CN116250106A - Electrochemical device and electronic device - Google Patents
Electrochemical device and electronic device Download PDFInfo
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- CN116250106A CN116250106A CN202280006591.6A CN202280006591A CN116250106A CN 116250106 A CN116250106 A CN 116250106A CN 202280006591 A CN202280006591 A CN 202280006591A CN 116250106 A CN116250106 A CN 116250106A
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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
- H01M10/05—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
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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
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- H—ELECTRICITY
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
An electrochemical device is provided, which comprises an electrode assembly, wherein the electrode assembly comprises an electrode pole piece, the electrode pole piece comprises a blank current collector and a composite layer arranged on the blank current collector, the composite layer comprises an insulating layer and a functional layer, the functional layer is positioned between the blank current collector and the insulating layer, the thickness of the functional layer is H1 mu m, and the thickness of the insulating layer is H2 mu m, and H1/H2 is less than or equal to 1 and less than or equal to 20. The electrochemical device has good appearance, high liquid retention and high safety. The present application also provides an electronic device including an electrochemical device.
Description
Technical Field
The present application relates to the field of energy storage, and in particular, to an electrochemical device and an electronic device.
Background
Secondary batteries (electrochemical devices) are increasingly used in a wide range of applications, and have been closely related to people's daily lives. With the rapid development of intelligent electronic products, various properties (e.g., energy density, cycle life, and safety) of secondary batteries are increasingly demanded. Currently, in order to improve the energy density of a secondary battery, the compacted density of positive and negative electrode plates is continuously improved, the electrolyte is absorbed by positive and negative electrode active substances less and less due to the high compacted density, and the unabsorbed electrolyte is free on the inner surface of a packaging bag (such as an aluminum plastic film), so that the uneven packaging bag of the secondary battery, the liquid rising in appearance and the energy density of the secondary battery are easily caused. In addition, improvement in safety performance of secondary batteries is demanded. Therefore, it is highly demanded to provide a technical means capable of remarkably improving the flatness of the external appearance, the liquid retention amount and the safety performance of the secondary battery.
Disclosure of Invention
In view of the shortcomings of the prior art, the present application provides an electrochemical device and an electronic device including the same. The electrochemical device has good appearance, high liquid retention and high safety.
In a first aspect, the present application provides an electrochemical device comprising an electrode assembly, the electrode assembly comprising an electrode sheet comprising a blank current collector and a composite layer disposed on the blank current collector, the composite layer comprising an insulating layer and a functional layer, wherein the functional layer is located between the blank current collector and the insulating layer, the functional layer has a thickness of H1 μm, and the insulating layer has a thickness of H2 μm, 1.ltoreq.H2.ltoreq.H2.ltoreq.20. The inventor of the application researches and discovers that through arranging an insulating layer and a functional layer capable of absorbing electrolyte in a current collector area where an active material is not arranged on a pole piece, namely a blank current collector, on one hand, the functional layer can improve the liquid retention capacity of an electrochemical device and simultaneously prevent uneven surface of the electrochemical device caused by uneven free electrolyte in a packaging bag (such as an aluminum plastic film) so as to improve the appearance flatness of the electrochemical device and reduce the energy density loss of the electrochemical device. On the other hand, the insulating layer can avoid the failure caused by internal short circuit generated when the electrochemical device is pierced by external force, and further the safety performance of the electrochemical device in piercing test is effectively improved. When the ratio of the thicknesses of the functional layer and the insulating layer is within the above range, the electrochemical device can have the lowest energy density loss on the premise of satisfying high liquid retention and safety performance.
According to some embodiments of the present application, 2.ltoreq.H2.ltoreq.H2.ltoreq.10.
According to some embodiments of the present application, 1.ltoreq.H1.ltoreq.20. In some embodiments, the functional layer is for absorbing an electrolyte. The functional layer is mainly used for absorbing electrolyte, and when the thickness of the functional layer is too low, the electrolyte retention rate of the functional layer is low, so that the appearance of the electrochemical device is not improved. When the thickness of the functional layer is too high, the energy density of the electrochemical device may be reduced.
According to some embodiments of the present application, 1.ltoreq.H2.ltoreq.10. The insulating layer can avoid failure caused by internal short circuit generated when the electrochemical device is pierced by external force, and the safety performance of the electrochemical device is improved. However, when the thickness of the insulating layer is too high, the energy density of the electrochemical device is also reduced.
According to some embodiments of the present application, the bond strength between the functional layer and the blank current collector is greater than the bond strength between the insulating layer and the functional layer. The adhesive strength of the insulating layer is too high, so that adhesive rollers are easy to generate in the preparation process, and the processing is not facilitated.
According to some embodiments of the present application, the electrode assembly is a rolled electrode assembly, wherein the composite layer is disposed on a blank current collector at the rolled end of the electrode sheet.
According to some embodiments of the present application, the coverage of the composite layer at the wound end of the electrode sheet is 80% to 100% of the blank current collector.
According to some embodiments of the present application, the projected area of the insulating layer in the thickness direction of the electrode tab is equal to or larger than the projected area of the functional layer in the thickness direction of the electrode tab.
According to some embodiments of the application, a nondestructive ultrasonic intelligent diagnosis system is used for testing, ultrasonic waves are emitted to the electrochemical device along the thickness direction of the electrochemical device, a signal feedback distribution diagram of the electrochemical device on the ultrasonic waves is obtained, and the area ratio of an area with the ultrasonic signal intensity of more than or equal to 1333mV is 30-95% based on the area of the electrochemical device in the signal feedback distribution diagram. The ultrasonic wave is a mechanical wave which needs to be transmitted by means of a medium, when electrolyte is not soaked between electrode materials, the ultrasonic wave can be transmitted only by means of direct contact among electrode material particles, the ultrasonic wave is reflected and refracted in a large quantity due to irregular particles, the signal intensity is seriously attenuated, and when the electrolyte can completely soak the electrode materials, a good transmission way is provided for the ultrasonic wave by the liquid environment, and a considerable part of the ultrasonic wave is not interfered by the particles, so that the signal intensity is ensured. Therefore, in the nondestructive ultrasonic intelligent diagnosis system test, the distribution and infiltration conditions of electrolyte in the electrochemical device can be well represented by the signal feedback intensity of each position of the electrochemical device on ultrasonic waves, and the higher the area ratio of high signal intensity is, the more uniform the electrolyte is distributed in the electrochemical device.
