Patent Application
20230387380
The disclosure relates to the field of batteries, and in particular to a secondary battery, a battery module, a battery pack and a power consuming device.
In recent years, with the increasing application range of secondary batteries, secondary batteries are widely used in energy storage power systems such as hydroelectric, thermal, wind and solar power stations, as well as electric tools, electric bicycles, electric motorcycles, electric vehicles, military equipment, aerospace and other fields. Due to the great development of secondary batteries, higher requirements have also been placed on the secondary batteries in terms of energy density, cycle performance, safety performance, etc.
However, lithium dendrites generated during the use of secondary batteries, especially lithium-ion secondary batteries, will puncture a separator, thereby causing short-circuits, and resulting in unsafe phenomena such as battery burning, explosion, and scrapping. Therefore, one approach in the existing technology is to provide a coating on a separator of a battery to avoid puncturing the separator after the rapid growth of lithium dendrites. However, during the actual battery use, the tension of the separator is relatively large, and in the process of puncturing the separator by lithium dendrites, the separator may be ruptured and the coating on the surface is broken, making it ineffective. Furthermore, there is also a problem that the lithium storage amount of the material of the coating is low.
In order to prevent lithium evolution during the use of a battery, one solution in the existing technology is to use a design in which the capacity of the positive electrode of the battery is smaller than that of the negative electrode of the battery. Although setting the capacity ratio of the positive and negative electrodes in this way can avoid lithium evolution, it will result in a thicker cell thickness, which will seriously reduce the energy density of the battery. Therefore, the existing battery structure still needs to be improved.
The present application has been made in view of the above-mentioned problems, and an objective thereof is to provide a secondary battery which can not only improve the energy density but also solve the problem of lithium evolution.
In order to achieve the above objective, the present application provides a secondary battery and a battery module comprising the secondary battery, a battery pack comprising the battery module, and a power consuming device, as described below.
A first aspect of the present application provides a secondary battery comprising a positive electrode plate and a negative electrode plate, wherein the negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer provided on at least one surface of the negative electrode current collector, an insulation layer and a reaction layer are sequentially provided on the surface of the negative electrode active material layer on the side opposite to the negative electrode current collector side, and the reaction layer comprises at least one of graphite, silicon, silicon oxide, silicon suboxide, tin oxide, copper oxide, or zinc oxide, and when the capacity of the positive electrode active material layer per unit area in the positive electrode plate is denoted as A1, and the capacity of the negative electrode active material layer per unit area in the negative electrode plate is denoted as B1, B1/A1<1, optionally 0.3≤B1/A1≤1, more optionally 0.5≤B1/A1≤0.91.
Therefore, in the present application, the capacity of the positive electrode active material layer per unit area in the positive electrode plate is larger than the capacity of the negative electrode active material layer per unit area in the negative electrode plate, such that the energy density of the battery is higher than that of the conventional battery; and a specific layer structure is provided, and particularly, an insulation layer and a reaction layer are provided on the surface of the negative electrode active material layer, such that the lithium evolution problem can be effectively prevented, thereby improving the energy density, safety and cycle performance of the secondary battery.
In any embodiment, the insulation layer comprises at least one of aluminum oxide, boehmite, zirconium oxide, titanium oxide, magnesium oxide, cobalt oxide, nickel oxide, gallium oxide, germanium oxide, yttrium oxide, strontium oxide, barium oxide, or molybdenum oxide. As a result, a barrier can be formed physically, to inhibit growth of lithium dendrites.
In any embodiment, the battery satisfies that:
By satisfying the thickness of the reaction layer and the capacities of the active material layer per unit area in the positive electrode plate and negative electrode plate with the above relationships, the reaction layer can fully absorb the lithium dendrites passing through the insulation layer, thereby ensuring the safety and cycle performance of the secondary battery. In any embodiment, the gram capacity m1 of the reaction layer satisfies m1≥150 mAh/g, optionally 1000 mAh/g≤m1≤2500 mAh/g. Thereby, lithium dendrites can be better absorbed, and the volume occupied by the reaction layer is reduced.
In any embodiment, the density p of the reaction layer satisfies 0.2 g/cm3≤ρ≤3 g/cm3, optionally 1 g/cm3≤ρ≤2 g/cm3. Thereby, lithium dendrites can be better absorbed.
In any embodiment, the thickness of the reaction layer is 1 μm-30 μm, optionally 2 μm-μm, such that the volume of the battery is not increased while lithium dendrites are fully absorbed.
In any embodiment, the thickness of the insulation layer is 1 μm-10 μm, optionally 2 μm-4 μm. Thereby, the volume of the battery is not increased while the physical barrier effect is exerted.
