technical scheme is as follows: an electrode, comprising: the metal foil is provided with a first surface and a second surface, the first surface and the second surface are respectively provided with a plurality of first units and second units, the first units comprise first convex parts and first concave parts, the second units comprise second convex parts and second concave parts, the second concave parts correspond to the first convex parts in position, and the second convex parts correspond to the first concave parts in position; and the active layer is attached to the surface of the first unit and/or the second unit to form a first active material layer and/or a second active material layer. The electrode and the battery using the electrode can effectively inhibit the situation of local deficiency of electrolyte, thereby solving the problems of increased internal consumption and shortened service life of the battery.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to an electrode, an alkaline storage battery using the electrode and a preparation method of the electrode.
Background
An alkaline storage battery is commonly used as a battery for a vehicle, and this type of alkaline storage battery has an electrode assembly in which a plurality of electrodes are laminated via separators. Further, a nonwoven fabric is used as the separator, and the electrolyte solution is held in the gaps between the fibers constituting the nonwoven fabric. The separator is arranged in close contact with the electrode, so that the electrolyte held inside the separator can be quickly supplied to the electrode.
In the charging process of the alkaline storage battery, the positive electrode shrinks and the negative electrode expands, and the shrinkage of the positive electrode and the expansion of the negative electrode are not completely the same at the moment; during discharging, the positive electrode expands and the negative electrode contracts, and the expansion amount of the positive electrode and the contraction amount of the negative electrode are not completely the same; this causes the distance between the electrodes in the stacking direction of the electrode assembly to vary according to the charging rate or the discharging rate. When the distance between the electrodes is narrowed during charge or discharge, the separator disposed between the electrodes is pressed, and the electrolyte held in the separator is transferred to the outside of the electrode assembly via the side circumferential surface of the separator. When the distance between the electrodes is widened, the thickness of the separator recovers as the distance between the electrodes increases, the electrolyte squeezed out from the separator is reabsorbed into the separator from the side circumferential surface of the separator, and the portion farther away from the side circumferential surface of the separator requires a longer electrolyte refilling time than the portion closer, during which there may occur a case where the electrolyte is not locally present in the separator, which may increase the internal resistance of the battery, increase the internal consumption of the battery, and reduce the service life.
Disclosure of Invention
The invention provides an electrode for an alkaline storage battery, the alkaline storage battery and a preparation method of the electrode, aiming at the problems that the prior electrode is deformed during charging and discharging to cause uneven distribution of electrolyte, further the internal resistance of the battery is increased, the internal consumption of the battery is increased, and the service life is reduced.
The technical scheme adopted by the invention is as follows:
an electrode, comprising:
a metal foil having a first surface and a second surface, the first surface and the second surface having a plurality of first cells and second cells, respectively, distributed in an array,
the first unit comprises a first convex part and a first concave part which are connected, the second unit comprises a second convex part and a second concave part which are connected, the second concave part corresponds to the first convex part in position, and the second convex part corresponds to the first concave part in position;
and the active layer is attached to the surface of the first unit and/or the second unit to form a first active material layer and/or a second active material layer which is matched with the surface shape of the first unit and/or the second unit.
The electrode of the present application can be used as a positive electrode or a negative electrode, and when used in combination with a separator, a gap is formed between the first active material layer and/or the second active material layer and the separator, and an electrolyte is located in the gap when the electrode is not deformed, when the deformation occurs, the electrolyte is partially extruded, the electrolyte remained in the gap can be rapidly and smoothly supplemented to the surface convex part of the first active material layer and/or the second active material layer, when the deformation is relieved, the electrolyte is backfilled, the electrolyte at the convex part on the surface of the first active material layer and/or the second active material layer can flow back to the gap, thus, even if the shape of the battery is changed during charging and discharging, the electrode and the diaphragm can always contact with the electrolyte, the situation of local deficiency of the electrolyte is effectively inhibited, and further solves the problems of increased internal consumption and reduced service life caused by increased internal resistance of the battery.
Further, a thickness of the first active material layer formed at the first convex portion is a first thickness, a thickness of the first active material layer formed at the first concave portion is a second thickness, and the first thickness is smaller than the second thickness; wherein the first thickness is 10-50 μm, and the second thickness is 50-150 μm. By setting the thickness of the active layer within the above-described specific range, it is possible to realize a rapid and smooth supply of the electrolyte. The thickness setting is easier to form by adopting a simple coating mode, and the forming difficulty is effectively reduced.
