CN113066959B - Battery cell - Google Patents

Battery cell Download PDF

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CN113066959B
CN113066959B CN202110310554.1A CN202110310554A CN113066959B CN 113066959 B CN113066959 B CN 113066959B CN 202110310554 A CN202110310554 A CN 202110310554A CN 113066959 B CN113066959 B CN 113066959B
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active material
material layer
pole piece
thickness
current collector
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CN113066959A (en
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秦一鸣
明帮生
余舒娴
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The application provides a battery cell, which is formed by sequentially superposing and winding a first pole piece, a diaphragm and a second pole piece. The first pole piece comprises a first current collector, and a first active material layer and a second active material layer which are coated on the surface of the first current collector, wherein the first active material layer is at least coated on the surface of the first current collector positioned on the outermost ring. The application provides an electric core, outermost circle select for use the first active material layer of energy type in order to play the effect of protection electric core safety, and the inner circle selects for use the second active material layer of safe type in order to improve the energy density of electric core, has balanced the security performance and the capacity demand of electric core.

Description

Battery cell
Technical Field
The application relates to the technical field of batteries, in particular to a battery cell capable of having high capacity and high safety.
Background
The performance of the anode material of the lithium ion battery is an important factor influencing the capacity and safety of the lithium battery, and common anode materials include lithium cobaltate, lithium iron phosphate, ternary materials and the like. Energy type materials such as lithium cobaltate or ternary materials can improve energy density but have poor safety, a soft-package battery cell or a hard-shell battery cell made of the materials can cause local short circuit due to external force damage, the battery cell is caused to be short-circuited, smoke, catch fire and the like, and the through nail and impact can also cause the battery cell to be short-circuited and influence the safety performance of the battery cell. Batteries made of safety materials such as lithium iron phosphate have good safety but low energy density, and consumers have poor feedback when using the batteries.
Disclosure of Invention
In view of the above, there is a need to provide a novel battery cell to solve the problem that the existing battery cell has high capacity and good safety.
In order to achieve the purpose, the technical scheme of the application is as follows: the utility model provides an electric core, it is superpose in proper order and is convoluteed by first pole piece, diaphragm and second pole piece and form, first pole piece includes the first mass flow body and coats in the first active material layer and the second active material layer on the surface of the first mass flow body, the first active material layer coats at least in the surface of the first mass flow body that is located the outer lane. The first current collector of the outermost ring comprises a first bent part and a second bent part which are oppositely arranged, a first connecting part connected with the first bent part and the second bent part, and a second connecting part connected with the second bent part and oppositely arranged with the first connecting part.
The first active material layer is different from the second active material layer, the first active material layer includes a security type material, the second active material layer includes a security type material, and the security type material is different from the security type materialThe active material layer includes an energy type material. The safety material is a material which can protect the battery core from smoking and firing when the battery core is damaged from outside to inside. The energy type material refers to a material which can ensure the circulation and capacity performance of the battery core. In one embodiment, the first active material layer includes lithium iron phosphate (LiFePO)4) Lithium manganate (LiMn)2O4) And lithium manganese iron phosphate LiFe1-yMnyPO4At least one of (1), wherein y is 0.5. ltoreq<1.0. In one embodiment, the second active material layer comprises a nickel-cobalt-manganese ternary material LiNi1-y-zMnyCozO2And nickel cobalt aluminum ternary material LiNi1-y-zCoyAlzO2At least one of (1), wherein y is 0.5. ltoreq<1.0。
The conventional active substances are replaced by the first active material layer (the safety material) in the outermost ring, when the battery cell is damaged from outside to inside due to trauma, nail penetration, impact and the like, the safety material of the outermost ring can protect the whole battery cell, the effects of no smoke and no fire are achieved, and the safety performance of the battery cell is improved. The use of the second active material layer (energy type material) in the inner ring can improve the energy density of the cell.
In one embodiment, the first active material layer and the second active material layer have a gap therebetween, the gap having a length less than or equal to 2 mm.
