CN117117078B - Lithium ion battery and negative electrode plate thereof - Google Patents
Lithium ion battery and negative electrode plate thereof Download PDFInfo
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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
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The application provides a lithium ion battery and a negative electrode plate thereof, wherein the lithium ion battery comprises a battery cell, electrolyte and a packaging film, wherein the battery cell is formed by separating and laminating a positive electrode plate and a negative electrode plate through a diaphragm; the negative electrode plate is a negative electrode current collector and a negative electrode active substance; the negative electrode active material is bonded with the negative electrode current collector, the negative electrode current collector is an object with roughness on the surface, and the roughness index of the negative electrode current collector is configured to enable the stripping force between the negative electrode current collector and the negative electrode active material to be greater than or equal to a preset stripping force. According to the application, the copper current collector with certain roughness is adopted, so that the contact area between the copper current collector and the negative electrode active material is increased, the physical interlocking between the negative electrode active material and the copper current collector is further enhanced, the stripping force of the negative electrode plate is increased, the stripping problem of the plate is effectively inhibited, and the service life of the lithium ion battery is prolonged.
Description
Technical Field
The application relates to the technical field of electronics, in particular to a lithium ion battery and a negative electrode plate thereof.
Background
Lithium ion batteries, which are secondary batteries, operate primarily by means of lithium ions moving between a positive electrode and a negative electrode. Compared with the traditional battery, the lithium ion battery is faster to charge and longer to use, and the lithium ion battery with high power density can realize longer battery service time. Along with the development of electronic technology, the demands of people for thinning and long endurance of electronic products such as mobile phones, notebook computers and the like are continuously increased, and further, the volume energy density of lithium ion batteries is required to be continuously increased. The improvement of gram capacity of the anode and cathode materials is an important measure for improving the volume energy density of the battery, and the silicon material with the advantages of high gram capacity, moderate lithium intercalation and deintercalation potential, rich reserve and the like is considered to be one of ideal materials for replacing graphite materials to be used as anode active materials of lithium ion batteries.
The negative electrode plate of the lithium ion battery generally adopts an adhesive to bond the negative electrode active material to the negative electrode current collector, however, for the high-silicon negative electrode plate with high silicon content, the negative electrode active material containing silicon is bonded with the negative electrode current collector only through the adhesive, so that the problem of negative electrode plate demoulding often exists, and the service life of the lithium ion battery is shortened.
Disclosure of Invention
The application provides a lithium ion battery and a negative electrode plate thereof, and aims to solve the problem of stripping of the negative electrode plate of the lithium ion battery.
In order to achieve the above purpose, the application adopts the following technical scheme:
First aspect: the embodiment of the application provides a negative electrode plate of a lithium ion battery, which comprises the following components: a negative electrode current collector and a negative electrode active material; wherein the negative electrode active material is bonded to the negative electrode current collector, the negative electrode current collector is an object with roughness on the surface, and the roughness index of the negative electrode current collector is configured such that the peeling force between the negative electrode current collector and the negative electrode active material is greater than or equal to a preset peeling force.
According to the application, the negative electrode current collector with certain roughness is adopted, so that the contact area between the negative electrode current collector and the negative electrode active material is increased, the physical interlocking between the negative electrode active material and the negative electrode current collector is further enhanced, the stripping force of the negative electrode plate is increased, the stripping problem of the plate is effectively inhibited, and the service life of the lithium ion battery is prolonged.
In one possible implementation, the indicator of roughness includes an arithmetic mean deviation of the contours; the negative electrode active material is silicon negative electrode active material containing silicon, and the gram capacity of the silicon negative electrode active material is more than or equal to 400mAh/g; the negative electrode current collector is a copper current collector made of a copper material, and when the preset peeling force is 20N/m, the arithmetic mean deviation of the profile of the copper current collector is configured to be greater than or equal to 0 μm and less than or equal to 2 μm.
In one possible implementation, the indicator of roughness further includes a contour maximum height; the maximum height of the profile of the copper current collector is configured to be greater than or equal to 0 μm and less than or equal to 5 μm.
In one possible implementation, the copper current collector has a thickness greater than or equal to 4 μm and less than or equal to 16 μm. On the basis of adopting a copper current collector with certain roughness, the thickness of the copper current collector is increased to enhance the tensile strength of the copper current collector, so that the bonding strength between the copper current collector and a negative electrode active substance is improved, the contact resistance between the negative electrode active substance and the copper current collector is reduced, meanwhile, the rate discharge performance and the cycle stability of the lithium ion battery are enhanced to a certain extent, the problem of demolding of a negative electrode plate is further restrained, and the service life of the lithium ion battery is prolonged.
In one possible implementation, the ratio of the arithmetic mean deviation of the profile of the copper current collector to the thickness is greater than or equal to 0 and less than or equal to 0.5.
In one possible implementation, the product of the ratio of the arithmetic mean deviation of the profile of the copper current collector to the thickness, multiplied by the gram capacity of the negative electrode active material, is greater than or equal to 200mAh/g.
In one possible implementation, the product of the ratio of the arithmetic mean deviation of the profile of the copper current collector to the thickness, and the peel force is greater than or equal to 5N/m.
In one possible implementation, the rate of change of the indicator of the roughness of the copper current collector after a predetermined number of charge and discharge cycles of the lithium ion battery is less than or equal to 20%.