In any embodiment, the Young's Modulus of the insulation layer is greater than or equal to 6 GPa, optionally 6 GPa−30 GPa. Thereby, the physical barrier effect can be better exerted.
In any embodiment, the particle size of the material in the reaction layer is 0.1 μm-4 μm, optionally 0.1 μm-0.8 μm; and/or the particle size of the material in the insulation layer is 0.1 optionally 0.1 μm-4 μm. Thereby, the effect of preventing lithium evolution of each of the reaction layer and the insulation layer can be better exerted.
In any embodiment, the capacity B1 of the negative electrode active material layer per unit area in the negative electrode plate is 0.3 mAh/cm2-7 mAh/cm2, optionally 1 mAh/cm2-5 mAh/cm2.
In any embodiment, the capacity A1 of the positive electrode active material layer per unit area in the positive electrode plate is 1 mAh/cm2-7 mAh/cm2, optionally 2 mAh/cm2-5 mAh/cm2. Thereby, the energy density of the battery can be improved.
A second aspect of the present application provides a battery module comprising the secondary battery of the first aspect of the present application.
A third aspect of the present application provides a battery pack comprising the battery module of the second aspect of the present application.
A fourth aspect of the present application provides a power consuming device comprising at least one selected from the secondary battery of the first aspect of the present application, the battery module of the second aspect of the present application, or the battery pack of the third aspect of the present application.
The present application achieves the following technical effects:
preventing lithium dendrites formed after lithium evolution during the use of a battery from puncturing a separator, resulting in a short-circuit failure of the battery. Specifically, when lithium dendrites are formed by lithium evolution in a cell, the insulation layer can form a barrier physically to inhibit the growth of the lithium dendrites, and when the lithium evolution amount is too large, after the lithium dendrites penetrate the insulation layer, the reaction layer can react with the same to ablate the part of the lithium dendrites that passes through the insulation layer.
In addition, the two coatings on the negative electrode, namely the insulation layer and the reaction layer, can prevent failures caused by battery manufacturing defects, for example, inward insertion of tabs, folding of plates, accidental falling of dust particles, and the like. Specifically, when the tabs are folded, the insulation layer and the reaction layer can function to increase the short-circuit resistance, which prevents an aluminum foil in the positive electrode and dust particles from contacting the negative electrode active material layer.
The design in which the capacity of the positive electrode is larger than that of the negative electrode used in the present application can improve the energy density; however, if the above coatings are not added, the design will fail due to the formation of lithium dendrites, and after the above coatings are added, the design can be used safely.
The two coatings provided on the negative electrode in the present application have a synergistic effect, where the dendrite-suppressing effect of the insulation layer can prevent the reaction layer from conducting electricity at the beginning, resulting in capacity loss, and the combination of the both makes the reaction layer react with only the dendrites that emerge and pose a risk, which improves the safety performance of the battery, and finally a battery with both high energy density and high safety is obtained.
1 Battery pack; 2 upper box body; 3 lower box body; 4 battery module; 5 secondary battery; 51 housing; 52 electrode assembly; 53 top cover assembly; 500 negative electrode current collector; 501 negative electrode active material layer; 502 insulation layer; and 503 reaction layer.
Hereafter, embodiments of a secondary battery, a battery module, a battery pack and a power consuming device of the present application are specifically disclosed in the detailed description with reference to the accompanying drawings as appropriate. However, unnecessary detailed illustrations may be omitted in some instances. For example, there are situations where detailed description of well known items and repeated description of actually identical structures are omitted. This is to prevent the following description from being unnecessarily verbose, and facilitates understanding by those skilled in the art. Moreover, the accompanying drawings and the descriptions below are provided for enabling those skilled in the art to fully understand the present application, rather than limiting the subject matter disclosed in claims.
“Ranges” disclosed in the present application are defined in the form of lower and upper limits, and a given range is defined by selection of a lower limit and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if the ranges of 60-120 and 80-110 are listed for a particular parameter, it should be understood that the ranges of 60-110 and are also contemplated. Additionally, if minimum range values 1 and 2 are listed, and maximum range values 3, 4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In the present application, unless stated otherwise, the numerical range “a-b” denotes an abbreviated representation of any combination of real numbers between a and b, where both a and b are real numbers. For example, the numerical range “0-5” means that all real numbers between “0-5” have been listed herein, and “0-5” is just an abbreviated representation of combinations of these numerical values. In addition, when a parameter is expressed as an integer of ≥2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and the like.
All the embodiments and optional embodiments of the present application can be combined with one another to form new technical solutions, unless otherwise stated.
All technical features and optional technical features of the present application can be combined with one another to form a new technical solution, unless otherwise stated.
