CN116706353B - Battery shell, preparation method thereof, secondary battery formed by battery shell and power utilization device - Google Patents
Battery shell, preparation method thereof, secondary battery formed by battery shell and power utilization device Download PDFInfo
- Publication number
- CN116706353B CN116706353B CN202310978818.XA CN202310978818A CN116706353B CN 116706353 B CN116706353 B CN 116706353B CN 202310978818 A CN202310978818 A CN 202310978818A CN 116706353 B CN116706353 B CN 116706353B
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- China
- Prior art keywords
- shell
- protective layer
- insulating protective
- battery
- resin prepolymer
- Prior art date
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- 238000012360 testing method Methods 0.000 claims description 15
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- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- JOUIQRNQJGXQDC-AXTSPUMRSA-N namn Chemical compound O1[C@@H](COP(O)([O-])=O)[C@H](O)[C@@H](O)[C@@H]1[N+]1=CC=CC(C(O)=O)=C1 JOUIQRNQJGXQDC-AXTSPUMRSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- FPBMTPLRBAEUMV-UHFFFAOYSA-N nickel sodium Chemical compound [Na][Ni] FPBMTPLRBAEUMV-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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 of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
- H01M50/1245—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure characterised by the external coating on the casing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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
-
- 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 of a single cell or a single battery
- H01M50/14—Primary casings, jackets or wrappings of a single cell or a single battery for protecting against damage caused by external factors
- H01M50/145—Primary casings, jackets or wrappings of a single cell or a single battery for protecting against damage caused by external factors for protecting against corrosion
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
Abstract
The application provides a battery shell, a preparation method thereof, a secondary battery formed by the battery shell and an electric device. A battery case comprises a shell, wherein at least part of the surface of the shell is provided with an insulating protective layer; the shearing force between the insulating protective layer and the shell is 1-20 MPa. The preparation method comprises the following steps: coating a resin prepolymer on at least part of the surface of the shell, and then crosslinking and curing; the resin prepolymer has the structure of the following general formula:wherein n1=0 to 2, n2=0 to 2, m=1 to 200, q=1 to 200. The application solves the problem of insufficient corrosion resistance of the battery shell.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a battery shell, a preparation method thereof, a secondary battery formed by the same and an electric device.
Background
The battery shell is mainly used for protecting the battery inner cell and preventing external oxygen, moisture and the like from contacting with materials such as electrolyte, electrodes and the like in the battery. The corrosion resistance and insulation of the battery case are very important for the life and safety of the battery, since the battery case is charged by long-term contact with the electrolyte and the battery cells. In order to improve corrosion resistance of a battery case and avoid short circuit, a corrosion-resistant insulating layer is generally added on the case, however, the insulating layer adopted by the related art has limited corrosion resistance.
For this purpose, the present application is proposed.
Disclosure of Invention
The present application has been made in view of the above problems, and an object of the present application is to provide a battery case, a method for producing the same, a secondary battery having the same, and an electric device, which solve the problem of insufficient corrosion resistance of the battery case.
In order to achieve the above purpose, the present application provides the following technical solutions.
A first aspect of the present application provides a battery case comprising a case body, at least part of the surface of which is provided with an insulating protective layer;
the shearing force between the insulating protective layer and the shell is 1-20 MPa, and the insulating protective layer comprises resin after cross-linking and curing of a resin prepolymer with the following general structure:
wherein,
n1=0~2，n2=0~2，m=1~200，q=1~200。
therefore, the resin after the cross-linking and curing of the prepolymer with the structural formula is used as the insulating protective layer, and compared with other materials, the shearing force between the resin and the shell is improved, namely the adhesive force of the insulating protective layer on the shell is improved, so that the falling-off time of the insulating protective layer is prolonged.
In any embodiment, the swelling rate of the insulating protective layer in electrolyte soaked for 24 hours reaches 0.01% -10%; the electrolyte for testing the swelling ratio includes dimethyl carbonate, ethylene carbonate, and lithium salt, and dimethyl carbonate: vinyl carbonate volume ratio = 1:1, lithium salt is 1mol/L LiPF 6 。
The swelling rate of the insulating protective layer is also obviously reduced, the corrosion resistance of the insulating protective layer in electrolyte is stronger, and the swelling is delayed, so that the problem that a film layer falls off after the electrolyte is soaked for a long time is solved. Therefore, the application can solve the problem of insufficient corrosion resistance of the shell from various aspects.
In any embodiment, the weight percentage of hydroxymethyl in the resin prepolymer is 5% -22.89%, preferably 15% -20%.
The content of the hydroxymethyl is controlled within the reasonable range, so that the low swelling rate and the high mechanical strength can be achieved. If the hydroxymethyl content is less than 5%, the crosslinking degree of the prepolymer after curing is low, and swelling is easy to occur when the prepolymer is immersed in electrolyte. If the hydroxymethyl content is more than 22.89%, the crosslinking degree after curing is too high, the rigidity is too strong, the mechanical strength is poor, and the fracture is easy.
In any embodiment, the molecular weight of the resin prepolymer is 442 to 48720, preferably 4000 to 30000.
The molecular weight is controlled within the above reasonable range, and the processability and electrolyte resistance can be both achieved. If the molecular weight is less than 442, the polymer is hardly polymerized and crosslinked to form a polymer, and the electrolyte resistance is poor. If the molecular weight is >48720, the dissolution is difficult, the viscosity is high, and the processing is difficult.
In any embodiment, the shearing force between the insulating protective layer and the shell is 3-20 mpa, preferably 6-20 mpa, and preferably 6.4-20 mpa.