In one embodiment, the first active material layer partially overlaps the second active material layer, and a difference between a thickness of the overlapping region and a thickness of the second active material layer is 30 μm or less. The first active material layer and the second active material layer may be in direct contact without additional processing.
In one embodiment, the gap or the overlapping region is located at the first bending portion.
In one embodiment, along the length direction of the first pole piece, the length of the first active material layer accounts for 3% -70% of the length of the first pole piece.
In one embodiment, the first active material layer has a thickness of 20 μm to 120 μm, and the second active material layer has a thickness of 20 μm to 120 μm.
In one embodiment, the thickness of the first active material layer is less than or equal to the thickness of the second active material layer, and the difference in thickness between the second active material layer and the first active material layer is less than 30 μm.
In one embodiment, the mass of the first active material layer is less than or equal to the mass of the second active material layer.
In one embodiment, the battery cell further includes a tab, the tab is disposed in the middle of the first pole piece in the length direction, and the tab is disposed in the first pole piece region where the first active material layer is located, or the tab is disposed in the first pole piece region where the second active material layer is located.
The application provides an electric core, outermost circle select for use the first active material layer of energy type in order to play the effect of protection electric core safety, and the inner circle selects for use the second active material layer of safe type in order to improve the energy density of electric core, has balanced the security performance and the capacity demand of electric core.
Drawings
The present application will be described in further detail with reference to the following drawings and detailed description.
Fig. 1 is a schematic structural diagram of a battery cell according to an embodiment of the present application.
Fig. 2 is a schematic structural diagram of a first pole piece and a tab according to an embodiment of the present disclosure.
Fig. 3 is a schematic structural diagram of a first pole piece and a tab according to another embodiment of the present disclosure.
Description of the main element symbols:
first pole piece 10
Diaphragm 30
Second pole piece 50
Tab 70
First current collector 101
First active material layer 102
Second active material layer 103
A first bending part 104
A second bent portion 105
First connection portion 106
Second connecting portion 107
Coated area 1011
Empty foil region 1012
The following detailed description will further describe embodiments of the present application in conjunction with the above-described figures.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiments of this application belong. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the present application.
Referring to fig. 1, the present application provides a battery cell, which is formed by sequentially stacking and winding a first pole piece 10, a separator 30 and a second pole piece 50. Referring to fig. 1 and 2, the first pole piece 10 includes a first current collector 101, and a first active material layer 102 and a second active material layer 103 coated on a surface of the first current collector 101, where the first active material layer 102 is coated on at least a surface of the first current collector 101 located at an outermost circle. The first pole piece 10 is a positive pole piece, and the second pole piece 50 is a negative pole piece. Referring to fig. 2, the surface of the first current collector 101 includes a coated region 1011 coated with an active material (the first active material layer 102 or the second active material layer 103) and a vacant foil region 1012 not coated with an active material. It is understood that the first active material layer 102 is coated on at least the surface of the first current collector 101 positioned at the outermost circle means that within the coating area 1011, the first active material layer 102 is positioned at the outermost circle of the coating area 1011 relative to the second active material layer 103. That is, the first active material layer 102 is coated on at least the coating area 1011 of the first current collector 101 located at the outermost circle. In this application, the outermost circle refers to a layer structure located on the outermost side relative to the center of the battery cell in a multilayer structure formed by winding the first pole piece 10, the diaphragm 30 and the second pole piece 50 after being stacked in a clockwise direction or a counterclockwise direction, and may be the first pole piece 10 or the second pole piece 50.