Second aspect: the embodiment of the application provides a negative electrode plate of a lithium ion battery, which comprises the following components: a negative electrode current collector and a negative electrode active material; wherein the negative electrode active material is bonded to the negative electrode current collector, and the thickness of the negative electrode current collector is configured such that a peeling force between the negative electrode current collector and the negative electrode active material is greater than or equal to a preset peeling force.
The application adopts the negative electrode current collector with a certain thickness, and increases the tensile strength of the negative electrode current collector by increasing the thickness of the negative electrode current collector, thereby improving the bonding strength between the negative electrode current collector and the negative electrode active substance, reducing the contact resistance between the negative electrode active substance and the negative electrode current collector, enhancing the multiplying power discharge performance and the cycle stability of the lithium ion battery to a certain extent, effectively inhibiting the problem of demoulding of the negative electrode plate, and prolonging the service life of the lithium ion battery.
In one possible implementation, the anode active material is a silicon anode active material comprising silicon, the gram capacity of the silicon anode active material being greater than or equal to 400mAh/g; the negative electrode current collector is a copper current collector made of a copper material, and when the preset stripping force is 20N/m, the thickness of the copper current collector is configured to be greater than or equal to 4 mu m and less than or equal to 16 mu m, and the tensile strength of the copper current collector is greater than or equal to 300Mpa.
In one possible implementation, the product of the ratio of the arithmetic mean deviation of the profile of the copper current collector to the thickness, and the peel force is greater than or equal to 5N/m.
Third aspect: the embodiment of the application provides a lithium ion battery, which comprises a battery cell, electrolyte and a packaging film, wherein the battery cell is formed by separating a positive pole piece and a negative pole piece through a diaphragm and laminating the positive pole piece and the negative pole piece; the negative electrode plate is the negative electrode plate of the lithium ion battery in the first aspect or the second aspect.
It should be appreciated that the description of technical features, aspects, benefits or similar language in the present application does not imply that all of the features and advantages may be realized with any single embodiment. Conversely, it should be understood that the description of features or advantages is intended to include, in at least one embodiment, the particular features, aspects, or advantages.
Drawings
FIG. 1 is a schematic illustration of a silicon negative pole piece release film;
Fig. 2 is a schematic structural diagram of an electronic device according to an embodiment of the present application;
Fig. 3 is a schematic structural diagram of a lithium ion battery according to an embodiment of the present application;
fig. 4 is a schematic view of a negative electrode plate according to an embodiment of the present application;
Fig. 5 is a schematic diagram of a negative electrode plate according to an embodiment of the present application;
fig. 6 is a gram-volume comparison schematic diagram of a negative electrode active material according to an embodiment of the present application;
Fig. 7 is a schematic view showing the effect of bonding between a high-coarseness copper current collector and a silicon anode active material according to an embodiment of the present application.
Detailed Description
The terms first, second, third and the like in the description and in the claims and in the drawings are used for distinguishing between different objects and not for limiting the specified order.
In embodiments of the application, words such as "exemplary" or "such as" are used to mean serving as an example, instance, or illustration. Any embodiment or design described herein as "exemplary" or "e.g." in an embodiment should not be taken as preferred or advantageous over other embodiments or designs. Rather, the use of words such as "exemplary" or "such as" is intended to present related concepts in a concrete fashion.
Based on the advantages of high energy density, high platform voltage, small self-discharge, wide allowable working temperature range, long cycle service life and the like, the lithium ion battery has been widely applied to electronic equipment such as mobile phones, notebook computers and the like. Along with the continuous improvement of the demands of people for light and thin electronic equipment and long endurance, the volume Energy Density (ED) of the lithium ion battery is higher and higher, and the improvement of the gram capacity of positive and negative active substances is an important measure for improving the volume energy density of the battery.
The gram capacity of graphite materials commonly used in lithium ion batteries is close to the theoretical limit, the theoretical limit is 372 milliamperes per gram (mAh/g), and the theoretical limit of the gram capacity of silicon materials is up to 4200mAh/g, which is far higher than the gram capacity of graphite materials, wherein the gram capacity refers to the ratio of the capacitance capable of being released by active substances in the battery to the mass of the active substances. Meanwhile, the silicon material has the advantages of moderate lithium intercalation and deintercalation potential, abundant reserve, low price, environmental protection, no toxicity, mature preparation process and the like. Therefore, the silicon material with high gram capacity is used as the negative electrode active material of the lithium ion battery, the volume energy density of the battery can be effectively improved, and the silicon material is currently considered as one of ideal materials for replacing graphite materials to be used as the negative electrode active material of the lithium ion battery.
In the prior art, an adhesive is generally adopted to bond a negative electrode active material to a negative electrode current collector to form a negative electrode plate, wherein the adhesive can be used for simulating the cohesive force reduction of the negative electrode active material caused by expansion to a certain extent. However, since the volume effect of the silicon material is great, the volume change rate due to expansion/contraction during the repeated lithium intercalation/deintercalation process is as high as 400%. This causes continuous destruction/repair of a solid electrolyte phase interface (SEI) film on the surface of a silicon material during charge/discharge, continuously consumes active lithium ions, and forms a byproduct layer on the surface, directly resulting in an increase in the cycle capacity fade rate and the thickness expansion rate of the lithium ion battery. As shown in fig. 1, which is a schematic view of the stripping of the silicon negative electrode tab, it can be seen that in the case where the silicon negative electrode active material is bonded to the negative electrode current collector by only the binder, there is a significant gap between the silicon negative electrode active material having silicon as the active material and the negative electrode current collector. Due to the existence of the gaps, the anode active material is easy to peel off from the anode current collector, and the problem of stripping of the silicon anode pole piece occurs. Furthermore, for negative electrode tabs with high silicon content, the silicon negative electrode active material is bonded with the negative electrode current collector only by the binder, and there is often a problem of negative electrode tab stripping, which results in a shortened service life of the lithium ion battery.