Further, the thickness of the second active material layer formed at the second convex portion is a third thickness, the thickness of the second active material layer formed at the second concave portion is a fourth thickness, and the third thickness is smaller than the fourth thickness; wherein the third thickness is 10-50 μm, and the fourth thickness is 50-150 μm. By setting the thickness of the active layer within the above-described specific range, it is possible to realize a rapid and smooth supply of the electrolyte. The thickness setting is easier to form by adopting a simple coating mode, and the forming difficulty is effectively reduced.
Furthermore, the first units are in a quadrangular pyramid shape, and adjacent first convex parts are connected to form a grid shape;
or the first unit is conical, and the first concave parts are arranged at equal intervals;
or the first unit is in a cone shape with a smooth top, and the first concave parts are arranged at equal intervals.
In the structure, the first concave part is surrounded by the first convex part, and the gaps between the electrodes and the diaphragm can be arranged at equal intervals, so that the electrolyte is uniformly distributed, and the condition of local deficiency of the electrolyte can be effectively inhibited when the battery deforms; because the electrolyte can be uniformly distributed among the battery diaphragms, the uniformity of the system is ensured, and the internal resistance of the alkaline storage battery can be further reduced.
The first protrusions may be scattered or linearly extended in a plan view as viewed from the thickness direction of the metal foil, the first protrusions may be formed in various shapes (e.g., pyramid shape, conical shape or smooth conical shape), and the first protrusions may take a corresponding sectional shape (e.g., triangle shape, trapezoid shape or arc shape) in a section perpendicular to the extending direction.
Further, the metal foil comprises nickel, the active layer comprises nickel hydroxide and a binder, the binder comprises polyvinylidene fluoride, and the nickel hydroxide and the binder are (1-9) in parts by mass: (1-9).
An alkaline storage battery comprising a plurality of alternately arranged electrodes and separators, said electrodes being the above-mentioned electrodes.
Further, the alkaline storage battery further comprises a hollow sealing part, and a first restraining member and a second restraining member which respectively cover both ends of the sealing part, both ends of the metal foil are inserted into an inner wall of the sealing part, the first restraining member is connected with a first terminal electrode, the second restraining member is connected with a second terminal electrode, and active layers are respectively arranged between the first terminal electrode and an adjacent diaphragm and between the second terminal electrode and the adjacent diaphragm.
The electrodes and the diaphragms are alternately arranged, a small space is enclosed between each electrode and the diaphragm, gaps are formed between the first active material layer and/or the second active material layer and the diaphragms, the electrolyte is positioned in the gaps when the electrolyte is not deformed, when the deformation occurs, the electrolyte is partially squeezed out, the electrolyte remained in the gap can be quickly and smoothly supplemented to the surface convex part of the first active material layer and/or the second active material layer, when the deformation is relieved, the electrolyte is backfilled, the electrolyte at the convex part on the surface of the first active material layer and/or the second active material layer can flow back to the gap, thus, even if the shape of the battery is changed during charging and discharging, the electrode and the diaphragm can always contact with the electrolyte, the situation of local deficiency of the electrolyte is effectively inhibited, and further solve the problem that the internal consumption is increased and the service life is reduced due to the increase of the internal resistance of the battery.
A separator known for nickel metal hydride storage batteries, for example, a nonwoven fabric having a hydrophilic functional group can be used, and a polyolefin resin such as polyethylene, polypropylene, or an ethylene-propylene copolymer can be used as a resin constituting the nonwoven fabric. These options are prior art.
The preparation method of the electrode for the alkaline storage battery comprises the following steps:
step 3, coating the slurry on the first unit and/or the second unit, and then drying the slurry at the temperature of 80-200 ℃ for 0.1-48 hours to fully remove the solvent;
and 4, applying pressure of 1-20 MPa along the thickness direction to enable the active layer to be in close contact with the metal foil, and finally obtaining the electrode.
The electrode is prepared by forming a rugged shape on a metal foil, then coating an active layer on the surface of the metal foil in conformity with the rugged shape, and applying pressure to the active layer and the metal foil in order to increase the bonding force of the active layer and the metal foil, thereby obtaining an electrode having satisfactory performance. When the slurry is applied, the liquid surface of the slurry on the metal foil tends to be flat due to surface tension. Therefore, it is easy to realize that the thickness of the paste on the surfaces of the two concave portions is thicker than that on the surfaces of the two convex portions.
