CN116864837A - Secondary battery and electricity utilization device - Google Patents
Secondary battery and electricity utilization device Download PDFInfo
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- CN116864837A CN116864837A CN202311130205.7A CN202311130205A CN116864837A CN 116864837 A CN116864837 A CN 116864837A CN 202311130205 A CN202311130205 A CN 202311130205A CN 116864837 A CN116864837 A CN 116864837A
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- positive electrode
- secondary battery
- active material
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- 239000007774 positive electrode material Substances 0.000 claims abstract description 108
- 239000010410 layer Substances 0.000 claims abstract description 92
- 239000002131 composite material Substances 0.000 claims abstract description 87
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- 230000003446 memory effect Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
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- 239000007773 negative electrode material Substances 0.000 description 1
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Classifications
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The application discloses a secondary battery and an electric device. The positive electrode plate of the secondary battery comprises a positive electrode current collector and a positive electrode film layer arranged on at least one surface of the positive electrode current collector, wherein the positive electrode film layer is provided with a first surface close to the positive electrode current collector and a second surface opposite to the first surface, the thickness of the positive electrode film layer is marked as H, a first area of the positive electrode film layer is marked as a thickness range from the first surface of the positive electrode film layer to 0.1H, and a second area is marked as a thickness range from the second surface of the positive electrode film layer to 0.1H; the first region includes a composite material including a core including a lithium replenishing agent and a coating layer disposed on at least a portion of a surface of the core, the coating layer including a first positive electrode active material, and the second region including a second positive electrode active material. The application provides a slow lithium release effect by arranging the composite material containing the lithium supplementing agent in the first area close to the positive electrode current collector, and the secondary battery has good cycle capacity retention rate.
Description
Technical Field
The application belongs to the technical field of batteries, and particularly relates to a secondary battery and an electric device.
Background
In recent years, new energy automobiles are vigorously developed, a battery driving system is a main factor influencing the performance and cost of the new energy automobiles, and a secondary battery is a preferred scheme of a power battery in the current new energy automobile battery driving system due to the characteristics of high energy density, low memory effect, high working voltage and the like.
The Lithium Ion Battery (LIB) is used as one of secondary batteries, and has the characteristics of high energy density, long service life, energy conservation, environmental protection and the like. However, after the lithium ion battery is recycled for a long time, a lithium ion loss defect occurs, so that the cycle capacity is easy to decay.
Disclosure of Invention
In view of the above, the present application provides a secondary battery and an electric device, which aim to solve the technical problem of how to improve the cycle capacity retention rate of a lithium ion battery.
In a first aspect, an embodiment of the present application provides a secondary battery, including a positive electrode sheet including a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector, the positive electrode film layer having a first surface adjacent to the positive electrode current collector and a second surface disposed opposite to the first surface, the thickness of the positive electrode film layer being denoted as H, a region ranging from the first surface of the positive electrode film layer to 0.1H being denoted as a first region of the positive electrode film layer, and a region ranging from the second surface of the positive electrode film layer to 0.1H being denoted as a second region of the positive electrode film layer; the first region includes a composite material including a core including a lithium replenishing agent and a coating layer disposed on at least a portion of a surface of the core, the coating layer including a first positive electrode active material, and the second region including a second positive electrode active material.
The lithium-supplementing agent of the inner core can be timely supplemented with lithium after the composite material coating layer close to one side of the current collector breaks, so that the composite material in the first area can achieve a slow lithium-releasing effect, and the cycle capacity retention rate can be improved. Therefore, the secondary battery provided by the embodiment of the application is based on the special positive electrode film layer on the surface of the positive electrode plate, so that the secondary battery has good cycle capacity retention rate.
In one embodiment, the volume distribution particle size Dv50 of the second positive electrode active material is less than the volume distribution particle size Dv50 of the composite material.
Based on the fact that one side, far away from the current collector, of the second area can be contacted with electrolyte earlier, the second positive electrode active material in the second area is smaller in Dv50, so that the specific surface area is larger, the second positive electrode active material can be fully soaked with the electrolyte, internal resistance can be reduced, and energy conversion efficiency is improved. Such secondary batteries have both high energy conversion efficiency and high cycle capacity retention.
In some embodiments, the volume distribution particle size Dv50 of the composite material is 4-10 μm; and/or the number of the groups of groups,
the volume distribution particle size Dv50 of the second positive electrode active material is 1-3 μm.
The composite material can well supplement lithium in the particle size range, and has small internal resistance; the second positive electrode active material is favorable for electrolyte infiltration within the particle size range, and has small internal resistance. The composite material and the second positive electrode active material are combined and matched, so that the secondary battery has the effects of better energy conversion efficiency and circulation capacity retention rate.
In some embodiments, the mass ratio of the first positive electrode active material to the lithium supplementing agent is (0.005-0.05): 1.
the lithium supplementing agent and the first positive electrode active material form a composite material with a core-shell structure according to the mass ratio, so that on one hand, the lithium supplementing effect is good, the cycle capacity retention rate can be improved, and on the other hand, the influence on the available capacity and the safety performance of the secondary battery is small.
In some embodiments, the mass ratio of the first positive electrode active material to the lithium supplementing agent is (0.01-0.02): 1.
the secondary battery formed by the first positive electrode active material and the lithium supplementing agent has better comprehensive effects of the cycle capacity retention rate and the safety performance.
In some embodiments, the intermediate region between the first region and the second region comprises a composite material and/or a second positive electrode active material.