The application provides a lithium ion battery, which comprises a battery cell, electrolyte and a packaging film, wherein the battery cell is formed by separating a positive pole piece and a negative pole piece through a diaphragm and laminating the positive pole piece and the negative pole piece. The negative electrode plate of the lithium ion battery comprises a negative electrode current collector and a negative electrode active substance; wherein the anode active material is bonded to the anode current collector, and the roughness index of the anode current collector is configured such that the peeling force between the anode current collector and the anode active material is greater than or equal to a preset peeling force. According to the application, the negative electrode current collector with certain roughness is adopted, so that the contact area between the negative electrode current collector and the negative electrode active material is increased, the physical interlocking between the negative electrode active material and the negative electrode current collector is further enhanced, the stripping force of the negative electrode plate is increased, the stripping problem of the plate can be effectively restrained, and the service life of the lithium ion battery is prolonged.
The lithium ion battery can be applied to various electronic devices to supply power for the use of the electronic devices. The electronic device may be a mobile phone, a tablet computer, a desktop, a laptop, a notebook, an Ultra-mobile Personal Computer (UMPC), a handheld computer, a netbook, a Personal digital assistant (Personal DIGITAL ASSISTANT, PDA), a wearable electronic device, a smart watch, or the like, and the specific form of the electronic device is not particularly limited in the present application. In this embodiment, the structure of the electronic device may be shown in fig. 2, and fig. 2 is a schematic structural diagram of the electronic device according to the embodiment of the present application.
As shown in fig. 2, the electronic device may include a processor 110, an external memory interface 120, an internal memory 121, a universal serial bus (universal serial bus, USB) interface 130, a charge management module 140, a power management module 141, a battery 142, and the like. Specifically, the battery 142 may be a lithium ion battery provided by an embodiment of the present application, and the lithium ion battery is composed of a battery cell, an electrolyte and a packaging film, wherein the battery cell is formed by separating a positive pole piece and a negative pole piece through a separator and laminating the positive pole piece and the negative pole piece.
In one embodiment provided by the present application, a negative electrode tab includes: a negative electrode current collector and a negative electrode active material; wherein the negative electrode active material is bonded to the negative electrode current collector, and the index of roughness of the negative electrode current collector is configured such that the peeling force between the negative electrode current collector and the negative electrode active material is greater than or equal to a preset peeling force.
In another embodiment provided by the present application, a negative electrode tab includes: a negative electrode current collector and a negative electrode active material; wherein the negative electrode active material is bonded to the negative electrode current collector, and the thickness of the negative electrode current collector is configured such that a peeling force between the negative electrode current collector and the negative electrode active material is greater than or equal to a preset peeling force.
It is to be understood that the configuration illustrated in this embodiment does not constitute a specific limitation on the electronic apparatus. In other embodiments, the electronic device may include more or fewer components than shown, or certain components may be combined, or certain components may be split, or different arrangements of components. The illustrated components may be implemented in hardware, software, or a combination of software and hardware.
The processor 110 may include one or more processing units, such as: the processor 110 may include an application processor (application processor, AP), a modem processor, a graphics processor (graphics processing unit, GPU), an image signal processor (IMAGE SIGNAL processor, ISP), a controller, a video codec, a digital signal processor (DIGITAL SIGNAL processor, DSP), a baseband processor, and/or a neural-Network Processor (NPU), etc. Wherein the different processing units may be separate devices or may be integrated in one or more processors.
The controller can be a neural center and a command center of the electronic device. The controller can generate operation control signals according to the instruction operation codes and the time sequence signals to finish the control of instruction fetching and instruction execution.
In some embodiments, the processor 110 may include one or more interfaces. The interfaces may include a mobile industry processor interface (mobile industry processor interface, MIPI), a general-purpose input/output (GPIO) interface, a subscriber identity module (subscriber identity module, SIM) interface, and/or a universal serial bus (universal serial bus, USB) interface, etc.
The USB interface 130 is an interface conforming to the USB standard specification, and may specifically be a Mini USB interface, a Micro USB interface, a USB Type C interface, or the like. The USB interface 130 may be used to connect a charger to charge an electronic device, or may be used to transfer data between the electronic device and a peripheral device. The interface may also be used to connect other electronic devices, such as AR devices, etc.
It should be understood that the connection relationship between the modules illustrated in this embodiment is only illustrative, and does not limit the structure of the electronic device. In other embodiments of the present application, the electronic device may also use different interfacing manners, or a combination of multiple interfacing manners in the foregoing embodiments.
The charge management module 140 is configured to receive a charge input from a charger. The charger can be a wireless charger or a wired charger. In some wired charging embodiments, the charge management module 140 may receive a charging input of a wired charger through the USB interface 130. In some wireless charging embodiments, the charge management module 140 may receive wireless charging input through a wireless charging coil of the electronic device. The charging management module 140 may also supply power to the electronic device through the power management module 141 while charging the battery 142.