The invention has the following beneficial effects: when the battery is matched with a diaphragm for use, a gap is formed between the first active material layer and/or the second active material layer and the diaphragm, electrolyte is positioned in the gap when the battery is not deformed, when the battery is deformed, the electrolyte is partially extruded, the electrolyte remained in the gap can be quickly and smoothly supplemented to the surface convex part of the first active material layer and/or the second active material layer, when the deformation is relieved, the electrolyte is backfilled, and the electrolyte at the surface convex part of the first active material layer and/or the second active material layer can flow back to the gap, so that even if the battery is charged and discharged, the electrode and the diaphragm can always contact the electrolyte, the condition of local deficiency of the electrolyte is effectively inhibited, and the problems of internal consumption increase and service life reduction caused by the increase of internal resistance of the battery are solved. When the electrode is prepared, firstly, the uneven shape is formed on the metal foil, then the slurry is coated on the surface of the metal foil and then dried, an active layer matched with the uneven shape of the metal foil is formed, and in order to increase the bonding force between the active layer and the metal foil, pressure is applied to the active layer and the metal foil, so that the electrode with the performance meeting the requirement is obtained.
Drawings
FIG. 1 is a plan view of an electrode in example 1 of the present application;
FIG. 2 is a sectional view taken along line A-A of FIG. 1;
FIG. 3 is a schematic view of a partial structure in the metal foil of example 1;
FIG. 4 is a partial sectional view of an electrode according to embodiment 2;
FIG. 5 is a schematic view of a partial structure in the metal foil of example 2;
FIG. 6 is a sectional view of an alkaline storage battery according to embodiment 3;
in the figure: 1-an electrode; 2-a metal foil; 21-a first projection; 22-a first recess; 23-peripheral edge, 24-second projection; 25-a second recess; 31-a first active material layer; 32-a second active material layer; 4-a separator; 51-a first restraining member; 52-a second binding member; 53-a seal; 54-a first terminal electrode; 55-a second terminal electrode; c-gap.
Detailed Description
The technical solutions of the embodiments of the present invention are explained and explained below with reference to the drawings of the present invention, but the following embodiments are only preferred embodiments of the present invention, and not all embodiments. Other embodiments obtained by persons skilled in the art without making creative efforts based on the embodiments in the implementation belong to the protection scope of the invention.
Example 1
As shown in fig. 1 to 3, the electrode 1 of the present embodiment includes:
a metal foil 2 having a first surface and a second surface, the first surface and the second surface having a plurality of first cells and second cells, respectively, distributed in an array,
the first unit comprises a first convex part 21 and a first concave part 22 which are connected, the second unit comprises a second convex part 24 and a second concave part 25 which are connected, the second concave part 25 corresponds to the first convex part 21 in position, and the second convex part 24 corresponds to the first concave part 22 in position;
and an active layer attached to the surfaces of the first and second cells to form a first active material layer 31 and a second active material layer 32 having a shape corresponding to the surface shape of the first and second cells. The first active material layer 31 and the second active material layer 32 may be two identical layers, or two layers formed by different active material ratios, which is not particularly limited herein and is within the protection scope of the present patent. In particular, in order to save manufacturing costs and improve production efficiency, the first active material layer 31 and the second active material layer 32 may be two layers that are identical or two layers that are formed of identical raw materials and differ only in thickness.
The first and second cells are spaced from the edges of the metal foil in this application to form a peripheral edge portion 23.
The electrode of the present application can be used as a positive electrode or a negative electrode, and when used in combination with the separator 4, a gap C is formed between the first active material layer 31 and/or the second active material layer 32 and the separator 4, and the electrolyte is located in the gap C when not deformed, when the deformation occurs, the electrolyte is partially squeezed out, the electrolyte remaining in the clearance C can be quickly and smoothly replenished to the convex portions on the surfaces of the first active material layer 31 and the second active material layer 32, when the deformation is released, the electrolyte is refilled, the electrolyte at the convex portions of the surfaces of first active material layer 31 and second active material layer 32 can flow back into gap C, thus, even if the shape of the battery is changed during charging and discharging, the electrode and the diaphragm 4 can always contact with the electrolyte, the condition of local deficiency of the electrolyte is effectively inhibited, and further solve the problem that the internal consumption is increased and the service life is reduced due to the increase of the internal resistance of the battery.