Along with the increase of the shearing force, the connecting force between the insulating protective layer and the shell is increased, the insulating protective layer is not easy to fall off, and the service life of the battery shell is longer.
In any embodiment, the swelling rate of the insulating protective layer soaked in the electrolyte for 24 hours reaches 0.01% -1%, preferably 0.01% -0.5%.
With the reduction of the swelling rate, the electrolyte resistance of the insulating protective layer is increased, the blocking time is longer, the insulating protective layer is not easy to fall off, and the service life of the battery shell is longer.
In any embodiment, the insulating protective layer has a falling rate of 1% or more when immersed in an electrolyte at 60 ℃ for 1 monthAnd (3) downwards. The electrolyte for testing the exfoliation rate includes dimethyl carbonate, ethylene carbonate, and lithium salt, and dimethyl carbonate: vinyl carbonate volume ratio = 1:1 lithium salt is 1mol/L LiPF 6 。
Since batteries often operate in high temperature environments, the high temperature resistance of the insulating protective layer also has a significant impact on the battery safety. The high temperature resistance of the insulating protective layer is improved, so that the insulating protective layer still has higher adhesive force after being exposed to high temperature for a long time, and is not easy to fall off.
In any embodiment, the thickness of the insulating protective layer is 1-1000 μm.
The insulating protective layer is not easy to fall off and swell, so the thickness on the shell is not easy to be limited, and the thickness can be adjusted within a wide range of 1-1000 mu m.
In any embodiment, the inner wall of the housing is provided with the insulating protective layer.
Preferably, both the inner wall and the outer wall of the housing are provided with the insulating protection layer.
The service life of the battery shell is longer after the inner wall and the outer wall are provided with the insulating protective layers, and the safety is higher.
In any embodiment, the insulating protective layer is a resin protective layer.
In any embodiment, the housing comprises at least one of: an aluminum shell and an aluminum alloy shell.
The second aspect of the present application also provides a method for manufacturing a battery case, comprising:
coating a resin prepolymer on at least part of the surface of the shell, and then crosslinking and curing;
the resin prepolymer has the structure of the following general formula:
wherein,
n1=0~2，
n2=0~2，
m=1~200，
q=1~200。
the resin prepolymer adopted in the application can be stably combined on the surface of the shell through chemical bonds after crosslinking and curing, so that the shearing force between the formed insulating protective layer and the shell can reach at least 1-20 MPa. Meanwhile, the resin prepolymer can form a stable and uniform three-dimensional network structure after being crosslinked and solidified, is resistant to electrolyte invasion and difficult to swell, and the swelling rate of the resin prepolymer after being soaked in the electrolyte for 24 hours can reach a lower range of 0.01% -10%. Therefore, the application uses the mode of coating and then crosslinking the prepolymer of a specific type and then carrying out in-situ polymerization on the surface of the shell, thereby improving the corrosion resistance of the shell and ensuring that the insulating protective layer is not easy to fall off and swell.
In any embodiment, the weight percentage of hydroxymethyl in the resin prepolymer is 5% -22.89%, preferably 15% -20%.
The content of the hydroxymethyl is controlled within the reasonable range, so that the low swelling rate and the high mechanical strength can be achieved. If the hydroxymethyl content is less than 5%, the crosslinking degree of the prepolymer after curing is low, and swelling is easy to occur when the prepolymer is immersed in electrolyte. If the hydroxymethyl content is more than 22.89%, the crosslinking degree after curing is too high, the rigidity is too strong, the mechanical strength is poor, and the fracture is easy.
In any embodiment, the molecular weight of the resin prepolymer is 442 to 48720, preferably 4000 to 30000.
The molecular weight is controlled within the above reasonable range, and the processability and electrolyte resistance can be both achieved. If the molecular weight is less than 442, the polymer is hardly polymerized and crosslinked to form a polymer, and the electrolyte resistance is poor. If the molecular weight is >48720, the dissolution is difficult, the viscosity is high, and the processing is difficult.
In any embodiment, the crosslinking curing comprises: reacting for 5 to 500 minutes at the temperature of 25 to 300 ℃.
If the curing temperature is too low, the curing takes too long. If the curing temperature is too high, the case is easily damaged. The curing temperature and time are controlled within the above ranges, so that economic benefits and product quality can be considered.
In any embodiment, the crosslinking curing further comprises: adding a curing agent;
the curing agent preferably comprises at least one of the following: hexamethylenetetramine, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, p-phenylenediamine, m-phenylenediamine, terephthalic acid, maleic anhydride, phthalic anhydride;
the mass ratio of the curing agent to the resin prepolymer is 1% -20% and 99% -80%.
The addition of the curing agent helps to improve the reaction efficiency.
In any embodiment, the shell surface is further subjected to an activation treatment prior to the coating: and (3) performing at least one of laser cleaning, plasma cleaning and acid cleaning on the surface of the shell.
After the shell surface is treated by adopting the modes of laser cleaning, plasma cleaning, acid cleaning and the like, the shell surface can form a shell body rich in active groups such as-OH, -C=O, O and-COOH, and the surface is rough and the surface area is larger. The above activation treatment can increase the shear force between the insulation shield and the shell both chemically and physically, as the above reactive groups facilitate covalent bonding with the prepolymer and the roughened surface can promote mechanical interlocking of the polymer with the shell.
A third aspect of the present application provides a secondary battery comprising the battery case of the first aspect of the present application or the battery case prepared according to the method of the second aspect of the present application.
