CN116454545A - Secondary battery and electric equipment - Google Patents
Secondary battery and electric equipment Download PDFInfo
- Publication number
- CN116454545A CN116454545A CN202310278177.7A CN202310278177A CN116454545A CN 116454545 A CN116454545 A CN 116454545A CN 202310278177 A CN202310278177 A CN 202310278177A CN 116454545 A CN116454545 A CN 116454545A
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- Prior art keywords
- binder
- coating
- secondary battery
- coating layer
- organic
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- 239000006183 anode active material Substances 0.000 description 6
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- 239000004698 Polyethylene Substances 0.000 description 4
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
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- 229910003002 lithium salt Inorganic materials 0.000 description 4
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- 239000010941 cobalt Substances 0.000 description 2
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
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- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
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- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
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- 229910001486 lithium perchlorate 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
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms 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
- 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
- H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- 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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Abstract
The embodiment of the application discloses secondary battery and consumer, through set up first coating in the one side of base film towards the anodal pole piece, set up the second coating in the one side of base film towards the negative pole piece, and first coating contains pottery, organic binder and inorganic binder, form ceramic coating, the heat stability of diaphragm can be improved to highly heat-resisting pottery, compare in only adopting organic binder, inorganic binder and organic binder blending use in the first coating, can further improve the heat stability and the oxidation resistance of diaphragm, the second coating contains organic binder and inorganic binder, form the glue film, compare in only adopting inorganic binder, inorganic binder and organic binder's combination can effectively promote the adhesion of diaphragm and negative pole piece.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a secondary battery and electric equipment.
Background
The separator is an important component of the secondary battery, and needs to have good thermal stability and electrochemical stability, and good adhesion between the separator and the pole piece, and easy shaping of the battery core, so that the cycle stability of the battery is improved.
In order to improve the thermal stability of the diaphragm, the diaphragm is formed by bonding a ceramic coating on the surface of the base film, and although the thermal stability and the electrochemical stability of the diaphragm are improved to a great extent by the ceramic coating, the ceramic is generally bonded on the base film by an inorganic adhesive, and the thermal stability and the electrochemical stability of the diaphragm are not high enough due to poor thermal stability and low electrochemical stability of the inorganic adhesive.
In addition, organic glue is coated on the surface of the base film to form a diaphragm to bond the diaphragm and the pole piece, however, in the long-term circulation process of the battery core, the continuous lithium intercalation process leads the interface between the diaphragm and the pole piece to be poorer and poorer, so that the circulation stability of the secondary battery is poor.
Therefore, modification of conventional separators is required in order to obtain better thermal and electrochemical stability.
Disclosure of Invention
The embodiment of the application provides a secondary battery and electric equipment, which can solve the problem that the thermal stability and electrochemical stability of the existing diaphragm are not high.
A first aspect of the present application provides a secondary battery, including a positive electrode sheet, a negative electrode sheet, and a separator, the separator being disposed between the positive electrode sheet and the negative electrode sheet, the separator including a base film, a first coating layer, and a second coating layer, the first coating layer being disposed on a surface of the base film facing the positive electrode sheet, the second coating layer being disposed on a surface of the base film facing the negative electrode sheet; wherein the first coating comprises a ceramic, an organic binder, and an inorganic binder; the second coating layer includes an organic binder and an inorganic binder.
Optionally, the weight part of the inorganic binder in the first coating layer is m based on the mass of the first coating layer 1a The weight part of the ceramic is m 1b The weight part of the organic adhesive is m 1c If the ratio is 1% or less 1a /(m 1b +m 1c )≤10％。
Optionally, the weight part of the inorganic binder in the second coating layer is m based on the mass of the second coating layer 2a The weight part of the organic adhesive is m 2c If the ratio is 10% or less 2a /m 2c ≤100％。
Optionally, the ceramic comprises gamma-AlOOH, siO 2 、MgO、Al 2 O 3 、ZnO 2 At least one of them.
Optionally, the inorganic binder includes at least one of a silicate binder, a sulfate binder, a phosphate binder, a borate binder, a carbonate binder, and a nitrate binder.
Optionally, the organic binder in the first coating layer and the organic binder in the second coating layer respectively include at least one of polyvinyl alcohol, polyacrylic acid, styrene-butadiene rubber, sodium carboxymethyl cellulose, polyacrylate binder, polyvinylidene fluoride, and polyacrylonitrile binder.
Optionally, the organic binder in the second coating layer comprises at least two of polyvinyl alcohol, polyacrylic acid, styrene-butadiene rubber, sodium carboxymethyl cellulose, polyacrylate binder, polyvinylidene fluoride and polyacrylonitrile binder; at least two of the organic binders are oppositely charged in aqueous solution.
Optionally, the membrane has a mechanical heat shrinkage of T after being maintained at 150 ℃ for 0.5h 1 ％，6.3≤T 1 ≤7.1。
Optionally, the oxidative decomposition voltage of the base film is V 1 V, the oxidative decomposition voltage of the diaphragm is V 2 V，4.9V≤V 2 ≤6.4V，4.2V≤V 1 ≤4.3V。
Optionally, the adhesion force between the diaphragm and the negative electrode piece is X 1 N/m，5.1≤X 1 ≤7.1。
A second aspect of the present application provides a powered device comprising a secondary battery as described above.