The power management module 141 is used for connecting the battery 142, and the charge management module 140 and the processor 110. The power management module 141 receives input from the battery 142 and/or the charge management module 140 to power the processor 110, the internal memory 121, etc. The power management module 141 may also be configured to monitor battery capacity, battery cycle number, battery health (leakage, impedance) and other parameters. In other embodiments, the power management module 141 may also be provided in the processor 110. In other embodiments, the power management module 141 and the charge management module 140 may be disposed in the same device.
The external memory interface 120 may be used to connect an external memory card, such as a Micro SD card, to enable expansion of the memory capabilities of the electronic device. The external memory card communicates with the processor 110 through an external memory interface 120 to implement data storage functions. For example, files such as video images are stored in an external memory card.
The internal memory 121 may be used to store computer executable program code including instructions. The processor 110 executes various functional applications of the electronic device and data processing by executing instructions stored in the internal memory 121. In addition, the internal memory 121 may include a high-speed random access memory, and may further include a nonvolatile memory such as at least one magnetic disk storage device, a flash memory device, a universal flash memory (universal flash storage, UFS), and the like. The processor 110 performs various functional applications of the electronic device and data processing by executing instructions stored in the internal memory 121 and/or instructions stored in a memory provided in the processor.
In addition, an operating system is run on the components. Such as the iOS operating system developed by apple corporation, the Android open source operating system developed by google corporation, the Windows operating system developed by microsoft corporation, etc. An operating application may be installed on the operating system.
Embodiment one:
The embodiment of the application provides a lithium ion battery which consists of a battery cell, electrolyte and a packaging film, wherein the battery cell is formed by separating and laminating a positive pole piece and a negative pole piece through a diaphragm. The negative electrode plate of the lithium ion battery comprises a negative electrode current collector and a negative electrode active substance; wherein the negative electrode active material is bonded to the negative electrode current collector, and the index of roughness of the negative electrode current collector is configured such that the peeling force between the negative electrode current collector and the negative electrode active material is greater than or equal to a preset peeling force.
Specifically, the negative electrode current collector provided by the embodiment of the application adopts the copper current collector with a certain roughness on the surface, and the conductive contact area of the negative electrode active substance and the copper current collector is increased by increasing the roughness index of the surface of the copper current collector, so that the adhesive strength between the negative electrode active substance and the copper current collector is improved, the physical interlocking between the negative electrode active substance and the negative electrode current collector is enhanced, the stripping force of the negative electrode plate is increased, the stripping problem of the negative electrode plate is effectively inhibited, the service life of the lithium ion battery is prolonged, and the lithium ion battery has higher cycle stability. The stripping force is a force required to strip the negative electrode active material from the copper current collector. The roughness index is used to characterize roughness, and may include the arithmetic mean deviation (Ra) of the profile and the maximum height (Rz) of the profile.
As shown in fig. 3, the structure of a lithium ion battery provided by the embodiment of the application is schematically shown, and a battery cell is formed by separating and laminating a positive electrode plate 301 and a negative electrode plate 302 through a diaphragm 303. The negative electrode plate of the lithium ion battery comprises a negative electrode current collector and a negative electrode active substance, wherein the negative electrode active substance is coated on the negative electrode current collector, as shown in fig. 4, which is a schematic diagram of the negative electrode plate provided by the embodiment of the application, the negative electrode active substance 401 is coated on a copper (Cu) current collector 402, and the copper current collector 402 is the negative electrode current collector made of copper materials.
The negative electrode current collector is used for bearing a negative electrode active material and collecting and outputting current generated by the negative electrode active material so as to reduce the internal resistance of the lithium ion battery and improve the coulomb efficiency, the circulation stability and the multiplying power performance of the lithium ion battery. In general, the material of the negative electrode current collector needs to satisfy the conditions of high conductivity, good chemical and electrochemical stability, high mechanical strength, good compatibility with the negative electrode active material, good binding force, and the like. Copper is an excellent metal conductor with conductivity inferior to silver, and has the advantages of abundant resources, low cost, easy obtainment, good ductility and the like. Copper is easily oxidized at higher potentials and is therefore often used as a negative current collector.
In some embodiments of the present application, in order to increase the adhesion between the anode active material and the copper current collector, the anode current collector may employ a copper current collector having a certain roughness on the surface.
Illustratively, the index of roughness includes a contour arithmetic mean deviation (Ra) configured to be greater than or equal to 0 μm and less than or equal to 2 μm when the preset peeling force is 20N/m, whereby the conductive contact area of the anode active material with the copper current collector can be increased, thereby enhancing physical interlocking between the copper current collector and the anode active material. Wherein Ra represents the arithmetic average value of the absolute value of the profile offset within a sampling length, the sampling length is a datum line length specified by evaluating the surface roughness, the length which can reflect the surface roughness characteristic is selected, and the specific length can be determined according to the formation condition of the actual surface of the copper current collector and the texture characteristic.
Further, the index of roughness may further include a contour maximum height (Rz), and while the contour arithmetic mean deviation of the copper current collector is configured to be greater than or equal to 0 μm and less than or equal to 2 μm, configuring the contour maximum height of the copper current collector to be greater than or equal to 0 μm and less than or equal to 5 μm may further enhance physical interlocking between the copper current collector and the anode active material, suppressing the problem of the stripping of the anode tab. Where Rz represents the sum of the average of the five largest profile peak heights and the average of the five largest profile valley depths over the sample length.