Unless otherwise stated, all the steps of the present application can be performed sequentially or randomly, in some embodiments sequentially. For example, the method including steps (a) and (b) indicates that the method may include steps (a) and (b) performed sequentially, and may also include steps (b) and (a) performed sequentially. For example, reference to “the method may further include step (c)” indicates that step (c) may be added to the method in any order, e.g., the method may include steps (a), (b) and (c), steps (a), (c) and (b), and also steps (c), (a) and (b), etc.
The terms “comprise” and “include” mentioned in the present application are open-ended, unless otherwise stated. For example, “comprise” and “include” may mean that other components not listed may further be comprised or included.
In the present application, the term “or” is inclusive unless otherwise specified. For example, the phrase “A or B” means “A, B, or both A and B”. More specifically, a condition “A or B” is satisfied by any one of the following: A is true (or present) and B is false (or not present); A is false (or not present) and B is true (or present); or both A and B are true (or present).
In one embodiment of the present application, a secondary battery comprising a positive electrode plate and a negative electrode plate is provided, wherein the negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer provided on at least one surface of the negative electrode current collector, an insulation layer and a reaction layer are sequentially provided on the surface of the negative electrode active material layer on the side opposite to the negative electrode current collector side, and the reaction layer comprises at least one of graphite, silicon, silicon oxide, silicon suboxide, tin oxide, copper oxide, or zinc oxide, and when the capacity of the positive electrode active material layer per unit area in the positive electrode plate is denoted as A1, and the capacity of the negative electrode active material layer per unit area in the negative electrode plate is denoted as B1, B1/A1<1.
In some embodiments, 0.3≤B1/A1<1, for example, 0.5≤B1/A1≤0.91. The design can be made according to customer requirements, and for example, if the usage scenario is high battery service life, but a long cycle is not required, a design with extremely low B1/A1 may be used. The B1/A1 value is related to the theoretical gram capacity of positive and negative electrode active materials, the coating thickness of positive and negative electrodes, and the proportion of active materials, and the like.
In terms of battery design, in order to prevent lithium evolution during battery use, the capacity ratio of the positive and negative electrodes of a battery generally needs to be less than a certain value to ensure that during normal use, the battery does not undergo obvious lithium evolution, resulting in battery failure. Although setting the capacity ratio of the positive and negative electrodes in this way can avoid lithium evolution, it will result in a thicker cell thickness, which will seriously reduce the energy density of the battery.
In contrast to conventional batteries, in the present application, the capacity of the positive electrode active material layer per unit area in the positive electrode plate (hereinafter sometimes also referred to as the capacity of the positive electrode) is larger than the capacity of the negative electrode active material layer per unit area in the negative electrode plate (hereinafter sometimes also referred to as the capacity of the negative electrode), and the energy density of the battery can be higher than that of a conventional battery. However, in the design in which the capacity of the positive electrode is larger than that of the negative electrode used in the present application, the battery may fail due to the formation of a large number of lithium dendrites. Further, the applicant of the present application has found that by providing a special layer structure, particularly providing an insulation layer and a reaction layer on a surface of the negative electrode active material layer, namely, a composite coating, the lithium evolution problem can be effectively prevented. In this way, for the battery of the disclosure, not only the improvement of the energy density of the secondary battery is achieved, but also the hidden danger in safety is solved.
In the battery of the disclosure, the insulation layer provided on a surface of the negative electrode active material layer acts physically to prevent lithium dendrites from puncturing the layer of the separator, and the reaction layer provided on the insulation layer acts chemically to prevent lithium dendrites from puncturing the layer of the separator. The insulation layer may be a coating applied to the surface of the negative electrode active material layer, and the reaction layer may be a coating applied to the insulation layer. After the insulation layer and the reaction layer are provided, the safety of the battery is guaranteed. A battery with the capacity of the positive electrode being greater than that of the negative electrode will undergo lithium evolution in the process of any cycle, where most of the lithium layer exists under the insulation layer, and a part of the lithium that evolutes forms lithium dendrites that puncture the insulation layer, and the lithium dendrites passing through the insulation layer will be absorbed by the reaction layer once touching the same, so that the dendrites will no longer grow.