The thickness of the first active material layer 31 formed at the first convex portion 21 is a first thickness, and the thickness of the first active material layer 31 formed at the first concave portion 22 is a second thickness, the first thickness being 25 μm, and the second thickness being 135 μm. By setting the thickness of the active layer within the above-described specific range, it is possible to realize a rapid and smooth supply of the electrolyte. The thickness setting is easier to form by adopting a simple coating mode, and the forming difficulty is effectively reduced.
The thickness of the second active material layer 32 formed at the second protruding portion 24 is a third thickness, and the thickness of the second active material layer 32 formed at the second recessed portion 25 is a fourth thickness, the third thickness being 45 μm, and the fourth thickness being 145 μm. By setting the thickness of the active layer within the above-described specific range, it is possible to realize a rapid and smooth supply of the electrolyte. The thickness setting is easier to form by adopting a simple coating mode, and the forming difficulty is effectively reduced.
The first unit is in a quadrangular pyramid shape, and adjacent first convex parts 21 are connected to form a grid shape. In the structure, the first concave part 22 is surrounded by the first convex part 21, the gaps C between the electrodes and the diaphragm 4 can be arranged at equal intervals, so that the electrolyte is uniformly distributed, the local deficiency of the electrolyte can be effectively inhibited when the battery deforms, the lithium ions can be transmitted in a uniform system, the local deficiency of the electrolyte can be effectively inhibited when the battery deforms, and the problems of internal consumption increase and service life reduction caused by the increase of the internal resistance of the battery are solved;
the first convex portion 21 of the present application may take a corresponding sectional shape (e.g., a triangle shape) in a section perpendicular to the extending direction, as viewed from the thickness direction of the metal foil.
The metal foil comprises nickel, the active layer comprises nickel hydroxide and a binder, polyvinylidene fluoride (PVDF) can be adopted as the binder in the embodiment, and the nickel hydroxide and the binder are (1-9) in parts by mass: (1-9).
Example 2
As shown in fig. 4 to 5, the present embodiment is different from embodiment 1 in that: the first unit is of a smooth top smooth conical shape, and the first recesses 22 are arranged equidistantly.
Example 3
As shown in fig. 6, the alkaline storage battery using the electrode of example 1 further includes a plurality of alternately arranged electrodes and separators 4, a hollow sealing portion 53, and first and second constraining members 51 and 52 covering both ends of the sealing portion 53, respectively, the peripheral portion 23 of the end portion of the metal foil is inserted into the inner wall of the sealing portion 53, the first constraining member 51 is connected to a first terminal electrode 54, the second constraining member 52 is connected to a second terminal electrode 55, a first active material layer 31 is provided between the first terminal electrode 54 and the adjacent separator 4, and a second active material layer 32 is provided between the second terminal electrode 55 and the adjacent separator 4.
When a bipolar electrode is used, the number of single cells can be increased relative to the total number of electrodes, as compared with the case where a unipolar electrode is used. When the total number of electrodes is the same, the number of single cells can be increased as compared with the case of using a unipolar electrode. When the number of single cells is the same, the total number of electrodes can be reduced, and the size of the alkaline storage battery in the stacking direction can be made smaller, as compared with the case of using a unipolar electrode.
Example 4
The method of making the electrode of example 1, comprising the steps of:
step 3, coating the slurry on the first unit and the second unit by using a bar coating machine or a roller coating machine, and drying at the temperature of 80-200 ℃ for 0.1-48 hours to fully remove the solvent; preferably drying at 100 ℃ for 8 h; the weight per unit area of the first active material layer 31 can be set to be suitably 20 to 50mg/cm2Preferably 23 mg-cm2(ii) a The weight of the second active material layer 32 per unit area can be set to be suitably 20 to 60mg/cm2Preferably 48mg/cm2;
And 4, applying pressure of 1-20 MPa in the thickness direction by using a laminating machine to enable the active layer to be in close contact with the metal foil, and finally obtaining the electrode.
While the invention has been described with reference to specific embodiments, the scope of the invention is not limited thereto, and those skilled in the art will appreciate that the invention includes, but is not limited to, the accompanying drawings and the description of the embodiments above. Any modification which does not depart from the functional and structural principles of the present invention is intended to be included within the scope of the claims.