The first active material layer 102 is different from the second active material layer 103, the first active material layer 102 includes a security type material, and the second active material layer 103 includes an energy type material. The safety material is a material which can protect the battery core from smoking and firing when the battery core is damaged from outside to inside. The energy type material refers to a material which can ensure the circulation and capacity performance of the battery core. Further, the first active material layer (safety type material) includes lithium iron phosphate (LiFePO)4) Lithium manganate (LiMn)2O4) And lithium manganese iron phosphate LiFe1-yMnyPO4At least one of (1), wherein y is 0.5. ltoreq<1.0. Further, the second active material layer (energy type material) includes a nickel-cobalt-manganese ternary material LiNi1-y- zMnyCozO2And nickel cobalt aluminum ternary material LiNi1-y-zCoyAlzO2At least one of (1), wherein y is 0.5. ltoreq<1.0。
The conventional positive active material is replaced by the first active material layer 102 (the safety material) in the outermost ring, when the battery cell is damaged from outside to inside due to trauma, nail penetration, impact and the like, the whole battery cell can be protected by the safety material in the outermost ring, the effects of no smoke and no fire are achieved, and the safety performance of the battery cell is improved. A second active material layer 103 (energy type material) is used at the inner ring to increase the energy density of the cell. The first active material layer 102 provides safety protection, and the second active material layer 103 ensures the cycle and capacity performance of the cell, which can improve the performance of the cell in two aspects. In this application, the inner circle refers to the one or more layers of the stacked multilayer structure formed by winding the first pole piece 10, the diaphragm 30 and the second pole piece 50 in the clockwise direction or the counterclockwise direction, and is located at the non-outermost side with respect to the center of the battery cell.
Further, a gap is formed between the first active material layer 102 and the second active material layer 103, and the length of the gap is less than or equal to 2 mm. The gap should not be too large to prevent loss of cell energy density.
Further, the first active material layer 102 partially overlaps the second active material layer 103, and a difference between a thickness of an overlapping region (i.e., a sum of a thickness of the first active material layer 102 and a thickness of the second active material layer 103) and a thickness of the second active material layer 103 is less than or equal to 30 μm. The first active material layer 102 and the second active material layer 103 may be in direct contact without additional processing.
With reference to fig. 1, the first current collector 101 located at the outermost circle includes a first bent portion 104 and a second bent portion 105 that are disposed opposite to each other, a first connecting portion 106 connecting the first bent portion 104 and the second bent portion 105, and a second connecting portion 107 connecting the second bent portion 105 and disposed opposite to the first connecting portion 106. Preferably, the gap or the overlapping region is located at the first bending portion 104, that is, the intersection of the first active material layer 102 and the second active material layer 103 is preferably located at a corner region of the cell. Thus, the safety performance of the corner area which is easy to damage is improved, and smoking or fire is prevented.
In some embodiments, the first active material layer 102 has a thickness of 20 μm to 120 μm, and the second active material layer 103 has a thickness of 20 μm to 120 μm. Wherein, when the thickness of the first active material layer 102 is 50 μm, the thickness of the second active material layer 103 is preferably 60 μm.
Further, the thickness of the first active material layer 102 is less than or equal to the thickness of the second active material layer 103, and the difference between the thicknesses of the second active material layer 103 and the first active material layer 102 is less than 30 μm. Wherein the thickness of the first active material layer 102 is 50 μm, the thickness of the second active material layer 103 is 60 μm, and the difference in thickness is preferably 10 μm. The coating thickness of the first active material layer 102 is smaller than that of the second active material layer 103, so that the migration distance of electrons of the active material layer of the second pole piece (negative pole piece) on the first active material layer 102 with relatively large resistance is small, and the total internal resistance is reduced, so as to meet the requirement of improving the energy density of the battery cell.
Further, the mass of the first active material layer 102 is less than or equal to the mass of the second active material layer 103. The mass of the first active material layer 102 is smaller than that of the second active material layer 103, so that the migration distance of electrons of the active material layer of the second pole piece (negative pole piece) on the first active material layer 102 with relatively large resistance is small, and the total internal resistance is reduced, so as to meet the requirement of improving the energy density of the battery cell.
In some embodiments, the length of the first active material layer 102 accounts for 3% -70% of the length of the first pole piece 10 along the length direction of the first pole piece 10. The length of the first active material layer 102 is preferably 20% to 30% of the length of the first pole piece 10, and at this time, the first active material layer 102 just coats the outermost ring of the first current collector 101 (excluding the empty foil area 1012). Therefore, the safety performance of the battery cell can be ensured, and the energy density of the battery cell can be improved to the maximum extent.