A fourth aspect of the application provides an electric device comprising the secondary battery of the third aspect of the application.
In conclusion, compared with the prior art, the application achieves the following technical effects:
(1) The corrosion resistance of the battery shell is improved by improving the shearing force between the insulating protective layer and the shell, reducing the swelling rate of the insulating protective layer, improving the high temperature resistance of the insulating protective layer and the like, so that the service life is prolonged, and the safety is improved.
(2) The preparation method of the battery shell adopts the prepolymer with high hydroxyl content and high hydroxymethyl content phenol as monomers, and can realize the effects of high cohesive force, low swelling rate, high temperature resistance and the like of an insulating protective layer on the shell in the process of in-situ polymerization on the shell.
(3) The shearing force between the insulating protective layer and the shell can be further improved by activating the surface of the shell before in-situ polymerization.
Drawings
FIG. 1 is a structural formula of a resin prepolymer employed in some embodiments 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 the 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 the embodiment of the present application shown in fig. 5.
Fig. 7 is a schematic view of an electric device in which a secondary battery according to an embodiment of the present application is used as a power source.
Reference numerals illustrate:
1, a battery pack; 2, upper box body; 3, lower box body; 4, a battery module; 5 a secondary battery; 51 an outer housing; 52 electrode assembly; 53 cover plates.
Detailed Description
Hereinafter, embodiments of a battery case, a method of manufacturing the same, a secondary battery, and an electrical device according to the present application are specifically disclosed with reference to the accompanying drawings as appropriate. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the drawings and the following description are provided for a full understanding of the present application by those skilled in the art, and are not intended to limit the subject matter recited in the claims.
The "range" disclosed herein is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can 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 the present application, unless otherwise indicated, 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, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed 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 of the application and alternative embodiments may be combined with each other to form new solutions, unless otherwise specified.
All technical features and optional technical features of the application may be combined with each other to form new technical solutions, unless specified otherwise.
All the steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, "comprising" and "including" may mean that other components not listed may also be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
The corrosion resistance and insulation of the battery case are very important for the life and safety of the battery, since the battery case is charged by long-term contact with the electrolyte and the internal cells. In order to improve corrosion resistance and insulation of a battery case, a corrosion-resistant insulating layer is generally added to the case, and a resin is generally used for the insulating layer. However, the resin insulation layer is attached to the surface of the housing by means of adhesion or the like, and the adhesive force is limited, so that the resin insulation layer is easy to fall off. In addition, weak van der Waals force is adopted between the molecular chains of the resin at present, the solvent molecules can permeate between the molecular chains of the insulating layer after being soaked in the electrolyte for a long time, so that the insulating layer swells, an ion passage is formed between the shell and the bare cell, and corrosion of the shell cannot be effectively prevented.
In order to improve the bonding force between the insulating layer and the shell and reduce the swelling rate, the application provides a battery shell, which comprises a shell, wherein at least part of the surface of the shell is provided with an insulating protective layer;
The shearing force between the insulating protective layer and the shell is 1-20 MPa, and the insulating protective layer comprises resin after cross-linking and curing of a resin prepolymer with the following general structure:
wherein n1=0 to 2, n2=0 to 2, m=1 to 200, q=1 to 200.
The swelling ratio of the application refers to the change degree of the adhesion volume of the insulating protective layer after soaking in the electrolyte for 24 hours. The specific test process is as follows: the sample was immersed in the electrolyte for 24 hours, and the dimensional change before and after the immersion was measured, and the swelling ratio= (immersion)Post-soak volume-pre-soak volume)/pre-soak volume is 100%. The electrolyte for swelling ratio includes dimethyl carbonate, ethylene carbonate, and lithium salt, and dimethyl carbonate: vinyl carbonate volume ratio = 1:1 lithium salt is 1mol/L LiPF 6 。
Therefore, the resin after the cross-linking and curing of the prepolymer with the structural formula is used as the insulating protective layer, and compared with other materials, the shearing force between the resin and the shell is improved, namely the adhesive force of the insulating protective layer on the shell is improved, so that the falling-off time of the insulating protective layer is prolonged.
The resin formed by using the prepolymer as an insulating protective layer can also reduce the swelling rate. For example, the swelling rate of the insulating protective layer in electrolyte soaked for 24 hours can reach 0.01% -10%; the electrolyte for swelling ratio includes dimethyl carbonate, ethylene carbonate, and lithium salt, and dimethyl carbonate: vinyl carbonate volume ratio = 1:1 lithium salt is 1mol/L LiPF 6 . The corrosion resistance of the insulating protective layer in the electrolyte can be improved by reducing the swelling rate, and the swelling is delayed, so that the problem that the film layer falls off after the electrolyte is soaked for a long time is solved. Therefore, the invention solves the problem of insufficient corrosion resistance of the shell from various aspects.
The above resin prepolymer has two end regions and two repeating units, specifically as indicated by the dashed boxes in fig. 1, comprising: end region one, repeat unit one, end region two, and repeat unit two.
In the above resin prepolymer, the chemical bonds interconnecting the first terminal region, the first repeating unit, the second terminal region and the second repeating unit may be any positions ortho, meta or para to the phenolic hydroxyl group. The hydroxymethyl group of the repeating unit II may be located at any position of ortho-, meta-, or para-position with respect to the phenolic hydroxyl group. The hydroxymethyl groups in the first and second end regions may be at any position ortho, meta, or para to the phenolic hydroxyl group.
The hydroxymethyl group attached to the benzene ring of the terminal region one may be 0, 1 or 2, i.e., n1 may be 0, 1 or 2.
