CN115842202A - External package, preparation method thereof, secondary battery, battery module and battery pack - Google Patents
External package, preparation method thereof, secondary battery, battery module and battery pack Download PDFInfo
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- CN115842202A CN115842202A CN202111403638.6A CN202111403638A CN115842202A CN 115842202 A CN115842202 A CN 115842202A CN 202111403638 A CN202111403638 A CN 202111403638A CN 115842202 A CN115842202 A CN 115842202A
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
The application provides an outer package and a preparation method thereof, a secondary battery, a battery module, a battery pack and an electric device, wherein the outer package comprises a base material, and a ceramic layer, a waterproof layer and an insulating layer which are sequentially arranged on the surface of the base material, wherein the ceramic layer comprises alpha-alumina and/or zirconia and has the thickness of 5-15 mu m; the waterproof layer comprises at least one of nano silicon dioxide powder, nano titanium dioxide powder and nano ceramic powder, and the thickness of the waterproof layer is 5-15 μm; the insulating layer comprises nano barium salt and a composite resin material, and the thickness of the insulating layer is 45-55 mu m. The application provides an extranal packing has good anti deformability, waterproof performance and insulating properties, is favorable to improving secondary cell's electric leakage phenomenon, improves secondary cell's security performance. In addition, the thickness of the exterior package is not more than 85 μm, which is advantageous for improving the energy density of the secondary battery.
Description
Technical Field
The application relates to the technical field of lithium batteries, in particular to an outer package, a preparation method of the outer package, a secondary battery, a battery module, a battery pack and an electric device.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, no memory effect and the like, so that the lithium ion battery is widely applied to the fields of wearable equipment, smart phones, unmanned planes, electric automobiles, large-scale energy storage equipment and the like, and becomes a novel green chemical power supply with the most development potential in the world at present.
In the preparation process of the lithium ion battery, a layer of insulating blue film is usually coated outside the outer package to play a role in insulation protection. However, the blue film has an overlapping region in the coating process, which causes the thickness uniformity of the battery cell to decrease, and the energy density of the lithium ion battery is also affected when the thickness of the blue film commonly used in the prior art is 110 μm. Secondly, the blue film is coated in the later period, so that the blue film cannot completely fit with an outer package, and the risk of electric leakage exists.
Disclosure of Invention
The present invention has been made in view of the above problems, and an object thereof is to improve the safety performance of a secondary battery.
In order to achieve the above objects, the present application provides an exterior package, a method of manufacturing the same, a secondary battery, a battery module, a battery pack, and an electric device.
The first aspect of the application provides an outer package, which comprises a substrate, and a ceramic layer, a waterproof layer and an insulating layer which are sequentially arranged on the surface of the substrate, wherein the ceramic layer comprises alpha-alumina and/or zirconia and has the thickness of 5-15 μm; the waterproof layer comprises at least one of nano silicon dioxide powder, nano titanium dioxide powder and nano ceramic powder, and the thickness of the waterproof layer is 5-15 micrometers; the insulating layer comprises nano barium salt and a composite resin material, and the thickness of the insulating layer is 45-55 mu m. The application provides an extranal packing has good anti deformability, waterproof performance and insulating properties, is favorable to improving secondary cell's electric leakage phenomenon, improves secondary cell's security performance. In addition, the thickness of the exterior package is not more than 85 μm, which is advantageous for improving the energy density of the secondary battery.
In any embodiment, the ceramic layer further comprises a binder, the mass percentage of the binder is 0.5% -2.5% based on the mass of the ceramic layer, and the binder comprises at least one of polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer and fluorine-containing acrylate resin. By selecting the binder and regulating the mass percentage of the binder to be within the range, the deformation resistance of the outer package is favorably improved.
In any embodiment, the nanoceramic powder comprises an alumina ceramic and/or a zirconia ceramic. By selecting the nano ceramic powder, the waterproof performance of the outer package is improved.
In any embodiment, the particle size of the nano-silica powder, the nano-titania powder, and the nano-ceramic powder is each independently selected from 20nm to 500nm. By regulating the particle sizes of the nano silicon dioxide powder, the nano titanium dioxide powder and the nano ceramic powder within the range, the waterproof performance of the outer package is improved.
In any embodiment, the mass ratio of the nano barium salt to the composite resin material is 1. The insulating property of the external package can be improved by regulating the mass ratio of the nano barium salt to the composite resin material within the range.
In any embodiment, the nano barium salt comprises at least one of barium sulfate and barium carbonate, and the composite resin material comprises epoxy resin-oxazolidone. By selecting the nano barium salt and the composite resin material, the obtained outer package has good insulating property.