The beneficial effects of this application lie in, the consumer that provides a secondary cell and have this secondary cell, through set up first coating in the one side of base film towards the anodal pole piece, set up the second coating in the one side of base film towards the negative pole piece, and first coating contains pottery, organic binder and inorganic binder, form ceramic coating, high heat-resisting pottery can improve the heat stability of diaphragm, compare in only adopting organic binder, inorganic binder and organic binder blending use in the first coating, can further improve the heat stability and the oxidation resistance of diaphragm, the second coating contains organic binder and inorganic binder, form the glue film, compare in only adopting inorganic binder, inorganic binder and organic binder's combination can effectively promote the adhesion of diaphragm and negative pole piece. The first coating has good thermal stability and oxidation resistance, and the second coating has good adhesion, and the two coatings are matched so as to improve the discharge capacity retention rate of the battery.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly introduced below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic view of a separator made in accordance with an embodiment of the present application;
wherein, 1, diaphragm, 11, base film, 12, first coating, 13, second coating.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and explanation only and is not intended to limit the present application.
In the detailed description and claims, a list of items connected by the term "at least one of" may mean any combination of the listed items. For example, if items a and B are listed, the phrase "at least one of a and B" means only a; only B; or A and B. In another example, if items A, B and C are listed, then the phrase "at least one of A, B and C" means only a; or only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or A, B and C. Item a may comprise a single element or multiple elements. Item B may comprise a single element or multiple elements. Item C may comprise a single element or multiple elements. At least one of the terms "has the same meaning as at least one of the terms".
In the present specification, a numerical range shown by using "to" means a range including numerical values described before and after "to" as a minimum value and a maximum value, respectively.
The embodiment of the application provides a secondary battery and have consumer of this secondary battery, through set up first coating in the one side of base film towards the anodal pole piece, set up the second coating in the one side of base film towards the negative pole piece, and first coating contains pottery, organic binder and inorganic binder, form ceramic coating, the heat stability of diaphragm can be improved to highly heat-resisting pottery, compare in only adopting organic binder, inorganic binder and organic binder blending use in the first coating, can further improve the heat stability and the oxidation resistance of diaphragm, the second coating contains organic binder and inorganic binder, form the glue film, compare in only adopting inorganic binder, inorganic binder and organic binder's combination can effectively promote the adhesion of diaphragm and negative pole piece. The first coating has good thermal stability and oxidation resistance, and the second coating has good adhesion, and the two coatings are matched so as to improve the discharge capacity retention rate of the battery.
In an embodiment of the present application, a secondary battery is provided, which includes a positive electrode tab, a negative electrode tab, a separator, an electrolyte, and a case.
I. Diaphragm
The separator is disposed between the positive electrode sheet and the negative electrode sheet, and referring to fig. 1, the separator 1 includes a base film 11, a first coating layer 12, and a second coating layer 13. The first coating 12 is disposed on a surface of the base film 11 facing the positive electrode sheet, and the second coating 13 is disposed on a surface of the base film 11 facing the negative electrode sheet.
First coating layer
In some embodiments, the first coating comprises a ceramic, an organic binder, and an inorganic binder.
In the conventional separator for secondary batteries, the thermal stability of the separator is improved by providing a ceramic coating layer on the surface of a base film, but the thermal stability and electrochemical stability of the separator are generally improved, but an inorganic adhesive is generally used for bonding the ceramic on the base film, and the thermal stability and electrochemical stability of the separator are affected due to the poor thermal stability and low electrochemical stability of the inorganic adhesive.
In the secondary battery provided in this embodiment, the ceramic, the inorganic adhesive and the organic adhesive are added in the first coating 12, and the first coating 12 is disposed on the surface of the base film 11 facing the positive electrode plate, and the high voltage easily causes the oxidative decomposition of the organic adhesive, and the ceramic is added in the first coating 12, so that the heat stability of the first coating 12 can be improved, and compared with the organic adhesive, the heat stability of the inorganic adhesive and the voltage of the oxidative decomposition resistance are higher, and therefore, the heat stability and the voltage of the oxidative decomposition resistance of the first coating 12 can be further improved, but the inorganic adhesive is mainly used for bonding between the ceramic and the ceramic, and between the ceramic and the base film 11, the bonding force between the first coating 12 and the positive electrode plate can be affected, and the bonding force between the first coating 12 and the positive electrode plate can be improved, the stability of the assembly between the diaphragm 1 and the positive electrode plate can be ensured, and the situation that the interface between the diaphragm 1 and the positive electrode plate is poor and the bonding interface between the diaphragm 1 and the positive electrode plate can not occur in the long-term circulation process of the secondary battery.
In some embodiments, the organic binder is separated from the inorganic binder by solvent dissolution, and the organic binder and the inorganic binder are then compositionally and structurally identified.
The organic adhesive can be detected by the following method: determining the type of the characteristic functional group and the nuclear structure of nuclear magnetic resonance spectrum by an infrared spectrum method, so as to realize qualitative analysis; analyzing element composition by an element analysis method, and determining the molecular weight and molecular weight distribution by gel permeation chromatography to realize quantitative analysis; the structure and components of the organic adhesive are determined by combining the above methods.
The inorganic binder can be detected by the following method: determining the type of the characteristic functional group by an infrared spectrometry method, determining a crystal structure by a transmission electron microscope method and an X-ray diffraction method, and realizing qualitative analysis; analyzing element composition by an element analysis method, and determining a molecular structure and an atomic valence state by an X-ray photoelectron spectroscopy to realize quantitative analysis; the structure and components of the inorganic adhesive are determined by combining the above methods.