According to some embodiments of the present application, the functional layer has a swelling degree of 200% to 800%. When the swelling degree of the functional layer is less than 200%, the electrolyte retention rate of the functional layer is low, which is unfavorable for the improvement of the appearance of the electrochemical device. When the swelling degree of the functional layer is more than 800%, the stability of the functional layer itself is poor, and the stripping easily occurs during the cycle to affect the performance of the electrochemical device. In some embodiments, the functional layer has a swelling degree of 300% to 600%.
According to some embodiments of the present application, using fourier infrared testing, the functional layer comprises a substance having a spectrum with absorption peaks in at least one of the following ranges: 2700cm -1 To 3100cm -1 、1600cm -1 To 1800cm -1 、1100cm -1 To 1200cm -1 。
According to some embodiments of the present application, the functional layer comprises a polymer formed from at least one of an acrylic monomer, a styrenic monomer.
According to some embodiments of the present application, the insulating layer includes a binder and inorganic particles.
According to some embodiments of the present application, the content of the binder is 3% to 20% based on the mass of the insulating layer. The content of the binder is within the above range, so that the function layer can be ensured to promote the liquid retention function in the electrochemical device, and the binding force of the function layer can be ensured.
According to some embodiments of the present application, the binder comprises at least one of an acrylate, an acrylate copolymer, acrylonitrile, an acrylate copolymer, acrylic acid, an acrylate, a carboxymethyl cellulose salt, a nitrile rubber, polyvinylidene fluoride, or polytetrafluoroethylene.
According to some embodiments of the present application, the inorganic particles comprise at least one of boehmite, diaspore, alumina, barium sulfate, calcium sulfate, or calcium silicate.
According to some embodiments of the present application, the inorganic particles have a Dv90 of D1 μm, wherein D1.ltoreq.H2.ltoreq.10. The thickness of the functional layer can be controlled by controlling the size of the Dv90 particles, and the thickness of the functional layer is enabled to be smaller on the premise of ensuring the liquid retention amount of the functional layer, so that the energy density loss of the electrochemical device is reduced.
According to some embodiments of the present application, the adhesion between the composite layer and the blank current collector is greater than or equal to 100N/m.
According to some embodiments of the present application, the electrolyte retention of the composite layer is 40% to 120%.
According to some embodiments of the present application, the flatness of the electrochemical device is 0 to 0.50mm.
In a second aspect, the present application provides an electronic device comprising the electrochemical device of the first aspect.
According to the electrochemical device, the insulating layer and the functional layer capable of absorbing electrolyte are arranged in the current collector area where the active material is not arranged on the pole piece, on one hand, the functional layer can improve the liquid retention capacity of the electrochemical device and simultaneously prevent uneven surface of the electrochemical device caused by uneven free electrolyte in the packaging bag (such as an aluminum plastic film), so that the appearance flatness of the electrochemical device is improved, and the energy density loss of the electrochemical device is reduced. On the other hand, the insulating layer can avoid the failure caused by internal short circuit generated when the electrochemical device is pierced by external force, and further effectively improve the safety performance of the electrochemical device in piercing test.
Drawings
FIG. 1 is a schematic illustration of an electrode pad in an electrochemical device according to some embodiments of the present application, wherein 1-current collectors; 2-an active material layer; 3-a functional layer; 4-insulating layer.
Detailed Description
The present application is further described below in conjunction with the detailed description. It should be understood that these specific embodiments are presented by way of example only and are not intended to limit the scope of the present application.
1. Electrochemical device
The application provides an electrochemical device, which comprises an electrode assembly, wherein the electrode assembly comprises an electrode pole piece, the electrode pole piece comprises a blank current collector and a composite layer arranged on the blank current collector, the composite layer comprises an insulating layer and a functional layer, wherein the functional layer is positioned between the blank current collector and the insulating layer, the thickness of the functional layer is H1 mu m, the thickness of the insulating layer is H2 mu m, and the thickness of the insulating layer is 1 & ltoreq, H1/H2 & ltoreq, 20. The inventor of the application researches and discovers that by arranging an insulating layer and a functional layer capable of absorbing electrolyte in a current collector area where an active material is not arranged on a pole piece, on one hand, the functional layer can improve the liquid retention capacity of an electrochemical device, and meanwhile, prevent uneven surface of the electrochemical device caused by uneven free of surplus electrolyte in a packaging bag (such as an aluminum plastic film) so as to improve the appearance flatness of the electrochemical device and reduce the energy density loss of the electrochemical device. On the other hand, the insulating layer can avoid the failure caused by internal short circuit generated when the electrochemical device is pierced by external force, and further effectively improve the safety performance of the electrochemical device in piercing test.
According to some embodiments of the present application, H1/H2 is 1.5, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 11, 12, 13, 14, 15, 16, 17, 18, 19 or a range of any two of these values. When the ratio of the thicknesses of the functional layer and the insulating layer is within the above range, the electrochemical device can have the lowest energy density loss on the premise of satisfying high liquid retention and safety performance. In some embodiments, 2.ltoreq.H2.ltoreq.H2.ltoreq.10.
According to some embodiments of the present application, 1.ltoreq.H1.ltoreq.20. In some embodiments, H1 is 1.5, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 11, 12, 13, 14, 15, 16, 17, 18, 19, or a range of any two of these values. In some embodiments, the functional layer is for absorbing an electrolyte. The functional layer is mainly used for absorbing electrolyte, and when the thickness of the functional layer is too low, the electrolyte retention rate of the functional layer is low, so that the appearance of the electrochemical device is not improved. When the thickness of the functional layer is too high, the energy density of the electrochemical device may be reduced.