According to the embodiment of the application, the mass ratio of the composite material in the positive electrode film layer to the second positive electrode active material can be controlled by regulating and controlling the materials of the first region, the middle region and the second region in the positive electrode film layer, so that the effect of improving the circulation capacity retention rate is further realized.
In some embodiments, the mass ratio of the composite material in the positive electrode film layer to the second positive electrode active material is (1:9) - (9:1).
The composite material and the second positive electrode active material are matched in the positive electrode film layer according to the mass ratio, so that the energy conversion efficiency of the secondary battery is improved, and the cycle capacity retention rate is improved. And the lithium release function of the composite material is improved by improving the relative proportion of the composite material in the positive electrode film layer.
In some embodiments, the mass ratio of the composite material in the positive electrode film layer to the second positive electrode active material is (1:1) - (7:3).
The secondary battery formed by the positive electrode film layer with the mass ratio has better comprehensive effects of energy conversion efficiency and cycle capacity retention rate.
In some embodiments, the first positive electrode active material and the second positive electrode active material are positive electrode active materials having the same material.
The first positive electrode active material and the second positive electrode active material adopt positive electrode active materials of materials, so that the first area and the second area of the positive electrode film layer have good compatibility, and lithium ions can stably migrate when the secondary battery is charged and discharged.
In some embodiments, the positive electrode active material includes lithium iron phosphate.
The lithium iron phosphate has the characteristics of long service life, safe use and quick charging, but the tap density is lower under the normal condition; in the embodiment of the application, the lithium iron phosphate coated lithium supplementing agent is distributed in the first area, and the lithium iron phosphate serving as the second positive electrode active material is distributed in the second area, so that the lithium iron phosphate tap density can be further improved by the positive electrode film layer.
In a second aspect, an embodiment of the present application provides an electrical device, including the secondary battery provided in the first aspect of the present application.
By adopting the secondary battery provided by the first aspect of the embodiment of the application, the power utilization device has good charge and discharge performance and can work more stably and permanently.
The foregoing description is only an overview of the present application, and is intended to be implemented in accordance with the teachings of the present application in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present application more readily apparent.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the application. Also, like reference numerals are used to designate like parts throughout the accompanying drawings. In the drawings:
fig. 1 is a schematic structural view of a positive electrode sheet in a secondary battery according to an embodiment of the present application;
fig. 2 is a schematic diagram showing a battery cell structure of an embodiment of a secondary battery according to the embodiment of the present application;
fig. 3 is an exploded view of a battery cell of the secondary battery shown in fig. 2;
FIG. 4 is a schematic diagram of a battery module according to an embodiment of the present application;
FIG. 5 is a schematic view showing the structure of a battery pack according to an embodiment of the present application;
fig. 6 is an exploded view of the battery pack of fig. 5;
fig. 7 is a schematic diagram of an embodiment of an electric device including a secondary battery as a power source according to an embodiment of the present application.
Reference numerals illustrate:
11-positive electrode current collector; 12-an anode film layer; 121-a first region; 122-a second region; 123-middle region;
20-battery cells; 21-a housing; 22-a top cap assembly; 23-an electrode assembly; 30-battery module; 40-battery pack; 41-upper box body; 42-lower box.
Detailed Description
Embodiments of the technical scheme of the present application will be described in detail below with reference to the accompanying drawings. The following examples are only for more clearly illustrating the technical aspects of the present application, and thus are merely examples, and are not intended to limit the scope of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application; the terms "comprising" and "having" and any variations thereof in the description of the application and the claims and the description of the drawings above are intended to cover a non-exclusive inclusion.
In the description of embodiments of the present application, the technical terms "first," "second," and the like are used merely to distinguish between different objects and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated, a particular order or a primary or secondary relationship. In the description of the embodiments of the present application, the meaning of "plurality" is two or more unless explicitly defined otherwise.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.
In the description of the embodiments of the present application, the term "and/or" is merely an association relationship describing an association object, and indicates that three relationships may exist, for example, a and/or B may indicate: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
In the description of the embodiments of the present application, the term "plurality" means two or more (including two), and similarly, "plural sets" means two or more (including two), and "plural sheets" means two or more (including two). "at least one" means more than one (including one, two, three, etc.).
In the description of the embodiments of the present application, the orientation or positional relationship indicated by the technical terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. are based on the orientation or positional relationship shown in the drawings, and are merely for convenience of description and simplification of the description, and do not indicate or imply that the apparatus or element referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the embodiments of the present application.
In the description of the embodiments of the present application, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured" and the like should be construed broadly and may be, for example, fixedly connected, detachably connected, or integrally formed; or may be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the embodiments of the present application will be understood by those of ordinary skill in the art according to specific circumstances.
With the increasing decrease of traditional energy resources, the development of new energy storage devices is becoming more and more important. Among them, the secondary battery has been attracting attention due to its high energy density, high theoretical capacity, good cycle stability and environmental protection characteristics. The secondary battery can be widely applied to various fields such as electric bicycles, electric motorcycles, electric vehicles and the like, as well as energy storage power supply systems such as hydraulic power, thermal power, wind power and solar power stations. With the continuous expansion of the application field of secondary batteries as power batteries, the market demand of the secondary batteries is also continuously expanding, and the requirements on the cycle performance and the like of the batteries are also higher and higher.