In some embodiments, the inorganic binder in the first coating layer 12 is present in an amount of m based on the mass of the first coating layer 12 1a The weight part of the ceramic is m 1b The weight part of the organic adhesive is m 1c If the ratio is 1% or less 1a /(m 1b +m 1c ) Less than or equal to 10 percent, in particular, m 1a /(m 1b +m 1c ) May be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.8%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% or a range of any two numbers therein. Mass fraction m of inorganic binder in the first coating 12 1a Weight part m of ceramic 1b Weight part m of organic adhesive 1c The sum is simply the sum of the two (m 1b +m 1c ) 1% -10% of the inorganic binder in the first coating layer 12, the inorganic binder in the first coating layer 12 mainly bonds the ceramic and the ceramic, the organic binder in the first coating layer 12 mainly bonds the ceramic and the base film 11, if the content of the inorganic binder in the first coating layer 12 is too high, the bonding force between the first coating layer 12 and the base film 11 is affected, and if the content of the inorganic binder in the first coating layer 12 is too low, the thermal stability and the oxidative decomposition resistance voltage of the first coating layer 12 are affected (because the excessive voltage of the positive electrode sheet can cause oxidative decomposition of the organic binder), and the bonding force between the first coating layer 12 and the base film 11 are also affected. Thus, when m 1a /(m 1b +m 1c ) When the ratio of (c) is within the above range, the first coating layer 12 has higher thermal stability and oxidation-decomposition-resistant voltage, and has better adhesion with the positive electrode sheet.
With the increase of the mass fraction ratio of the inorganic binder relative to the ceramic and the organic binder in the first coating layer, for example, the ratio is increased from 1% to 10%, the MD thermal shrinkage rate of the separator is gradually reduced, the oxidative decomposition voltage of the separator is gradually increased, and the discharge capacity retention rate of the secondary battery after 5000 cycles is increased and then reduced, because the inorganic binder has better high temperature resistance and better oxidative decomposition resistance than the organic binder, thereby inhibiting the shrinkage of the separator and improving the oxidative decomposition voltage of the separator, the content of the inorganic binder in the first coating layer is too high, which affects the cohesive force of the first coating layer, so that the adhesive force between the first coating layer and the base film is poor, and the long-term cycle performance of the secondary battery is reduced.
In some embodiments, the ceramic comprises gamma-AlOOH (alumina hydrate), siO 2 (silica), mgO (magnesia), al 2 O 3 (aluminum oxide), znO 2 At least one of (zinc oxide). The ceramic is preferably gamma-AlOOH (hydrated alumina).
In some embodiments, the inorganic binder in the first coating 12 includes silicate-based binders (e.g., water glass), sulfate-based binders (e.g., gypsum), phosphate-based binders (e.g., cuO-phosphate), borate-based binders (e.g., pbO-B) 2 O 3 ) At least one of a carbonate-based binder (e.g., calcium carbonate), a nitrate-based binder (e.g., zinc nitrate). Silicate-based adhesives, such as water glass, clay, are preferred.
In some embodiments, the organic binder in the first coating 12 includes at least one of polyvinyl alcohol (PVA), polyacrylic acid (PAA), styrene Butadiene Rubber (SBR), sodium carboxymethyl cellulose (CMC-Na), polyacrylate binder (900B), polyvinylidene fluoride (PVDF), polyacrylonitrile-based binder (LA 133). At least one of polyvinyl alcohol (PVA), polyacrylic acid (PAA), and polyacrylate adhesive (900B) is preferable. Wherein 900B is a modified acrylic resin adhesive, specifically BM-900B, available from ZEON Co., ltd.
Second coating
In some embodiments, the second coating 13 comprises an organic binder and an inorganic binder.
The second coating 13 faces the negative electrode plate, the potential of the negative electrode plate is lower than that of the positive electrode plate, namely, the potential generated by the negative electrode plate can not cause the oxidative decomposition of the organic adhesive in the second coating 13, the thermal stability and the oxidative decomposition-resistant voltage of the second coating 13 can be effectively improved by combining the inorganic adhesive, and compared with the combination of the organic adhesive and the inorganic adhesive in the second coating 13, the stability of the bonding between the diaphragm 1 and the negative electrode plate is improved by only adopting the inorganic adhesive, and the condition that the interface bonding between the diaphragm 1 and the negative electrode plate is poorer and worse in the continuous lithium removing process in the long-term circulation process of the secondary battery can not occur.
In some embodiments, the inorganic binder in the second coating layer 13 is m in parts by weight based on the mass of the second coating layer 13 2a The weight part of the organic adhesive is m 2c If the ratio is 10% or less 2a /m 2c Less than or equal to 100 percent. Specifically, m 2a /m 2c May be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100% or a range consisting of any two of them. When m is 2a /m 2c When the ratio of (2) is in the above range, the second coating layer 13 has thermal stability and oxidation-decomposition-resistant voltage compatible with the negative electrode tab, and has better adhesion with the negative electrode tab.
In some embodiments, the inorganic binder in the second coating 13 includes at least one of a silicate binder, a sulfate binder, a phosphate binder, a borate binder, a carbonate binder, and a nitrate binder. Silicate-based adhesives, such as water glass, clay, are preferred.
In some embodiments, the organic binder in the second coating 13 includes at least one of polyvinyl alcohol (PVA), polyacrylic acid (PAA), styrene Butadiene Rubber (SBR), sodium carboxymethyl cellulose (CMC-Na), polyacrylate binder (900B), polyvinylidene fluoride (PVDF), polyacrylonitrile-based binder (LA 133). At least one of polyvinyl alcohol (PVA), polyacrylic acid (PAA), and polyacrylate adhesive (900B) is preferable. Wherein 900B is a modified acrylic resin adhesive, specifically BM-900B, available from ZEON Co., ltd.