According to some embodiments of the present application, 1.ltoreq.H2.ltoreq.10. In some embodiments, H2 is 1.5, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, or a range of any two of these values. The insulating layer can avoid failure caused by internal short circuit generated when the electrochemical device is pierced by external force, and the safety performance of the electrochemical device is improved. However, when the thickness of the insulating layer is too high, the energy density of the electrochemical device is lowered.
According to some embodiments of the present application, the bond strength between the functional layer and the blank current collector is greater than the bond strength between the insulating layer and the functional layer. The adhesive strength of the insulating layer is too high, so that adhesive rollers are easy to generate in the preparation process, and the processing is not facilitated.
According to some embodiments of the present application, the electrode assembly is a rolled electrode assembly, wherein the composite layer is disposed on a blank current collector at the rolled end of the electrode sheet.
According to some embodiments of the present application, the coverage of the composite layer at the wound end of the electrode sheet is 80% to 100% of the blank current collector. In some embodiments, the coverage is 85%, 90%, or 95%. When the coverage is within the above range, the safety of the electrochemical device can be improved and a larger amount of liquid retention can be improved.
In the present application, the coverage of the blank current collector at the winding end of the composite layer indicates the coverage degree of the composite layer to the blank current collector surface, and is determined by the following manner: and (3) removing the pole piece coated with the composite layer from the electrochemical device in the environment of (25+/-3) DEG C. And (3) drying in an oven at 85 ℃, and respectively measuring the area W3 of the composite layer and the total area W2 of the blank current collector at the winding end of the pole piece, wherein the coverage rate of the composite layer on the blank current collector at the winding end of the electrode pole piece is W3/W2 multiplied by 100%.
According to some embodiments of the present application, the projected area of the insulating layer in the thickness direction of the electrode tab is equal to or larger than the projected area of the functional layer in the thickness direction of the electrode tab.
According to some embodiments of the application, a nondestructive ultrasonic intelligent diagnosis system is used for testing, ultrasonic waves are emitted to the electrochemical device along the thickness direction of the electrochemical device, a signal feedback distribution diagram of the electrochemical device on the ultrasonic waves is obtained, and the area ratio of an area with the ultrasonic signal intensity of more than or equal to 1333mV is 30-95% based on the area of the electrochemical device in the signal feedback distribution diagram. The ultrasonic wave is a mechanical wave which needs to be transmitted by means of a medium, when electrolyte is not soaked between electrode materials, the ultrasonic wave can be transmitted only by means of direct contact among electrode material particles, the ultrasonic wave is reflected and refracted in a large quantity due to irregular particles, the signal intensity is seriously attenuated, and when the electrolyte can completely soak the electrode materials, a good transmission way is provided for the ultrasonic wave by the liquid environment, and a considerable part of the ultrasonic wave is not interfered by the particles, so that the signal intensity is ensured. Therefore, in the nondestructive ultrasonic intelligent diagnosis system test, the distribution and infiltration conditions of electrolyte in the electrochemical device can be well represented by the signal feedback intensity of each position of the electrochemical device on ultrasonic waves, and the higher the area ratio of high signal intensity is, the more uniform the electrolyte is distributed in the electrochemical device.
According to some embodiments of the present application, the area ratio of the region having a signal strength greater than or equal to 1333mV is 35%, 38%, 40%, 45%, 47%, 50%, 53%, 55%, 57%, 60%, 63%, 65%, 67%, 70%, 73%, 75%, 77%, 80%, 83%, 85%, 87%, 90%, 92%, 94% or a range consisting of any two of these values. In some embodiments, the area ratio of the region having a signal strength greater than or equal to 1333mV is 50% to 95%.
According to some embodiments of the present application, the functional layer has a swelling degree of 200% to 800%. In some embodiments, the functional layer has a swelling degree of 220%, 250%, 270%, 320%, 350%, 370%, 390%, 400%, 420%, 450%, 470%, 500%, 520%, 540%, 570%, 600%, 620%, 650%, 670%, 700%, 720%, 750%, 770%, or a range of any two of these values. When the swelling degree of the functional layer is less than 200%, the electrolyte retention rate of the functional layer is low, which is unfavorable for the improvement of the appearance of the electrochemical device. When the swelling degree of the functional layer is more than 800%, the stability of the functional layer itself is poor, and the stripping easily occurs during the cycle to affect the performance of the electrochemical device. In some embodiments, the functional layer has a swelling degree of 300% to 600%.
According to some embodiments of the present application, using fourier infrared testing, the functional layer comprises a substance having a spectrum with absorption peaks in at least one of the following ranges: 2700cm -1 To 3100cm -1 、1600cm -1 To 1800cm -1 、1100cm -1 To 1200cm -1 。
In the present application, in the Fourier infrared test spectrogram, at 2700cm -1 To 3100cm -1 、1600cm -1 To 1800cm -1 And 1100cm -1 To 1200cm -1 Absorption peaks in the range represent vibrations of the ester group. The functional layer contains ester groups, so that the swelling property of the functional layer can be provided, and the high swelling property can absorb more electrolyte, so that the liquid retention rate is improved.
According to some embodiments of the present application, the functional layer comprises a polymer formed from at least one of an acrylic monomer, a styrenic monomer.
In some embodiments, the acrylic monomer comprises at least one of the compounds of formula I,
wherein R is 1 Selected from hydrogen or C 1 -C 10 Alkyl, halogen substituted C 1 -C 10 An alkyl group. According to some embodiments of the application, R 1 Selected from C 1 -C 6 Alkyl, halogen substituted C 1 -C 6 An alkyl group. In some embodiments of the present application, R 1 Selected from methyl, ethyl, fluoroethyl, propyl, fluoropropyl, butyl, fluorobutyl, pentyl or fluoropentyl.
In some embodiments, the acrylic monomer includes at least one of acrylic acid, methacrylic acid, ethacrylic acid.