The lithium ion battery is used as one of secondary batteries, and has the characteristics of high energy density, long service life, energy conservation, environmental protection and the like. However, lithium ion batteries have a defect of lithium ion loss after long-term cyclic use, and thus the cyclic capacity is easily attenuated.
At present, the monocrystal particles and the secondary particles of the positive electrode active material are mixed, and the monocrystal particles are filled into particle gaps of the secondary particles, so that the diaphragm resistance of the positive electrode plate can be reduced while the compacted density of the electrode plate is further improved, and the cycle performance of the battery is improved. However, by physical mixing of the single crystal particles and the secondary particles, the depths of lithium intercalation and lithium deintercalation of the positive electrode active materials of the two particles are inconsistent in the charge and discharge processes, so that the capacity of the positive electrode active materials cannot be effectively utilized in the later period of circulation, and the circulation capacity retention rate is affected.
Based on the above consideration, in order to improve the cycle capacity retention rate of the secondary battery, a positive electrode film layer including a first region and a second region is disposed on at least one surface of the positive electrode current collector, and a composite material of a core-shell structure, i.e., a first positive electrode active material of a coating layer, is used in the first region near one side of the positive electrode current collector to coat a lithium supplementing agent of the core, so that a slow lithium releasing effect is achieved by using the composite material of the first region to improve the cycle capacity retention rate. The following technical scheme is proposed.
Secondary battery
The secondary battery comprises a positive electrode plate, as shown in fig. 1, wherein the positive electrode plate comprises a positive electrode current collector 11 and a positive electrode film layer 12, and the positive electrode film layer 12 can be arranged on at least one surface of the positive electrode current collector 11, namely on one surface of the positive electrode current collector 11, or on two opposite surfaces of the positive electrode current collector 11.
The positive electrode film layer 12 has two opposite surfaces: a first surface adjacent to the positive electrode current collector 11 and a second surface disposed opposite to the first surface. The thickness of the positive electrode film layer 12 is denoted as H.
The region ranging from the first surface of the positive electrode film layer 12 to 0.1H in thickness is denoted as a first region 121 of the positive electrode film layer 12, wherein the first region 121 includes a composite material of a core-shell structure. Specifically, the composite material comprises a core and a coating layer arranged on at least a part of the surface of the core, wherein the core comprises a lithium supplementing agent, and the coating layer comprises a first positive electrode active material.
The area ranging from the second surface of the positive electrode film layer 12 to a thickness of 0.1H is denoted as a second area 122 of the positive electrode film layer 12. The second region 122 includes a second positive electrode active material.
In the embodiment of the application, the positive electrode film layer 12 including the first region 121 and the second region 122 is disposed on at least one surface of the positive electrode current collector 11, and the composite material in the first region 121 forms a core-shell structure through the lithium supplementing agent of the core coated by the first positive electrode active material of the coating layer, so that lithium can be slowly released through the lithium supplementing agent of the core. Specifically, as the secondary battery is continuously charged and discharged, the secondary battery is slowly polarized from the second region 122 to the first region 121 in the direction perpendicular to the surface of the positive electrode plate, so that after long-term cyclic use, the coating layer of the composite material close to one side of the positive electrode current collector 11 is broken, and the lithium supplementing agent of the core has a timely lithium supplementing effect, so that the slow lithium releasing effect is achieved by utilizing the composite material of the first region 121, and the cyclic capacity retention rate can be improved. Therefore, the secondary battery of the embodiment of the application is based on the specific positive electrode film layer 12 on the surface of the positive electrode plate, so that the secondary battery has good cycle capacity retention rate.
In one embodiment, the volume distribution particle size Dv50 of the second positive electrode active material is less than the volume distribution particle size Dv50 of the composite material.
The size of the particulate material is referred to as the particle size, the percentage of particles in the different size intervals to the total amount is referred to as the particle size distribution, and the volume distribution particle size is the particle size calculated cumulatively in units of the volume of the particles. For example, dv50 represents the particle size corresponding to a cumulative volume particle size distribution percentage of 50% in a sample, and in particular embodiments, the average particle size may be measured using a particle size tester.
Based on the second region 122 being far away from the positive electrode current collector 11, the second positive electrode active material in the second region 122 can be earlier contacted with the electrolyte, and the second positive electrode active material in the second region 122 has smaller Dv50, so that the specific surface area is larger, and the second positive electrode active material can be fully infiltrated with the electrolyte, thereby reducing the internal resistance and improving the energy conversion efficiency. Such secondary batteries have both high energy conversion efficiency and high cycle capacity retention.
In some embodiments, the volume distribution particle size Dv50 of the composite material in the first region 121 is 4-10 μm; specifically, the composite Dv50 may be 4 μm, 5 μm, 6 μm, 8 μm, 10 μm, etc. The composite material can well supplement lithium in the particle size range, and has small internal resistance.
In some embodiments, the volume distribution particle size Dv50 of the second positive electrode active material in the second region 122 is 1-3 μm. Specifically, the second positive electrode active material Dv50 may be 1 μm, 2 μm, 3 μm, or the like. The second positive electrode active material is not easy to agglomerate in the particle size range, is favorable for electrolyte infiltration, and has small internal resistance.
In some embodiments, the volume distribution particle size Dv50 of the composite material in the first region 121 is 4-10 μm; the volume distribution particle size Dv50 of the second positive electrode active material in the second region 122 is 1 to 3 μm. The combination and collocation of the composite material and the second positive electrode active material in the particle size range can enable the secondary battery to have better effects of energy conversion efficiency and circulation capacity retention rate.