In some embodiments, the organic binder in the second coating layer 13 employs a composite binder, and in particular, the organic binder in the second coating layer 13 includes at least two of polyvinyl alcohol (PVA), polyacrylic acid (PAA), styrene-butadiene rubber (SBR), sodium carboxymethyl cellulose (CMC-Na), polyacrylate binder (900B), polyvinylidene fluoride (PVDF), and polyacrylonitrile-based binder (LA 133). At least two of polyvinyl alcohol (PVA), polyacrylic acid (PAA), and polyacrylate adhesive (900B) are preferable. The organic adhesive adopts a composite adhesive, and along with m 2a /m 2c The adhesive force of the separator and the discharge capacity retention rate of the secondary battery show a tendency to increase and decrease first, that is, as the weight part m of the inorganic binder in the second coating layer 13 increases 2a The adhesion and the discharge capacity retention rate of the second coating layer 13 show a tendency of increasing and then decreasing, in particular, m 2a /m 2c At a ratio of 30%, the adhesion of the separator and the discharge capacity retention rate of the secondary battery were maximized. The reason is that the organic adhesive in the second coating layer 13 adopts a polymer material as the adhesive, the cohesive force of which is an important index for representing the adhesive strength of the adhesive, and the cohesive force sources of the adhesive are as follows: hydrogen bonding and physical entanglement. The higher the cohesion, the tighter the polymeric material, the stronger the adhesion; the lower the cohesion, the looser the polymeric material and the weaker the adhesion.
In some examples, the two organic binders in the second coating 13 are oppositely charged in aqueous solution, i.e., one organic binder is positively charged in aqueous solution and the other organic binder is negatively charged in aqueous solution. So that in the aqueous solution, one organic adhesive has the same charge as the inorganic adhesive, and the other organic adhesive has the opposite charge as the inorganic adhesive, so that the inorganic adhesive and the organic adhesive release more groups at the bonding interface for bonding the interface between the second coating 13 of the separator 1 and the negative electrode sheet through hydrogen bonding and intermolecular forces.
Specifically, taking an inorganic adhesive as clay and an organic adhesive as a composite adhesive of PVA (polyvinyl alcohol) and PAA (polyacrylic alcohol) as an example, the following description is made on the interaction force between the inorganic adhesive and the composite organic adhesive in the second coating in an aqueous solution:
first, PVA and PAA provide cohesion of the composite adhesive through physical entanglement between molecular chains; secondly, hydroxyl in PVA and carboxyl in PAA can provide hydrogen bond sources, and hydrogen bonds can be formed between hydroxyl and hydroxyl, carboxyl and carboxyl, and hydroxyl and carboxyl, and further cohesive force of the composite adhesive is provided, so that adhesive force is improved. Secondly, because the inorganic adhesive (clay) is added, the inorganic adhesive contains silanol groups, the inorganic adhesive presents negative charges in the aqueous solution, after the inorganic adhesive is added into the PVA-PAA composite adhesive, the inorganic adhesive can form weakening of hydrogen bonds in the PVA through electrostatic attraction with PVA which presents positive charges in the aqueous solution, and because the clay presents negative charges in the aqueous solution, PAA which presents negative charges in the aqueous solution is repelled by electrostatic repulsion, hydrogen bonds in the PAA are not consumed, so that more free PAA is released, more free PAA is generated at the interface between the second coating 13 and the negative electrode plate, the hydrogen bonds in the free PAA are used for bonding the second coating 13 and the surface of the negative electrode plate, and because only a small amount of inorganic adhesive is complexed with the hydrogen bonds in the PVA, more PVA is complexed with the PAA to generate the effect, and the bonding force of the PVA-PAA composite adhesive is ensured. Therefore, a small amount of inorganic adhesive can release more free PAA to improve the adhesive force of the second coating, improve the adhesive stability and firmness between the second coating 13 and the negative electrode plate, and improve the overall thermal stability and oxidative decomposition resistance voltage of the second coating 13, so that the organic adhesive cannot be decomposed due to high-potential oxidation, and further the discharge capacity retention rate of the secondary battery is improved.
However, since a part of hydrogen bonds in PVA are used to generate hydrogen bond interaction with PAA to promote cohesive force of the composite adhesive, and another part of hydrogen bonds are used to bond the second coating 13 to the surface of the negative electrode sheet, when the inorganic adhesive is excessive, excessive hydrogen bonds in PVA are consumed, so that the hydrogen bonds in PVA are insufficient to complex with the hydrogen bonds in PAA to generate hydrogen bond interaction, cohesive force of the PVA-PAA composite adhesive is reduced, and adhesive force is reduced, so that adhesive force of the whole second coating 13 is poor.
In addition, the composite adhesive proposed in the examples of the present application is not limited to the combination of PVA and PAA, as long as two organic adhesives that exhibit opposite electric charges in aqueous solution are combined (i.e., one organic adhesive exhibits positive charges in aqueous solution and the other organic adhesive exhibits negative charges in aqueous solution).
Base film
In some embodiments, the base film 11 comprises one or more of a commercial polyolefin separator.
In some embodiments, the base film 11 is selected from one of a polyethylene (PP) film, a Polypropylene (PE) film, a PP/PE/PP three-layer film.
In some embodiments, after the separator 1 is maintained at 150 ℃ for 0.5h, the Mechanical Direction (MD) heat shrinkage is T 1 ％，6.3≤T 1 Less than or equal to 7.1, specifically T 1 May be 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1 or any two of these numbers.