In any embodiment, a stearic acid coating is present on the surface of the nano barium salt particles, and the stearic acid coating comprises stearic acid (octadecanoic acid). The nano barium salt is coated with the stearic acid coating layer, so that the mechanical property of the external package and the performance of high-current impact resistance are favorably improved.
A second aspect of the present application provides a method of preparing an overpack in any one of the preceding embodiments, comprising the steps of:
providing a ceramic layer, a waterproof layer and an insulating layer, and sequentially arranging the ceramic layer, the waterproof layer and the insulating layer on the surface of a substrate;
the ceramic layer comprises alpha-alumina and/or zirconia, and the thickness of the ceramic layer is 5-15 μm;
the waterproof layer comprises at least one of nano silicon dioxide powder, nano titanium dioxide powder and nano ceramic powder, and the thickness of the waterproof layer is 5-15 mu m;
the insulating layer comprises nano barium salt and a composite resin material, and the thickness of the insulating layer is 45-55 mu m.
A third aspect of the present application provides a secondary battery including the exterior package of the first aspect of the present application.
A fourth aspect of the present application provides a battery module including the secondary battery of the third aspect of the present application.
A fifth aspect of the present application provides a battery pack including the battery module of the fourth aspect of the present application.
A sixth aspect of the present application provides an electric device including at least one selected from the secondary battery of the third aspect of the present application, the battery module of the fourth aspect of the present application, or the battery pack of the fifth aspect of the present application.
The beneficial effect of this application:
the application provides an outer package and a preparation method thereof, a secondary battery, a battery module, a battery pack and an electric device, wherein the outer package comprises a base material, and a ceramic layer, a waterproof layer and an insulating layer which are sequentially arranged on the surface of the base material, wherein the ceramic layer comprises alpha-alumina and/or zirconia and has the thickness of 5-15 micrometers; the waterproof layer comprises at least one of nano silicon dioxide powder, nano titanium dioxide powder and nano ceramic powder, and the thickness of the waterproof layer is 5-15 μm; the insulating layer comprises nano barium salt and a composite resin material, and the thickness of the insulating layer is 45-55 mu m. The ceramic layer is in direct contact with the base material, and has good deformation resistance and is combined with the waterproof layer and the insulating layer, so that the outer package has good deformation resistance, waterproof performance and insulating performance. Meanwhile, the ceramic layer, the waterproof layer and the insulating layer are directly and sequentially arranged on the base material to form a whole, the thickness uniformity is good, the base material can be completely covered, the electric leakage phenomenon of the secondary battery is favorably improved, and the safety performance of the secondary battery is improved. In addition, the thickness of the exterior package is not more than 85 μm, which is advantageous for improving the energy density of the secondary battery.
Drawings
FIG. 1 is a schematic cross-sectional view of an overwrap according to an embodiment of the present application;
fig. 2 is a schematic view of a secondary battery according to an embodiment of the present application;
fig. 3 is an exploded view of a secondary battery according to an embodiment of the present application shown in fig. 2;
FIG. 4 is a schematic view of a battery module according to an embodiment of the present application;
fig. 5 is a schematic view of a battery pack according to an embodiment of the present application;
fig. 6 is an exploded view of the battery pack of an embodiment of the present application shown in fig. 5;
fig. 7 is a schematic diagram of an electric device in which a secondary battery according to an embodiment of the present application is used as a power source.
Description of the reference numerals:
10 a battery pack; 11, loading the box body; 12, a lower box body; 20 a substrate; 31 a ceramic layer; 32 a waterproof layer; 33 an insulating layer; 4 a battery module; 5 a secondary battery; 51 a housing; 52 an electrode assembly; 53 cover plate.
Detailed Description
Hereinafter, embodiments of the exterior package and the method of manufacturing the same, the secondary battery, the battery module, the battery pack, and the electrical device of the present application are specifically disclosed in detail with reference to the accompanying drawings as appropriate. But a detailed description thereof will be omitted. For example, detailed descriptions of already known matters and repetitive descriptions of actually the same configurations may be omitted. This is to avoid unnecessarily obscuring the following description, and to facilitate understanding by those skilled in the art. The drawings and the following description are provided for those skilled in the art to fully understand the present application, and are not intended to limit the subject matter recited in the claims.
The "ranges" disclosed herein are defined in terms of lower limits and upper limits, with a given range being defined by a selection of one lower limit and one upper limit that define the boundaries of the particular range. Ranges defined in this manner may or may not include endpoints and may be arbitrarily combined, i.e., any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the 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 this application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is only a shorthand representation of the combination of these numbers. In addition, when a parameter is an integer of 2 or more, it is equivalent to disclose that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, or the like.