As shown in fig. 5, the graph is a comparative schematic diagram of a negative electrode sheet provided by the embodiment of the present application, it can be seen that before and after the roughness index of the copper current collector 402 is raised, there is a significant difference in the positional relationship between the negative electrode active material 401 and the copper current collector 402, that is, after the roughness index of the copper current collector 402 is raised, the positional relationship between the negative electrode active material 401 and the copper current collector 402 is more compact, so that the physical interlocking capability between the copper current collector 402 and the negative electrode active material 401 is raised. It was thus demonstrated that the negative current collector of the negative electrode tab employs a copper current collector 402 having a certain roughness, the conductive contact area of the negative electrode active material 401 with the copper current collector 402 is increased, and the physical interlocking ability between the negative electrode active material 401 and the copper current collector 402 is enhanced.
The method for preparing the copper current collector is not limited, and exemplary methods for preparing the copper current collector include an electrolytic method and a calendaring method. Compared with an electrolytic method, the copper current collector obtained by the calendaring method has higher conductivity and better extension effect.
The negative electrode active material needs to be made of a material with a lower potential than that of lithium ions, and the negative electrode active material is mainly made of carbon material graphite, however, as the requirements of users on the capabilities of thinning electronic equipment, long endurance and the like are higher and higher, the volumetric energy density of the lithium ion battery is higher and higher, and the improvement of the gram capacity of the positive electrode active material and the negative electrode active material is an effective way for improving the volumetric energy density of the lithium ion battery.
The gram capacity of the traditional graphite material is close to the theoretical limit, and in order to improve the gram capacity of the negative electrode active material and improve the volume energy density of the lithium ion battery, the negative electrode active material in the embodiment of the application adopts a silicon material with high gram capacity. As shown in fig. 6, which is a schematic diagram showing gram volume comparison of a negative electrode active material according to an embodiment of the present application, gram volume values of various negative electrode active materials are shown, wherein the gram volume value of conventional natural graphite is 360-370mAh/g, and the gram volume value of artificial graphite is 340-360mAh/g. The gram capacity of the silicon material is far higher than that of the traditional negative electrode active material, and the theoretical limit is 4200mAh/g, which is 10 times that of the graphite material. The gram capacity of the silicon-carbon material is lower than that of the silicon material due to the doping of carbon, but is still higher than that of common negative electrode active substances, such as lithium titanate (165-170 mAh/g), nickel-cobalt-manganese ternary material (155-190 mAh/g), lithium iron phosphate (130-150 mAh/g) and the like. Therefore, the silicon material is used as the negative electrode active material of the lithium ion battery, and the gram capacity of the battery cell can be effectively improved.
In the embodiment of the application, the negative electrode active material with high silicon content, namely the silicon negative electrode active material is adopted, and the gram capacity (C) is more than or equal to 400mAh/g. On this basis, the ratio of the arithmetic mean deviation of the profile of the copper current collector to the thickness is greater than or equal to 0 and less than or equal to 0.5, and the product of the ratio and the gram capacity of the negative electrode active material is greater than or equal to 200mAh/g.
For example, in addition to silicon, other elements, such as oxygen, carbon, etc., may be mixed in the silicon anode active material to increase the conductivity of the silicon anode active material, and the gram capacity of the silicon anode active material mixed with the other elements is reduced as compared with the gram capacity of the pure silicon material of up to 4200mAh/g, but still much higher than the gram capacity of the conventional anode active material, such as 2615mAh/g of theoretical gram capacity of silicon oxide.
In the embodiment of the application, when the roughness index comprises the arithmetic mean deviation of the contour, under the condition that a copper current collector with Ra being more than or equal to 0 and less than or equal to 2 mu m and a silicon negative electrode active material with C being more than or equal to 400mAh/g and C being more than or equal to 1500mAh/g are adopted, the stripping force (f) between the copper current collector and the silicon negative electrode active material is more than or equal to 20N/m and less than or equal to 100N/m. On the basis, the ratio of the arithmetic mean deviation of the profile of the copper current collector to the thickness is greater than or equal to 0 and less than or equal to 0.5, and the product of the ratio and the gram capacity of the negative electrode active material is greater than or equal to 200mAh/g and less than or equal to 750mAh/g, namely, 200mAh/g is less than or equal to C× (Ra/H) is less than or equal to 750mAh/g, wherein H is the thickness of the copper current collector. The product of the ratio of the arithmetic mean deviation of the profile of the copper current collector to the thickness and the peeling force is more than or equal to 5N/m and less than or equal to 25N/m. In the lithium ion battery after the preset cycle charge and discharge, the change rate of the roughness index of the copper current collector is less than or equal to 20%.
The battery positive electrode plate comprises a positive electrode current collector and a positive electrode active material, wherein the positive electrode active material can be lithium-containing transition metal oxide, phosphide such as LiCoO 2、LiFePO4 and the like, and conductive polymer such as polyacetylene, polyphenyl, polypyrrole, polythiophene, active polysulfide and the like; the lithium intercalation compound positive electrode material is an important component of lithium ion batteries.
The positive electrode active material occupies a larger proportion in the lithium ion battery, so that the selection of the positive electrode active material influences the performance of the lithium ion battery. For example, many LiCoO 2 are currently used in lithium ion batteries, and the lithium ion batteries have the advantages of high working voltage, stable charge and discharge voltage, suitability for large-current charge and discharge, high specific energy, good cycle performance and the like. In addition, the Li-Mn-O positive electrode material has great development potential due to rich manganese resource, low price, no toxicity and no pollution, wherein the spinel-type LiMn 2O4 has the advantages of good safety, easy synthesis and the like. Also, liFePO 4 having high energy density, low price, and excellent safety is a positive active material of a lithium ion battery having a good development prospect because of abundant iron resources, low price, and non-toxicity.