In some embodiments, the oxidative decomposition voltage of the base film 11 is V 1 V, the oxidative decomposition voltage of the diaphragm 1 is V 2 V, the inorganic additives are added into the first coating 12 and the second coating 13 in the diaphragm 1, so that the oxidative decomposition voltage V of the diaphragm 1 2 Gao Yuji film 11 has an oxidative decomposition voltage of V 1 I.e. V 2 ＞V 1 。
In some embodiments, the oxidative decomposition voltage V of the base film 11 1 The base film 11 is a PP film (polyethylene film) having a voltage of 4.2V to 4.3V.
In some embodiments, the oxidative decomposition voltage V of the diaphragm 1 2 Is 4.9V to 6.4V, specifically, the oxidative decomposition voltage V of the diaphragm 1 2 May be 4.9V, 5.0V, 5.1V, 5.2V, 5.3V, 5.4V, 5.5V, 5.6V, 5.7V, 5.8V, 5.9V, 6.0V, 6.1V, 6.2V, 6.3V, 6.4V or a range of any two of these numbers.
In some embodiments, separator 1 is in contact with the negative electrode sheetThe adhesive force is X 1 N/m，5.1≤X 1 Less than or equal to 7.1, specifically X 1 May be 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1 or a range of any two numbers therein.
II. Positive electrode plate
The positive electrode plate comprises a positive electrode current collector and a positive electrode active material layer arranged on the positive electrode current collector, wherein the positive electrode active material layer contains a positive electrode active material.
Positive electrode active material layer
The positive electrode active material layer may be one or more layers. Each layer of the multi-layer positive electrode active material may contain the same or different positive electrode active materials. The positive electrode active material is any substance capable of reversibly intercalating and deintercalating metal ions such as lithium ions.
In some embodiments, the positive electrode active material comprises one or more of lithium manganate, lithium iron phosphate (LFP), and ternary materials.
In some embodiments, the positive electrode active material comprises a ternary material, which may comprise lithium nickel cobalt manganese oxide and/or lithium nickel cobalt aluminum oxide.
In some embodiments, the positive electrode active material includes lithium nickel cobalt manganese oxide, and the content of nickel element is greater than or equal to 0.5 in terms of a molar ratio of nickel element, cobalt element, and manganese element of 1.
In some embodiments, the positive electrode active material includes lithium nickel cobalt manganese oxide, and the content of nickel element is less than or equal to 0.85 in terms of a molar ratio of nickel element, cobalt element, and manganese element of 1.
In some embodiments, the positive electrode active material includes a doping element and/or a cladding element, which are not particularly required as long as the positive electrode active material can be made more stable.
In addition, the positive electrode active material further includes a positive electrode conductive agent and a positive electrode binder.
Positive electrode conductive agent
The kind of the positive electrode conductive agent is not limited, and any known conductive agent may be used. Examples of the positive electrode conductive agent may include, but are not limited to, carbon materials such as natural graphite, artificial graphite, acetylene black, needle coke, carbon nanotubes, graphene, and the like. The above positive electrode conductive agents may be used alone or in any combination.
Positive electrode adhesive
The type of the positive electrode binder used in the production of the positive electrode active material layer is not particularly limited, and in the case of the coating method, the binder may be any material that is soluble or dispersible in a liquid medium used in the production of the electrode. Examples of positive electrode binders may include, but are not limited to, one or more of the following: resin polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polyimide, aromatic polyamide, cellulose, and nitrocellulose; rubbery polymers such as Styrene Butadiene Rubber (SBR), nitrile Butadiene Rubber (NBR), fluororubber, isoprene rubber, and ethylene-propylene rubber; thermoplastic elastomer-like polymers such as styrene-butadiene-styrene block copolymer or its hydrogenated product, ethylene-propylene-diene terpolymer (EPDM), styrene-ethylene-butadiene-ethylene copolymer, styrene-isoprene-styrene block copolymer or its hydrogenated product; soft resinous polymers such as syndiotactic-1, 2-polybutadiene, polyvinyl acetate, ethylene-vinyl acetate copolymer and propylene- α -olefin copolymer; fluorine-containing polymers such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene, fluorinated polyvinylidene fluoride, and polytetrafluoroethylene-ethylene copolymer; and polymer compositions having ion conductivity of alkali metal ions (particularly lithium ions). The positive electrode binder may be used alone or in any combination.
The type of solvent used to form the positive electrode slurry is not limited as long as it is a solvent capable of dissolving or dispersing the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder. Examples of the solvent used to form the positive electrode slurry may include any one of an aqueous solvent and an organic solvent. Examples of the aqueous medium may include, but are not limited to, water, a mixed medium of alcohol and water, and the like. Examples of the organic-based medium may include, but are not limited to, diethylenetriamine, N-dimethylaminopropylamine, diethyl ether, propylene oxide, tetrahydrofuran (THF), N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, hexamethylphosphoramide, dimethylsulfoxide, and the like.
Positive electrode current collector
The kind of the positive electrode current collector is not particularly limited, and it may be any material known to be suitable for use as a positive electrode current collector. Examples of the positive electrode current collector may include, but are not limited to, metal materials such as aluminum, stainless steel, nickel plating, titanium, tantalum, and the like; carbon materials such as carbon cloth and carbon paper; a composite of a polymer and a metal layer. In some embodiments, the positive electrode current collector is a metal material. In some embodiments, the positive electrode current collector is aluminum.
The form of the positive electrode current collector is not particularly limited. The positive electrode current collector may be a metal material. The positive electrode current collector may be a carbon material. In some embodiments, the positive current collector is a metal foil. In some embodiments, the metal foil is mesh-like. The thickness of the metal foil is not particularly limited. In some embodiments, the metal foil has a thickness of greater than 1 μm, greater than 3 μm, or greater than 5 μm. In some embodiments, the metal foil has a thickness of less than 1mm, less than 50 μm, or less than 20 μm. In some embodiments, the thickness of the metal foil is in the range consisting of any two of the values described above.
