Patent Application
20230124276
The present application relates to the technical field of lithium-ion batteries, and in particular relates to a lithium-ion battery, and a battery module, a battery pack and a power consuming device comprising the lithium-ion battery.
Lithium-ion batteries have advantages such as high energy density, high cycle performance, high voltage, low self-discharge and light weight, and are widely used in portable electronic products such as laptop computers, digital cameras, mobile phones and watches. With the wide application of various portable electronic products, people have higher and higher requirements on the performance of lithium-ion batteries, especially the energy density and cycle performance of the lithium-ion batteries.
Current lithium-ion batteries are usually designed in a wound structure. During the cycle process of a battery, the intercalation and de-intercalation of lithium ions may occur between a positive electrode and a negative electrode of the battery. During the migration of the lithium ions from the positive electrode to the negative electrode, since in a bending part of a cell, there is a gap in an inner ring due to the limitation of a wound structure of the battery, such that the capacity ratio of the negative electrode to the positive electrode of the battery is lower than in other positions in the cell, there are too many lithium ions from the positive electrode to be intercalated into the negative electrode, and the negative electrode has no enough capacity for the intercalation of lithium ions, causing the excess lithium ions to precipitate in an area of the negative electrode in the inner ring wrapped by the positive electrode. The lithium precipitation in the negative electrode will seriously degrade the cycle performance of the battery.
Lithium thus-precipitated forms into a dendritic morphology, which may puncture a separator and connect the positive and negative electrodes, to cause a short circuit, resulting in a serious safety accident.
The disclosure has been made in view of the above issues, and an objective of the disclosure is to provide a lithium-ion battery, which can eliminate lithium dendrites generated in an electrode plate of a wound-type cell, especially in a bending part, improve the problem of lithium precipitation at the corner of the cell, and improve the cycle performance and safety of the lithium-ion battery.
To achieve the above objective, a first aspect of the present application provides a lithium-ion battery, comprising a wound structure formed by winding a negative electrode plate, a separator and a positive electrode plate in a winding direction, the wound structure comprising an arc-shaped bending part, wherein the negative electrode plate comprises a negative electrode material layer, and an insulation layer and a reaction layer located on a surface of the insulation layer are provided on a surface of the negative electrode material layer in the bending part, the reaction layer comprising a lithium storage material.
By providing the insulation layer and the reaction layer located on the surface of the insulation layer on the surface of the negative electrode material layer, the insulation layer enables physical isolation of lithium dendrites, and even when the insulation layer is punctured by the lithium dendrites, the reaction layer on the surface of the insulation layer can react with the lithium dendrites, thus eliminating the lithium dendrites.
In some embodiments, the thickness d of the reaction layer satisfies that:
in some embodiments, the thickness d of the reaction layer satisfies that:
and in some embodiments, the thickness d of the reaction layer satisfies that:
where,
h1: the thickness of a single layer of the negative electrode material layer, in μm;
h2: the thickness of a single layer of the positive electrode material layer, in μm;
h3: the thickness of the separator, in μm;
x: the distance between the negative electrode material layer and the positive electrode material layer in the bending part, in μm;
q: the capacity of a single layer of the negative electrode active material layer in the bending part, in mAh;
a: the area of a single layer of the negative electrode active material layer in the bending part, in cm2;
m1: the gram capacity of the reaction layer, in mAh/g;
ρ: the density of the reaction layer, in g/cm3;
d: in μm.
By satisfying the thickness of the reaction layer with the above relationships, the reaction layer is enabled to sufficiently react with the lithium dendrites which puncture and pass through the insulation layer, thus improving the cycle performance and safety of the lithium-ion battery.
In some embodiments, the lithium storage material comprises at least one of graphite (which may be artificial graphite or natural graphite), elemental silicon, silicon oxide, silicon suboxide, tin oxide, copper oxide, or zinc oxide.
By using such a reaction layer, when the insulation layer is punctured by the lithium dendrites, the lithium dendrites can well react with the reaction layer, eliminating the lithium dendrites, and thereby improving the safety of the battery.
In some embodiments, the insulation layer comprises at least one of aluminum oxide, boehmite, zirconium oxide, titanium oxide, magnesium oxide, lithium oxide, silicon oxide, cobalt oxide, nickel oxide, zinc oxide, gallium oxide, germanium oxide, yttrium oxide, strontium oxide, barium oxide, or molybdenum oxide.
