CN112687842A - Bipolar electrode and battery - Google Patents
Bipolar electrode and battery Download PDFInfo
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- CN112687842A CN112687842A CN202011568838.2A CN202011568838A CN112687842A CN 112687842 A CN112687842 A CN 112687842A CN 202011568838 A CN202011568838 A CN 202011568838A CN 112687842 A CN112687842 A CN 112687842A
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Abstract
The invention provides a bipolar electrode, which comprises a composite bipolar current collector, a positive electrode material, a negative electrode material and two conductive sealing films, wherein the composite bipolar current collector is arranged between the positive electrode material and the negative electrode material; the composite bipolar current collector comprises a base film, a first conducting layer and a second conducting layer, wherein the first conducting layer and the second conducting layer are coated on two sides of the base film; the conductive sealing film comprises a sealing conductive layer and a polymer layer, the two conductive sealing films are respectively arranged at two ends of the composite bipolar current collector, two ends of the sealing conductive layer of the conductive sealing film are respectively connected with the first conductive layer and the second conductive layer, the polymer layer wraps the outer side of the sealing conductive layer, the polymer layer is located on two sides of the sealing conductive layer and is provided with a blank area, and the blank areas on two sides of the polymer layer are respectively connected with the first conductive layer and the second conductive layer. The conductive sealing film is introduced, so that the first conductive layer and the second conductive layer on two sides of the composite bipolar current collector can be connected, and the internal resistance of the composite bipolar current collector is reduced.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a bipolar electrode and a battery.
Background
The bipolar battery is formed by respectively coating active substances with different polarities on two sides of a composite bipolar current collector and stacking the units in series, and has the characteristics of high voltage, high energy density and high overcurrent capacity. As an important component of a bipolar battery, a copper-aluminum composite foil obtained by directly compounding copper foil and aluminum foil is generally used for the composite bipolar current collector, but the copper-aluminum composite foil is relatively thick and cannot meet the requirement of weight reduction. Therefore, a composite bipolar current collector obtained by compounding metal foils on two surfaces of an insulating polymer film is produced, and the composite bipolar current collector is more advantageous in weight because the composite bipolar current collector takes the insulating polymer film as a base film, but the base film is insulating and cannot form an electronic channel.
In addition, in the bipolar battery, independent electrochemical reactions are performed in each battery cell, and if the sealing performance of the battery cells is poor, leakage of electrolyte is easily caused, so that the liquid connection between adjacent battery cells is caused, and the overall performance of the battery is affected.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a bipolar electrode and a battery.
The invention provides a bipolar electrode, which comprises a composite bipolar current collector, a positive electrode material, a negative electrode material and two conductive sealing films; the composite bipolar current collector comprises a base film, a first conducting layer and a second conducting layer, wherein the first conducting layer and the second conducting layer are coated on two sides of the base film; the conductive sealing film comprises a sealing conductive layer and a polymer layer, the two conductive sealing films are respectively arranged at two ends of the composite bipolar current collector, two ends of the sealing conductive layer of the conductive sealing film are respectively connected with the first conductive layer and the second conductive layer, the polymer layer wraps the outer side of the sealing conductive layer, the polymer layer is located on two sides of the sealing conductive layer and is provided with a blank area, and the blank areas on two sides of the polymer layer are respectively connected with the first conductive layer and the second conductive layer.
Preferably, the sealing conductive layer is connected with the first conductive layer and the second conductive layer by welding.
Preferably, the thickness of the sealing conductive layer is 0.01-5 μm; preferably, the thickness of the sealing conductive layer is 0.5 to 1.5 μm.
Preferably, the conductive material of the sealing conductive layer is one or more of gold, silver, copper, aluminum, zinc, iron, nickel and graphite particles; preferably, the sealing conductive layer is formed on the polymer layer by vacuum evaporation, magnetron sputtering, ion plating, electrodeposition or coating with a conductive material.
Preferably, the material of the polymer layer is one of polyethylene terephthalate, polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyimide and polyamide, and the thickness of the polymer layer is 1-30 μm; preferably, the thickness of the polymer layer is 5-15 μm.
Preferably, the thickness of the composite bipolar current collector is 1-50 μm; preferably, the thickness of the composite bipolar current collector is 3-20 μm.