III, negative pole piece
The negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer arranged on at least one surface of the negative electrode current collector, wherein the negative electrode active material layer contains a negative electrode active material, and the negative electrode active material contains graphite.
The negative electrode plate is a single-sided plate or a double-sided plate, when the negative electrode plate is a single-sided plate, the negative electrode active material layer is arranged on one surface of the negative electrode current collector, and when the negative electrode plate is a double-sided plate, the negative electrode active material layer is arranged on two surfaces of the negative electrode current collector. The negative electrode piece can also have a single-sided negative electrode piece area and a double-sided negative electrode piece area.
Negative electrode current collector
In some embodiments, the negative electrode current collector is a metal foil. In some embodiments, the negative electrode current collector is aluminum foil or copper foil. As used herein, the term "copper foil" includes copper alloy foils.
In some embodiments, the negative electrode current collector is a conductive resin. In some embodiments, the conductive resin includes a film obtained by vapor plating copper on a polypropylene film.
Negative electrode active material layer
The anode active material layer may be one or more layers, and each of the multiple anode active material layers may contain the same or different anode active materials. The negative electrode active material is any substance capable of reversibly intercalating and deintercalating metal ions such as lithium ions. In some embodiments, the chargeable capacity of the negative active material is greater than the discharge capacity of the positive active material to prevent precipitation of lithium metal on the negative electrode tab during charging.
In some embodiments, the anode active material layer includes an anode active material, a conductive agent, a binder, and a dispersant.
Negative electrode active material
In some embodiments, the negative electrode active material is selected from at least one of natural graphite, artificial graphite, hard carbon, soft carbon, mesophase carbon microspheres, silicon-based alloys, silicon oxides, silicon/carbon composites, silicon oxide/carbon composites.
Conductive agent
In some embodiments, the conductive agent comprises one or more of carbon black, graphite, carbon fiber, carbon nanotubes, or graphene, preferably carbon black.
Adhesive agent
The binder may improve adhesion between the anode active materials. The kind of the binder is not particularly limited as long as it is a material stable to the electrolyte or the solvent used in the production of the electrode. In some embodiments, the binder includes sodium carboxymethyl cellulose and styrene butadiene rubber. In some embodiments, the binder includes sodium carboxymethyl cellulose, oxidized starch, and styrene butadiene rubber.
IV, electrolyte
The electrolyte includes a lithium salt, an organic solvent, and an additive.
Lithium salt
In some embodiments, the lithium salt comprises at least one of lithium hexafluorophosphate, lithium organoborate, lithium perchlorate, and lithium sulfonimide salts. The content of the lithium salt is not particularly limited as long as the effect of the present application is not impaired.
Organic solvents
In some embodiments, the organic solvent includes cyclic carbonates and chain carbonates.
Specifically, the organic solvent is one or more mixed solvents among EC (ethylene carbonate), DEC (diethyl carbonate), DMC (dimethyl carbonate) and EMC (ethylmethyl carbonate).
Additive agent
In some embodiments, the additive includes at least one of vinylene carbonate, 1, 3-propane sultone, lithium difluorophosphate, fluoroethylene carbonate (FEC), lithium difluorooxalato borate, tripropynyl phosphate, triallyl isocyanurate. In some embodiments, fluoroethylene carbonate (FEC) is preferred.
V, application
The embodiment of the application also provides a battery pack comprising the secondary battery. As a typical application, the battery pack may be used for, but is not limited to, electric toys, electric tools, battery cars, electric automobiles, energy storage devices, ships, spacecraft, and the like.
The following description is made with reference to specific examples for the preparation method of the separator in the secondary battery provided in the present application:
example 1
The first coating provided in this embodiment includes ceramic γ -AlOOH, organic binder 900B and water glass, and the weight portions of the first coating are 90 portions of γ -AlOOH, 10 portions of the first coating 900B and 1 portion of water glass. The second coating comprises PVA (polyvinyl alcohol), PAA (polyacrylic acid) and clay, wherein the weight parts of PVA, PAA and clay are 4 parts, 6 parts and 5 parts, the base film is a PP (polyethylene) base film, and the thickness of the PP base film is 12 mu m.
The preparation method of the diaphragm 1 comprises the following steps:
(1) Adding 90 parts of gamma-AlOOH, 10 parts of 900B and 1 part of water glass into pure water, and stirring until the mixture is uniformly dispersed to obtain a first dispersion liquid;
(2) And coating the first dispersion liquid on one surface of the PP base film, carrying out doctor blade coating, and drying to obtain a first coating, wherein the thickness of the first coating is 3 mu m.
(3) Adding 4 parts of PVA, 6 parts of PAA and 5 parts of clay into pure water, and stirring until the mixture is uniformly dispersed to obtain a second dispersion liquid;
(4) And (3) coating the second dispersion liquid on the other surface of the PP base film, carrying out doctor blade coating, and drying to obtain a second coating, wherein the thickness of the second coating is 3 mu m.
Example 2
A separator was prepared according to the method of example 1, except for the following differences:
the first coating comprises 90 parts by weight of gamma-AlOOH, 10 parts by weight of 900B and 3 parts by weight of water glass.
Example 3
A separator was prepared according to the method of example 1, except for the following differences:
the first coating comprises 90 parts by weight of gamma-AlOOH, 10 parts by weight of 900B and 5 parts by weight of water glass.
Example 4
A separator was prepared according to the method of example 1, except for the following differences:
the first coating comprises 90 parts by weight of gamma-AlOOH, 10 parts by weight of 900B and 7 parts by weight of water glass.