The material that can be used in the reaction layer may be any material, as long as it can chemically react with lithium dendrites, so as to prevent lithium dendrites from puncturing the separator, and for example, the same active material as in the negative electrode active material layer may be used. Examples of such a material that reversibly reacts with lithium dendrites may include, for example, graphite, silicon, silicon oxide, silicon suboxide and the like, and particularly optionally, silicon suboxide. In addition, since the proportion of the lithium ions in the whole battery which form the lithium dendrites penetrating the insulation layer to be consumed by the reaction layer is not too much, even if the reaction layer is a material that irreversibly reacts with the lithium dendrites, it will have little effect on the capacity. Examples of such an irreversible material be for example tin may oxide, copper oxide, zinc oxide, etc., which can form LiM alloys with lithium metal, thus contributing to better deposition of lithium. In some embodiments, the insulation layer comprises at least one of aluminum oxide, boehmite, zirconium oxide, titanium oxide, magnesium oxide, cobalt oxide, nickel oxide, gallium oxide, germanium oxide, yttrium oxide, strontium oxide, barium oxide, or molybdenum oxide. Particularly optionally, boehmite is used. By forming the insulation layer from the material comprising the above substances, a barrier can be formed physically, which prevents lithium dendrites generated during the battery use from puncturing the separator, thus ensuring the safety of the battery.
In some embodiments, the above-mentioned battery satisfies that:
By satisfying the thickness of the reaction layer and the capacities of the active material layer per unit area in the positive electrode plate and negative electrode plate with the above relationships, the reaction layer can fully absorb the lithium dendrites passing through the insulation layer, thereby ensuring the safety and cycle performance of the secondary battery, and also ensuring that the battery volume is not excessively increased.
In some embodiments, the gram capacity m1 of the reaction layer satisfies m1≥150 mAh/g, optionally 150 mAh/g−3000 mAh/g, more optionally 1000 mAh/g−2500 mAh/g. Thereby, lithium dendrites can be better absorbed, and the volume occupied by the reaction layer is reduced.
In some embodiments, the density p of the reaction layer satisfies 0.2 g/cm3≤ρ≤3 g/cm3, optionally 1 g/cm3≤ρ≤2 g/cm3. Thereby, lithium dendrites can be better absorbed.
In some embodiments, the thickness of the reaction layer is 1 μm-30 μm, optionally 2 μm-30 μm, such that the volume of the battery is not increased while lithium dendrites are fully absorbed.
In some embodiments, the thickness of the insulation layer is 1 μm-10 μm, optionally 2 μm-4 μm. Thereby, the volume of the battery is not increased while the barrier is formed physically. The thickness of the insulation layer depends on the particle size of the material constituting the insulation layer and the process of forming the insulation layer. A certain range of thickness does not affect the cycle performance, and if the process can meet the requirements, the thinner the better, provided that complete insulation can be achieved, otherwise active lithium will be consumed initially.
In some embodiments, the Young's Modulus of the insulation layer is greater than or equal to 6 GPa, optionally 6 GPa-30 GPa. Thereby, the physical barrier effect can be better exerted. The mechanical puncture strength of lithium dendrites is 6 GPa, and in order to exert the physical barrier effect, the Young's Modulus of the insulation layer needs to be greater than or equal to 6 GPa.
In some embodiments, the particle size of the material constituting the reaction layer is μm-4 μm, optionally 0.1 μm-0.8 μm; and/or the particle size of the material constituting the insulation layer is 0.1 μm-10 μm, optionally 0.1 μm-4 μm. Herein, the particle size of the material in the reaction layer is not larger than the thickness of the reaction layer, and the particle size of the material in the insulation layer is not larger than the thickness of the insulation layer. Thereby, the effect of preventing lithium evolution of each of the reaction layer and the insulation layer can be better exerted.
In some embodiments, the capacity of the negative electrode active material layer per unit area in the negative electrode plate is 0.3 mAh/cm2-7 mAh/cm2, optionally 1 mAh/cm2-5 mAh/cm2. In some embodiments, the capacity of the positive electrode active material layer per unit area in the positive electrode plate is 1 mAh/cm2-7 mAh/cm2, optionally 2 mAh/cm2-5 mAh/cm2. Thereby, the energy density of the battery can be improved.
A second aspect of the present application provides a battery module comprising the secondary battery of the first aspect of the present application.
A third aspect of the present application provides a battery pack comprising the battery module of the second aspect of the present application.
A fourth aspect of the present application provides a power consuming device comprising at least one selected from the secondary battery of the first aspect of the present application, the battery module of the second aspect of the present application, or the battery pack of the third aspect of the present application.
In addition, the secondary battery, battery module, battery pack, and power consuming device of the present application will be described below by appropriately referring to the accompanying drawings.
In one embodiment of the present application, a secondary battery is provided.
Typically, a secondary battery comprises a positive electrode plate, a negative electrode plate, an electrolyte and a separator. During the charge/discharge process of the battery, active ions are intercalated and de-intercalated back and forth between the positive electrode plate and the negative electrode plate. The electrolyte is located between the positive electrode plate and the negative electrode plate and functions for ionic conduction. The separator is provided between the positive electrode plate and the negative electrode plate, and mainly prevents the positive and negative electrodes from short-circuiting and enables ions to pass through.