In some embodiments, the mass ratio of the composite material in the first region 121, the first positive electrode active material and the lithium supplementing agent is (0.005-0.05): 1, a step of; specifically, the mass ratio of the first positive electrode active material to the lithium supplementing agent is 0.005: 1. 0.008: 1. 0.01: 1. 0.02: 1. 0.04: 1. 0.05:1, etc. The lithium supplementing agent and the first positive electrode active material form a composite material with a core-shell structure according to the mass ratio, so that on one hand, the lithium supplementing effect is good, the cycle capacity retention rate can be improved, and on the other hand, the influence on the available capacity and the safety performance of the secondary battery is small.
Further alternatively, the mass ratio of the first positive electrode active material to the lithium supplementing agent is (0.01-0.02): 1. this makes the secondary battery better in the combination of the cycle capacity retention rate amount and the safety performance.
In some embodiments, the positive electrode film layer 12 further includes an intermediate region 123 between the first region 121 and the second region 122 and having a thickness of 0.8H (H represents the thickness of the positive electrode film layer 12); specifically, the first region 121, the second region 122, and the intermediate region 123 located between the first region 121 and the second region 122 constitute the positive electrode film layer 12.
In some embodiments, the intermediate region 123 between the first region 121 and the second region 122 includes a composite material and/or a second positive electrode active material. For example, the intermediate region 123 may be identical in composition to the first region 121, whereby the distribution region of the composite material in the thickness direction of the positive electrode film layer 12 is in the thickness range from the first surface of the positive electrode film layer 12 to 0.9H. Alternatively, the intermediate region 123 may be identical in composition to the second region 122, whereby the distribution region of the second positive electrode active material in the thickness direction of the positive electrode film layer 12 is in the thickness range from the second surface of the positive electrode film layer 12 to 0.9H. Alternatively, the middle region 123 includes both the composite material and the second positive electrode active material, and at this time, the middle region 123 includes both the layer structure having the composite material and the layer structure having the second positive electrode active material.
According to the embodiment of the application, the mass ratio of the composite material in the positive electrode film layer 12 to the second positive electrode active material can be controlled by regulating and controlling the materials of the first region 121, the middle region 123 and the second region 122 in the positive electrode film layer 12, so that the effect of improving the circulation capacity retention rate is further realized.
In some embodiments, the mass ratio of the composite material in the positive electrode film layer 12 to the second positive electrode active material is (1:9) - (9:1); specifically, the mass ratio of the composite material to the second positive electrode active material in the positive electrode film layer 12 is 1: 9. 2: 8. 3: 7. 4: 6. 5: 5. 4: 6. 3: 7. 2: 8. 1:9, etc.
The composite material and the second positive electrode active material are matched in the positive electrode plate according to the mass ratio, so that the dosage of the composite material can be basically used in the thickness range from the first surface of the positive electrode film layer 12 to (0.1-0.9) H. For example, the mass ratio of the composite material to the second positive electrode active material is 1:9, the corresponding composite material can be distributed on the first surface of the positive electrode film layer 12 to a thickness range of 0.1H; alternatively, the mass ratio of the composite material to the second positive electrode active material is 9:1, the corresponding composite material can be distributed on the first surface of the positive electrode film layer 12 to a thickness range of 0.9H; and so on. The composite material and the second positive electrode active material within the mass ratio range not only improve the energy conversion efficiency of the secondary battery, but also improve the cycle capacity retention rate.
Further optionally, in the whole positive electrode film layer 12, the mass ratio of the composite material to the second positive electrode active material is (1:1) - (7:3). Thus, the relative proportion of the composite material is improved, and the high proportion composite material has more lithium releasing function, so that the comprehensive effect of the energy conversion efficiency and the cycle capacity retention rate of the secondary battery is better.
In some embodiments, the first and second positive electrode active materials of the composite material in the positive electrode film layer 12 as a whole are positive electrode active materials having the same material. Specifically, it may be a lithium ion battery positive electrode active material having the same chemical formula. Based on the first positive electrode active material and the second positive electrode active material, the positive electrode active material of the lithium ion battery with the same chemical formula is adopted, so that the first region 121, the second region 122 and the middle region 123 of the positive electrode film layer 12 have good compatibility, and lithium ions can stably migrate when the secondary battery is charged and discharged.
In some embodiments, the lithium ion battery positive electrode active material comprises lithium iron phosphate. The lithium iron phosphate has the characteristics of long service life, safe use and quick charging, and the lithium iron phosphate coating lithium supplementing agent is distributed in the first area 121, and the lithium iron phosphate serving as the second positive electrode active material is distributed in the second area 122, so that the tap density of the lithium iron phosphate can be further improved by the positive electrode film layer 12.
Further, by distributing the composite material (e.g., lithium iron phosphate coated lithium supplement agent) with a large volume distribution particle size in the first region 121 and distributing the lithium iron phosphate (e.g., small-particle single-crystal lithium iron phosphate material) with a small volume distribution particle size in the second region 122, the lithium iron phosphate tap density can be further increased.
In some embodiments, the lithium supplement agentComprises Li 2 NiO 2 、Li 5 FeO 4 、Li 2 MnO 3 、Li 6 CoO 4 、Li 2 At least one of O. The lithium supplementing agent has good lithium supplementing effect.