All embodiments and alternative embodiments of the present application may be combined with each other to form new solutions, if not specifically stated.
All technical and optional features of the present application may be combined with each other to form new solutions, if not otherwise specified.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, if not specifically stated. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, and may also comprise steps (b) and (a) performed sequentially. For example, reference to the process further comprising step (c) means that step (c) may be added to the process in any order, for example, the process may comprise steps (a), (b) and (c), may also comprise steps (a), (c) and (b), may also comprise steps (c), (a) and (b), etc.
The terms "comprises" and "comprising" as used herein mean either open or closed unless otherwise specified. For example, the terms "comprising" and "comprises" may mean that additional components not listed may also be included or included, or that only listed components may be included or included.
In this application, the term "or" is inclusive, if not otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, any one of the following conditions satisfies the condition "a or B": 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).
The applicant of the present invention has found that, in the prior art, in order to improve the insulation of a secondary battery, a battery case is usually coated with a blue film in order to improve the insulation of the secondary battery, but the blue film has an overlapping region in the coating process, which reduces the thickness uniformity of a battery core, and the blue film is coated in a later stage, which may not be completely attached to the external package, thereby causing a risk of electric leakage. In addition, the thickness of the commonly used blue film is 110 μm, which affects the energy density of the lithium ion battery. In order to improve the safety performance of the secondary battery, the present application provides an outer package which can be used as an outer package of the secondary battery to improve the safety performance of the secondary battery, so that the secondary battery has better safety performance when applied to an electric device.
In one embodiment of the present application, the present application provides an external package, as shown in fig. 1, which is a schematic cross-sectional structure of the external package along a thickness direction thereof, wherein the external package comprises a base material 20, and a ceramic layer 31, a waterproof layer 32 and an insulating layer 33 sequentially disposed on a surface of the base material 20, the ceramic layer comprises α -alumina and/or zirconia, and has a thickness of 5 μm to 15 μm; the waterproof layer comprises at least one of nano silicon dioxide powder, nano titanium dioxide powder and nano ceramic powder, and the thickness of the waterproof layer is 5-15 mu m; the insulating layer comprises nano barium salt and a composite resin material, and the thickness of the insulating layer is 45-55 mu m.
Although the mechanism is not clear, the applicant has surprisingly found that: ceramic layer and substrate direct contact in this application extranal packing because the ceramic layer has good anti deformability, combines with waterproof layer and insulating layer in the extranal packing for extranal packing has good anti deformability, waterproof performance and insulating properties simultaneously. Meanwhile, the ceramic layer, the waterproof layer and the insulating layer are directly and sequentially arranged on the base material to form a whole, the thickness uniformity is good, the base material can be completely covered, the electric leakage phenomenon of the secondary battery is favorably improved, and the safety performance of the secondary battery is improved. In addition, the total thickness of the ceramic layer, the waterproof layer and the insulating layer is not more than 85 μm, which is beneficial to improving the energy density of the secondary battery.
In some embodiments, the ceramic layer further comprises a binder, wherein the binder is present in an amount of 0.5% to 2.5% by mass based on the mass of the ceramic layer, and the binder comprises at least one of polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluoroacrylate resin. When the binder content is too low (e.g., less than 0.5%) or too high (e.g., greater than 2.5%), the deformation resistance of the overwrap may be compromised. By selecting the binder and regulating the mass percentage of the binder to be within the range, the deformation resistance of the outer package is favorably improved.
The particle size of the α -alumina and zirconia is not particularly limited as long as the object of the present invention can be achieved, and for example, the particle size of the α -alumina is 20nm to 500nm, and the particle size of the zirconia is 20nm to 500nm.
In some embodiments, the nanoceramic powder comprises an alumina ceramic and/or a zirconia ceramic. By selecting the nano ceramic powder, the waterproof performance of the outer package is improved.
In some embodiments, the particle size of the nano-silica powder, the nano-titania powder, and the nano-ceramic powder is each independently selected from 20nm to 500nm. By regulating the particle sizes of the nano silicon dioxide powder, the nano titanium dioxide powder and the nano ceramic powder within the range, the waterproof performance of the outer package is improved.
In some embodiments, the mass ratio of the nano barium salt to the composite resin material is 1. When the mass of the nano barium salt and the composite resin material is relatively small (for example, less than 1. The insulating property of the external package can be improved by regulating the mass ratio of the nano barium salt to the composite resin material within the range.