[Positive Electrode Plate]
The positive electrode plate comprises a positive electrode current collector and a positive electrode active material layer provided on at least one surface of the positive electrode current collector.
As an example, the positive electrode current collector has two surfaces opposite in its own thickness direction, and the positive electrode active material layer is provided on either or both of the two opposite surfaces of the positive electrode current collector.
In some embodiments, the positive electrode current collector can be a metal foil or a composite current collector. For example, as a metal foil, an aluminum foil can be used. The composite current collector may comprise a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector can be formed by forming a metal material (aluminum, an aluminum alloy, nickel, a nickel alloy, titanium, a titanium alloy, silver and a silver alloy, etc.) on a polymer material substrate (e.g., polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, a positive electrode active material known in the art for batteries can be used in the positive electrode active material layer. As an example, the positive electrode active material may include at least one of the following materials: lithium-containing phosphates of an olivine structure, lithium transition metal oxides and their respective modified compounds. However, the present application is not limited to these materials, and other conventional materials that can be used as positive electrode active materials for batteries may also be used. These positive electrode active materials may be used alone or in combination of two or more. Herein, examples of lithium transition metal oxides may include, but are not limited to, at least one of lithium cobalt oxide (e.g. LiCoO2), lithium nickel oxide (e.g. LiNiO2), lithium manganese oxide (e.g. LiMnO2, LiMn2O4), lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (e.g. LiNi1/3Co1/3Mn1/3O2 (also referred to as NCM333), LiNi0.5Co0.2Mn0.3O2 (also referred to as NCM523), LiNi0.5Co0.25Mn0.25O2 (also referred to as NCM211), LiNi0.6Co0.2Mn0.2O2 (also referred to as NCM622), LiNi0.8Co0.1Mn0.1O2 (also referred to as NCM811)), lithium nickel cobalt aluminum oxide (e.g. LiNi0.85Co0.15Al0.05O2), or modified compounds thereof, and the like. Examples of lithium-containing phosphates of olivine structure may include, but are not limited to, at least one of lithium iron phosphate (e.g. LiFePO4 (also referred to as LFP)), lithium iron phosphate and carbon composites, lithium manganese phosphate (e.g. LiMnPO4), lithium manganese phosphate and carbon composites, lithium iron manganese phosphate, or lithium iron manganese phosphate and carbon composites.
In some embodiments, the positive electrode active material layer may also optionally comprise a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, or fluorine-containing acrylate resin. In some embodiments, the positive electrode active material layer may also optionally comprise a conductive agent. 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, or carbon nanofibers.
In some embodiments, the positive electrode plate can be prepared as follows: the above-mentioned components for preparing the positive electrode plate, for example, positive electrode active material, conductive agent, binder and any other components, are dispersed in a solvent (e.g. N-methylpyrrolidone) to form a positive electrode slurry; and the positive electrode slurry is coated onto a positive electrode current collector, and is then subjected to procedures such as drying and cold pressing, so as to obtain the positive electrode plate.
[Negative Electrode Plate]
The negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer provided on at least one surface of the negative electrode current collector, and an insulation layer and a reaction layer are sequentially provided on the surface of the negative electrode active material layer on the side opposite to the negative electrode current collector side.
As an example, the negative electrode current collector has two opposite surfaces in its own thickness direction, and the negative electrode active material layer is provided on either or both of the two opposite surfaces of the negative electrode current collector.
In some embodiments, the negative electrode current collector can be a metal foil or a composite current collector. For example, as a metal foil, a copper foil can be used. The composite current collector may comprise a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector can be formed by forming a metal material (copper, a copper alloy, nickel, a nickel alloy, titanium, a titanium alloy, silver and a silver alloy, etc.) on a polymer material substrate (e.g., polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, a negative electrode active material known in the art for batteries can be used in the negative electrode active material layer. As an example, the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, a silicon-based material, a tin-based material and lithium titanate, etc. The silicon-based material may be selected from at least one of elemental silicon, silicon oxides, silicon carbon composites, silicon nitrogen composites, or silicon alloys. The tin-based material may be selected from at least one of elemental tin, tin oxides, or tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as negative electrode active materials for batteries can also be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the negative electrode active material layer may also optionally comprise a binder. The binder can be a binder commonly used in the battery field, and there is no particular limitation, and the binder may be selected from at least one of 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), polyvinylidene fluoride, acryl-based polymers, diene-based polymers, or natural rubber. Particularly, a polystyrene-acrylate emulsion binder can be used.