In some embodiments, the acrylate monomer comprises at least one of the compounds of formula II,
wherein R is 2 Selected from hydrogen, C 1 -C 10 Alkyl-or halogen-substituted C 1 -C 10 An alkyl group; r is R 3 Selected from C 1 -C 10 Alkyl, halogen substituted C 1 -C 10 An alkyl group. According to some embodiments of the application, R 2 Selected from hydrogen, C 1 -C 6 Alkyl-or halogen-substituted C 1 -C 6 An alkyl group; r is R 3 Selected from C 1 -C 6 Alkyl, halogen substituted C 1 -C 6 An alkyl group. In some embodiments of the present application, R 2 Selected from hydrogen, methyl, ethyl or propyl; r is R 3 Selected from methyl, ethyl, fluoroethyl, propyl, fluoropropyl, butyl, fluorobutyl, pentyl or fluoropentyl.
In some embodiments, the acrylic monomer includes at least one of methyl acrylate, methyl methacrylate, methyl ethacrylate, ethyl acrylate, ethyl methacrylate, ethyl ethacrylate, propyl acrylate, propyl methacrylate, propyl ethacrylate, butyl acrylate, butyl methacrylate, butyl ethacrylate, pentyl methacrylate, or pentyl acrylate.
According to some embodiments of the present application, the styrenic monomer comprises at least one of the compounds of formula III,
wherein n is an integer from 1 to 5, such as 2, 3 or 4; each R 4 The same or different are independently selected from hydrogen, C 1 -C 10 Alkyl-or halogen-substituted C 1 -C 10 An alkyl group; r is R 5 And R is 6 The same or different are independently selected from hydrogen, C 1 -C 10 Alkyl-or halogen-substituted C 1 -C 10 An alkyl group. According to some embodiments of the application, R 4 Selected from hydrogen, C 1 -C 6 Alkyl-or halogen-substituted C 1 -C 6 An alkyl group; r is R 5 And R is 6 The same or different, independently selected C 1 -C 16 Alkyl-or halogen-substituted C 1 -C 6 An alkyl group. In some embodiments of the present application, R 4 、R 5 And R is 6 Independently selected from hydrogen, methyl, ethyl or propyl.
In some embodiments, the styrenic monomer comprises at least one of styrene, methyl styrene, 2-methyl styrene, 2, 4-dimethyl styrene.
According to some embodiments of the present application, the functional layer forming raw material includes at least one of a pure acrylic emulsion, a styrene acrylic emulsion, or an acrylate emulsion. In some embodiments, the functional layer comprises at least one of a pure acrylic emulsion, a styrene acrylic emulsion, or an acrylate emulsion.
According to some embodiments of the present application, the functional layer comprises a pure acrylic emulsion, a styrene acrylic emulsion, and an acrylate emulsion. In some embodiments, the functional layer-forming materials include pure acrylic emulsion, styrene acrylic emulsion, and acrylate emulsion. In some embodiments, the mass content of the pure acrylic emulsion is 40% to 95%, the mass content of the styrene acrylic emulsion is 5% to 50%, and the mass content of the acrylate emulsion is 1% to 15% based on the total mass of the pure acrylic emulsion, the styrene acrylic emulsion, and the acrylate emulsion.
According to some embodiments of the present application, the functional layer comprises a pure acrylic emulsion and an acrylate emulsion. In some embodiments, the functional layer forming materials include pure acrylic emulsions and acrylate emulsions. In some embodiments, the mass content of the pure acrylic emulsion is from 70% to 95% and the mass content of the acrylate emulsion is from 5% to 30% based on the total mass of the pure acrylic emulsion and the acrylate emulsion.
According to some embodiments of the present application, the functional layer comprises a pure acrylic emulsion and a styrene acrylic emulsion. In some embodiments, the functional layer-forming materials include pure acrylic emulsion and styrene acrylic emulsion. In some embodiments, the mass content of the pure acrylic emulsion is 70% to 95% and the mass content of the styrene acrylic emulsion is 5% to 30% based on the total mass of the pure acrylic emulsion and the styrene acrylic emulsion.
According to some embodiments of the present application, the functional layer includes a styrene-acrylic emulsion and an acrylate emulsion. In some embodiments, the functional layer-forming materials include styrene-acrylic emulsion and acrylate emulsion. In some embodiments, the mass content of the styrene-acrylic emulsion is 70% to 95% and the mass content of the acrylate emulsion is 5% to 30% based on the total mass of the styrene-acrylic emulsion and the acrylate emulsion.
According to some embodiments of the present application, the insulating layer includes a binder and inorganic particles.
According to some embodiments of the present application, the content of the binder is 3% to 20% based on the mass of the insulating layer. In some embodiments, the binder content is 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or a range consisting of any two of these values. The content of the binder is within the above range, so that the function layer can be ensured to promote the liquid retention function in the electrochemical device, and the binding force of the function layer can be ensured.
According to some embodiments of the present application, the binder comprises at least one of an acrylate, an acrylate copolymer, acrylonitrile, an acrylate copolymer, acrylic acid, an acrylate, a carboxymethyl cellulose salt, a nitrile rubber, polyvinylidene fluoride, or polytetrafluoroethylene.
According to some embodiments of the present application, the inorganic particles comprise at least one of boehmite, diaspore, alumina, barium sulfate, calcium sulfate, or calcium silicate.
According to some embodiments of the present application, the inorganic particles have a Dv90 of D1 μm, wherein D1.ltoreq.H2.ltoreq.10. The thickness of the functional layer can be controlled by controlling the size of the Dv90 particles, and the thickness of the functional layer is enabled to be smaller on the premise of ensuring the liquid retention amount of the functional layer, so that the energy density loss of the electrochemical device is reduced.
In the present application, dv90 means that the inorganic particles have a particle size distribution of 90% of the particles having a particle size smaller than this value.
According to some embodiments of the present application, the adhesion between the composite layer and the blank current collector is greater than or equal to 100N/m. In some embodiments, the adhesion between the composite layer and the blank current collector is 100N/m to 300N/m, such as 120N/m, 150N/m, 170N/m, 200N/m, 220N/m, 250N/m, or 270N/m.