The hydroxymethyl group attached to the benzene ring of the terminal region two may be 0, 1 or 2, i.e., n2 may be 0, 1 or 2.
m may be any positive integer of 1 to 200, and further may be 1 to 10, 10 to 100, 50 to 100, 100 to 200, or the like.
q may be any positive integer of 1 to 200, and further may be 1 to 10, 10 to 100, 50 to 100, 100 to 200, or the like.
If m or q is too large, the linear chain segment length or the molecular weight is too large, the electrolyte resistance is poor, and the solubility is low.
In some embodiments, the hydroxymethyl content of the resin prepolymer is 5% -22.89%, including but not limited to 5%, 10%, 15%, 20%, 22.89%, etc., and may also range from 15% -20%, 10% -15%, etc. Hydroxymethyl content refers to weight percent.
The content of the hydroxymethyl is controlled within the reasonable range, so that the low swelling rate and the high mechanical strength can be achieved. If the hydroxymethyl content is less than 5%, the crosslinking degree of the prepolymer after curing is low, and swelling is easy to occur when the prepolymer is immersed in electrolyte. If the hydroxymethyl content is more than 22.89%, the crosslinking degree after curing is too high, the rigidity is too strong, the mechanical strength is poor, and the fracture is easy.
The hydroxymethyl content in the present application refers to weight percent.
In some embodiments, the molecular weight of the resin prepolymer is 442-48720, including but not limited to 442, 500, 1000, 3000, 5000, 10000, 20000, 30000, 40000, 48720, etc., and may also range from 4000-30000, 2000-5000, etc.
The molecular weight is controlled within the above reasonable range, and the processability and electrolyte resistance can be both achieved. If the molecular weight is less than 442, the polymer is hardly polymerized and crosslinked to form a polymer, and the electrolyte resistance is poor. If the molecular weight is >48720, the dissolution is difficult, the viscosity is high, and the processing is difficult.
The molecular weight in the present application means an average molecular weight.
The shell in the application refers to a main body with a supporting function, and preferably adopts materials with the characteristics of light weight, low cost, easy processing, good mechanical performance or good thermal conductivity, and the like, including but not limited to an aluminum shell, an aluminum alloy shell and the like. The shearing force between the insulating protective layer and the shell can be any value within the range of 1-20 MPa, including but not limited to 1MPa, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa, 15MPa, 16MPa, 17MPa, 18MPa, 20MPa and the like, and the shearing force between the protective layer and the shell can be the same or different at different positions of the shell.
Generally, with the increase of the shearing force, the connecting force between the insulating protective layer and the shell is increased, the insulating protective layer is not easy to fall off, and the service life of the battery shell is longer. In some embodiments, the shear force between the protective layer and the shell is 3-20 mpa, 6-20 mpa, 6.4-20 mpa, 8-20 mpa, 10-20 mpa, 12-20 mpa, 15-20 mpa, or the like.
The swelling rate of the insulating protective layer soaked in the electrolyte for 24 hours can be any value within the range of 0.01% -10%, including but not limited to 0.01%, 0.02%, 0.03%, 0.05%, 0.07%, 0.1%, 0.3%, 0.5%, 0.7%, 1%, 3%, 5%, 7%, 10% and the like. In general, along with the reduction of the swelling rate, the electrolyte resistance of the insulating protective layer is increased, the blocking time is longer, the insulating protective layer is not easy to fall off, and the service life of the battery shell is longer. In some embodiments, the swelling rate of the insulating protective layer soaked in the electrolyte for 24 hours reaches 0.01% -5%, 0.01% -1%, 0.01% -0.5%, 0.01% -0.1% or 0.01% -0.5% and the like.
Since batteries often operate in high temperature environments, the high temperature resistance of the insulating protective layer also has a significant impact on the battery safety. The high temperature resistance of the insulating protective layer is improved, so that the insulating protective layer still has higher adhesive force after being exposed to high temperature for a long time, and is not easy to fall off. For this reason, in some embodiments, the insulating protective layer has a falling rate of 1% or less when immersed in an electrolyte at 60 ℃ for 1 month. The shedding rate of the application refers to the ratio of the shedding area of the insulating protective layer to the original area after being soaked in the electrolyte of the commercial lithium battery at 60 ℃ for 1 month. Specific detection conditions include: the commercial lithium battery electrolyte was soaked for 1 month at 60 ℃ with the rate of shedding = shedding area/total area, the total area being the area of the insulation protection layer before soaking. In the test process, the insulation protection layer is taken as falling off, foaming and peeling. The composition of the commercial lithium battery electrolyte is as follows: dimethyl carbonate: vinyl carbonate volume ratio = 1:1 lithium salt is 1mol/L LiPF 6 。
The thickness of the insulating protective layer on the shell is not easy to fall off and swell, so the thickness of the insulating protective layer on the shell is not easy to limit and can be adjusted within a wide range of 1-1000 mu m, including but not limited to 1-10 mu m, 10-100 mu m, 100-1000 mu m, 10-50 mu m, 50-100 mu m, 100-500 mu m, 500-1000 mu m and the like.
The arrangement position and the area of the insulating protective layer can be adjusted, for example, the insulating protective layer is arranged on the inner wall of the shell, or the insulating protective layer is arranged on the outer wall of the shell, or the protective layers are arranged on the inner wall and the outer wall of the shell.
The material of the insulating protective layer is not particularly limited, and is generally insulating, and the shearing force, swelling ratio and high temperature resistance can meet the above conditions, including inorganic and materials, organic materials or inorganic-organic composite materials, preferably resins, which are easy to process and wide in types.