Claims (10)
1. An electrode, comprising:
the metal foil is provided with a first surface and a second surface, the first surface and the second surface are respectively provided with a plurality of first units and second units which are distributed in an array mode, the first units comprise first convex parts and first concave parts which are connected, the second units comprise second convex parts and second concave parts which are connected, the second concave parts correspond to the first convex parts in position, and the second convex parts correspond to the first concave parts in position;
and the active layer is attached to the surface of the first unit and/or the second unit to form a first active material layer and/or a second active material layer which is matched with the surface shape of the first unit and/or the second unit.
2. The electrode according to claim 1, wherein a thickness of the first active material layer formed at the first convex portion is a first thickness, a thickness of the first active material layer formed at the first concave portion is a second thickness, and the first thickness is smaller than the second thickness.
3. The electrode of claim 2, wherein the first thickness is 10 to 50 μm and the second thickness is 50 to 150 μm.
4. The electrode according to claim 1, wherein a thickness of the second active material layer formed at the second convex portion is a third thickness, and a thickness of the second active material layer formed at the second concave portion is a fourth thickness, and the third thickness is smaller than the fourth thickness.
5. The electrode of claim 4, wherein the third thickness is 10-50 μm and the fourth thickness is 50-150 μm.
6. The electrode according to claim 1, wherein the first unit is of a quadrangular pyramid type, and adjacent first protrusions are in a grid shape;
or the first unit is conical;
or the first unit is in a cone shape with a smooth top.
7. The electrode according to claim 1, wherein the metal foil comprises nickel, the active layer comprises nickel hydroxide and a binder, the binder comprises polyvinylidene fluoride, and the nickel hydroxide and the binder are (1-9) in parts by mass: (1-9).
8. An alkaline storage battery comprising a plurality of alternately arranged electrodes and separators, wherein the electrodes are the electrodes according to any one of claims 1 to 7.
9. The alkaline storage battery according to claim 8, further comprising a hollow sealing part, and a first restriction member and a second restriction member respectively covering both ends of the sealing part, wherein both ends of the metal foil are inserted into an inner wall of the sealing part, wherein the first restriction member has a first terminal electrode connected thereto, the second restriction member has a second terminal electrode connected thereto, and active layers are provided between the first terminal electrode and the separator and between the second terminal electrode and the separator.
10. A method of manufacturing an electrode according to any one of claims 1 to 7, comprising the steps of:
step 1, rolling a metal foil, and forming a plurality of first units and second units which are distributed in an array form on a first surface and a second surface of the metal foil respectively;
step 2, mixing nickel hydroxide, a binder and a solvent according to a proportion to obtain slurry;
step 3, coating the slurry on the first unit and/or the second unit, and drying at the temperature of 80-200 ℃ for 0.1-48 hours to fully remove the solvent;
and 4, applying pressure of 1-20 MPa along the thickness direction to enable the active layer to be in close contact with the metal foil, and finally obtaining the electrode.
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JP2002270186A (en) * | 2001-03-09 | 2002-09-20 | Sumitomo Metal Steel Products Inc | Metallic foil for secondary battery current collection material and manufacturing method therefor |
CN1426611A (en) * | 2000-04-28 | 2003-06-25 | 松下电器产业株式会社 | Electrode plate for cell and method for manufacturing same |
CN105190955A (en) * | 2013-05-31 | 2015-12-23 | 株式会社安永 | Electrode for non-aqueous electrolyte secondary battery, and manufacturing method of electrode for non-aqueous electrolyte secondary battery |
JP2018185999A (en) * | 2017-04-26 | 2018-11-22 | 株式会社豊田自動織機 | Electrode for alkaline storage battery and alkaline storage battery |
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2022
- 2022-03-08 CN CN202210220028.0A patent/CN114430026A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1426611A (en) * | 2000-04-28 | 2003-06-25 | 松下电器产业株式会社 | Electrode plate for cell and method for manufacturing same |
JP2002270186A (en) * | 2001-03-09 | 2002-09-20 | Sumitomo Metal Steel Products Inc | Metallic foil for secondary battery current collection material and manufacturing method therefor |
CN105190955A (en) * | 2013-05-31 | 2015-12-23 | 株式会社安永 | Electrode for non-aqueous electrolyte secondary battery, and manufacturing method of electrode for non-aqueous electrolyte secondary battery |
JP2018185999A (en) * | 2017-04-26 | 2018-11-22 | 株式会社豊田自動織機 | Electrode for alkaline storage battery and alkaline storage battery |
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