According to some embodiments of the present application, the electrolyte retention of the composite layer is 40% to 120%. In some embodiments, the functional layer has an electrolyte retention of 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, 105%, 110%, 115%, or a range of any two of these values. Under the condition that the appearance of the electrochemical device meets the requirement, the electrolyte retention rate is improved, and the later-stage circulation stability of the electrochemical device is improved.
According to some embodiments of the present application, the flatness of the electrochemical device is 0 to 0.50mm.
According to some embodiments of the present application, the electrode tab further includes an active material layer that is a positive electrode active material layer and/or a negative electrode active material layer.
According to some embodiments of the present application, the positive electrode active material layer includes a positive electrode active material, a binder, and a conductive agent. In some embodiments, the positive electrode active material may include at least one of lithium cobaltate, lithium nickel manganese aluminate, lithium iron phosphate, lithium vanadium phosphate, lithium cobalt phosphate, lithium manganese phosphate, lithium iron silicate, lithium vanadium silicate, lithium cobalt silicate, lithium manganese silicate, spinel type lithium manganate, spinel type lithium nickel manganate, and lithium titanate. In some embodiments, the binder may include various binder polymers, such as at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyolefins, sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, modified polyvinylidene fluoride, modified SBR rubber, or polyurethane. In some embodiments, any conductive material may be used as the conductive agent as long as it does not cause a chemical change. Examples of the conductive agent include: carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, and the like; metal-based materials such as metal powders or metal fibers including copper, nickel, aluminum, silver, and the like; conductive polymers such as polyphenylene derivatives and the like; or mixtures thereof.
According to some embodiments of the present application, the anode active material layer includes an anode active material, a binder, and a conductive agent. In some embodiments, the anode active material may include a material that reversibly intercalates/deintercalates lithium ions or sodium ions, lithium metal alloy, or transition metal oxide. In some embodiments, the negative electrode active material includes at least one of a carbon material including at least one of graphite, hard carbon, or a silicon material including at least one of silicon, a silicon oxygen compound, a silicon carbon compound, or a silicon alloy. In some embodiments, the binder includes at least one of styrene-butadiene rubber, polyacrylic acid, polyacrylate, polyimide, polyamideimide, polyvinylidene fluoride, polytetrafluoroethylene, aqueous acrylic resin, polyvinyl formal, or styrene-acrylic copolymer resin. In some embodiments, any conductive material may be used as the conductive material as long as it does not cause chemical changes. In some embodiments, the conductive material comprises at least one of conductive carbon black, acetylene black, carbon nanotubes, ketjen black, conductive graphite, or graphene.
According to some embodiments of the present application, the electrode tab includes a current collector, and the blank current collector is a region on the current collector where the active material layer is not disposed. In some embodiments, the current collector is a positive electrode current collector and/or a negative electrode current collector. In some embodiments, the positive current collector may employ a metal foil or a composite current collector. For example, aluminum foil may be used. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, or the like) on a polymer substrate. In some embodiments, the negative electrode current collector may be copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, or a combination thereof.
The electrochemical device of the present application further includes a separator, and the material and shape of the separator used in the electrochemical device of the present application are not particularly limited, and may be any of the techniques disclosed in the prior art. In some embodiments, the separator comprises a polymer or inorganic, etc., formed from a material that is stable to the electrolyte of the present application. For example, the release film may include a substrate layer and a surface treatment layer. The substrate layer is a non-woven fabric, a film or a composite film with a porous structure, and the material of the substrate layer is at least one selected from polyethylene, polypropylene, polyethylene terephthalate and polyimide. Specifically, a polypropylene porous membrane, a polyethylene porous membrane, a polypropylene nonwoven fabric, a polyethylene nonwoven fabric or a polypropylene-polyethylene-polypropylene porous composite membrane can be selected.
The surface treatment layer is provided on at least one surface of the base material layer, and the surface treatment layer may be a polymer layer or an inorganic layer, or may be a layer formed by mixing a polymer and an inorganic substance.
The inorganic layer includes inorganic particles and a binder, the inorganic particles being at least one selected from the group consisting of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium oxide, tin oxide, cerium oxide, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and barium sulfate. The binder is at least one selected from polyvinylidene fluoride, copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyethylene alkoxy, polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene.
The polymer layer contains a polymer, and the material of the polymer is at least one selected from polyamide, polyacrylonitrile, acrylic polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl alkoxy, polyvinylidene fluoride and poly (vinylidene fluoride-hexafluoropropylene).
The electrochemical device of the present application further comprises an electrolyte. The electrolytes useful in the present application may be electrolytes known in the art.
In some embodiments, the electrolyte includes an organic solvent, a lithium salt, and optional additives. The organic solvent of the electrolyte according to the present application may be any organic solvent known in the art as a solvent of the electrolyte. The electrolyte used in the electrolyte according to the present application is not limited, and may be any electrolyte known in the art. The additive of the electrolyte according to the present application may be any additive known in the art as an electrolyte additive. In some embodiments, the organic solvent includes, but is not limited to: ethylene Carbonate (EC), propylene Carbonate (PC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), dimethyl carbonate (DMC), propylene carbonate or ethyl propionate. In some embodiments, the organic solvent comprises an ether-type solvent, for example, comprising at least one of 1, 3-Dioxapentacyclic (DOL) and ethylene glycol dimethyl ether (DME). In some embodiments, the lithium salt includes at least one of an organic lithium salt or an inorganic lithium salt. In some embodiments, lithium salts include, but are not limited to: lithium hexafluorophosphate (LiPF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium difluorophosphate (LiPO) 2 F 2 ) Lithium bis (trifluoromethanesulfonyl) imide LiN (CF) 3 SO 2 ) 2 (LiTFSI), lithium bis (fluorosulfonyl) imide Li (N (SO) 2 F) 2 ) (LiLSI), lithium bisoxalato borate LiB (C) 2 O 4 ) 2 (LiBOB) or lithium difluorooxalato borate LiBF 2 (C 2 O 4 )(LiDFOB)。
In some embodiments, the electrochemical devices of the present application include, but are not limited to: primary batteries, secondary batteries, or capacitors of all kinds. In some embodiments, the electrochemical device is a secondary battery. In some embodiments, secondary batteries include, but are not limited to: lithium metal secondary batteries, lithium ion secondary batteries, sodium ion secondary batteries, lithium polymer secondary batteries or lithium ion polymer secondary batteries.