By using such an insulation layer, a barrier can be formed physically, to inhibit the growth of the lithium dendrites.
In some embodiments, the thickness of the insulation layer is 1 to 10 μm, and in some embodiments, 2 to 4 km.
Technically, it is difficult to achieve the thickness of the insulation layer of less than 1 m. The upper limit of the thickness of the insulation layer is not particularly limited, and from the viewpoint of cost, the upper limit can be set to 10 μm, at which point, the role of physically isolating the lithium dendrites can be fully exerted.
In some embodiments, the Young's modulus of the insulation layer is greater than or equal to 6 GPa, and in some embodiments, 6 to 30 GPa.
By making the Young's modulus of the insulation layer greater than or equal to 6 GPa, the role of physically isolating the lithium dendrites can be fully exerted.
In some embodiments, the gram capacity of the reaction layer is 300 to 5000 mAh/g, and in some embodiments, 1000 to 4000 mAh/g.
By making the gram capacity of the reaction layer be 300 to 5000 mAh/g, the lithium dendrites can be better absorbed, and the volume occupied by the reaction layer can be reduced.
In some embodiments, the particle size of the reaction layer is 0.1 to 6 μm, and in some embodiments, 0.1 to 2 μm, and the particle size of the insulation layer is 0.1 to 10 μm, and in some embodiments, 0.1 to 4 μm.
By making the particle size of the reaction layer be 0.1 to 6 μm and the particle size of the insulation layer be 0.1 to 10 μm, the respective layers can be uniformly formed, and thus the respective roles of preventing lithium precipitation of the reaction layer and the insulation layer can be better exerted.
A second aspect of the present application provides a battery module comprising the lithium-ion 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 lithium-ion 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.
According to the disclosure, the separator being punctured due to the formation of the lithium dendrites at the bend of the wound structure and thus causing a short-circuit failure of the battery can be prevented. When the lithium dendrites are formed at the bend of the wound structure, the insulation layer can form a barrier physically to inhibit the growth of the lithium dendrites. When the amount of the released lithium is too large and the lithium dendrites grow further and puncture the insulation layer, the reaction layer can react with and ablate some of the lithium dendrites which pass through the insulation layer, and thus, the cycle performance and safety of the lithium-ion battery can be improved.
A: bending part; B: planar part; 101: positive electrode plate; 102: negative electrode plate; 103: separator; 104: reaction layer; 106: insulation layer; x: distance between the negative electrode material layer and the positive electrode material layer in the bending part; 1: battery pack; 2: upper box body; 3: lower box body; 4: battery module; 5: lithium-ion battery; 51: housing; 52: electrode assembly; 53: top cover assembly.
Hereafter, embodiments of a lithium-ion battery and a method for manufacturing the same, and 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 to 120 and 80 to 110 are listed for a particular parameter, it should be understood that the ranges of 60 to 110 and 80 to 120 are also contemplated. In addition, 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 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4 and 2 to 5. In the present application, unless stated otherwise, the numerical range “a to 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 to 5” means that all real numbers between “0 to 5” have been listed herein, and “0 to 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 stated otherwise, 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).
A first aspect of the present application provides a lithium-ion battery. The lithium-ion battery of the present application comprises a wound structure formed by winding a negative electrode plate, a separator and a positive electrode plate in a winding direction, the wound structure comprising an arc-shaped bending part, wherein the negative electrode plate comprises a negative electrode material layer, and an insulation layer and a reaction layer located on a surface of the insulation layer are provided on a surface of the negative electrode material layer in the bending part, the reaction layer comprising a lithium storage material.
When the lithium-ion battery is of a wound structure, the lithium precipitation is prone to occur due to a gap in an arc-shaped bending part of the wound structure, and the lithium dendrites formed by lithium thus-precipitated may overgrow and puncture the separator. In the lithium-ion battery of the present application, by providing an insulation layer on the surface of the negative electrode material layer in the bending part, the insulation layer can isolate the lithium dendrites physically, to inhibit the growth of the lithium dendrites and prevent the lithium dendrites from puncturing the separator. By further providing a reaction layer on a surface of the insulation layer, when the lithium dendrites overgrow to puncture the insulation layer, the reaction layer can react with the lithium dendrites, thus eliminating the lithium dendrites, which can further prevent the lithium dendrites from puncturing the separator.