In some embodiments, the nano barium salt includes at least one of barium sulfate and barium carbonate, and the composite resin material includes epoxy-oxazolidone. By selecting the nano barium salt and the composite resin material, the obtained outer package has good insulating property. The particle size of the nano barium salt is not particularly limited as long as the object of the present application can be achieved, and for example, the particle size of the nano barium salt is 10nm to 500nm.
In some embodiments, the surface of the nano barium salt particles is coated with stearic acid, and the stearic acid coating comprises stearic acid (octadecanoic acid). The nano barium salt is coated with the stearic acid coating layer, so that the mechanical property of the external package and the performance of high-current impact resistance are favorably improved. The method for preparing the stearic acid coating layer of the nano barium salt is not particularly limited, and a preparation method known in the art can be adopted as long as the purpose of the present application can be achieved.
In some embodiments, the insulating layer comprises a dark dye, the insulating layer is dark, and the waterproof layer is exposed when the insulating layer is unevenly or incompletely coated during the process of preparing the outer package, so that the defective products in the production process can be found. The dark color dye is not particularly limited as long as the object of the present application can be achieved, and may be, for example, a black dye or a dark blue dye. The kind of the dark dye is not particularly limited in the present application, and a dark dye known in the art may be used as long as the insulating property of the insulating layer is not affected.
The present application also provides a method of making an overwrap in any of the preceding embodiments, comprising the steps of: providing a ceramic layer, a waterproof layer and an insulating layer, and sequentially arranging the ceramic layer, the waterproof layer and the insulating layer on the surface of the substrate; the ceramic layer comprises alpha-alumina and/or zirconia, and the thickness of the ceramic layer is 5-15 μm; the waterproof layer comprises at least one of nano silicon dioxide powder, nano titanium dioxide powder and nano ceramic powder, and the thickness of the waterproof layer is 5-15 μm; the insulating layer comprises nano barium salt and a composite resin material, and the thickness of the insulating layer is 45-55 mu m.
The preparation method of the ceramic layer, the waterproof layer and the insulating layer is not particularly limited as long as the purpose of the present application can be achieved, for example, the preparation method of the ceramic layer may include, but is not limited to, plasma arc spraying, thermal spraying, magnetron sputtering, etc., the preparation method of the waterproof layer may include, but is not limited to, dispenser spraying, etc., and the preparation method of the insulating layer may include, but is not limited to, coating method, etc.
In some embodiments, the substrate of the outer package may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, or the like. The substrate of the outer package may also be a soft bag, for example a pouch-type soft bag. The material of the soft bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
The secondary battery, the battery module, the battery pack, and the electric device according to the present invention will be described below with reference to the drawings as appropriate.
In one embodiment of the present application, a secondary battery is provided. Including the overwrap of any of the embodiments above or the overwrap made by the method of making of any of the embodiments above.
In general, a secondary battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. In the process of charging and discharging the battery, active ions are embedded and separated back and forth between the positive pole piece and the negative pole piece. The electrolyte plays a role in conducting ions between the positive pole piece and the negative pole piece. The isolating membrane is arranged between the positive pole piece and the negative pole piece, mainly plays a role in preventing the short circuit of the positive pole and the negative pole, and can enable ions to pass through.
[ Positive electrode sheet ]
The positive pole piece comprises a positive pole current collector and a positive pole film layer arranged on at least one surface of the positive pole current collector.
As an example, the positive electrode current collector has two surfaces opposite in its own thickness direction, and the positive electrode film layer is disposed on either or both of the two opposite surfaces of the positive electrode current collector.
In some embodiments, the positive electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a base material of a polymer material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the positive active material may employ a positive active material for a battery, which is well known in the art. As an example, the positive electrode active material may include at least one of the following materials: olivine structured lithium-containing phosphates, 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 a positive electrode active material of a battery may be used. These positive electrode active materials may be used alone or in combination of two or more. Among them, examples of the lithium transition metal oxide may include, but are not limited to, lithium cobalt oxide (e.g., liCoO) 2 ) Lithium nickel oxide (e.g., liNiO) 2 ) Lithium manganese oxides (e.g., liMnO) 2 、LiMn 2 O 4 ) Lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (e.g., liNi) 1/3 Co 1/3 Mn 1/3 O 2 (may also be abbreviated as NCM) 333 )、LiNi 0.5 Co 0.2 Mn 0.3 O 2 (may also be abbreviated as NCM) 523 )、LiNi 0.5 Co 0.25 Mn 0.25 O 2 (may also be abbreviated as NCM) 211 )、LiNi 0.6 Co 0.2 Mn 0.2 O 2 (may also be abbreviated as NCM) 622 )、LiNi 0.8 Co 0.1 Mn 0.1 O 2 (may also be abbreviated as NCM) 811 ) Lithium nickel cobalt aluminum oxides (e.g., liNi) 0.85 Co 0.15 Al 0.05 O 2 ) And modified compounds thereof, and the like. Examples of olivine structured lithium-containing phosphates may include, but are not limited to, lithium iron phosphate (e.g., liFePO) 4 (also referred to as LFP for short)), a composite material of lithium iron phosphate and carbon, and lithium manganese phosphate (e.g., liMnPO) 4 ) At least one of a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.