In some embodiments, the negative electrode active material layer may also optionally comprise a conductive agent. The conductive agent may be selected from at least one of superconductive carbon, acetylene black, carbon black, ketjenblack, carbon dots, carbon nanotubes, graphene, or carbon nanofibers.
In some embodiments, a dispersant may also be used in preparing the negative electrode active material layer. The dispersant is used to improve the dispersion uniformity and coating property, and can be a commonly used dispersant in the battery field, for example, a polymer dispersant. The polymer dispersant can be polyvinyl alcohol, modified polyvinyl alcohol having functional groups other than hydroxyl group, for example, acetyl group, sulfo group, carboxyl group, carbonyl group, amino group, polyvinyl alcohol-based resins modified with various salts, modified with anions or cations, and acetal-modified with aldehydes, or various (meth)acrylic-based polymers, polymers derived from ethylenically unsaturated hydrocarbons, cellulose-based resins, etc., or copolymers thereof, but is not limited to these. The polymer dispersant may be used alone or in combination of two or more.
In some embodiments, the negative electrode active material layer may also optionally comprise other auxiliary agents, for example, thickener (e.g. sodium carboxymethyl cellulose (CMC-Na)) and the like.
In some embodiments, for the reaction layer, at least one material of graphite, silicon, silicon oxide, silicon suboxide, tin oxide, copper oxide and zinc oxide may be used. For the insulation layer, at least one material of aluminum oxide, boehmite, zirconium oxide, titanium oxide, magnesium oxide, cobalt oxide, nickel oxide, gallium oxide, germanium oxide, yttrium oxide, strontium oxide, barium oxide, and molybdenum oxide may be used.
In some embodiments, the negative electrode plate can be prepared as follows: the above components for preparing the negative electrode plate, such as negative electrode active material, conductive agent, binder and any other component, are dispersed in a solvent (e.g., deionized water) to form a slurry for negative electrode material layer; the above materials for forming the insulation layer, and a dispersant, a binder and any other component, are dispersed in a solvent (e.g., deionized water) to form a slurry for insulation layer, wherein the dispersant and the binder may be the above materials listed in the negative electrode active material layer; the above materials for forming the reaction layer, and a dispersant, a binder and any other component, are dispersed in a solvent (e.g., deionized water) to form a slurry for reaction layer, wherein the dispersant and the binder may be the above materials listed in the negative electrode active material layer; and the negative electrode slurry is coated onto the negative electrode current collector and dried, and then the slurry for insulation layer and the slurry for reaction layer are applied sequentially, and subjected to procedures such as drying and cold pressing, to obtain the negative electrode plate, wherein the coating operation can also be achieved by a one-step coating forming, for example, by a double-layer microgravure device on an extrusion coater; or by a multi-layer coater.
[Electrolyte]
The electrolyte is located between the positive electrode plate and the negative electrode plate and functions for ionic conduction. The type of the electrolyte is not specifically limited in the present application, and can be selected according to actual requirements. For example, the electrolyte may be liquid, gel or all solid.
In some embodiments, an electrolyte solution is used as the electrolyte. The electrolyte solution comprises an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonimide, lithium bistrifluoromethanesulfonimide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalate borate, lithium dioxalate borate, lithium difluorodioxalate phosphate, or lithium tetrafluorooxalate phosphate.
In some embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl 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, ethyl methyl sulfone, and diethyl sulfone.
In some embodiments, the electrolyte solution may optionally comprise an additive. For example, the additive can include a negative electrode film-forming additive, a positive electrode film-forming additive, and also an additive that can improve certain performances of the battery, such as an additive that improve the overcharge performance of the battery, or an additive that improve the high temperature performance or low-temperature performance of the battery.
[Separator]
In some embodiments, the secondary battery further comprises a separator. The type of the separator is not particularly limited in the present application, and any well known porous-structure separator with good chemical stability and mechanical stability may be selected.
In some embodiments, the material of the separator may be selected from at least one of glass fibers, non-woven fabrics, polyethylene, polypropylene, or polyvinylidene fluoride. The separator may be a single-layer film and also a multi-layer composite film, and is not limited particularly. When the separator is a multi-layer composite film, the materials in the respective layers may be same or different, which is not limited particularly.
In some embodiments, an electrode assembly may be formed by a positive electrode plate, a negative electrode plate and a separator by a winding process or a laminating process.
In some embodiments, the secondary battery may comprise an outer package. The outer package can be used to encapsulate the above-mentioned electrode assembly and electrolyte.