The thickness d of the reaction layer satisfies that:
where, h1: the thickness of a single layer of the negative electrode material layer, in μm;
h2: the thickness of a single layer of the positive electrode material layer, in μm;
h3: the thickness of the separator, in μm;
x: the distance between the negative electrode material layer and the positive electrode material layer in the bending part, in μm;
q: the capacity of a single layer of the negative electrode active material layer in the bending part, in mAh;
a: the area of a single layer of the negative electrode active material layer in the bending part, in cm2;
m1: the gram capacity of the reaction layer, in mAh/g;
p: the density of the reaction layer, in g/cm3;
d: in μm.
By satisfying the thickness of the reaction layer with the above relationship, the reaction layer is enabled to sufficiently react with the lithium dendrites which puncture the insulation layer and pass through the insulation layer, thus improving the cycle performance and safety of the lithium-ion battery.
In some embodiments, the thickness d of the reaction layer satisfies that:
Further in some embodiments, the thickness d of the reaction layer satisfies that:
In addition, in some embodiments, from the viewpoints of coating process and cost, the upper limit of the thickness of the reaction layer is 200 km.
The lithium storage material that can be used in the reaction layer may be any material, as long as it can chemically react with the lithium dendrites, so as to prevent the lithium dendrites from puncturing the separator, and for example, the same active material as in the negative electrode material layer may be used. Examples of such a material that can react with the lithium dendrites may be for example at least one of graphite, elemental silicon, silicon oxide, silicon suboxide, tin oxide, copper oxide, or zinc oxide. Herein, in some embodiments, a material that can reversibly react with the lithium dendrites is used, for example, graphite, elemental silicon, silicon oxide or silicon suboxide, and particularly in some embodiments elemental silicon or silicon suboxide. In addition, since the proportion of the lithium ions in the whole battery which form the lithium dendrites puncturing and passing through the insulation layer to be ablated 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 may be for example tin oxide, copper oxide, zinc oxide, etc., which can form LiM alloys with lithium metal, thus contributing to better deposition of lithium.
By using such a reaction layer, when the insulation layer is punctured by the lithium dendrites and the lithium dendrites pass through the insulation layer, the lithium dendrites can well react with the reaction layer, eliminating the lithium dendrites, and thereby improving the safety of the battery.
The insulation layer that can be used in the lithium-ion battery of the present application may comprise at least one of aluminum oxide, boehmite, zirconium oxide, titanium oxide, magnesium oxide, lithium oxide, silicon oxide, cobalt oxide, nickel oxide, zinc oxide, gallium oxide, germanium oxide, yttrium oxide, strontium oxide, barium oxide, or molybdenum oxide. In some embodiments, the insulation layer comprises boehmite, aluminum oxide or zirconium oxide.
By using such an insulation layer, a barrier can be formed physically, to inhibit the growth of the lithium dendrites and prevent the lithium dendrites generated in the use of a battery from puncturing the separator, thereby improving the safety of the lithium-ion battery.
The thickness of the insulation layer is 1 to 10 μm, and in some embodiments, 2 to 4 km.
Technically, it is difficult to achieve the thickness of the insulation layer of less than 1 μm. The upper limit of the thickness of the insulation layer is not particularly limited, and from the viewpoint of cost, the upper limit can be set to 10 μm, at which point, the role of physically isolating the lithium dendrites can be fully exerted.
The Young's modulus of the insulation layer is greater than or equal to 6 GPa, and in some embodiments, 6 to 30 GPa.
By making the Young's modulus of the insulation layer greater than or equal to 6 GPa, the role of physically isolating the lithium dendrites can be fully exerted.
The gram capacity of the reaction layer is 300 to 5000 mAh/g, and in some embodiments, 1000 to 4000 mAh/g.
By making the gram capacity of the reaction layer be 300 to 5000 mAh/g, the reaction layer can better react with the lithium dendrites, thus eliminating the lithium dendrites, and the volume occupied by the reaction layer is reduced.