In some embodiments, the positive electrode film layer 12 has a thickness H of 50 to 200 μm. Specifically, the thickness H of the positive electrode film layer 12 may be 50 μm, 60 μm, 80 μm, 100 μm, 120 μm, 150 μm, 200 μm, or the like.
The positive electrode film layer 12 in the above thickness range, in which the composite material of the first region 121 is not easily peeled off, the second positive electrode active material of the second region 122 is not easily peeled off, and the secondary battery has excellent energy density.
In some embodiments, the first region 121, the second region 122, and the middle region 123 of the positive electrode film layer 12 further optionally include a conductive agent and/or a binder for the positive electrode sheet.
In one embodiment, the secondary battery comprises a lithium ion battery. Specifically, the separator comprises a positive pole piece, a negative pole piece and a separation film arranged between the positive pole piece and the negative pole piece. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film.
In some embodiments, the positive electrode tab includes a positive electrode current collector 11 and a positive electrode film layer 12 disposed on at least one surface of the positive electrode current collector 11.
In some embodiments, the positive electrode current collector 11 may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.
In some embodiments, the first region 121 of the positive electrode film layer 12 includes a composite material, a conductive agent, and a binder, wherein the mass ratio of the composite material, the conductive agent, and the binder may be (97-99): (0.5 to 1.5): (0.5 to 1.5). The second region 122 of the positive electrode film layer 12 includes a second positive electrode active material, a conductive agent and a binder, wherein the mass ratio of the second positive electrode active material, the conductive agent and the binder may be (97-99): (0.5 to 1.5): (0.5 to 1.5). Further, the middle region 123 of the positive electrode film layer 12 includes a composite material and/or a second positive electrode active material, as well as a conductive agent and a binder.
In some embodiments, the method for preparing the positive electrode film layer 12 includes: coating a first positive electrode slurry containing the composite material, the conductive agent and the binder in the proportion on a current collector, and drying to obtain a first region 121 and a part of middle region 123 of the positive electrode film layer 12; a second positive electrode slurry containing the above-described proportion of the second positive electrode active material, the conductive agent, and the binder is coated on the above-described part of the intermediate region 123, and dried to obtain the remaining intermediate region 123 and the second region 122 of the positive electrode film layer 12. The first region 121, the middle region 123, and the second region 122 form the positive electrode film layer 12.
As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin.
As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the negative electrode tab includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector. The negative electrode current collector can be a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.
The negative electrode film layer contains a negative electrode active material, and comprises at least one of artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based material, tin-based material and the like. And optionally also includes a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA) and carboxymethyl chitosan (CMCS). The anode active layer may further optionally include a conductive agent. The conductive agent is at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
In some embodiments, the negative electrode film layer may optionally further include other adjuvants, such as dispersants, thickeners (e.g., sodium carboxymethyl cellulose), and the like.
The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The embodiment of the application has no specific limitation on the type of electrolyte, and can be selected according to requirements. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is an electrolyte. The electrolyte includes an electrolyte salt and a solvent. For the secondary battery to be a lithium ion battery, the electrolyte salt may be at least one selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium difluorosulfonimide, lithium bistrifluoromethanesulfonimide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorooxalato phosphate, and lithium tetrafluorooxalato phosphate.
In some embodiments, the solvent in the electrolyte may be selected from at least one of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylene propylene carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1, 4-butyrolactone, sulfolane, dimethyl sulfone, methyl sulfone, and diethyl sulfone.
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
In some embodiments, the secondary battery of the embodiment of the present application may include any one of a battery cell, a battery module, and a battery pack.
The battery cell is a battery cell including a battery case and an electrode assembly encapsulated in the battery case. The shape of the battery cell is not particularly limited, and may be cylindrical, square, or any other shape. Such as the square-structured battery cell 20 shown in fig. 2.
In some embodiments, as shown in fig. 3, the exterior packaging of the battery cell 20 may include a housing 21 and a cap assembly 22. The housing 21 may include a bottom plate and a side plate coupled to the bottom plate, the bottom plate and the side plate enclosing to form a receiving cavity. The housing 21 has an opening communicating with the accommodation chamber, and the cap assembly 22 is used to cover the opening to close the accommodation chamber. The positive electrode sheet, the separator and the negative electrode sheet included in the secondary battery according to the embodiment of the present application may be formed into the electrode assembly 23 through a winding process and/or a lamination process. The electrode assembly 23 is packaged in the receiving chamber. The electrolyte is impregnated in the electrode assembly 23. The number of the electrode assemblies 23 included in the battery cell 20 may be one or more, and may be adjusted according to actual needs.
Methods of preparing the battery cells 20 are well known. In some embodiments, the positive, separator, and negative electrode tabs and electrolyte may be assembled to form the battery cell 20. As an example, the positive electrode sheet, the separator and the negative electrode sheet may be wound or laminated to form the electrode assembly 23, the electrode assembly 23 is placed in an external package, dried, and then the electrolyte is injected, and the battery cell 20 is obtained through vacuum packaging, standing, formation, shaping, and the like.
The battery module is assembled from the battery cells 20, that is, may contain a plurality of the battery cells 20, and the specific number may be adjusted according to the application and capacity of the battery module.
In some embodiments, fig. 4 is a schematic diagram of a battery module 30 as one example. In the battery module 30, the plurality of battery cells 20 may be sequentially arranged in the longitudinal direction of the battery module 30. Of course, the arrangement may be performed in any other way. The plurality of battery cells 20 may be further fixed by fasteners.