2. Electronic device
The present application further provides an electronic device comprising the electrochemical device of the first aspect of the present application.
The electronic apparatus or device of the present application is not particularly limited. In some embodiments, the electronic devices of the present application include, but are not limited to, notebook computers, pen-input computers, mobile computers, electronic book players, cellular telephones, portable fax machines, portable copiers, portable printers, headsets, video recorders, liquid crystal televisions, hand-held cleaners, portable CD players, mini-compact discs, transceivers, electronic notepads, calculators, memory cards, portable audio recorders, radios, backup power supplies, motors, automobiles, motorcycles, mopeds, bicycles, lighting fixtures, toys, gaming machines, watches, power tools, flashlights, cameras, home-use large storage batteries, lithium ion capacitors, and the like.
In the following examples and comparative examples, reagents, materials and instruments used, unless otherwise specified, were commercially available.
Examples and comparative examples
Preparing functional layer slurry: the binder (specific composition is shown in the following table) and the solvent were mixed uniformly to prepare a slurry, which was designated as slurry a. The slurry needs to be controlled: viscosity of 200-3000 mPa.S and solid content of 35% -50%. Wherein the solvent is selected according to the kind of the binder. When the binder is aqueous, an aqueous solvent (e.g., deionized water, etc.) may be selected; when the binder is oily, an oily solvent (e.g., N-methylpyrrolidone, etc.) may be selected.
Preparing insulating layer slurry: the binder, inorganic particles (specific composition see table below) and solvent were mixed uniformly to prepare a slurry, designated as slurry B. The slurry has the parameters of viscosity of 200-800 mPa.S and solid content of 20% -30%. Wherein the solvent is selected according to the kind of the binder. When the binder is aqueous, an aqueous solvent (e.g., deionized water, etc.) may be selected; when the binder is oily, an oily solvent (e.g., N-methylpyrrolidone, etc.) may be selected.
Preparing an electrode plate: and setting the slurry A in a target area, and drying the solvent to obtain the functional layer. And setting the slurry B in the same target area, completely covering the functional layer, and drying to obtain the composite layer. Setting slurry containing active material in the area without composite layer, stoving and rolling to obtain electrode sheet
Wherein the slurry containing the active material is a positive electrode active material slurry or a negative electrode active material slurry. Specifically, the positive electrode active material slurry is: mixing lithium cobaltate, conductive carbon and polyvinylidene fluoride according to a mass ratio of 96:2:2, and adding a solvent N-methyl-2-pyrrolidone (NMP) to prepare slurry. The anode active material slurry was: graphite, polymethacrylic acid and styrene-butadiene rubber are mixed according to the mass ratio of 98:1:1, and deionized water is added to prepare slurry.
Preparation of secondary battery: sequentially stacking an anode, a separation film (PE porous polymer film) and a cathode to ensure that the separation film is positioned between the anode and the cathode to play a role of separation, and then winding or sequentially stacking to obtain an electrode assembly; the electrode assembly was placed in an overwrapped aluminum plastic film, and the electrolyte (solvent was EC and DMC in a volume ratio of 1:1, 1M LiPF 6 Solution) is injected into the dried battery, and the secondary battery is prepared through the procedures of vacuum packaging, standing, formation, shaping and the like.
Test method
1. Ultrasonic detection
Ultrasonic waves (50 MHz, 400 mV) are transmitted to the secondary battery along the thickness direction of the secondary battery by using a nondestructive ultrasonic intelligent diagnosis device (model: UBSC-LD), and a signal feedback distribution diagram of the ultrasonic waves is obtained everywhere of the battery. Using integration software, such as JMP software, to calculate the total area of the cell test in the signal feedback profile as S, and the area of the region with signal strength greater than or equal to 1333mV as S1, the duty cycle of the region with signal strength greater than or equal to 1333mV is: S1/S×100%.
2. Cohesive force
The bonding force between the composite layer and the current collector is tested by adopting a high-speed rail tension machine and a 90-degree angle method which are commonly used in the lithium battery industry, namely:
making part of the pole piece coated with the composite layer in the secondary battery into a strip shape, and adhering part of the pole piece to a steel plate through double-sided adhesive tape from one end of the pole piece along the length direction; and then fixing the steel plate at the corresponding position of the high-speed rail tensile machine, pulling up the pole piece which is not adhered to the steel plate, putting the pole piece into a chuck through a connector or directly clamping, and starting to test by the high-speed rail tensile machine when the tension of the clamping opening is more than 0kgf and less than 0.02kgf, wherein the average value of the tension in the stable region is finally measured and recorded as the adhesion force between the composite layer and the current collector.
3. Electrolyte retention rate
a) And (3) removing the pole piece coated with the composite layer from the secondary battery in the environment of (25+/-3) DEG C. If there are other layers on the other side of the current collector coated with the composite layer, the other layers need to be removed by physical or chemical methods, but the composite layer cannot be damaged. Then, a cutting machine is used for completely cutting the composite layer (comprising the current collector);
b) Respectively weighing the cut composite layers (comprising current collectors) at least 3 times by using an electronic day, and respectively marking the cut composite layers as m1; m2; m3 … …, the average value m is obtained;
c) Putting the weighed composite layer (comprising the current collector) into an oven at 85 ℃, baking for 30-60 min to ensure that the electrolyte inside the composite layer is completely baked, and then weighing the composite layer again respectively, wherein the weights of the composite layer are respectively recorded as M1; m2; m3 … …, taking an average value M;
d) Removing the composite layer by a physical or chemical method, but not damaging the corresponding current collector, weighing the corresponding current collector and recording the weight as G1; g2; g3 … …, taking the average G;
e) The electrolyte retention rate of the composite layer is recorded as follows: r= (M-M)/(M-G).