The particle size of the reaction layer is 0.1 to 6 μm, and in some embodiments, 0.1 to 2 μm, and the particle size of the insulation layer is 0.1 to 10 μm, and in some embodiments, 0.1 to μm.
By making the particle size of the reaction layer be 0.1 to 6 μm and the particle size of the insulation layer be 0.1 to 10 μm, the respective layers can be uniformly formed, and thus the respective roles of preventing lithium precipitation of the reaction layer and the insulation layer can be better exerted.
A second aspect of the present application provides a battery module comprising the lithium-ion 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 lithium-ion 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 lithium-ion 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 an embodiment of the present application, a lithium-ion battery is provided.
The lithium-ion 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 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 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 for batteries well known in the art can be used in the positive electrode 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. LiNi1/3Co1/3MnO13O2 (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), LiNi0.5Co0.1Mn0.1O2 (also referred to as NCM811)), lithium nickel cobalt aluminum oxide (e.g. LiNi0.85Co0.15Al0.05O2), and 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 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 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 material layer provided on at least one surface of the negative electrode current collector.
As an example, the negative electrode current collector has two opposite surfaces in its own thickness direction, and the negative electrode material layer is provided on either or both of the two opposite surfaces of the negative electrode current collector.
An insulation layer and a reaction layer located on a surface of the insulation layer are provided on a surface of the negative electrode material layer in the bending part.
As an example, the insulation layer and the reaction layer are located on a surface of the negative electrode material layer that faces the outside after winding.
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 for batteries well known in the art can be used in the negative electrode 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 at least one selected from elemental silicon, silicon oxides (silicon oxide, silicon suboxide, etc.), silicon carbon composites, silicon nitrogen composites and silicon alloys. The tin-based material may be at least one selected from elemental tin, tin oxides (tin oxide) and 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 material layer may also optionally comprise a binder. The binder may be at least one selected from a 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).
In some embodiments, the negative electrode material layer may also optionally comprise a conductive agent. The conductive agent may be at least one selected from superconductive carbon, acetylene black, carbon black, ketjenblack, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the negative electrode material layer may also optionally comprise other auxiliary agents, such as thickener (e.g., sodium carboxymethyl cellulose (CMC-Na)) and the like.
In some embodiments, a dispersant may also be used in preparing the negative electrode 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, at least one material of graphite, silicon oxide, silicon suboxide, tin oxide, copper oxide and zinc oxide may be used in the reaction layer.
In some embodiments, the insulation layer may comprise at least one material of aluminum oxide, boehmite, zirconium oxide, titanium oxide, magnesium oxide, lithium oxide, silicon oxide, cobalt oxide, nickel oxide, zinc oxide, gallium oxide, germanium oxide, yttrium oxide, strontium oxide, barium oxide, and molybdenum oxide.
In some embodiments, the negative electrode plate can be prepared as follows: the above components for preparing the negative electrode plate, such as a negative electrode active material, a conductive agent, a 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 materials listed above; 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 materials listed above; 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 at the position of the bending part calculated according to the winding method, and subjected to procedures such as drying and cold pressing, to obtain the negative electrode plate.
Herein, the slurry for insulation layer and the slurry for reaction layer can be coated by an one-step forming coating process or a two-step coating process. In the one-step forming coating process, for example, in a double gravure coating device installed in an extrusion coater, the slurry for insulation layer and the slurry for reaction layer are loaded into the coating device along with the slurry for negative electrode material layer, where the slurry for negative electrode material layer is subjected to continuous extrusion coating, and the slurry for insulation layer and the slurry for reaction layer are subjected to intermittent gravure coating. In the two-step coating process, after the negative electrode material layer is formed on the negative electrode plate, the position of the bending part is determined, and when passing through the bending part, coating is carried out by means of two-step gravure coating using a gravure roller.
[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 at least one selected from 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 and lithium tetrafluorooxalate phosphate.
In some embodiments, the solvent may be at least one selected from 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 also 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 the present application, the lithium-ion battery also comprises a separator, wherein the positive electrode plate, the negative electrode plate and the separator are made into an electrode assembly having a wound structure by a winding process. 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 at least one selected from glass fibers, non-woven fabrics, polyethylene, polypropylene and 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, the lithium-ion 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 lithium-ion battery may be a hard shell, for example, a hard plastic shell, an aluminum shell, a steel shell, etc. The outer package of the lithium-ion 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 lithium-ion battery is not particularly limited in the present application, and can be a cylindrical shape, a square shape or any other shape. For example,
In some embodiments, referring to
In some embodiments, a lithium-ion battery can be assembled into a battery module, and the number of the lithium-ion batteries contained in the battery module 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 module.