In some embodiments, the positive electrode film layer further optionally comprises a positive electrode film layer binder. As an example, the positive electrode film binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluorine-containing acrylate resin.
In some embodiments, the positive electrode film layer further optionally includes 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, and carbon nanofibers.
In some embodiments, the positive electrode sheet may be prepared by: dispersing the above components for preparing the positive electrode sheet, such as the positive active material, the conductive agent, the binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; and coating the positive electrode slurry on a positive electrode current collector, and drying, cold pressing and the like to obtain the positive electrode piece.
[ negative electrode sheet ]
The negative pole piece includes the negative current collector and sets up the negative pole rete on the negative current collector at least one surface, the negative pole rete includes negative active material.
As an example, the negative electrode current collector has two surfaces opposite in its own thickness direction, and the negative electrode film layer is disposed on either or both of the two surfaces opposite to the negative electrode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, a copper foil can be used. The composite current collector may include a polymer base layer and a metal layer formed on at least one surface of the polymer base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a base material of a polymer material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the negative active material may employ a negative active material for a battery known in the art. As an example, the anode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate and the like. The silicon-based material can be at least one selected from elemental silicon, silicon-oxygen compounds, silicon-carbon compounds, silicon-nitrogen compounds and silicon alloys. The tin-based material may be selected from at least one of elemental tin, tin-oxygen compounds, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery negative active material may also be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the anode film layer further optionally includes an anode film layer binder. The negative electrode film layer binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. The conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the negative electrode film layer may also optionally include other adjuvants, such as thickeners (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments, the negative electrode sheet can be prepared by: dispersing the above components for preparing a negative electrode sheet, such as a negative electrode active material, a conductive agent, a binder and any other components, in a solvent (e.g., deionized water) to form a negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and drying, cold pressing and the like to obtain the negative electrode pole piece.
[ electrolyte ]
The electrolyte plays a role in conducting ions between the positive pole piece and the negative pole piece. The kind of the electrolyte is not particularly limited and may be selected as desired. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is an electrolytic solution. The electrolyte includes 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 bis-fluorosulfonylimide, lithium bis-trifluoromethanesulfonylimide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium dioxaoxalato borate, lithium difluorodioxaoxalato phosphate, and lithium tetrafluorooxalato 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, dimethylsulfone, methylethylsulfone, and diethylsulfone.
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include a negative electrode film forming additive, a positive electrode film forming additive, and may further include additives capable of improving certain properties of the battery, such as an additive for improving overcharge properties of the battery, an additive for improving high-temperature or low-temperature properties of the battery, and the like.
[ isolation film ]
In some embodiments, a separator is further included in the secondary battery. The type of the separator is not particularly limited, and any known separator having a porous structure and good chemical and mechanical stability may be used.
In some embodiments, the material of the isolation film may be at least one selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, a secondary battery may include the outer package of any of the preceding embodiments. The exterior package may be used to enclose the electrode assembly and electrolyte.
The shape of the secondary battery is not particularly limited, and may be a cylindrical shape, a square shape, or any other arbitrary shape. For example, fig. 2 is a secondary battery 5 of a square structure as an example.
In some embodiments, referring to fig. 3, the outer package may include a housing 51 and a cover plate 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose to form an accommodating cavity. The housing 51 has an opening communicating with the accommodation chamber, and a cover plate 53 can be provided to cover the opening to close the accommodation chamber. The positive electrode tab, the negative electrode tab, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. An electrode assembly 52 is enclosed within the receiving cavity. The electrolyte is impregnated into the electrode assembly 52. The number of the electrode assemblies 52 contained in the secondary battery 5 may be one or more, and those skilled in the art can select them according to specific practical needs.
In some embodiments, the secondary batteries may be assembled into a battery module, and the number of the secondary batteries contained in the battery module may be one or more, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery module.