Alternatively, the battery module 30 may further include a case having an accommodating space in which the plurality of battery cells 20 are accommodated.
The battery pack is assembled from the above battery cells 20, that is, may contain a plurality of battery cells 20, wherein a plurality of battery cells 20 may be assembled into the above battery module 30. The specific number of battery cells 20 or battery modules 30 included in the battery pack may be adjusted according to the application and capacity of the battery pack.
Fig. 5 and 6 are schematic views of a battery pack 40 as one example, as in the embodiment. A battery case and a plurality of battery modules 30 disposed in the battery case may be included in the battery pack 40. The battery case includes an upper case 41 and a lower case 42, the upper case 41 being for covering the lower case 42 and forming a closed space for accommodating the battery module 30. The plurality of battery modules 30 may be arranged in the battery case in any manner.
Power utilization device
In a second aspect, the embodiment of the application also provides an electric device, which comprises the secondary battery according to the embodiment of the application. The secondary battery may be used as a power source of an electric device, or may be used as an energy storage unit of an electric device. Therefore, the embodiment of the application has high capacity retention rate of the power utilization device and can work well.
The electric device may be, but is not limited to, a mobile device (e.g., a cellular phone, a notebook computer, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), an electric train, a ship, a satellite, an energy storage system, etc. The power utilization device may select a secondary battery, a battery module, or a battery pack according to its use requirements.
Fig. 7 is a schematic diagram of an electrical device as one example. The electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. To meet the high power and high energy density requirements of the power device, a battery pack or battery module may be employed.
As another example, the power consumption device may be a mobile phone, a tablet computer, a notebook computer, or the like. The electric device is required to be light and thin, and a secondary battery can be used as a power source.
Examples
Hereinafter, embodiments of the present application are described. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
A secondary battery monomer comprises an electrode assembly formed by a positive electrode plate, a separation film and a negative electrode plate, and further comprises electrolyte. The preparation method of the secondary battery monomer comprises the following steps:
preparing a positive electrode plate:
taking methyl pyrrolidone (NMP) as a solvent, and mixing a composite material, conductive carbon black (Super P) and polyvinylidene fluoride (PVDF) according to a mass ratio of 97:2:1, mixing and dissolving in a solvent to prepare first anode slurry; the first positive electrode slurry was uniformly coated on an aluminum foil, and the aluminum foil was double-coated and dried to obtain a first region (thickness: 0.1H) and a part of an intermediate region (thickness: 0.6H) of the positive electrode film layer.
Taking methyl pyrrolidone (NMP) as a solvent, mixing a second positive electrode active material, conductive carbon black (Super P) and polyvinylidene fluoride (PVDF) according to a mass ratio of 97:2:1, mixing and dissolving in a solvent to prepare second anode slurry; the second positive electrode slurry was coated on the above part of the intermediate region, and the other part of the intermediate region (thickness: 0.2H) and the second region (thickness: 0.1H) of the positive electrode film layer were obtained by double-sided coating and drying. And finally, cold pressing and cutting to obtain the positive pole piece.
Wherein the positive electrode film layer includes a first region (thickness: 0.1H), an intermediate region (thickness: 0.8H), and a second region (thickness: 0.1H) in the thickness direction. The composite material comprises an inner core and a coating layer for coating the inner core, wherein the inner core material is lithium supplementing agent Li 2 NiO 2 The coating layer is made of a first positive electrode active material, the first positive electrode active material is first lithium iron phosphate, and the mass ratio of the first lithium iron phosphate to the lithium supplementing agent is 0.01:1, the Dv50 of the composite material is 10 mu m; the second positive electrode active material was a second lithium iron phosphate, and Dv50 was 3 μm. The total thickness H of the positive electrode film layer was 100. Mu.m.
Preparing a negative electrode plate: taking water as a solvent, and mixing artificial graphite, conductive carbon black, a sodium carboxymethyl cellulose dispersing agent and a styrene-butadiene rubber binder according to the mass ratio of 96:1:1:2, mixing to prepare negative electrode slurry; and uniformly coating the negative electrode slurry on an aluminum foil, performing double-sided coating, and fully drying, cold pressing and cutting to obtain the negative electrode plate.
Preparing an electrolyte: mixing Ethylene Carbonate (EC)/diethyl carbonate (DEC) at room temperature according to a volume ratio of 1:1, and adding LiPF into the mixed solution 6 A solution having a concentration of 1mol/L was obtained as an electrolyte.
And (3) battery assembly: and stacking and winding the prepared positive pole piece and negative pole piece in the order of positive pole piece, isolating film and negative pole piece to form an electrode assembly, and then filling electrolyte to assemble the lithium ion secondary battery monomer.
Example 2
A secondary battery monomer comprises an electrode assembly formed by a positive electrode plate, a separation film and a negative electrode plate, and further comprises electrolyte. The secondary battery cell was prepared by the steps different from those of example 1:
the Dv50 of the composite material was 4 μm; the Dv50 of the second positive electrode active material was 3 μm; the other components are the same as in example 1.
Example 3
A secondary battery monomer comprises an electrode assembly formed by a positive electrode plate, a separation film and a negative electrode plate, and further comprises electrolyte. The secondary battery cell was prepared by the steps different from those of example 1:
the Dv50 of the composite material was 6 μm; the Dv50 of the second positive electrode active material was 1 μm; the other components are the same as in example 1.