Preferably, the base film of the composite bipolar current collector is made of one of polyethylene terephthalate, polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyimide and polyamide; the thickness of the basement membrane is 1-20 μm; preferably, the thickness of the base film is 3 to 8 μm.
Preferably, the first conductive layer is made of metal aluminum, and the second conductive layer is made of one or two of metal copper and nickel; preferably, a first conductive layer and a second conductive layer are formed on the base film in a vacuum evaporation mode, a magnetron sputtering mode, an ion plating mode or an electrodeposition mode; preferably, the thickness of the first conductive layer and the second conductive layer is 0.01 to 5 μm and the thickness of the first conductive layer is greater than or equal to the thickness of the second conductive layer.
Preferably, a first conductive coating with the thickness of 0.01-2 μm is arranged between the positive electrode material and the first conductive layer, and a second conductive coating with the thickness of 0.01-2 μm is arranged between the negative electrode material and the second conductive layer; preferably, the first conductive coating and the second conductive coating are made of one or more of conductive carbon black, graphene, carbon nanotubes and acetylene black.
The invention also provides a bipolar battery, which comprises a diaphragm, electrolyte, a conductive sealing film, a positive current collecting plate, a negative current collecting plate, an aluminum plastic film and a plurality of bipolar electrodes as claimed in any one of claims 1 to 9, wherein the bipolar electrodes are stacked side by side in sequence, and polymer layers of the conductive sealing films at the end parts of any two adjacent bipolar electrodes are integrally formed in a hot pressing mode.
According to the bipolar electrode, the conductive sealing film is introduced, and the first conductive layer and the second conductive layer on two sides of the composite bipolar current collector can be connected, so that the problem that the conductive layers on two sides of the composite bipolar current collector are not conducted is solved, and the internal resistance of the composite bipolar current collector is reduced. The invention provides a bipolar battery, which takes a conductive sealing film as a sealing member and can effectively seal each battery unit, and prevent the electrolyte of a single battery unit from leaking and connecting with the electrolyte of an adjacent battery unit.
Drawings
FIG. 1 is a schematic structural diagram of a bipolar electrode according to the present invention;
FIG. 2 is a schematic view of another structure of a bipolar electrode according to the present invention;
FIG. 3 is a schematic structural diagram of a conductive sealing film in a bipolar electrode according to the present invention;
fig. 4 is a schematic structural diagram of a bipolar battery according to the present invention.
Detailed Description
Referring to fig. 1-4, the invention provides a bipolar electrode and a battery, comprising a composite bipolar current collector 1, a positive electrode material 2, a negative electrode material 3 and two conductive sealing films 4; wherein:
the composite bipolar current collector 1 comprises a base film 11, and a first conductive layer 12 and a second conductive layer 13 coated on two sides of the base film 11, wherein a positive electrode material 2 and a negative electrode material 3 are respectively attached to the first conductive layer 12 and the second conductive layer 13. The conductive sealing film 4 comprises a sealing conductive layer 41 and a polymer layer 42, the two conductive sealing films 4 are respectively arranged at two ends of the composite bipolar current collector 1, two ends of the sealing conductive layer 41 of the conductive sealing film 4 are respectively connected with the first conductive layer 12 and the second conductive layer 13, the polymer layer 42 wraps the outer side of the sealing conductive layer 41, the polymer layer 42 is positioned at two sides of the sealing conductive layer 41 and is provided with a blank area, and the blank areas at two sides of the polymer layer 42 are respectively connected with the first conductive layer 12 and the second conductive layer 13.
The conductive sealing film 4 is introduced, so that the first conductive layer 12 and the second conductive layer 13 on the two sides of the composite bipolar current collector 1 can be connected, and the internal resistance of the composite bipolar current collector 1 is reduced.
In the present embodiment, the sealing conductive layer 41 is connected to the first conductive layer 12 and the second conductive layer 13 by soldering. The welding method is one of ultrasonic welding, laser welding or pulse welding, and the ultrasonic welding is preferred. The realization form of welding can be spot welding or roll welding, the welding marks are at least two rows, and the width W of the welding marks is more than or equal to 3 mm.
In the present embodiment, the thickness of the sealing conductive layer 41 is 0.01 to 5 μm, preferably 0.5 to 1.5 μm. The conductive material of the sealing conductive layer 41 is one or more of gold, silver, copper, aluminum, zinc, iron, nickel, and graphite particles. The sealing conductive layer 41 is formed on the polymer layer 42 by vacuum evaporation, magnetron sputtering, ion plating, electrodeposition or coating with a conductive material.