The method for preparing the battery shell with the characteristics of the insulating protective layer can possibly comprise a plurality of methods, and the application provides a preparation method with simple flow and easily available raw materials, which comprises the following steps:
coating a resin prepolymer on at least part of the surface of the shell, and then crosslinking and curing;
the resin prepolymer has the structure of the following general formula:
wherein,
n1=0~2，
n2=0~2，
m=1~200，
q=1~200。
the above resin prepolymer is the same as described above, having two end regions and two repeating units, specifically as indicated by the dashed boxes in FIG. 1, comprising: end region one, repeat unit one, end region two, and repeat unit two.
In the above resin prepolymer, the chemical bonds interconnecting the first terminal region, the first repeating unit, the second terminal region and the second repeating unit may be any positions ortho, meta or para to the phenolic hydroxyl group. The hydroxymethyl group of the repeating unit II may be located at any position of ortho-, meta-, or para-position with respect to the phenolic hydroxyl group. The hydroxymethyl groups in the first and second end regions may be at any position ortho, meta, or para to the phenolic hydroxyl group.
The hydroxymethyl group attached to the benzene ring of the terminal region one may be 0, 1 or 2, i.e., n1 may be 0, 1 or 2.
The hydroxymethyl group attached to the benzene ring of the terminal region two may be 0, 1 or 2, i.e., n2 may be 0, 1 or 2.
m may be any positive integer of 1 to 200, and further may be 1 to 10, 10 to 100, 50 to 100, 100 to 200, or the like.
q may be any positive integer of 1 to 200, and further may be 1 to 10, 10 to 100, 50 to 100, 100 to 200, or the like.
If m or q is too large, the linear chain segment length or the molecular weight is too large, the electrolyte resistance is poor, and the solubility is low.
Coating in the present application includes, but is not limited to, spraying, painting, dipping, and the like.
Crosslinking curing in the present application includes, but is not limited to, thermal curing, ultraviolet curing, and the like.
The resin prepolymer adopted by the application has high active group content and takes benzene ring as a framework, so that on one hand, the resin prepolymer can be stably combined with the surface of a shell through chemical bonds after crosslinking and curing, and the shearing force between the formed insulating protective layer and the shell can reach at least 1-20 MPa; on the other hand, after crosslinking and curing, a stable and uniform three-dimensional network structure can be formed, electrolyte invasion is resisted, swelling is not easy to occur, and the swelling rate in the electrolyte soaking for 24 hours reaches a lower range of 0.01% -10%.
Therefore, the application uses the mode of coating and then crosslinking the prepolymer of a specific type and then carrying out in-situ polymerization on the surface of the shell, thereby improving the corrosion resistance of the shell and ensuring that the insulating protective layer is not easy to fall off and swell.
On this basis, the hydroxymethyl content and molecular weight in the prepolymer, the crosslinking curing conditions, the surface activation treatment and the like can be adjusted to improve the shearing force of the insulating protective layer and the shell, or to reduce the swelling rate of the protective layer, or to improve the temperature resistance and the like, as listed below.
In some embodiments, the hydroxymethyl content of the resin prepolymer is 5% -22.89%, including but not limited to 5%, 10%, 15%, 20%, 22.89%, etc., and may also range from 15% -20%, 10% -15%, etc. Hydroxymethyl content refers to weight percent.
The content of the hydroxymethyl is controlled within the reasonable range, so that the low swelling rate and the high mechanical strength can be achieved. If the hydroxymethyl content is less than 5%, the crosslinking degree of the prepolymer after curing is low, and swelling is easy to occur when the prepolymer is immersed in electrolyte. If the hydroxymethyl content is more than 22.89%, the crosslinking degree after curing is too high, the rigidity is too strong, the mechanical strength is poor, and the fracture is easy.
The hydroxymethyl content in the present application refers to weight percent.
In some embodiments, the molecular weight of the resin prepolymer is 442-48720, including but not limited to 500, 1000, 3000, 5000, 10000, 20000, 30000, 40000, 48720, etc., and may also range from 4000-30000, 2000-5000, etc.
The molecular weight is controlled within the above reasonable range, and the processability and electrolyte resistance can be both achieved. If the molecular weight is less than 442, the polymer is hardly polymerized and crosslinked to form a polymer, and the electrolyte resistance is poor. If the molecular weight is >48720, the dissolution is difficult, the viscosity is high, and the processing is difficult.
The molecular weight in the present application means an average molecular weight.
In some embodiments, crosslinking curing comprises: reacting for 5 to 500 minutes at the temperature of 25 to 300 ℃.
If the curing temperature is too low, the curing takes too long. If the curing temperature is too high, the case is easily damaged. The curing temperature and time are controlled within the above ranges, so that economic benefits and product quality can be considered.
In some embodiments, the crosslinking curing further comprises: and adding a curing agent. The addition of the curing agent helps to improve the reaction efficiency.
The curing agent may include at least one of the following: hexamethylenetetramine, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, p-phenylenediamine, m-phenylenediamine, terephthalic acid, maleic anhydride, phthalic anhydride.
The mass ratio of the curing agent to the resin prepolymer is 1-20% to 99-80%.
In some embodiments, the shell surface is also subjected to an activation treatment prior to coating: and (3) performing at least one of laser cleaning, plasma cleaning and acid cleaning on the surface of the shell.