4. Swelling degree
a) And (3) removing the pole piece coated with the functional layer from the secondary battery in the environment of (25+/-3) DEG C. If there are other layers on the other side of the current collector coated with the functional layer, the other layers need to be removed by a physical or chemical method, but the functional layer cannot be damaged. Then, the functional layer is completely cut by a cutting machine; placing into dimethyl carbonate DMC to remove electrolyte dissolved in the functional layer, taking out the electrolyte to be air-dried, then placing the electrolyte into water to be dissolved, pouring the dissolved solution into a glue film preparation mould, and lifting and removing if bubbles exist; the mold was placed in a 60 ℃ oven under the following conditions: after baking is finished at 60 ℃ for 12 hours, observing the appearance and hardness of the adhesive film; if not completely drying, continuing baking until drying;
b) Cutting the prepared adhesive film into small strips of about 2g by scissors;
c) Weighing the small adhesive film strips respectively; recording an initial weight a; put into a small bottle; electrolyte (solvent is EC and DMC in volume ratio of 1:1, based on electrolyte mass, liPF is added 6 12.5% by mass) exceeds 2-3 cm of the adhesive film, sealing the vial, and placing the vial into a vacuum drying furnace at 85 ℃ for 6 hours;
d) Testing the swelling degree of the adhesive film: the film was taken out and wiped clean with dust-free paper, and the film weight b, swelling degree= (b-a)/a×100% at this time was recorded. And 3 parallel samples are made, and the swelling degree of the functional layer is obtained by carrying out arithmetic average on the obtained swelling degree.
5. Thickness of functional layer and insulating layer
a) And (3) removing the pole piece coated with the composite layer from the secondary battery in the environment of (25+/-3) DEG C. If other material layers are arranged on the other side of the current collector coated with the composite layer, the other material layers need to be removed by a physical or chemical method, but the composite layer cannot be damaged;
b) Putting the composite layer (comprising the current collector) into an oven at 85 ℃ and baking for 30-60 min to ensure that the electrolyte inside the functional layer is completely baked;
c) Cutting the composite layer (comprising a current collector) into 6mm multiplied by 6mm by scissors, fixing the composite layer on a sample table by using paraffin, cutting a pole piece under Ar atmosphere by using an IB-09010 CP/ion polishing instrument, selecting 5 points for testing the thickness of a functional layer and the thickness of an insulating layer by using a JY/T O1O-1966 scanning tester, and obtaining the average value H1, the thickness of the insulating layer, H21, H22, H23, H24 and H25 and the average value H2 of the functional layer, wherein the thickness of the functional layer, H12, H13, H14 and H15 are respectively obtained.
6. Flatness of
The flatness of the secondary battery was tested by a laser scanning method. Specifically, the whole outline of the secondary battery is scanned by using optical equipment to manufacture a 3D model, and then the difference between the whole thickness value and the thickness value of the section is calculated and is marked as P, and the difference is the flatness of the secondary battery. If P is less than or equal to 0.50mm, the flatness of the secondary battery is OK at the moment, and the requirements are met; if P is more than 0.50mm, the flatness NG is not satisfactory.
7. Rate of passage of the through nails
And (3) constant-current charging the secondary battery to be tested to a designed full charge voltage at a multiplying power of 0.05 ℃, then charging the secondary battery to a current of 0.025C (off current) at the designed full charge voltage, so that the secondary battery reaches a full charge state, and recording the appearance of the secondary battery before testing. And (3) performing a penetrating nail test on the battery in an environment of 25+/-3 ℃, wherein the diameter of a steel nail is 4mm, the penetrating speed is 30mm/s, the penetrating nail is positioned at the geometric center of the secondary battery, the test is stopped after the surface temperature of the electrode assembly is reduced to 50 ℃ for 3.5min, 10 secondary batteries are taken as a group, the state of the secondary batteries in the test process is observed, and the secondary batteries are taken as judging standards of no combustion and no explosion.
8. Coverage of the composite layer at the winding end of the blank current collector
And (3) removing the pole piece coated with the composite layer from the electrochemical device in the environment of (25+/-3) DEG C. And (3) drying in an oven at 85 ℃, and respectively measuring the area W3 of the composite layer and the total area W2 of the blank current collector at the winding end of the pole piece, wherein the coverage rate of the composite layer on the blank current collector at the winding end of the electrode pole piece is W3/W2 multiplied by 100%.
Test results
TABLE 1
Note that: in each of examples and comparative examples in table 1, the binder was 100% (mass percent) of pure acrylic emulsion in the slurry for forming the functional layer, and the swelling degree of the functional layer was 550%; the insulating layer was 15% by mass of binder polyacrylic acid copolymer +85% by mass of inorganic particulate boehmite.
As can be seen from the data in Table 1, the H1/H2 ratio affects electrolyte retention and thus the ratio of the wavenumber region at a value of 1333 or more. As the ratio of H1/H2 increases, the electrolyte retention rate increases,
the duty ratio of the wave number region of 1333 is also increased. The area of the wave number is larger than or equal to 1333, which indicates that the electrolyte is uniformly distributed in the secondary battery, and the secondary battery has good flatness.
Further, as can be seen from the data of table 1, the insulating layer directly affects the safety performance of the secondary battery. The thickness of the insulating layer is reduced, the passing rate of the through nails is reduced, and the safety performance of the secondary battery is deteriorated.
TABLE 2
Note that: the percentage content of each component in the composition of the composite layer is mass fraction content.
As can be seen from the data in Table 2, the composition of the functional layer and the degree of swelling affect the electrolyte retention and the ratio of wavenumber region of 1333mV or more. With the increase of the swelling degree of the functional layer, the electrolyte retention rate is increased, and the wave number area ratio of more than or equal to 1333mV is also increased. The wave number area of more than or equal to 1333mV has large ratio, which indicates that the electrolyte is uniformly distributed in the secondary battery, and the secondary battery has good flatness.