The working principle of the positive electrode of the lithium ion battery is described by taking LiCoO 2 as an example. When the lithium ion battery is charged, under the action of an external electric field, lithium elements are separated from LiCoO 2 molecules of an active substance of the positive electrode to become positively charged lithium ions, and the positively charged lithium ions move from the positive electrode to the negative electrode; during discharge, lithium ions are deintercalated from the negative electrode, return to the positive electrode along the direction of an electric field, and are recombined into LiCoO 2 molecules. As shown in formula (1), it is a positive electrode reaction equation when LiCoO 2 is used as a positive electrode active material.
LiCoO2＝Li1-xCoO2+xLi++xe- (1)
The battery cell is formed by separating and laminating a positive pole piece and a negative pole piece through a diaphragm, the positive pole piece and the negative pole piece are separated through the diaphragm, the short circuit of the two pole pieces caused by contact is prevented, and meanwhile, the battery cell also has the function of enabling electrolyte ions to pass through.
The electrolyte is used for conducting electrons between the anode and the cathode in the lithium ion battery, and is generally prepared from high-purity organic solvent, electrolyte lithium salt, necessary additives and other raw materials according to a certain proportion under certain conditions. Wherein, the organic solvent can be mixed by high dielectric constant solvent and low viscosity solvent; the electrolyte lithium salt may be lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, or the like; the additive has the effects of improving the performance of SEI film, reducing trace water and fluorine hydrogen acid in electrolyte, and preventing overcharge, overdischarge and the like.
As shown in fig. 7, the effect of bonding between a copper current collector with high roughness index and a silicon negative electrode active material is schematically shown in fig. 7, and the bonding effect between the copper current collector 701 and the silicon negative electrode active material 702 shown in fig. 7 is obviously enhanced compared with that of fig. 1. In the embodiment of the application, the copper current collector with the roughness of which the surface is equal to or less than 0 mu m and equal to or less than 2 mu m is adopted by improving the index of the roughness of the surface of the copper current collector, so that the conductive contact area between the anode active material and the copper current collector is increased, the bonding strength between the anode active material and the anode active material is improved, the contact resistance between the anode active material and the copper current collector is reduced, the rate discharge performance and the circulation stability of the lithium ion battery are enhanced to a certain extent, the stripping force of the anode pole piece is increased, the stripping problem of the anode pole piece is effectively restrained, and the service life of the lithium ion battery is prolonged.
Embodiment two:
The embodiment of the application provides a lithium ion battery which consists of a battery cell, electrolyte and a packaging film, wherein the battery cell is formed by separating and laminating a positive pole piece and a negative pole piece through a diaphragm. The negative electrode plate of the lithium ion battery comprises a negative electrode current collector and a negative electrode active substance, wherein the negative electrode active substance is bonded with the negative electrode current collector, and the roughness index of the negative electrode current collector is configured to enable the stripping force between the negative electrode current collector and the negative electrode active substance to be larger than or equal to a preset stripping force. The negative electrode active material is silicon negative electrode active material containing silicon, and the gram capacity of the silicon negative electrode active material is more than or equal to 400mAh/g; the negative electrode current collector is a copper current collector made of copper material, and when the preset stripping force is 20N/m, the thickness of the copper current collector is configured to be more than or equal to 4 mu m and less than or equal to 16 mu m, and the tensile strength of the copper current collector is more than or equal to 300Mpa. Unlike the first embodiment, the thickness of the copper current collector is increased, and by increasing the thickness of the copper current collector, the tensile strength of the copper current collector is enhanced, the expansion rate of the copper current collector is reduced, the physical interlocking capability between the negative current collector and the copper current collector is enhanced, the problem of demoulding of the negative electrode plate is effectively restrained, and the service life of the lithium ion battery is prolonged.
In the embodiment of the application, in order to increase the binding force between the anode active material and the anode current collector, the anode current collector adopts a copper current collector with a certain thickness. For example, a copper current collector having a thickness (H) of 4 μm or more and 16 μm or less and a tensile strength of 300Mpa or more may be used. According to the embodiment of the application, the tensile strength of the copper current collector is enhanced by configuring the thickness of the copper current collector, so that the physical interlocking capability between the negative current collector and the copper current collector is enhanced, and the stripping force of the negative electrode plate is improved.
Further, when the thickness of the copper current collector meets H which is more than or equal to 4 microns and less than or equal to 16 microns, the ratio of the arithmetic mean deviation of the outline of the copper current collector to the thickness is more than or equal to 0 and less than or equal to 0.5, so that the physical interlocking capability between the negative current collector and the copper current collector can be further enhanced, and the stripping force of the negative electrode plate is improved.
The method for preparing the copper current collector is not limited in the present application, and exemplary methods for preparing the copper current collector include electrolytic method and calendaring method. Compared with an electrolytic method, the copper current collector obtained by the calendaring method has higher conductivity and better extension effect. The positive electrode sheet, the electrolyte and the packaging film adopted in this embodiment are the same as those in the first embodiment, and are not described here again.