In the present embodiment, the material of the polymer layer 42 is one of polyethylene terephthalate, polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyimide, and polyamide, and the thickness of the polymer layer 42 is 1 to 30 μm, preferably 5 to 15 μm.
In the present embodiment, the thickness of the composite bipolar current collector 1 is 1 to 50 μm, preferably 3 to 20 μm.
In this embodiment, the base film 11 of the composite bipolar current collector 1 is made of one of polyethylene terephthalate, polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyimide, and polyamide, such a base film 11 has a smaller weight, which is beneficial to increasing the energy density of the battery, and the formed composite bipolar current collector 1 has good mechanical strength, which can ensure the stability of the electrode plate. The thickness of the base film 11 affects the mechanical strength thereof, and when the thickness of the base film 11 is too small, the mechanical strength thereof is affected; when the thickness of the base film 11 is too large, improvement of the battery energy density is disadvantageous. The thickness of the base film 11 in this embodiment is 1 to 20 μm; preferably, the thickness of the base film 11 is 3 to 8 μm.
The polarities of the first conductive layer 12 and the second conductive layer 13 are opposite, and generally, the material of the first conductive layer 12 is metal aluminum, and the material of the second conductive layer 13 is one or two of metal copper and nickel. The first conductive layer 12 and the second conductive layer 13 are formed on the base film 11 by vacuum evaporation, magnetron sputtering, ion plating, or electrodeposition.
The thickness of the conductive layer directly affects the conductivity of the composite bipolar current collector 1, and when the thickness of the conductive layer is larger, the conductivity of the composite bipolar current collector 1 is improved, but the improvement of the energy density of the battery is not favorable. When the thickness of the conductive layer is small, the conductivity of the composite bipolar current collector 1 may be deteriorated. The thicknesses of the first conductive layer 12 and the second conductive layer 13 may be the same or different. The thicknesses of the first conductive layer 12 and the second conductive layer 13 are 0.01 to 5 μm and the thickness of the first conductive layer 12 is greater than or equal to the thickness of the second conductive layer 13.
In a specific embodiment, the material used for forming the positive electrode material 2 and the negative electrode material 3 layers is a conventional material used in the manufacturing process of the lithium ion battery, the positive electrode material 2 includes a positive electrode active material, a conductive material and a binder, and according to different requirements, a corresponding additive may be added, and the positive electrode active material may be one of lithium manganate, lithium cobaltate, lithium iron ferrite, a ternary material, and the like. The negative electrode material 3 comprises a negative electrode active material, a conductive material and a binder, and can be provided with corresponding additives according to different requirements, wherein the negative electrode active material can be one of lithium titanate, graphite, a silicon-carbon negative electrode, lithium metal and the like.
In a specific embodiment, a first conductive coating with a thickness of 0.01-2 μm is disposed between the cathode material 2 and the first conductive layer 12, and a second conductive coating with a thickness of 0.01-2 μm is disposed between the anode material 3 and the second conductive layer 13. The conductive coating can reduce the resistance between the composite bipolar current collector 1 and the anode material 2 layer or the cathode material 3 layer, and improve the conduction efficiency of electrons. The first conductive coating and the second conductive coating are made of one or more of conductive carbon black, graphene, carbon nano tubes and acetylene black.
Referring to fig. 4, the invention also provides a bipolar battery, which comprises a diaphragm 5, an electrolyte, a conductive sealing film 4, a positive current collecting plate 6, a negative current collecting plate 7, an aluminum-plastic film 8 and a plurality of bipolar electrodes, wherein the bipolar electrodes are stacked side by side in sequence, and polymer layers 42 of the conductive sealing films 4 at the end parts of any two adjacent bipolar electrodes are integrated into a whole in a hot pressing mode. The diaphragm 5, the electrolyte, the sealing colloid, the anode current collecting plate 6, the cathode current collecting plate 7, the aluminum-plastic film 8 and the like are all conventional materials used in the manufacturing process of the bipolar battery, and researchers can select the materials according to actual requirements. The conductive sealing film 4 seals each cell against leakage of the electrolyte of a single cell and electrolyte connection with adjacent cells.
The invention will be further illustrated with reference to the following specific examples.