Fig. 4 is a battery module 4 as an example. Referring to fig. 4, in the battery module 4, a plurality of secondary batteries 5 may be arranged in series along the longitudinal direction of the battery module 4. Of course, the arrangement may be in any other manner. The plurality of secondary batteries 5 may be further fixed by a fastener.
Alternatively, the battery module 4 may further include a case having an accommodation space in which the plurality of secondary batteries 5 are accommodated.
In some embodiments, the battery modules may be assembled into a battery pack, and the number of the battery modules contained in the battery pack may be one or more, and the specific number may be selected by one skilled in the art according to the application and the capacity of the battery pack.
Fig. 5 and 6 are a battery pack 10 as an example. Referring to fig. 5 and 6, a battery case and a plurality of battery modules 4 disposed in the battery case may be included in the battery pack 10. The battery box includes an upper case 11 and a lower case 12, and the upper case 11 can be covered on the lower case 12 and forms a closed space for accommodating the battery module 4. A plurality of battery modules 4 may be arranged in any manner in the battery box.
In addition, this application still provides a power consumption device, power consumption device includes at least one in secondary battery, battery module or the battery package that this application provided. The secondary battery, the battery module, or the battery pack may be used as a power source of the electric device, and may also be used as an energy storage unit of the electric device. The powered device may include, but is not limited to, 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, a ship, and a satellite, an energy storage system, etc.
As the electricity-using device, a secondary battery, a battery module, or a battery pack may be selected according to the use requirement thereof.
Fig. 7 is an electric device as an example. The electric device is a pure electric vehicle, a hybrid electric vehicle or a plug-in hybrid electric vehicle and the like. In order to meet the demand of the electric device for high power and high energy density of the secondary battery, a battery pack or a battery module may be used.
As another example, the device may be a cell phone, tablet, laptop, etc. The device is generally required to be thin and light, and a secondary battery may be used as a power source.
Examples
Hereinafter, examples of the present application will be described. The following description of the embodiments is merely exemplary in nature and is in no way intended to limit the present disclosure. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
< preparation of outer Package >
The aluminum plastic film shell is used as a base material.
(1) Preparation of ceramic layer
Adding alpha-alumina powder (with the particle size of 20nm-100 nm) into deionized water, uniformly dispersing the alpha-alumina powder in the deionized water by using ultrasonic vibration, then adding a binder, namely polyvinylidene fluoride, into a ball mill, carrying out ball milling for 2h, uniformly mixing to obtain mixed slurry, then drying in a spray drying mode, solidifying the mixed slurry into spherical particles, sieving to form micron-sized alumina nano particles, then sintering at the high temperature of 1100 ℃ for 5h, preserving heat for 10min, and then grinding to obtain the alumina ceramic material nano sintered powder. Wherein the mass percentage of the binder is 0.5 percent.
Heating the nano sintered powder of the alumina ceramic material to a molten state, and spraying the nano sintered powder onto one surface of the substrate by a plasma spray gun to form a ceramic layer with a thickness of 10 μm. Wherein the diameter of the nozzle of the spray gun is 2cm, and the spray height is 30cm.
(2) Preparation of the Water repellent layer
Mixing nano silicon dioxide powder with the particle size of 20nm-200nm, nano titanium dioxide powder with the particle size of 20nm-200nm and alumina nano ceramic powder with the particle size of 20nm-200nm according to a mass ratio of 2. And (3) spraying the waterproof layer slurry on the ceramic layer prepared in the step (2) through a dispenser to obtain a waterproof layer with the thickness of 10 microns. Wherein, the diameter of the nozzle of the dispenser is 0.5mm, the spraying atomization air pressure is 15psi, and the spraying height is 10cm.
(3) Preparation of insulating layer
Mixing natural mineral barium salt (with BaSO as main ingredient) 4 ) Ball-milling into nanometer powder with particle size of 50-200 nm by using a high-efficiency ball mill, adding dimethyl sulfoxide as a solvent to obtain a suspension with solid content of 20-30 wt%, uniformly stirring, and adding hydrochloric acid or sodium hydroxide to adjust the pH value of the suspension to 7-8. Then suction filtration is carried out, and the filter cake is washed by deionized water until 0.1mol/L AgNO is used 3 Detecting until no chloride ion exists in the solution, drying the filter cake at 120 ℃, and then crushing to obtain natural barium salt nano powder BaSO 4 Then grinding for 12h in a ball mill to obtain the nano barium salt BaSO with the particle size of 100nm 4 . And mixing the obtained nano barium salt with stearic acid according to a mass ratio of 9. Mixing the nano barium salt containing the stearic acid coating layer, the composite resin material epoxy resin-oxazolidone and the black pigment carbon black according to a mass ratio of 2.