In the embodiment of the application, a copper current collector with the thickness of more than or equal to 4 mu m and less than or equal to 16 mu m is adopted, and a silicon anode active material with the gram capacity (C) of more than or equal to 400mAh/g is adopted. On this basis, the ratio of the arithmetic mean deviation of the profile of the copper current collector to the thickness is greater than or equal to 0 and less than or equal to 0.5, and the product of the ratio and the gram capacity of the negative electrode active material is greater than or equal to 200mAh/g.
In the embodiment of the application, in the case of adopting the silicon anode active material with the thickness of 4 μm less than or equal to H less than or equal to 16 μm and 400mAh/g less than or equal to C less than or equal to 1500mAh/g, the peeling force (f) between the copper current collector and the silicon anode active material is more than or equal to 20N/m and less than or equal to 100N/m, and the tensile strength is more than or equal to 300Mpa and less than or equal to 600Mpa. On this basis, the ratio of the arithmetic mean deviation of the profile of the copper current collector to the thickness is greater than or equal to 0 and less than or equal to 0.5, and the product of the ratio and the gram capacity of the anode active material is greater than or equal to 200mAh/g and less than or equal to 750mAh/g. The product of the ratio of the arithmetic mean deviation of the profile of the copper current collector to the thickness and the peeling force is more than or equal to 5N/m and less than or equal to 25N/m. In the lithium ion battery after the preset cycle charge and discharge, the change rate of the copper current collector is less than or equal to 20 percent.
In summary, in the embodiment of the application, the copper current collector with a certain thickness is adopted, and the tensile strength of the copper current collector is improved by increasing the thickness of the copper current collector, so that the bonding strength between the copper current collector and the negative electrode active material is improved, the contact resistance between the negative electrode active material and the copper current collector is reduced, meanwhile, the rate discharge performance and the cycle stability of the lithium ion battery are enhanced to a certain extent, the problem of demoulding of the negative electrode plate is effectively restrained, and the service life of the lithium ion battery is prolonged.
Embodiment III:
The embodiment of the application provides a lithium ion battery which consists of a battery cell, electrolyte and a packaging film, wherein the battery cell is formed by separating and laminating a positive pole piece and a negative pole piece through a diaphragm. The negative electrode plate of the lithium ion battery comprises a negative electrode current collector and a negative electrode active material layer, wherein the negative electrode active material is bonded with the negative electrode current collector, and the roughness index of the negative electrode current collector is configured to enable the stripping force between the negative electrode current collector and the negative electrode active material to be larger than or equal to a preset stripping force. When the roughness index comprises the arithmetic mean deviation of the contour, the anode active material is silicon anode active material containing silicon, and the gram capacity of the silicon anode active material is more than or equal to 400mAh/g; the negative electrode current collector is a copper current collector made of a copper material, and when the preset stripping force is 20N/m, the arithmetic mean deviation of the profile of the copper current collector is configured to be greater than or equal to 0 μm and less than or equal to 2 μm, and the thickness of the copper current collector is configured to be greater than or equal to 4 μm and less than or equal to 16 μm. Unlike the first and second embodiments, in the present embodiment, the thickness of the copper current collector is increased while the index of the roughness of the copper current collector is increased, and the peeling force of the negative electrode tab is improved in combination with both aspects to suppress the problem of the peeling and the like.
In the embodiment of the application, in order to increase the binding force between the anode active material and the anode current collector, the anode current collector adopts a copper current collector with certain roughness, and when the roughness index comprises the arithmetic mean deviation of the outline, the copper current collector with Ra being more than or equal to 0 μm and less than or equal to 2 μm can be adopted, so that the conductive contact area between the anode active material and the copper current collector is increased, and the physical interlocking between the copper current collector and the anode active material is further enhanced.
Further, the index of roughness may further include a contour maximum height (Rz), and while the contour arithmetic mean deviation of the copper current collector is configured to be greater than or equal to 0 μm and less than or equal to 2 μm, configuring the contour maximum height of the copper current collector to be greater than or equal to 0 μm and less than or equal to 5 μm may further enhance physical interlocking between the copper current collector and the anode active material, suppressing the problem of the stripping of the anode tab. In order to further increase the binding force between the anode active material and the copper current collector, the embodiment of the application increases the thickness of the copper current collector while improving the index of the roughness of the copper current collector, and exemplarily, the copper current collector with H being more than or equal to 4 mu m and less than or equal to 16 mu m can be adopted to enhance the tensile strength of the copper current collector, so that the expansion rate of the copper current collector is reduced, the physical interlocking capability between the anode current collector and the copper current collector is enhanced, and the stripping problem of an anode piece is restrained.
Further, in the case where the roughness index and the thickness of the copper current collector satisfy the above conditions, when the ratio of the arithmetic mean deviation of the profile of the copper current collector to the thickness is greater than or equal to 0 and less than or equal to 0.5, that is, 0.ltoreq.Ra/H.ltoreq.0.5, the tensile strength of the copper current collector can be enhanced while increasing the conductive contact area of the negative electrode active material and the copper current collector, thereby further improving the physical interlocking capability between the negative electrode current collector and the copper current collector, enhancing the physical interlocking capability, and suppressing the problem of the negative electrode sheet from being de-molded. Further, the product of the ratio of the arithmetic mean deviation of the profile of the copper current collector to the thickness and the gram capacity of the anode active material is greater than or equal to 200mAh/g.
The method for preparing the copper current collector is not limited in the present application, and exemplary methods for preparing the copper current collector include electrolytic method and calendaring method. Compared with an electrolytic method, the copper current collector obtained by the calendaring method has higher conductivity and better extension effect. The positive electrode sheet, the electrolyte and the packaging film adopted in this embodiment are the same as those in the first embodiment, and are not described here again.