Example 4
A secondary battery monomer comprises an electrode assembly formed by a positive electrode plate, a separation film and a negative electrode plate, and further comprises electrolyte. The secondary battery cell was prepared by the steps different from those of example 1:
the Dv50 of the composite material is 11 μm; the Dv50 of the second positive electrode active material was 4 μm; the other components are the same as in example 1.
Example 5
A secondary battery monomer comprises an electrode assembly formed by a positive electrode plate, a separation film and a negative electrode plate, and further comprises electrolyte. The secondary battery cell was prepared by the steps different from those of example 1:
The Dv50 of the composite material was 6 μm; the Dv50 of the second positive electrode active material was 6 μm; the other components are the same as in example 1.
Example 6
A secondary battery monomer comprises an electrode assembly formed by a positive electrode plate, a separation film and a negative electrode plate, and further comprises electrolyte. The secondary battery cell was prepared by the steps different from those of example 1:
the Dv50 of the composite material was 2 μm; the Dv50 of the second positive electrode active material was 3 μm; the other components are the same as in example 1.
Example 7
A secondary battery monomer comprises an electrode assembly formed by a positive electrode plate, a separation film and a negative electrode plate, and further comprises electrolyte. The secondary battery cell was prepared by the steps different from those of example 1:
the Dv50 of the composite material was 6 μm; the Dv50 of the second positive electrode active material was 3 μm; the other components are the same as in example 1.
Example 8
A secondary battery monomer comprises an electrode assembly formed by a positive electrode plate, a separation film and a negative electrode plate, and further comprises electrolyte. The secondary battery cell was prepared by the steps different from those of example 1:
the mass ratio of the first positive electrode active material to the lithium supplementing agent is 0.02:1, a step of; the Dv50 of the composite material was 6 μm; the other components are the same as in example 1.
Example 9
A secondary battery monomer comprises an electrode assembly formed by a positive electrode plate, a separation film and a negative electrode plate, and further comprises electrolyte. The secondary battery cell was prepared by the steps different from those of example 1:
The mass ratio of the first positive electrode active material to the lithium supplementing agent is 0.005:1, a step of; the Dv50 of the composite material was 6 μm; the other components are the same as in example 1.
Example 10
A secondary battery monomer comprises an electrode assembly formed by a positive electrode plate, a separation film and a negative electrode plate, and further comprises electrolyte. The secondary battery cell was prepared by the steps different from those of example 1:
the mass ratio of the first positive electrode active material to the lithium supplementing agent is 0.05:1, a step of; the Dv50 of the composite material was 6 μm; the other components are the same as in example 1.
Example 11
A secondary battery monomer comprises an electrode assembly formed by a positive electrode plate, a separation film and a negative electrode plate, and further comprises electrolyte. The secondary battery cell was prepared by the steps different from those of example 1:
the mass ratio of the first positive electrode active material to the lithium supplementing agent is 0.004:1, a step of; the Dv50 of the composite material was 6 μm; the other components are the same as in example 1.
Example 12
A secondary battery monomer comprises an electrode assembly formed by a positive electrode plate, a separation film and a negative electrode plate, and further comprises electrolyte. The secondary battery cell was prepared by the steps different from those of example 1:
the mass ratio of the first positive electrode active material to the lithium supplementing agent is 0.06:1, a step of; the Dv50 of the composite material was 6 μm; the other components are the same as in example 1.
Comparative example 1
A secondary battery monomer comprises an electrode assembly formed by a positive electrode plate, a separation film and a negative electrode plate, and further comprises electrolyte. The secondary battery cell was prepared in the same manner as in example 1 except that the positive electrode sheet was prepared in different steps.
The preparation of the positive electrode sheet of this comparative example includes: the second positive electrode active material in example 1 was mixed with Carbon Nanotubes (CNT) and polyvinylidene fluoride (PVDF) in a mass ratio of 97:2:1, mixing and dissolving in a solvent to prepare anode slurry with the solid content of 80%; and uniformly coating the anode slurry on an aluminum foil, and performing double-sided coating, drying, cold pressing and cutting to obtain the anode plate. The amount of the second positive electrode active material of this comparative example was the same as the total amount of the composite material and the second positive electrode active material in example 1.
Comparative example 2
A secondary battery monomer comprises an electrode assembly formed by a positive electrode plate, a separation film and a negative electrode plate, and further comprises electrolyte. The secondary battery cell was prepared in the same manner as in example 1 except that the positive electrode sheet was prepared in different steps.
The coating order of the composite material and the second positive electrode active material of the positive electrode sheet of this comparative example was opposite to that of example 1, and the positive electrode sheet of this comparative example was prepared comprising:
The second positive electrode active material in example 1 was mixed with Carbon Nanotubes (CNT) and polyvinylidene fluoride (PVDF) in a mass ratio of 97:2:1, mixing and dissolving in a solvent to prepare first positive electrode slurry with 80% of solid content; uniformly coating the first positive electrode slurry on an aluminum foil, and performing double-sided coating and drying to obtain a first area and a part of middle area of a positive electrode film layer;
the composite material in example 1 was mixed with Carbon Nanotubes (CNT) and polyvinylidene fluoride (PVDF) in a mass ratio of 97:2:1, mixing and dissolving in a solvent to prepare second positive electrode slurry with the solid content of 80%; and uniformly coating the second positive electrode slurry on the partial middle area, and performing double-sided coating and drying to obtain the rest middle area and the second area of the positive electrode film layer. And finally cold pressing and cutting to obtain the positive pole piece.