After the shell surface is treated by adopting the modes of laser cleaning, plasma cleaning, acid cleaning and the like, the shell surface can form a shell body rich in active groups such as-OH, -C=O, O and-COOH, and the surface is rough and the surface area is larger. The above activation treatment can increase the shear force between the insulation shield and the shell both chemically and physically, as the above reactive groups facilitate covalent bonding with the prepolymer and the roughened surface can promote mechanical interlocking of the polymer with the shell.
The battery shell and the battery shell obtained by the preparation method can be used for any battery type, including but not limited to lithium batteries, sodium batteries and the like.
The secondary battery, the battery module, the battery pack, and the electric device according to the present application will be described below with reference to the drawings.
In one embodiment of the present application, a secondary battery is provided.
In general, a secondary battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film.
[ Positive electrode sheet ]
The positive electrode plate comprises a positive electrode current collector and a positive electrode film layer arranged on at least one surface of the positive electrode current collector, wherein the positive electrode film layer comprises the positive electrode active material of the first aspect of the application.
As an example, the positive electrode current collector has two surfaces opposing in its own thickness direction, and the positive electrode film layer is provided on either one or both of the two surfaces opposing the positive electrode current collector.
In some embodiments, the positive 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 polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, when the secondary battery is a lithium ion battery, the positive electrode active material may be a positive electrode active material for a lithium ion 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 battery positive electrode active material may be used. These positive electrode active materials may be used alone or in combination of two or more. Examples of lithium transition metal oxides may include, but are not limited to, lithium cobalt oxide (e.g., liCoO) 2 ) Lithium nickel oxide (e.g. LiNiO) 2 ) Lithium manganese oxide (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 (also referred to as NCM) 333 ）、LiNi 0.5 Co 0.2 Mn 0.3 O 2 (also referred to as NCM) 523 ）、LiNi 0.5 Co 0.25 Mn 0.25 O 2 (also referred to as NCM) 211 ）、LiNi 0.6 Co 0.2 Mn 0.2 O 2 (also referred to as NCM) 622 ）、LiNi 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM) 811 ) Lithium nickel cobalt aluminum oxide (e.g. LiNi 0.85 Co 0.15 Al 0.05 O 2 ) And at least one of its modified compounds 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 abbreviated as LFP)), composite material of lithium iron phosphate and carbon, and manganese lithium phosphate (such as LiMnPO) 4 ) At least one of a composite material of lithium manganese phosphate and carbon, and a composite material of lithium manganese phosphate and carbon.
In some embodiments, when the secondary battery is a sodium-ion battery, the positive electrode active material may employ a positive electrode active material for a sodium-ion battery, which is well known in the art. As an example, the positive electrode active material may be used alone, or two or more kinds may be combined. Wherein the positive electrode active material is selected from sodium-iron composite oxide (NaFeO) 2 ) Sodium cobalt composite oxide (NaCoO) 2 ) Sodium chromium composite oxide (NaCrO) 2 ) Sodium manganese composite oxide (NaMnO) 2 ) Sodium nickel composite oxide (NaNiO) 2 ) Sodium nickel titanium composite oxide (NaNi) 1/2 Ti 1/2 O 2 ) Sodium nickel manganese composite oxide (NaNi) 1/2 Mn 1/2 O 2 ) Sodium iron manganese composite oxide (Na 2/3 Fe 1/3 Mn 2/3 O 2 ) Sodium nickel cobalt manganese composite oxide (NaNi) 1/3 Co 1/3 Mn 1/3 O 2 ) Sodium iron phosphate compound (NaFePO) 4 ) Sodium manganese phosphate compound (NaMn) P O 4 ) Sodium cobalt phosphate compound (NaCoPO) 4 ) Prussian blue type materials, polyanionic materials (phosphates, fluorophosphates, pyrophosphates, sulfates), etc., but the present application is not limited to these materials, and other conventionally known materials that can be used as positive electrode active materials for sodium ion batteries may be used.
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin.
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 electrode 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 (3) coating the positive electrode slurry on a positive electrode current collector, and obtaining a positive electrode plate after the procedures of drying, cold pressing and the like.
[ negative electrode sheet ]
The negative electrode plate comprises a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, wherein the negative electrode film layer comprises a negative electrode active material.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode film layer is provided on either one or both of the two surfaces opposing the anode 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, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the anode active material may employ an anode active material for a battery, which is well 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 may be at least one selected from elemental silicon, silicon oxygen compounds, silicon carbon composites, silicon nitrogen composites, and silicon alloys. The tin-based material may be at least one selected from elemental tin, tin oxide, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery anode active material may be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the negative electrode film layer further optionally includes a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. The conductive agent is at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
In some embodiments, the negative electrode film layer may optionally further include other adjuvants, such as thickening agents (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments, the negative electrode sheet may be prepared by: dispersing the above components for preparing the 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 obtaining a negative electrode plate after the procedures of drying, cold pressing and the like.
[ electrolyte ]
The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The application is not particularly limited in the kind of electrolyte, and may be selected according to the need. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is an electrolyte. The electrolyte includes an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis-fluorosulfonyl imide, lithium bis-trifluoromethanesulfonyl imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorodioxaato phosphate, and lithium tetrafluorooxalato phosphate.
In some embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1, 4-butyrolactone, sulfolane, dimethyl sulfone, methyl sulfone, and diethyl sulfone.
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
[ isolation Membrane ]
In some embodiments, a separator is further included in the secondary battery. The type of the separator is not particularly limited, and any known porous separator having good chemical stability and mechanical stability can be used.
In some embodiments, the material of the isolating 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, the secondary battery may include an outer package. The outer package may be used to encapsulate the electrode assembly and electrolyte described above.