Examples
1. Preparation of bipolar electrode
Selecting a composite bipolar current collector: the base film is made of polyethylene terephthalate (PET), the selected thickness is 8 mu m, the first conducting layer is an aluminum plating layer and is 0.8 mu m, the second conducting layer is a copper plating layer and is 0.8 mu m, and the plating layer is formed in a vacuum evaporation mode.
Adding the ternary active material NCM622, the conductive agent CNTs and the binder PVDF into an organic solvent NMP according to the proportion of 97.3:1.5:1.2, and uniformly stirring to obtain the anode slurry. Adding graphite, a conductive agent SP, a binder CMC and SBR into deionized water according to the proportion of 96.4:0.7:1.4:1.5, and uniformly stirring to obtain negative electrode slurry.
Uniformly coating the positive electrode slurry on the surface of the first conductive layer of the composite bipolar current collector, and uniformly coating the negative electrode slurry on the surface of the second conductive layer of the composite bipolar current collector, wherein the single-sided surface density of the positive electrode is 195.1g/m2The density of the single-sided surface of the negative electrode is 110.5g/m2. Vacuum baking was carried out in an oven at 100 ℃ for 12 hours. Then rolling, slitting, laser cutting or die cutting are carried out to obtain the bipolar electrode pole piece.
Selecting a conductive sealing film, wherein the polymer layer is a PET film and has a thickness of 12 μm, the conductive layer of the sealing film is an aluminum plating layer and is formed by vacuum evaporation, and the thickness of the conductive layer is 0.75 μm. And (3) inwards forming a U-shaped conducting layer of the sealing film to wrap the conducting layer of the composite bipolar current collector, and connecting the conducting layer and the composite bipolar current collector together through ultrasonic welding. The welding is carried out in a roll welding mode, two rows of welding imprints are arranged, and the width of each welding imprint is 5 mm. And the polymer layer of the conductive sealing film is arranged on the outer side of the conductive layer of the sealing film, and the margin area of the polymer layer is connected with the first conductive layer and the second conductive layer of the composite bipolar current collector respectively.
2. Preparation of bipolar battery
The bipolar electrodes welded with the conductive sealing films and the diaphragms are alternately laminated, a positive electrode material layer, the diaphragms, the electrolyte and a negative electrode material layer on the adjacent bipolar electrodes form a battery unit, and each battery comprises four battery units. The polymer layer of the conductive sealing film is in contact with the polymer layer of the adjacent conductive sealing film, and after electrolyte is injected into the battery unit, the adjacent sealing colloid is bonded together after being hot-pressed, so that each battery unit is sealed. And the positive electrode and the negative electrode are respectively led out from the aluminum plastic film package by the positive current collector plate and the negative current collector plate, and then the preparation of the battery is completed through the working procedures of packaging, formation and the like.
The parameters of the composite bipolar current collector in each embodiment are shown in table 1, and it can be seen that after the conductive sealing films are used to connect the conductive layers on the two sides of the composite bipolar current collector, the sheet resistance of the composite bipolar current collector is reduced, and the larger the thickness of the first conductive layer is, the smaller the sheet resistance of the composite bipolar current collector is.
TABLE 1
And (3) manufacturing an electrode and a battery by using the current collector with the number 3, and carrying out a normal-temperature cycle test on the manufactured battery, wherein the multiplying power is 1C, and the voltage range is 12.0-16.8V. The cell tightness was evaluated during cycling: and disassembling the battery which is circulated for certain times, and observing whether the sealing part of the inner edge of the battery leaks the electrolyte. The results show that the battery manufactured by using the No. 3 current collector still keeps good sealing performance at the edge sealing part in the battery after 1000 cycles, and no electrolyte leakage is found.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A bipolar electrode is characterized by comprising a composite bipolar current collector, a positive electrode material, a negative electrode material and two conductive sealing films; the composite bipolar current collector comprises a base film, a first conducting layer and a second conducting layer, wherein the first conducting layer and the second conducting layer are coated on two sides of the base film; the conductive sealing film comprises a sealing conductive layer and a polymer layer, the two conductive sealing films are respectively arranged at two ends of the composite bipolar current collector, two ends of the sealing conductive layer of the conductive sealing film are respectively connected with the first conductive layer and the second conductive layer, the polymer layer wraps the outer side of the sealing conductive layer, the polymer layer is located on two sides of the sealing conductive layer and is provided with a blank area, and the blank areas on two sides of the polymer layer are respectively connected with the first conductive layer and the second conductive layer.