Further, when the index of roughness includes an arithmetic mean deviation of the contour, in the case of using a copper current collector with 0 μm or less than or equal to Ra.ltoreq.2 μm and a silicon anode active material with 400 mAh/g.ltoreq.C.ltoreq.1500 mAh/g, a peeling force (f) between the copper current collector and the silicon anode active material is 20N/m or more and 100N/m or less. On this basis, the ratio of the arithmetic mean deviation of the profile of the copper current collector to the thickness is greater than or equal to 0 and less than or equal to 0.5, and the product of the ratio and the gram capacity of the anode active material is greater than or equal to 200mAh/g and less than or equal to 750mAh/g. The product of the ratio of the arithmetic mean deviation of the profile of the copper current collector to the thickness and the peeling force is more than or equal to 5N/m and less than or equal to 25N/m. In the lithium ion battery after the preset cycle charge and discharge, the change rate of the roughness index of the copper current collector is less than or equal to 20%.
The change rate of the roughness index of the copper current collector in the lithium ion battery after the lithium ion battery is charged and discharged for a preset number of cycles is less than or equal to 20%. Illustratively, the ratio of the index F1 of the roughness of the copper current collector in the lithium ion battery after 700 cycles of charge and discharge to the index F0 of the roughness of the copper current collector in the initial lithium ion battery is less than or equal to 20%.
In summary, the embodiment of the application enhances the physical interlocking between the silicon negative electrode active material and the copper current collector by improving the roughness index of the copper current collector, enhances the thickness of the copper current collector on the basis, enhances the stripping force of the negative electrode plate in combination of the two aspects, effectively inhibits the problem of stripping of the negative electrode plate, and prolongs the service life of the lithium ion battery.
The foregoing is merely illustrative of specific embodiments of the present application, and the scope of the present application is not limited thereto, but any changes or substitutions within the technical scope of the present application should be covered by the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (8)
1. A negative electrode tab for a lithium ion battery, comprising:
A copper current collector made of copper material and a silicon negative electrode active material containing silicon; wherein the silicon negative electrode active material is bonded to the copper current collector, the copper current collector has a surface with a roughness, an index of the roughness of the copper current collector is configured such that a peeling force between the copper current collector and the silicon negative electrode active material is greater than or equal to a preset peeling force, the index of the roughness of the copper current collector corresponds to a gram capacity of the silicon negative electrode active material; the roughness index comprises a contour arithmetic average deviation, and the gram capacity of the silicon anode active material is more than or equal to 400mAh/g; when the preset peel force is 20N/m, the arithmetic mean deviation of the profile of the copper current collector is configured to be greater than or equal to 0 μm and less than or equal to 2 μm; the ratio of the arithmetic mean deviation of the profile of the copper current collector to the thickness is greater than or equal to 0 and less than or equal to 0.5; the product of the ratio and the gram-volume of the silicon negative electrode active material is greater than or equal to 200mAh/g.
2. The negative electrode tab of a lithium ion battery of claim 1, wherein the roughness index further comprises a profile maximum height; the maximum height of the profile of the copper current collector is configured to be greater than or equal to 0 μm and less than or equal to 5 μm.
3. The negative electrode tab of a lithium ion battery of claim 1, wherein the copper current collector has a thickness greater than or equal to 4 μιη and less than or equal to 16 μιη.
4. The negative electrode tab of a lithium ion battery of claim 1, wherein the product of the ratio and the peel force is greater than or equal to 5N/m.
5. The negative electrode tab of a lithium ion battery of any one of claims 1-4, wherein the rate of change of the indicator of roughness of the copper current collector is less than or equal to 20% after a predetermined number of charge-discharge cycles of the lithium ion battery.
6. A negative electrode tab for a lithium ion battery, comprising:
A copper current collector made of copper material and a silicon negative electrode active material containing silicon; wherein the silicon negative electrode active material is bonded to the copper current collector, and the thickness of the copper current collector is configured such that a peeling force between the copper current collector and the silicon negative electrode active material is greater than or equal to a preset peeling force, and a gram capacity of the silicon negative electrode active material is greater than or equal to 400mAh/g; when the preset peeling force is 20N/m, the thickness of the copper current collector is configured to be greater than or equal to 4 μm and less than or equal to 16 μm, and the tensile strength of the copper current collector is greater than or equal to 300Mpa.
7. The negative electrode tab of lithium ion battery of claim 6, wherein the product of the ratio of the arithmetic mean deviation of the profile of the copper current collector to the thickness and the peel force is greater than or equal to 5N/m.
8. A lithium ion battery, comprising:
The battery cell is formed by separating and laminating a positive pole piece and a negative pole piece through a diaphragm;
The negative electrode plate is a negative electrode plate of the lithium ion battery according to any one of claims 1 to 7.
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| KR101043157B1 (en) * | 2007-03-13 | 2011-06-20 | 파나소닉 주식회사 | A lithium secondary battery comprising a negative electrode for a lithium secondary battery, a manufacturing method thereof and a negative electrode for a lithium secondary battery |
| JP5128695B2 (en) * | 2010-06-28 | 2013-01-23 | 古河電気工業株式会社 | Electrolytic copper foil, electrolytic copper foil for lithium ion secondary battery, electrode for lithium ion secondary battery using the electrolytic copper foil, lithium ion secondary battery using the electrode |
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