Example 5
A separator was prepared according to the method of example 1, except for the following differences:
the first coating comprises 90 parts by weight of gamma-AlOOH, 10 parts by weight of 900B and 10 parts by weight of water glass.
Example 6
A separator was prepared according to the method of example 3, except for the following differences:
the second coating layer contains 4 parts by weight of PVA, 6 parts by weight of PAA and 1 part by weight of clay.
Example 7
A separator was prepared according to the method of example 3, except for the following differences:
the second coating layer contains 4 parts by weight of PVA, 6 parts by weight of PAA and 3 parts by weight of clay.
Example 8
A separator was prepared according to the method of example 3, except for the following differences:
the second coating layer contains 4 parts by weight of PVA, 6 parts by weight of PAA and 7 parts by weight of clay.
Example 9
A separator was prepared according to the method of example 3, except for the following differences:
the second coating layer contains 4 parts by weight of PVA, 6 parts by weight of PAA and 10 parts by weight of clay.
Example 10
The separator coating provided in this example differs from the separator prepared in example 3 in that:
adopts ceramics as SiO 2 。
Example 11
A separator was prepared according to the method of example 3, except for the following differences:
the ceramic is MgO.
Example 12
A separator was prepared according to the method of example 3, except for the following differences:
the ceramic is Al 2 O 3 。
Example 13
A separator was prepared according to the method of example 3, except for the following differences:
the ceramic is ZnO 2 。
Comparative example 1
The first coating provided in this example contains ceramic gamma-AlOOH and organic binder 900B, with parts by weight being 90 parts gamma-AlOOH and 10 parts 900B. The second coating provided comprises PVA and PAA, wherein the weight parts of PVA and PAA are 4 parts, the base film is a PP base film, and the thickness of the PP base film is 12 mu m.
The preparation method of the diaphragm comprises the following steps:
(1) Adding 90 parts of gamma-AlOOH and 10 parts of 900B into pure water, and stirring until the mixture is uniformly dispersed to obtain a first dispersion liquid;
(2) And coating the first dispersion liquid on one surface of the PP base film, carrying out doctor blade coating, and drying to obtain a first coating, wherein the thickness of the first coating is 3 mu m.
(3) Adding 4 parts of PVA and 6 parts of PAA into pure water, and stirring until the PVA and the PAA are uniformly dispersed to obtain a second dispersion liquid;
(4) And (3) coating the second dispersion liquid on the other surface of the PP base film, carrying out doctor blade coating, and drying to obtain a second coating, wherein the thickness of the second coating is 3 mu m.
Comparative example 2
The first coating provided in this embodiment includes ceramic γ -AlOOH, organic binder 900B and water glass, and the weight portions of the first coating are 90 portions of γ -AlOOH, 10 portions of the first coating 900B and 5 portions of water glass. The second coating provided comprises PVA and PAA, wherein the weight parts of PVA and PAA are 4 parts, the base film is a PP base film, and the thickness of the PP base film is 12 mu m.
The preparation method of the diaphragm comprises the following steps:
(1) Adding 90 parts of gamma-AlOOH, 10 parts of 900B and 5 parts of water glass into pure water, and stirring until the mixture is uniformly dispersed to obtain a first dispersion liquid;
(2) And coating the first dispersion liquid on one surface of the PP base film, carrying out doctor blade coating, and drying to obtain a first coating, wherein the thickness of the first coating is 3 mu m.
(3) Adding 4 parts of PVA and 6 parts of PAA into pure water, and stirring until the PVA and the PAA are uniformly dispersed to obtain a second dispersion liquid;
(4) And (3) coating the second dispersion liquid on the other surface of the PP base film, carrying out doctor blade coating, and drying to obtain a second coating, wherein the thickness of the second coating is 3 mu m.
Comparative example 3
The first coating provided in this example contains ceramic gamma-AlOOH and organic binder 900B, with parts by weight being 90 parts gamma-AlOOH and 10 parts 900B. The second coating comprises PVA, PAA and clay, wherein the weight parts of PVA, the weight parts of PAA and the weight parts of clay are 4 parts, the weight parts of PAA and the weight parts of clay are 6 parts, the base film is a PP base film, and the thickness of the PP base film is 12 mu m.
The preparation method of the diaphragm comprises the following steps:
(1) Adding 90 parts of gamma-AlOOH and 10 parts of 900B into pure water, and stirring until the mixture is uniformly dispersed to obtain a first dispersion liquid;
(2) And coating the first dispersion liquid on one surface of the PP base film, carrying out doctor blade coating, and drying to obtain a first coating, wherein the thickness of the first coating is 3 mu m.
(3) Adding 4 parts of PVA, 6 parts of PAA and 5 parts of clay into pure water, and stirring until the mixture is uniformly dispersed to obtain a second dispersion liquid;
(4) And (3) coating the second dispersion liquid on the other surface of the PP base film, carrying out doctor blade coating, and drying to obtain a second coating, wherein the thickness of the second coating is 3 mu m.
Diaphragm performance test
Mechanical Direction (MD) heat shrinkage:
mechanical Direction (MD) heat shrinkage= (L0-L1)/L0 x 100%, L0 is the initial length of the separator in the mechanical direction, and L1 is the length of the separator after baking in an oven at 150 ℃ for 0.5 h.
Adhesive force:
the diaphragm 1 was cut into 50mm 90mm shapes (90 mm MD and 50mm td), and then the diaphragm and pole piece laminate were hot pressed, and the diaphragm/pole piece adhesion was tested using a universal tensile machine in the 180 ° direction.