TABLE 3 Table 3
Note that: the percentage content of each component in the composition of the composite layer is mass fraction content; the thickness of the functional layers was 10 μm and the thickness of the insulating layers was 5 μm.
As can be seen from the data of table 3, the binder type and the inorganic particle type of the insulating layer affect the penetration rate of the secondary battery, when the ratio of the acrylate copolymer and the boehmite in the binder is 15%: at 85%, the safety effect of the secondary battery is better.
TABLE 4 Table 4
Note that: the percentage content of each component in the composition of the composite layer is mass fraction content; the thickness of the functional layers was 10 μm and the thickness of the insulating layers was 5 μm.
As can be seen from the data in Table 4, the coverage of the composite layer on the blank current collector affects the electrolyte retention and the wavenumber region duty cycle of 1333mV or more. As the coverage increases, the electrolyte retention increases, and the ratio of the wavenumber region of 1333mV or more increases. The wave number area of more than or equal to 1333mV has large ratio, which indicates that the electrolyte is uniformly distributed in the secondary battery, and the secondary battery has good flatness.
Although illustrative embodiments have been shown and described, it will be understood by those skilled in the art that the foregoing embodiments are not to be construed as limiting the application and that changes, substitutions and alterations of the embodiments may be made without departing from the spirit, principles and scope of the application.
Claims (15)
1. An electrochemical device comprises an electrode assembly, the electrode assembly comprises an electrode pole piece, the electrode pole piece comprises a blank current collector and a composite layer arranged on the blank current collector, the composite layer comprises an insulating layer and a functional layer,
the functional layer is positioned between the blank current collector and the insulating layer, the thickness of the functional layer is H1 mu m, and the thickness of the insulating layer is H2 mu m, wherein H1/H2 is more than or equal to 1 and less than or equal to 20.
2. The electrochemical device of claim 1, wherein 2.ltoreq.h1/h2.ltoreq.10.
3. The electrochemical device of claim 1, wherein 1.ltoreq.h1.ltoreq.20 and/or 1.ltoreq.h2.ltoreq.10.
4. The electrochemical device according to claim 1, wherein a bonding strength between the functional layer and the blank current collector is greater than a bonding strength between the insulating layer and the functional layer.
5. The electrochemical device according to claim 1, the functional layer being for absorbing an electrolyte.
6. The electrochemical device of claim 1, wherein the electrode assembly is a rolled electrode assembly, and the composite layer is disposed on a blank current collector at a rolled end of the electrode tab.
7. The electrochemical device of claim 6, wherein the coverage of the composite layer on the blank current collector at the winding end of the electrode tab is 80% -100%.
8. The electrochemical device according to claim 1, wherein an area of projection of the insulating layer in a thickness direction of the electrode tab is equal to or larger than an area of projection of the functional layer in the thickness direction of the electrode tab.
9. The electrochemical device according to claim 1, wherein the ultrasonic wave is emitted to the electrochemical device in a thickness direction of the electrochemical device by using a nondestructive ultrasonic intelligent diagnosis system test to obtain a signal feedback profile of the electrochemical device to the ultrasonic wave, and an area ratio of an area having a super signal intensity of 1333mV or more is 30% to 95% based on an area of the electrochemical device in the signal feedback profile.
10. The electrochemical device of claim 1, wherein the functional layer satisfies at least one of the following conditions (a) to (c):
(a) The swelling degree of the functional layer is 200% to 800%;
(b) Using fourier infrared testing, the functional layer comprises a substance having a spectrum with absorption peaks in at least one of the following ranges: 2700cm -1 To 3100cm -1 、1600cm -1 To 1800cm -1 、1100cm -1 To 1200cm -1 ；
(c) The functional layer includes a polymer formed of at least one of an acrylic monomer, and a styrene monomer.
11. The electrochemical device according to claim 10, wherein the functional layer has a swelling degree of 300% to 600%.
12. The electrochemical device of claim 1, wherein the insulating layer comprises a binder and inorganic particles.
13. The electrochemical device of claim 12, wherein the insulating layer satisfies at least one of the following conditions (d) to (g):
(d) The content of the binder is 3% to 20% based on the mass of the insulating layer;
(e) The binder comprises at least one of acrylic ester, acrylic ester copolymer, acrylonitrile, acrylic acid salt copolymer, acrylic acid salt, carboxymethyl cellulose salt, nitrile rubber, polyvinylidene fluoride or polytetrafluoroethylene;
(f) The inorganic particles comprise at least one of boehmite, diaspore, alumina, barium sulfate, calcium sulfate, or calcium silicate;
(g) The Dv90 of the inorganic particles is D1 mu m, wherein D1 is less than or equal to H2 and less than or equal to 10.
14. The electrochemical device according to claim 1, wherein the electrochemical device satisfies at least one of the following conditions (h) to (j):
(h) The bonding force between the composite layer and the blank current collector is more than or equal to 100N/m;
(i) The electrolyte retention rate of the composite layer is 40 to 120 percent;
(j) The flatness of the electrochemical device is 0 to 0.50mm.
15. An electronic device comprising the electrochemical device of any one of claims 1 to 14.
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| PCT/CN2022/084462 WO2023184365A1 (en) | 2022-03-31 | 2022-03-31 | Electrochemical device and electronic device |
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| JP2006024452A (en) * | 2004-07-08 | 2006-01-26 | Matsushita Electric Ind Co Ltd | Organic electrolyte primary battery |
| JP2010049909A (en) * | 2008-08-21 | 2010-03-04 | Sony Corp | Nonaqueous electrolyte secondary battery |
| CN111416103B (en) * | 2019-01-08 | 2022-07-22 | 宁德新能源科技有限公司 | Electrode with composite layer and protective layer of support structure for improving battery performance |
| CN213752753U (en) * | 2020-10-27 | 2021-07-20 | 恒大新能源技术(深圳)有限公司 | Lithium ion battery negative plate and soft package battery comprising same |
| CN214043710U (en) * | 2020-12-28 | 2021-08-24 | 珠海冠宇电池股份有限公司 | Positive plate and lithium ion battery |
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