In some embodiments, the outer package of the secondary battery can be a hard shell, for example, a hard plastic shell, an aluminum shell, a steel shell, etc. The outer package of the secondary battery may also be a soft bag, such as a pouch-type soft bag. The material of the soft bag may be plastics, and the examples of plastics may include polypropylene, polybutylene terephthalate, and polybutylene succinate, etc.
The shape of the secondary battery is not particularly limited in the present application, and may be cylindrical, square or of any other shape. For example,
In some embodiments, referring to
In some embodiments, the secondary battery can be assembled into a battery module, and the number of the secondary batteries contained in the battery module can be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
Optionally, the battery module 4 may also comprise a housing with an accommodating space, and a plurality of secondary batteries 5 are accommodated in the accommodating space.
In some embodiments, the above-mentioned battery module may also be assembled into a battery pack, the number of battery modules included in the battery pack may be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery pack.
In addition, the present application further provides a power consuming device. The power consuming device comprises at least one of the secondary battery, battery module, or battery pack provided by the present application. The secondary battery, battery module or battery pack may be used as a power source of the power consuming device or as an energy storage unit of the power consuming device. The power consuming device may include a mobile device (e.g., a mobile phone, a laptop 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), an electric train, ship, and satellite, an energy storage system, and the like, but is not limited thereto.
For the power consuming device, the secondary battery, battery module or battery pack can be selected according to the usage requirements thereof.
As another example, the device may be a mobile phone, a tablet, a laptop computer, etc. The device is generally required to be thin and light, and may use a secondary battery as a power source.
Hereinafter, the examples of the present application will be explained. The examples described below are exemplary and are merely for explaining the present application, and should not be construed as limiting the present application. The techniques or conditions that are not specified in examples are according to the techniques or conditions described in documents in the art or the product introduction. The reagents or instruments used, if they are not marked with the manufacturer, are common products that are commercially available.
Test methods:
(1) Test of cycle performance
The battery was repeatedly charged and discharged through the following steps, and the discharge capacity retention rate of the battery was calculated.
First, in an environment at 25° C., a first charge and discharge was performed: the battery was constant-current-charged at a charge current of 0.33 C (i.e., a current value when the theoretical capacity is completely discharged over 3 h), then charged with a constant voltage until the upper voltage limit was 4.25V, and then constant-current-discharged at a discharge current of until the final voltage was 2.8V, and the discharge capacity of the first cycle was recorded. Then charge and discharge cycles were performed until the battery capacity loss rate reached 20% (i.e., the capacity retention rate was 80%), and the number of cycles at this time was recorded.
Herein, according to the formula: capacity loss rate=((discharge capacity of the first cycle−discharge capacity after N cycles)/discharge capacity of the first cycle)×100%, the capacity loss rate of the battery after N cycles was calculated.
(2) Test of volumetric energy density
The capacity of the battery was tested by charging and discharging at a small rate (0.1-0.3 C), and the volumetric energy density was calculated by the following formula.
Volumetric energy density(Wh/L)=capacity(Ah)*plateau voltage(V)/cell volume (L)
1. Preparation of Secondary Battery
1) Preparation of Positive Electrode Plate:
A positive active material LiNi0.8Co0.1Mn0.1O2, superconducting carbon black SP as a conductive agent and polyvinylidene fluoride (PVDF) as a binder were dispersed in N-methylpyrrolidone (NMP) as a solvent in a mass ratio of 96:1.2:2.8 and mixed uniformly to obtain a positive electrode slurry; and the positive electrode slurry was evenly coated onto a positive electrode current collector aluminum foil, and was subjected to drying, cold pressing, slitting and cutting, so as to obtain the positive electrode plate.
2) Preparation of Separator:
A polyethylene film was selected as the separator.
3) Preparation of Negative Electrode Plate:
Preparation of slurry for insulation layer: Boehmite, a dispersant polyvinyl alcohol, and a binder polystyrene-acrylate emulsion were dispersed in deionized water as a solvent in a mass ratio of 96.5:0.5:3 and mixed uniformly. Herein, the particle size (namely, the median particle size Dv50) of the boehmite was 0.3 μm.
Preparation of slurry for reaction layer: Silicon suboxide, a dispersant polyvinyl alcohol, and a binder polystyrene-acrylate emulsion were dispersed in deionized water as a solvent in a mass ratio of 96.5:0.5:3 and mixed uniformly. Herein, the particle size (namely, the median particle size) of the silicon suboxide was 1 μm.
Preparation of slurry for negative electrode active material layer: A negative electrode active material artificial graphite, superconducting carbon black as a conductive agent, SBR as a binder, and CMC-Na as a thickener were dispersed in deionized water as a solvent in a mass ratio of 96:1:1:2 and mixed uniformly to obtain a negative electrode slurry.