Oxidative decomposition voltage:
and placing a diaphragm containing saturated electrolyte between the lithium sheet and the steel sheet, assembling a button cell, and testing a linear sweep voltammetry curve by adopting an electrochemical workstation.
Discharge capacity retention rate at 5000 th turn:
the positive electrode sheet is prepared by taking a nickel cobalt lithium manganate ternary material as a positive electrode material, the negative electrode sheet is prepared by taking graphite as a negative electrode material, a bare cell is obtained by winding the negative electrode sheet and the separator of examples 1-13 or the separator of comparative examples 1-3, and then the secondary battery is prepared by steps of baking, liquid injection, formation and the like, and the discharge capacity of the secondary battery at 5C is tested. The 5000 th turn discharge capacity divided by the 1 st turn discharge capacity is the 5000 th turn discharge capacity retention rate.
The lithium hexafluorophosphate of which the electrolyte is 1mol/L is dissolved in ethylene carbonate, dimethyl carbonate and ethylmethyl carbonate (volume ratio is 1:1:1).
The results of performance testing of the separators provided in examples 1 to 13 and comparative examples 1 to 3 are shown in table 1.
TABLE 1
As can be seen from table 1, in each of comparative examples 1 to 2, the inorganic binder was not added to the first coating layer and the second coating layer of comparative example 1, the inorganic binder was added to the first coating layer of comparative example 2, the inorganic binder was not added to the second coating layer, and in examples 1 to 9, the ceramic, the organic binder and the inorganic binder were added to the first coating layer, and the organic binder and the inorganic binder were added to the second coating layer, so that the MD heat shrinkage rate, the oxidative decomposition voltage of the separator, and the adhesion force of the separator to the negative electrode sheet of the separator prepared in examples 1 to 9 were superior to those of the separator prepared in comparative examples 1 and 2, and the discharge capacity retention rate after 5000 cycles of the secondary battery prepared using the separator provided in examples 1 to 9 was also superior to those of the secondary battery prepared using the separator provided in comparative examples 1 and 2.
In example 3 and examples 10 to 13, different ceramics were used, and the thermal stability, oxidative decomposition voltage, adhesion, and discharge capacity retention rate of the secondary battery of the separator were not greatly affected.
The secondary battery and the electric equipment provided by the embodiment of the application are described in detail, and specific examples are applied to illustrate the principle and the implementation of the application, and the description of the above embodiments is only used for helping to understand the method and the core idea of the application; meanwhile, those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, and the present description should not be construed as limiting the present application in view of the above.
Claims (11)
1. The secondary battery comprises a positive pole piece, a negative pole piece and a diaphragm, wherein the diaphragm is arranged between the positive pole piece and the negative pole piece,
the diaphragm comprises a base film, a first coating and a second coating, wherein the first coating is arranged on one surface of the base film facing the positive pole piece, and the second coating is arranged on one surface of the base film facing the negative pole piece;
wherein the first coating comprises a ceramic, an organic binder, and an inorganic binder; the second coating layer includes an organic binder and an inorganic binder.
2. The secondary battery according to claim 1, wherein the weight part of the inorganic binder in the first coating layer is m based on the mass of the first coating layer 1a The weight part of the ceramic is m 1b The weight part of the organic adhesive is m 1c If the ratio is 1% or less 1a /(m 1b +m 1c )≤10％。
3. The secondary battery according to claim 1, wherein the weight part of the inorganic binder in the second coating layer is m based on the mass of the second coating layer 2a The weight part of the organic adhesive is m 2c If the ratio is 10% or less 2a /m 2c ≤100％。
4. The secondary battery according to claim 1, wherein the ceramic comprises γ -AlOOH, siO 2 、MgO、Al 2 O 3 、ZnO 2 At least one of them.
5. The secondary battery according to claim 2 or 3, wherein the inorganic binder comprises at least one of a silicate binder, a sulfate binder, a phosphate binder, a borate binder, a carbonate binder, and a nitrate binder.
6. The secondary battery according to claim 1, wherein the organic binder in the first coating layer and the organic binder in the second coating layer each include at least one of polyvinyl alcohol, polyacrylic acid, styrene-butadiene rubber, sodium carboxymethyl cellulose, polyacrylate-type binders, polyvinylidene fluoride, and polyacrylonitrile-type binders.
7. The secondary battery according to claim 6, wherein the organic binder in the second coating layer comprises at least two of polyvinyl alcohol, polyacrylic acid, styrene-butadiene rubber, sodium carboxymethyl cellulose, polyacrylate-type binder, polyvinylidene fluoride, and polyacrylonitrile-type binder;
at least two of the organic binders are oppositely charged in aqueous solution.
8. The secondary battery according to claim 1, wherein the separator has a mechanical heat shrinkage ratio T after being maintained at 150 ℃ for 0.5h 1 ％，6.3≤T 1 ≤7.1。
9. The secondary battery according to claim 1, wherein the oxidative decomposition voltage of the base film is V 1 V, the oxidative decomposition voltage of the diaphragm is V 2 V，4.9V≤V 2 ≤6.4V，4.2V≤V 1 ≤4.3V。
10. The secondary battery according to claim 1, wherein the adhesion force of the separator to the negative electrode tab is X 1 N/m，5.1≤X 1 ≤7.1。
11. An electric device comprising the secondary battery according to any one of claims 1 to 10.
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| CN116799437A (en) * | 2023-08-18 | 2023-09-22 | 荣耀终端有限公司 | Battery and electronic equipment |
| CN116799437B (en) * | 2023-08-18 | 2023-10-31 | 荣耀终端有限公司 | Battery and electronic equipment |
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