In some embodiments, the exterior package of the secondary battery may be the battery case described in the foregoing of the present application.
The shape of the secondary battery is not particularly limited in the present application, and may be cylindrical, square, or any other shape. For example, fig. 2 is a secondary battery 5 of a square structure as one example.
In some embodiments, referring to fig. 3, the battery case may include an outer case 51 and a cover plate 53. The outer housing 51 may include a bottom plate and a side plate connected to the bottom plate, where the bottom plate and the side plate enclose a receiving chamber. The outer 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. The electrode assembly 52 is enclosed in the accommodating chamber. The electrolyte is impregnated in the electrode assembly 52. The number of electrode assemblies 52 included in the secondary battery 5 may be one or more, and those skilled in the art may select according to specific practical requirements. Both the outer case 51 and the cover 53 may adopt the structure of the battery case as described above.
In some embodiments, the secondary batteries may be assembled into a battery module, and the number of secondary batteries included in the battery module may be one or more, and the specific number may be selected by one 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 sequentially arranged in the longitudinal direction of the battery module 4. Of course, the arrangement may be performed in any other way. The plurality of secondary batteries 5 may be further fixed by fasteners.
Alternatively, the battery module 4 may further include a case having an accommodating space in which the plurality of secondary batteries 5 are accommodated.
In some embodiments, the above battery modules may be further assembled into a battery pack, and the number of battery modules included in the battery pack may be one or more, and a specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
Fig. 5 and 6 are battery packs 1 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 1. The battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4. The plurality of battery modules 4 may be arranged in the battery box in any manner.
In addition, the application also provides an electric device which comprises at least one of the secondary battery, the battery module or the battery pack. The secondary battery, the battery module, or the battery pack may be used as a power source of the power consumption device, and may also be used as an energy storage unit of the power consumption device. The power utilization device may include mobile devices (e.g., cell phones, notebook computers, etc.), electric vehicles (e.g., electric-only vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but is not limited thereto.
As the electricity consumption device, a secondary battery, a battery module, or a battery pack may be selected according to the use requirements thereof.
Fig. 7 is an electrical device as an example. The electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. In order to meet the high power and high energy density requirements of the secondary battery by the power consumption device, a battery pack or a battery module may be employed.
As another example, the device may be a cell phone, tablet computer, notebook computer, or the like. The device is generally required to be light and thin, and a secondary battery can be used as a power source.
Examples
Hereinafter, embodiments of the present application are described. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Examples 1 to 17
The battery shell is prepared by the following method:
s1, cleaning: a 500 μm thick aluminum shell was sanded sequentially on 200#, 500#, 1000#, 3000# sandpaper to remove the oxide layer on its surface.
S2, optionally carrying out surface activation: and (3) carrying out plasma cleaning on the surface of the aluminum shell treated in the step (S1): air is used as a gas source, and the surface of the aluminum shell is cleaned under the cleaning pressure of 100 Pa.
S3, coating a prepolymer: an organic solution of a resin prepolymer is coated on the inner and outer surfaces of the activated aluminum shell, and the types of the resin prepolymer are shown in Table 1 in detail.
S4, crosslinking and curing: referring to the curing conditions of table 1, an aluminum case with an insulating protective layer on the surface was obtained.
Comparative examples 1 to 3
See table 1.
Wherein, the preparation process of comparative example 3 is as follows.
S1, cleaning: a 500 μm thick aluminum shell was sanded sequentially on 200#, 500#, 1000#, 3000# sandpaper to remove the oxide layer on its surface.
S2, surface activation: and (3) carrying out plasma cleaning on the surface of the aluminum shell treated in the step (S1): air is used as a gas source, and the surface of the aluminum shell is cleaned under the cleaning pressure of 100 Pa.
S3, coating a polymer: and sticking polyimide adhesive tape on the surface of the aluminum shell.
Shear force between the insulation shield layer and the aluminum shell, insulation shield layer thickness and swelling ratio, corrosion resistance, and the like were measured in the products of each example and comparative example, and the test methods were as follows.
And (3) testing the shearing force of the insulating protective layer: test Standard GBT 7124/ISO 4587.
Thickness of the protective layer: the film thickness tester was used for testing.
Electrolyte resistance evaluation: using a conventional commercial electrolyte, immersing the shell sample at 60 ℃ for-1500 hours, taking out and performing insulation test: 1000V, resistance >1gΩ, withstand voltage test: DC 2700V,60s, repeated 25 times.
Swelling ratio test: according to the national standard GBT 14797.3-2008 test, a sample is soaked in an electrolyte for 24 hours, and the volume change before and after soaking is measured, and the swelling ratio= (volume after soaking-volume before soaking)/volume before soaking is 100%. The composition of the electrolyte is: dimethyl carbonate: vinyl carbonate volume ratio = 1:1 lithium salt is 1mol/L LiPF 6 。
And (3) performing outer lap corrosion test:
1) And (3) assembling a battery cell: and assembling the aluminum shells before and after the treatment and the bare cell into a finished product cell, and charging to 30% of SOC. The electrolyte of the bare cell is: dimethyl carbonate: vinyl carbonate volume ratio = 1:1 lithium salt is 1mol/L LiPF 6 。
2) And (3) manufacturing defects, namely communicating the shell with the cathode through a lead.
3) Standing and observing: standing for one month, and observing the corrosion condition of the shell.