And adding the prepared coating material into dimethyl sulfoxide serving as a solvent to obtain insulating layer slurry with the solid content of 20 wt%. And (4) coating the waterproof layer prepared in the step (3) by a coating method, and drying to obtain an insulating layer with the thickness of 50 micrometers.
< preparation of lithium ion Battery >
Stacking the positive pole piece, the isolating film and the negative pole piece in sequence to enable the isolating film to be positioned between the positive pole piece and the negative pole piece to play an isolating role, and then winding to obtain an electrode assembly; and (3) placing the electrode assembly in the prepared outer package, drying, injecting electrolyte, and performing vacuum packaging, standing, formation, shaping and other processes to obtain the lithium ion battery.
Examples 2 to 6
The procedure was as in example 1, except that the relevant production parameters were adjusted as shown in Table 1. Example 4 preparation of insulating layer with nano barium salt BaSO 4 Replacement with BaCO known in the prior art 3 。
Comparative example 1
The procedure of example 1 was repeated, except that the ceramic layer, the water-repellent layer and the insulating layer were not provided on the surface of the substrate, and the blue film having a thickness of 110 μm was coated on the surface of the substrate.
Comparative example 2
The procedure was repeated in the same manner as in example 1 except that the ceramic layer was not provided on the surface of the substrate.
Comparative example 3
The procedure was as in example 1, except that the relevant production parameters were adjusted as shown in Table 1.
And (3) performance testing:
and (3) testing leakage current failure rate:
and testing the leakage current of the lithium ion battery by adopting an insulation tester, wherein one probe in the insulation tester is in contact with an aluminum layer in an aluminum plastic film of the outer package, the other probe is in contact with an insulation layer or a blue film arranged on the outer package, the test voltage is 1500V, the test pressure is 800kgf, the test time is 3s, and when the leakage current is more than or equal to 1.5mA, the leakage current is marked as the leakage lithium ion battery.
The leakage current failure rate = the number of leakage lithium ion batteries/the total number of test lithium ion batteries × 100%, wherein the total number of test lithium ion batteries is 1000.
Thickness standard deviation σ calculation:
the thicknesses of 100 lithium ion batteries were measured with a micrometer, and then the standard deviation σ of the lithium ion battery thicknesses was calculated. The standard deviation is a standard deviation known in the art.
And (3) testing the waterproof performance:
the lithium ion battery is placed in a NaCl aqueous solution with the concentration of 3.5%, the water depth is 25mm, then the ohm grade of a universal meter is used for testing whether a leakage current phenomenon exists, one end of the universal meter is fixed on a top cover (a non-pole area) of the lithium ion battery, and the other end of the universal meter is placed in water. If the measured resistance value is greater than or equal to 1 megaohm, the waterproof performance test of the lithium ion battery is passed; if the measured resistance value is less than 1 megaohm, the waterproof performance test of the lithium ion battery fails. Each example and comparative example tested 100 lithium ion batteries and the number of lithium ion batteries tested that passed was recorded as the final result.
The preparation parameters and performance tests of each example and comparative example are shown in table 1.
TABLE 1
Note: the "/" in table 1 indicates that no corresponding manufacturing parameters or materials are present.
As shown in table 1, the leakage current failure rate of the lithium ion battery manufactured by using the outer package provided in the present application in example 1 is 0%, and the leakage current failure rate of the lithium ion battery manufactured by using the prior art in which the blue film is coated outside the outer package in comparative example 1 is 0.1%, which indicates that the leakage current phenomenon of the lithium ion battery can be improved by using the outer package provided in the present application, thereby improving the safety performance of the lithium ion battery. Meanwhile, the standard deviation sigma of the thickness of the lithium ion battery prepared by the outer package provided by the application in the example 1 is 0.059, while the standard deviation sigma of the thickness of the lithium ion battery prepared by the prior art in which the blue film is coated outside the outer package is 0.183 in the comparative example 1, which shows that the outer package provided by the application is beneficial to improving the thickness uniformity of the lithium ion batteries in the same batch. In addition, the number of passing lithium ion batteries in example 1 and comparative example 1 is 100 after the waterproof test, which shows that the outer package provided by the present application also has good waterproof performance.