Preparation of negative electrode plate: The slurry for negative electrode active material layer was uniformly coated on a negative electrode current collector copper foil, and after drying, the slurry for insulation layer was coated on the negative electrode active material layer, where the thickness of the insulation layer was 2 μm; after drying, the slurry for reaction layer was coated on the insulation layer, where the thickness of the reaction layer was 7 μm, and after drying, cold pressing, slitting and cutting, a negative electrode plate was obtained.
4) Preparation of Electrolyte Solution
Ethylene carbonate (EC), dimethyl carbonate (DMC), and diethyl carbonate (DEC) were mixed in a volume ratio of 1:1:1 into an organic solvent, and then the fully dried lithium salt LiPF6 was dissolved in the mixed organic solvent, so as to prepare an electrolyte solution with a concentration of 1 mol/L.
5) Preparation of Secondary Battery:
The above-mentioned positive electrode plate, separator, and negative electrode plate were stacked in sequence, such that the separator was placed between the positive electrode plate and the negative electrode plate to play a role of isolation, and then winding was performed to make a cell, where the negative electrode capacity was 0.3 times the positive electrode capacity; further, after winding, hot pressing was performed for the preparation of the cell; and then, the cell was placed in an outer package shell and dried, and the electrolyte solution was injected, followed by procedures such as vacuum encapsulating, standing, forming and shaping, to obtain a secondary battery.
2. Performance Test of Secondary Battery
The cycle performance and volumetric energy density of the obtained secondary battery were measured as described above.
A secondary battery was prepared as in Example 1 except that the reaction conditions were changed as shown in Table 1 and Table 2.
Herein, in Examples 2 to 11 shown in Table 1, the value of B1/A1 was changed by changing the negative electrode capacity B1, and the thickness d of the reaction layer was also changed. As shown in Table 2, in Examples 12 and 13, the type of material for insulation layer was changed; in Examples 14 and 15, the type and thickness of material for reaction layer were changed; in Examples 16 to 18, the thickness of the insulation layer was changed; and in Examples 19 to 23, the capacity A1 of the positive electrode active material layer per unit area in the positive electrode plate were changed by changing the thickness of the positive electrode active material layer, where thick coating is required, and it is difficult to achieve this for the existing process. The larger the value of A1, the higher the coating process requirements are, and if the coating is too thick, the solvent is difficult to volatilize, and thus the film is easy to crack.
A secondary battery was prepared as in Example 1 except that the reaction conditions were changed as shown in Table 3.
Herein, in Comparative Examples 1 to 3, the value of B1/A1 was greater than 1, and at least one of the insulation layer or the reaction layer was not provided; and in Comparative Examples 4 to 6, the value of B1/A1 was less than 1, at least one of the insulation layer or the reactive layer was not provided.
According to the above results, it can be seen that the examples show good performances in terms of volumetric energy density and cycle life. In contrast, in the comparative examples, both the volumetric energy density and the cycle life cannot be achieved simultaneously. Specifically, in Comparative Examples 1 to 3, the effect of the insulation layer and the reaction layer as the value of B1/A1 is greater than 1 has been investigated, and in Comparative Examples 4 and 5, the effect of the insulation layer and the reaction layer as the value of B1/A1 is less than 1 has been investigated. By comparison with Comparative Example 1, it can be seen that in Comparative Example 4, when the value of B1/A1 is reduced, the volumetric energy density can be improved, but the cycle life is extremely poor when the insulation layer and the reaction layer are not provided. As can be seen from Comparative Example 5, when only the insulation layer is provided without providing the reaction layer, the cycle life is still poor. As can be seen from Comparative Example 6, when only the reaction layer is provided without providing the insulation layer, the cycle life is greatly improved, but the cycle life is still shorter than that of Example 11 in which both the reaction layer and the insulation layer are provided. From this, it can be seen that by providing the reaction layer and the insulation layer on the negative electrode plate, the synergistic effect of greatly improving the safety can be achieved.
It should be noted that the present application is not limited to the above embodiments. The above embodiments are exemplary only, and any embodiment that has substantially same constitutions as the technical ideas and has the same effects within the scope of the technical solution of the present application falls within the technical scope of the present application. In addition, without departing from the gist of the present application, various modifications that can be conceived by those skilled in the art to the embodiments, and other modes constructed by combining some of the constituent elements of the embodiments also fall within the scope of the present application.
This application is a continuation of International Application No. PCT/CN2021/123995, filed on Oct. 15, 2021, the entire content of which is incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2021/123995 | Oct 2021 | US |
| Child | 18147201 | US |