Referring to fig. 2 and 3, the battery cell further includes a tab 70. Preferably, the tab 70 is disposed in the middle of the first pole piece 10 in the longitudinal direction. It is understood that, since the coating regions of the first and second active material layers 102 and 103 have various arrangements, the tab 70 may be located at an intermediate position on the current collector on which the first active material layer 102 is located, and may also be located on the current collector on which the second active material layer 103 is located. Specifically, as shown in fig. 2, the tab 70 is disposed on the first pole piece 10 region where the first active material layer 102 is located, or as shown in fig. 3, the tab 70 is disposed on the first pole piece 10 region where the second active material layer 103 is located.
The present application will be further described with reference to the following specific examples.
Example 1
Preparation of first Pole piece (Positive Pole piece)
The first active material (lithium iron phosphate, lithium manganate and LiFe)1-yMnyPO4Any one of the above materials), conductive carbon black (Super P) and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 97.5:1.0:1.5, N-methylpyrrolidone (NMP) is added as a solvent to prepare a slurry with the solid content of 0.75, and the slurry is uniformly stirred to prepare the first active material layer. Adding a second active material (LiNi)1-y-zMnyCozO2And LiNi1-y-zCoyAlzO2Any one of the above, conductive carbon black (Super P), and polyvinylidene fluoride (PVDF) were mixed at a mass ratio of 97.5:1.0:1.5, N-methylpyrrolidone (NMP) was added as a solvent, and a slurry having a solid content of 0.75 was prepared and stirred uniformly to obtain a second active material layer. And respectively coating a first active material layer and a second active material layer on the surface of a first current collector (aluminum foil), wherein the length of the first active material layer accounts for 25% of the length of the first pole piece, the coating thickness of one side of the first active material layer is 50 microns, the coating thickness of one side of the second active material layer is 60 microns, and the coating quality of the first active material layer is smaller than that of the second active material layer. And drying at 90 ℃ to obtain the first positive plate.
Preparation of the second Pole piece (negative Pole piece)
Mixing Graphite (Graphite) serving as a negative active material, conductive carbon black (Super P) and Styrene Butadiene Rubber (SBR) according to a weight ratio of 96:1.5:2.5, adding deionized water serving as a solvent, blending to obtain slurry with the solid content of 0.7, and uniformly stirring to obtain the negative slurry. And uniformly coating the negative electrode slurry on the surface of a second current collector (copper foil), and drying at 110 ℃ to obtain the negative electrode plate.
Preparation of the Battery
And selecting a polyethylene PE isolating film as a diaphragm, placing the diaphragm between the first pole piece and the second pole piece, winding, placing the diaphragm into an aluminum-plastic film, and performing top side sealing, liquid injection and packaging to finally obtain the lithium ion battery. Wherein the first active material layer is located at the outermost turn, which refers to the outermost turn of the void foil area from which the ending is removed.
Example 2
The difference from example 1 is that: the length of the first active material layer accounts for 3% of the length of the first pole piece, the coating thickness of one side of the first active material layer is 100 micrometers, and the coating thickness of one side of the second active material layer is 105 micrometers. The rest is the same as the embodiment 1, and the description is omitted.
Example 3
The difference from example 1 is that: the length of the first active material layer accounts for 70% of the length of the first pole piece, the coating thickness of the single surface of the first active material layer is 20 microns, and the coating thickness of the single surface of the second active material layer is 120 microns. The rest is the same as the embodiment 1, and the description is omitted.
Comparative example 1
The difference from example 1 is that: the first current collector (aluminum foil) is surface-coated with the first active material layer and is not coated with the second active material layer. The rest is the same as the embodiment 1, and the description is omitted.
Comparative example 2
The difference from example 1 is that: the surface of the first current collector (aluminum foil) is coated with the second active material layer, and the first active material layer is not coated. The rest is the same as the embodiment 1, and the description is omitted.
The batteries manufactured in the above examples and comparative examples were subjected to an energy density test and a needle punching test, respectively.