Further, the plurality of lithium-ion batteries 5 may be fixed by fasteners.
Optionally, the battery module 4 may also comprise a housing with an accommodating space, and the plurality of lithium-ion 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 also provides a power consuming device comprising at least one of the lithium-ion battery, battery module, or battery pack provided by the present application. The lithium-ion 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, etc.), an electric train, ship, and satellite, an energy storage system, and the like, but is not limited thereto.
For the power consuming device, the lithium-ion 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 lithium-ion 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.
1. Preparation of Battery Cell
1) Preparation of Positive Electrode Plate:
A positive electrode active material LiNi0.55Co0.05Mn0.4O2, 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 weight ratio of 96:1.2:2.8 and mixed uniformly to obtain a positive electrode slurry; and the positive electrode slurry was evenly coated with a thickness of 49 μm onto a positive electrode current collector aluminum foil, and was subjected to drying, cold pressing, slitting and cutting, to obtain a positive electrode plate.
2) Preparation of Separator:
A 10 μm polyethylene film was selected as a separator.
3) Preparation of Negative Electrode Plate:
A boehmite slurry used in an insulation layer was prepared by the following method: respective raw materials of boehmite with a particle size of 0.5 μm, a dispersant polyvinyl alcohol, and a binder polystyrene-acrylate emulsion were taken in a weight ratio of 96.5:0.5:3; deionized water was used as a solvent, and they were added into a mixer for stirring and dispersion; and a slurry with a solid content of 45% was obtained.
A silicon suboxide slurry used in a reaction layer was prepared by the following method: respective raw materials of silicon suboxide with a particle size of 1 μm, a dispersant polyvinyl alcohol, and a binder polystyrene-acrylate emulsion were taken in a weight ratio of 96.5:0.5:3; deionized water was used as a solvent, and they were added into a mixer for stirring and dispersion; and a slurry with a solid content of 45% was obtained.
A negative electrode active material graphite, superconducting carbon black SP as a conductive agent, SBR as a binder, and CMC-Na as a thickener were dispersed in deionized water as a solvent in a weight ratio of 96:1:1:2 and mixed uniformly to obtain a negative electrode slurry; the negative electrode slurry was evenly coated with a thickness of 65 μm onto a negative electrode current collector copper foil; and after drying, an electrode plate having a negative electrode material layer was obtained.
Next, the position of a bending part in a first inner ring, i.e., the innermost ring, was calculated, and a boehmite coating was applied at this position from the prepared boehmite slurry, with a coating thickness of 2 m; and then, a silicon suboxide coating was applied from the prepared silicon suboxide slurry, with a coating thickness of 27 μm, and subjected to drying, cold pressing, slitting and cutting, to obtain the negative electrode plate. Herein, the gram capacity of the reaction layer was 2350 mAh/g, and the density of the reaction layer material was 1.82 g/cm3.
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 Battery Cell:
The above positive electrode plate, separator, and negative electrode plate were stacked in sequence with the separator located 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; and then, the bare cell was placed in an outer package casing and dried, and then the electrolyte solution was injected, followed by procedures such as vacuum encapsulation, standing, forming and shaping, to obtain a battery cell.
Herein, a gap between the negative electrode material layer and the positive electrode material layer after winding, the capacity of the negative electrode material layer in the bending part, and the area of the negative electrode material layer in the bending part are shown in Table 1.
2. Performance Test of Battery Cell
After the battery was prepared, a test for self-discharge of the battery was performed. Herein, the self-discharge of the battery is evaluated in terms of a self-discharge rate which refers to the voltage drop of the battery per hour. An internal short circuit of the battery is reflected by the self-discharge rate, where the more serious the short circuit, the greater the value of the self-discharge rate.