As can be seen from example 1 and comparative example 2, when the exterior package simultaneously includes the ceramic layer, the waterproof layer, and the insulating layer, the lithium ion battery has better safety performance. In the process of preparing the ceramic layer, the waterproof layer and the insulating layer, the types of materials and the mass percentage of the binder in the ceramic layer, the thickness of the ceramic layer, the types of nano ceramic powder in the waterproof layer and the thickness of the waterproof layer, the mass ratio of nano barium salt to the composite resin material in the insulating layer, the types of nano barium salt and the thickness of the insulating layer generally influence the performance of the lithium ion battery, and as can be seen from examples 1 to 6, when the parameters are within the range of the application, the obtained lithium ion battery has good safety performance, waterproof performance and thickness uniformity; as can be seen from examples 1 to 6 and comparative example 3, when the thicknesses of the ceramic layer, the waterproof layer and the insulating layer are within the range of the present application, the lithium ion battery has both better safety and waterproof properties, and the lithium ion battery of the same batch has better thickness uniformity.
The present application is not limited to the above embodiments. The above embodiments are merely examples, and embodiments having substantially the same configuration as the technical idea and exhibiting the same operation and effect within the technical scope of the present application are included in the technical scope of the present application. In addition, various modifications that can be conceived by those skilled in the art are applied to the embodiments and other embodiments are also included in the scope of the present application, in which some of the constituent elements in the embodiments are combined and constructed, without departing from the scope of the present application.
Claims (12)
1. An outer package comprises a base material, and a ceramic layer, a waterproof layer and an insulating layer which are sequentially arranged on the surface of the base material,
the ceramic layer comprises alpha-alumina and/or zirconia and has a thickness of 5-15 μm;
the waterproof layer comprises at least one of nano silicon dioxide powder, nano titanium dioxide powder and nano ceramic powder, and the thickness of the waterproof layer is 5-15 micrometers;
the insulating layer comprises nano barium salt and a composite resin material, and the thickness of the insulating layer is 45-55 mu m.
2. The package of claim 1, wherein the ceramic layer further comprises a binder in an amount of 0.5-2.5% by weight based on the weight of the ceramic layer, the binder comprising at least one of polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluoroacrylate resin.
3. The overpack of claim 1, wherein the nanoceramic powder comprises an alumina ceramic and/or a zirconia ceramic.
4. The overpack of claim 1, wherein the particle size of the nano-silica powder, the nano-titania powder, and the nano-ceramic powder are each independently selected from 20nm-500nm.
5. The external package according to claim 1, wherein the mass ratio of the nano barium salt to the composite resin material is 1.
6. The overpack of claim 1, wherein the nano-barium salt comprises at least one of barium sulfate and barium carbonate, and the composite resin material comprises epoxy-oxazolidone.
7. The package of claim 1, wherein the nano barium salt particles have a stearic acid coating on the surface thereof, and the stearic acid coating comprises stearic acid.
8. A method of preparing the overpack of any of claims 1-7, comprising the steps of:
providing a ceramic layer, a waterproof layer and an insulating layer, and sequentially arranging the ceramic layer, the waterproof layer and the insulating layer on the surface of a substrate;
the ceramic layer comprises alpha-alumina and/or zirconia and has a thickness of 5-15 μm;
the waterproof layer comprises at least one of nano silicon dioxide powder, nano titanium dioxide powder and nano ceramic powder, and the thickness of the waterproof layer is 5-15 micrometers;
the insulating layer comprises nano barium salt and a composite resin material, and the thickness of the insulating layer is 45-55 mu m.
9. A secondary battery comprising the exterior package of any one of claims 1-7.
10. A battery module comprising the secondary battery according to claim 9.
11. A battery pack comprising the battery module of claim 10.
12. An electric device comprising at least one selected from the secondary battery of claim 9, the battery module of claim 10, or the battery pack of claim 11.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN202111403638.6A CN115842202A (en) | 2021-11-24 | 2021-11-24 | External package, preparation method thereof, secondary battery, battery module and battery pack |
| PCT/CN2022/124888 WO2023093340A1 (en) | 2021-11-24 | 2022-10-12 | Outer package and preparation method therefor, secondary battery, battery module and battery pack |
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| CN202111403638.6A CN115842202A (en) | 2021-11-24 | 2021-11-24 | External package, preparation method thereof, secondary battery, battery module and battery pack |
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| CN116769383A (en) * | 2023-08-21 | 2023-09-19 | 宁德时代新能源科技股份有限公司 | Epoxy resin powder coating material, battery case, secondary battery, and electric device |
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| CN116706353B (en) * | 2023-08-04 | 2023-11-14 | 宁德时代新能源科技股份有限公司 | Battery shell, preparation method thereof, secondary battery formed by battery shell and power utilization device |
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| WO2023093340A1 (en) | 2023-06-01 |
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