The method for testing the falling rate at high temperature comprises the following steps:
the commercial lithium battery electrolyte was soaked for 1 month at 60 ℃ with the rate of shedding = shedding area/total area, the total area being the area of the insulation protection layer before soaking. In the test process, the insulation protection layer is taken as falling off, foaming and peeling. The composition of the commercial lithium battery electrolyte is as follows: dimethyl carbonate: vinyl carbonate volume ratio = 1:1 lithium salt is 1mol/L LiPF 6 。
The results are shown in Table 1.
TABLE 1
The results of examples and comparative example 3 show that the in-situ polymerization mode of prepolymer coating can achieve the properties of shearing force, low swelling rate, electrolyte resistance, high temperature resistance and the like. The results of examples 1, 4, 5 and comparative example 1 show that if the molecular weight is too large, the swelling resistance of the product is significantly deteriorated. The results of examples 6-8 and comparative example 2 show that: if the hydroxyl group content is too high, the shear force is rather reduced, and the electrolyte resistance and the high temperature resistance are remarkably deteriorated.
The present application is not limited to the above embodiment. The above embodiments are merely examples, and embodiments having substantially the same configuration and the same effects as those of the technical idea within the scope of the present application are included in the technical scope of the present application. Further, various modifications that can be made to the embodiments and other modes of combining some of the constituent elements in the embodiments, which are conceivable to those skilled in the art, are also included in the scope of the present application within the scope not departing from the gist of the present application.
Claims (22)
1. The battery shell is characterized by comprising a shell, wherein at least part of the surface of the shell is provided with an insulating protective layer; the insulating protective layer comprises resin which is formed by coating resin prepolymer on at least part of the surface of the shell and then crosslinking and curing;
The shearing force between the insulating protective layer and the shell is 1-20 MPa, and the resin prepolymer has the following general structure:
wherein,
n1=0-2, n2=0-2, m=1-200, q=1-200, wherein the weight percentage of hydroxymethyl in the resin prepolymer is 5% -22.89%, and the molecular weight of the resin prepolymer is 442-48720.
2. The battery case according to claim 1, wherein the swelling ratio of the insulating protective layer in the electrolyte for soaking for 24 hours is 0.01% -10%; the electrolyte used in the measurement of the swelling ratio includes dimethyl carbonate, ethylene carbonate and lithium salt, andand dimethyl carbonate: vinyl carbonate volume ratio = 1:1 lithium salt is 1mol/L LiPF 6 。
3. The battery case according to claim 1, wherein the weight percentage of hydroxymethyl groups in the resin prepolymer is 15% -20%.
4. The battery case according to claim 1, wherein the molecular weight of the resin prepolymer is 4000 to 30000.
5. The battery case according to claim 1, wherein a shearing force between the insulating protective layer and the case is 3 to 20mpa.
6. The battery case according to claim 1, wherein a shearing force between the insulating protective layer and the case is 6 to 20mpa.
7. The battery case according to claim 2, wherein the swelling ratio of the insulating protective layer in the electrolyte for 24 hours is 0.01% -1%.
8. The battery case according to claim 2, wherein the swelling ratio of the insulating protective layer in the electrolyte for 24 hours is 0.01% -0.5%.
9. The battery case according to any one of claims 1 or 2 or 5 to 8, wherein the insulating protective layer has a falling rate of 1% or less when immersed in an electrolyte at 60 ℃ for 1 month; the electrolyte used in testing the exfoliation rate included dimethyl carbonate, ethylene carbonate, and lithium salt, and dimethyl carbonate: vinyl carbonate volume ratio = 1:1 lithium salt is 1mol/L LiPF 6 。
10. The battery case according to claim 1, wherein the thickness of the insulating protective layer is 1 to 1000 μm.
11. The battery case according to claim 1, wherein the inner wall of the case is provided with the insulating protective layer.
12. The battery case according to claim 11, wherein the insulating protective layer is provided on both the inner wall and the outer wall of the case.
13. The battery housing of claim 1, wherein the shell comprises at least one of: an aluminum shell and an aluminum alloy shell.
14. A method of manufacturing a battery case, comprising:
coating a resin prepolymer on at least part of the surface of the shell, and then crosslinking and curing;
the resin prepolymer has the structure of the following general formula:
wherein,
n1=0~2，
n2=0~2，
m=1~200，
q=1~200，
the weight percentage of the hydroxymethyl in the resin prepolymer is 5% -22.89%, and the molecular weight of the resin prepolymer is 442% -48720.
15. The method of claim 14, wherein the resin prepolymer comprises 15% -20% by weight of hydroxymethyl.
16. The method of claim 14, wherein the molecular weight of the resin prepolymer is 4000 to 30000.
17. The method of preparing according to claim 14, wherein the cross-linking curing comprises: reacting for 5 to 500 minutes at the temperature of 25 to 300 ℃.
18. The method of preparing according to claim 14, wherein the cross-linking curing further comprises: and adding a curing agent.
19. The method of preparing according to claim 18, wherein the curing agent comprises at least one of the following: hexamethylenetetramine, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, p-phenylenediamine, m-phenylenediamine, terephthalic acid, maleic anhydride, phthalic anhydride;
The mass ratio of the curing agent to the resin prepolymer is 1% -20% and 99% -80%.
20. The method of claim 14, wherein the shell surface is further subjected to an activation treatment prior to the coating: and (3) performing at least one of laser cleaning, plasma cleaning and acid cleaning on the surface of the shell.
21. A secondary battery comprising the battery case according to any one of claims 1 to 13 or the battery case produced by the production method according to any one of claims 14 to 20.
22. An electric device comprising the secondary battery according to claim 21.
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