Specifically, at 25° C., the battery cell obtained in Example 1-1 was charged to 4.25 V with a constant current at 0.33 C, then charged to 0.05 C with a constant voltage at 4.25 V, and then discharged to 2.8 V with a constant current at 0.33 C, which was taken as one cycle. After a particular number of cycles (300 cycles, 500 cycles, and 1000 cycles, respectively, in this example), the battery was full charged to 4.25 V, and allowed to stand for 24 h for the depolarization of the battery, and after standing for 24 h, the voltage V1 of the battery was measured; and after standing for further 48 h, the voltage V2 of the battery was measured.
Self-discharge rate of the battery (mV/h)=(V2−V1)/48
In addition, if burning or smoking occurred in the cycle process of the battery, it was determined that the battery had failed.
A lithium-ion battery was prepared in the same manner as in Example 1-1, except that the thickness of the reaction layer was changed as shown in Table 1.
A lithium-ion battery was prepared in the same manner as in Example 1-1, except that no insulation layer and reaction layer was provided.
A lithium-ion battery was prepared in the same manner as in Example 1-1, except that no reaction layer was provided.
A lithium-ion battery was prepared in the same manner as in Example 1-1, except that no insulation layer was provided.
A lithium-ion battery was prepared in the same manner as in Example 1-1, except that the thickness of the reaction layer was changed as shown in Table 2.
The lithium-ion batteries obtained in the above Example 1-1 to Example 1-8 and Comparative Example 1-1 to Comparative Example 1-4 were tested for performance, and the test results were recorded together in Table 1 and Table 2.
A lithium-ion battery was prepared in the same manner as in Example 1-1, except that the gap between the negative electrode material layer and the positive electrode material layer was 400 μm, and the thickness of the reaction layer was changed as shown in Table 3, or no insulation layer and/or reaction layer was provided.
The lithium-ion batteries obtained in the above Example 2-1 to Example 2-4 and Comparative Example 2-1 to Comparative Example 2-3 were tested for performance, and the test results were recorded together in Table 3.
A lithium-ion battery was prepared in the same manner as in Example 1-1, except that the materials of the reaction layer and/or the insulation layer were changed as shown in Table 4.
The lithium-ion batteries obtained in the above Example 3-1 to Example 3-9 were tested for performance, and the test results were recorded together in Table 4.
A lithium-ion battery was prepared in the same manner as in Example 1-1, except that the thickness of the insulation layer was changed as shown in Table 5.
The lithium-ion batteries obtained in the above Example 4-1 to Example 4-5 were tested for performance, and the test results were recorded together in Table 5.
In Example 5-1, a lithium-ion battery was prepared in the same manner as in Example 1-1, except that an insulation layer and a reaction layer were provided at each of a first bending part (35abelled as bending part 1 in Table 6), a second bending part (35abelled as bending part 2 in Table 6), and a third bending part (35abelled as bending part 3 in Table 6), counted from the inner ring, and that the gap between the negative electrode material layer and the positive electrode material layer was set as recorded in Table 6.
In Example 5-2, a lithium-ion battery was prepared in the same manner as in Example 5-1, except that an insulation layer and a reaction layer were provided at each of a first bending part and a second bending part.
In Example 5-3, a lithium-ion battery was prepared in the same manner as in Example 5-1, except that an insulation layer and a reaction layer were provided at only a first bending part.
In Comparative Example 5, a lithium-ion battery was prepared in the same manner as in Example 5-1, except that no insulation layer and reaction layer was provided.
The lithium-ion batteries obtained in the above Example 5-1 to Example 5-3 and Comparative Example 5 were tested for performance, and the test results were recorded together in Table 6.
Lithium-ion batteries in Test Example 1 and Comparative Test Example 1 were respectively prepared according to the preparation methods in the above Example 1-1 and Comparative Example 1-1, and after 500 cycles under the conditions of performance test, lithium dendrites at the bending part were observed with a scanning electron microscope.
As shown in
A lithium-ion battery in Test Example 2 was prepared according to the preparation method in the above Example 1-1, the charge-discharge cycle was carried out under the conditions of performance test, and after 1, 10, and 100 cycles, respectively, the production of lithium dendrites was observed using an in-situ microscope.
As shown by arrows in
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/CN2021/123970, filed on Oct. 15, 2021, the entire content of which is incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2021/123970 | Oct 2021 | US |
| Child | 18063405 | US |