Performance testing
The secondary battery cells of the above examples and comparative examples were respectively tested.
(1) Energy conversion efficiency test
The testing steps are as follows: the secondary battery cells in examples and comparative examples were taken to ensure at least 2 parallel samples. First, the secondary battery cell was left to stand in a constant temperature environment of 25 ℃ for 1 hour. And then constant-current charging is carried out on the secondary battery monomer at a charging rate of 2C, the secondary battery monomer is converted into constant-voltage charging after being charged to 3.65V, the charging is stopped when the charging current is lower than 0.05C, the secondary battery is placed for 5 minutes, the charging capacity and the charging voltage platform are obtained, then the secondary battery is discharged to 2.5V at a constant current by a discharging rate of 1C, the secondary battery is placed for 5 minutes, and the discharging capacity and the discharging flattening platform are obtained, so that the energy conversion efficiency = [ discharging capacity x discharging voltage platform ]/(charging capacity x charging voltage platform) ] x 100%.
(2) Cycle capacity retention test
The testing steps are as follows: room temperature 2C cycle test of secondary battery cell: the secondary battery cells of examples and comparative examples were taken, and at least 2 parallel samples were taken for each example. First, the battery cell was left to stand in a constant temperature environment of 25 ℃ for 1 hour. Then constant-current charging is carried out on the battery with the charging rate of 2C, the constant-voltage charging is carried out after the battery is charged to 3.65V, the charging is stopped when the charging current is lower than 0.05C, the battery is placed for 5 minutes, then the constant-current discharging rate of 1C is used for discharging the battery to 2.5V, the battery is placed for 5 minutes, the specific number of turns are circulated in the process, and the capacity retention rate is calculated: capacity retention ratio of the nth turn= (nth turn discharge capacity/second turn discharge capacity) ×100%, n=1000.
The results of the above energy conversion efficiency and cycle capacity retention test are shown in fig. 1.
From the data in table 1 above, it can be seen that: according to the application, the composite material with the core-shell structure is used in the first area, close to one side of the positive electrode current collector, of the positive electrode film layer, so that after long-time cyclic use, the inner core lithium supplementing agent has a slow lithium releasing effect, so that not only is the energy conversion efficiency high, but also the cyclic capacity retention rate can be improved, and the effect of the corresponding embodiment is better than that of the comparative example. The data from examples 1-7 show that: when the Dv50 of the composite material is 4-10 mu m, and the Dv50 of the second positive electrode active material is 1-3 mu m, the corresponding energy conversion efficiency and the circulation capacity retention rate are better. The data from examples 7-12 show that: when the mass ratio of the lithium supplementing agent to the first positive electrode active material of the coating layer is 0.005-0.05: 1, the corresponding energy conversion efficiency and the circulation capacity retention rate are better, and the mass ratio of the lithium supplementing agent to the first positive electrode active material of the coating layer is 0.01-0.02: the case of 1 is preferable.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application, and are intended to be included within the scope of the appended claims and description. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict. The present application is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.
Claims (11)
1. A secondary battery comprising a positive electrode sheet, characterized in that the positive electrode sheet comprises a positive electrode current collector and a positive electrode film layer provided on at least one surface of the positive electrode current collector, the positive electrode film layer having a first surface adjacent to the positive electrode current collector and a second surface provided opposite to the first surface, the thickness of the positive electrode film layer being denoted as H, a region ranging from the first surface to 0.1H of the positive electrode film layer being denoted as a first region of the positive electrode film layer, and a region ranging from the second surface to 0.1H of the positive electrode film layer being denoted as a second region of the positive electrode film layer; the first region includes a composite material including a core including a lithium supplementing agent and a coating layer disposed on at least a portion of a surface of the core, the coating layer including a first positive electrode active material, and the second region including a second positive electrode active material.
2. The secondary battery according to claim 1, wherein a volume distribution particle size Dv50 of the second positive electrode active material is smaller than a volume distribution particle size Dv50 of the composite material.
3. The secondary battery according to claim 2, wherein,
the volume distribution granularity Dv50 of the composite material is 4-10 mu m; and/or the number of the groups of groups,
the volume distribution granularity Dv50 of the second positive electrode active material is 1-3 mu m.
4. The secondary battery according to claim 1, wherein a mass ratio of the first positive electrode active material to the lithium supplementing agent is (0.005 to 0.05): 1.
5. the secondary battery according to claim 4, wherein a mass ratio of the first positive electrode active material to the lithium supplementing agent is (0.01 to 0.02): 1.
6. the secondary battery according to any one of claims 1 to 5, wherein an intermediate region between the first region and the second region includes the composite material and/or the second positive electrode active material.
7. The secondary battery according to claim 6, wherein a mass ratio of the composite material in the positive electrode film layer to the second positive electrode active material is (1:9) - (9:1).
8. The secondary battery according to claim 7, wherein a mass ratio of the composite material in the positive electrode film layer to the second positive electrode active material is (1:1) - (7:3).
9. The secondary battery according to any one of claims 1 to 5, wherein the first positive electrode active material and the second positive electrode active material are positive electrode active materials having the same material.
10. The secondary battery according to claim 9, wherein the positive electrode active material comprises lithium iron phosphate.
11. An electric device comprising the secondary battery according to any one of claims 1 to 10.
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