In the field of battery technology, the energy density is the cell capacity and the platform voltage/cell volume. The battery cell capacity refers to the capacity of 0.2C when constant current charging is carried out to cut-off voltage and then constant voltage charging is carried out to cut-off current of 0.02C, and C is charging multiplying power; the volume of the cell is equal to the length, width and thickness of the cell; under certain charge-discharge system conditions (such as 0.2C), the plateau voltage is represented by dQ/dV (the ratio of the measured two capacity differences before and after the measurement to the corresponding voltage difference, i.e., (Q2-Q1)/(V2-V1)) according to the charge-discharge curve, and the place where the plateau occurs can be regarded as the plateau voltage. The test results are: the energy density measured in comparative example 2 was the largest and slightly greater than the energy densities in examples 1, 2 and 3, the energy densities measured in the 3 examples did not differ much and the energy density measured in comparative example 1 was the smallest.
The needle punching test is to pierce the fully charged battery with a 5mm diameter steel needle at a fixed position, generally fixed at the left, center and right sides of the battery, with a needle speed of 30mm/s, and the nail left in the battery. If the judgment standard is that the battery does not smoke or fire, the battery passes the test. The test results are shown in Table 1. As can be seen from Table 1: all of the 10 cells in example 1 passed, all of the 10 cells in example 2 passed 9, all of the 10 cells in example 3 passed 9, all of the 10 cells in comparative example 1 passed, and all of the 10 cells in comparative example 2 failed.
TABLE 1
Figure BDA0002989508630000091
Figure BDA0002989508630000101
The application provides an electric core, the outer lane chooses for use the first active material layer of energy type in order to play the effect of protection electric core safety, and the inner circle chooses for use the second active material layer of safe type in order to improve the energy density of electric core, has balanced the security performance and the capacity demand of electric core.

Claims (10)

1. A battery cell is formed by sequentially overlapping and winding a first pole piece, a diaphragm and a second pole piece, and is characterized in that the first pole piece comprises a first current collector, a first active material layer and a second active material layer, wherein the first active material layer and the second active material layer are coated on the same side surface of the first current collector, and the first active material layer is at least coated on the surface of the first current collector positioned at the outermost ring; the first current collector at the outermost ring comprises a first bent part and a second bent part which are oppositely arranged, a first connecting part connected with the first bent part and the second bent part, and a second connecting part connected with the second bent part and oppositely arranged with the first connecting part;
the first active material layer comprises lithium iron phosphate, lithium manganate and LiFe1-yMnyPO4At least one of (1), wherein y is 0.5. ltoreq<1.0；
The second active material layerComprising LiNi1-y-zMnyCozO2And LiNi1-y-zCoyAlzO2At least one of (1), wherein y is 0.5. ltoreq<1.0。
2. The electrical core of claim 1, wherein the first active material layer and the second active material layer have a gap therebetween, and wherein the gap has a length of less than or equal to 2 mm.
3. The cell of claim 2, wherein the gap is located at the first bend.
4. The electrical core of claim 1, wherein the first active material layer partially overlaps the second active material layer, and a difference between a thickness of the overlapping region and a thickness of the second active material layer is less than or equal to 30 μ ι η.
5. The cell of claim 4, wherein the overlap region is located at the first bend.
6. The battery cell of claim 1, wherein, along a length direction of the first pole piece, a proportion of a length of the first active material layer in the length of the first pole piece is 3% to 70%.
7. The electrical core of claim 1, wherein the first active material layer has a thickness of 20 μ ι η to 120 μ ι η and the second active material layer has a thickness of 20 μ ι η to 120 μ ι η.
8. The electrical core of claim 1, wherein a thickness of the first active material layer is less than or equal to a thickness of the second active material layer, and a difference in the thickness of the second active material layer from the first active material layer is less than 30 μ ι η.
9. The electrical core of claim 1, wherein a mass of the first active material layer is less than or equal to a mass of the second active material layer.
10. The battery cell of claim 1, further comprising a tab disposed in a middle of the first pole piece in a length direction, wherein the tab is disposed in a first pole piece region where the first active material layer is located, or wherein the tab is disposed in a first pole piece region where the second active material layer is located.
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