2. The bipolar electrode of claim 1 wherein the sealing conductive layer is connected to the first and second conductive layers by welding.
3. The bipolar electrode of claim 1 wherein the thickness of the sealing conductive layer is 0.01-5 μ ι η; preferably, the thickness of the sealing conductive layer is 0.5 to 1.5 μm.
4. The bipolar electrode of any one of claims 1-3, wherein the electrically conductive material of the sealing and electrically conductive layer is one or more of gold, silver, copper, aluminum, zinc, iron, nickel, graphite particles; preferably, the sealing conductive layer is formed on the polymer layer by vacuum evaporation, magnetron sputtering, ion plating, electrodeposition or coating with a conductive material.
5. The bipolar electrode as claimed in any one of claims 1 to 3, wherein the polymer layer is made of one of polyethylene terephthalate, polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyimide, and polyamide, and has a thickness of 1 to 30 μm; preferably, the thickness of the polymer layer is 5-15 μm.
6. The bipolar electrode according to any of claims 1 to 3, wherein the thickness of the composite bipolar current collector is 1-50 μm; preferably, the thickness of the composite bipolar current collector is 3-20 μm.
7. The bipolar electrode as claimed in any one of claims 1 to 3, wherein the base film of the composite bipolar current collector is made of one of polyethylene terephthalate, polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyimide, and polyamide; the thickness of the basement membrane is 1-20 μm; preferably, the thickness of the base film is 3 to 8 μm.
8. The bipolar electrode according to any one of claims 1 to 3, wherein the first conductive layer is made of aluminum metal, and the second conductive layer is made of one or two of copper metal and nickel metal; preferably, a first conductive layer and a second conductive layer are formed on the base film in a vacuum evaporation mode, a magnetron sputtering mode, an ion plating mode or an electrodeposition mode; preferably, the thickness of the first conductive layer and the second conductive layer is 0.01 to 5 μm and the thickness of the first conductive layer is greater than or equal to the thickness of the second conductive layer.
9. The bipolar electrode according to any one of claims 1 to 3, wherein a first conductive coating having a thickness of 0.01 to 2 μm is disposed between the positive electrode material and the first conductive layer, and a second conductive coating having a thickness of 0.01 to 2 μm is disposed between the negative electrode material and the second conductive layer; preferably, the first conductive coating and the second conductive coating are made of one or more of conductive carbon black, graphene, carbon nanotubes and acetylene black.
10. A bipolar battery, which comprises a diaphragm, electrolyte, a conductive sealing film, a positive current collecting plate, a negative current collecting plate and an aluminum plastic film, and is characterized by further comprising a plurality of bipolar electrodes as claimed in any one of claims 1 to 9, wherein the bipolar electrodes are stacked side by side in sequence, and the polymer layers of the conductive sealing films at the end parts of any two adjacent bipolar electrodes are integrated into a whole in a hot pressing mode.
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Cited By (4)
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| CN113270589A (en) * | 2021-05-25 | 2021-08-17 | 厦门海辰新能源科技有限公司 | Lithium ion battery, bipolar current collector and manufacturing method thereof |
| 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 |
| CN115692722A (en) * | 2022-11-08 | 2023-02-03 | 厦门海辰储能科技股份有限公司 | Composite current collector, battery core, battery and preparation method of composite current collector |
| WO2024073892A1 (en) * | 2022-10-08 | 2024-04-11 | 宁德时代新能源科技股份有限公司 | Composite current collector, electrode, secondary battery and electric device |
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| CN113270589A (en) * | 2021-05-25 | 2021-08-17 | 厦门海辰新能源科技有限公司 | Lithium ion battery, bipolar current collector and manufacturing method thereof |
| 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 |
| WO2024073892A1 (en) * | 2022-10-08 | 2024-04-11 | 宁德时代新能源科技股份有限公司 | Composite current collector, electrode, secondary battery and electric device |
| CN115692722A (en) * | 2022-11-08 | 2023-02-03 | 厦门海辰储能科技股份有限公司 | Composite current collector, battery core, battery and preparation method of composite current collector |
| CN115692722B (en) * | 2022-11-08 | 2024-01-26 | 厦门海辰储能科技股份有限公司 | Composite current collector, battery cell, battery and preparation method of composite current collector |
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