CN114843702A - Metal compound diaphragm and preparation method and application thereof - Google Patents
Metal compound diaphragm and preparation method and application thereof Download PDFInfo
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- CN114843702A CN114843702A CN202210536146.2A CN202210536146A CN114843702A CN 114843702 A CN114843702 A CN 114843702A CN 202210536146 A CN202210536146 A CN 202210536146A CN 114843702 A CN114843702 A CN 114843702A
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- 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
- H01M50/431—Inorganic material
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- 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
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- 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- 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
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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
Abstract
The present invention provides a metal compound separator including a base film and a coating layer formed on at least one side of the base film, the coating layer including at least heat-resistant particles and metal oxide particles. The invention also provides a lithium battery, which comprises the metal compound diaphragm, a positive electrode and a negative electrode, wherein the metal compound diaphragm is positioned between the positive electrode and the negative electrode. The invention also provides a preparation method of the metal compound diaphragm, which comprises the following steps: mixing materials: mixing the heat-resistant particles, the metal oxide particles and a solvent to obtain a dispersion liquid; and dry coating: and coating the dispersion liquid on at least one side of the base film, and drying to obtain the metal compound diaphragm.
Description
Technical Field
The invention relates to the technical field of lithium batteries, and particularly relates to a metal compound diaphragm and a preparation method and application thereof.
Background
With the great breakthrough of the technical level of the lithium battery in recent years, the rapid development and growth are achieved in a plurality of application fields, particularly in the field of new energy automobiles. However, the formation of lithium dendrites in commercial lithium batteries during use can cause electrical performance degradation and safety hazards, and it is difficult to meet the user's requirements for long cycle, fast charging, and use in super-cold and super-hot environments.
At present, in order to inhibit the growth of lithium dendrites and reduce the risk of short circuit in the lithium battery, improvement is mainly carried out from various aspects such as a battery diaphragm coating, a pole piece coating, high-safety electrolyte and the like so as to reduce the risk of potential safety hazard caused by the fact that the lithium dendrites grow to puncture the diaphragm to cause short circuit in the battery.
In the aspect of the separator, it is common practice to add a ceramic coating to improve the structural strength of the separator. However, this method only reduces the risk of short circuit in the battery caused by the membrane being punctured at best, and cannot fundamentally inhibit the growth of lithium dendrite, and the membrane is eventually punctured after long-term use, and the battery performance degradation caused by the growth of lithium dendrite is not reduced.
Based on this, there is an urgent need to develop a stable high-performance composite separator and a preparation technology thereof, which fundamentally solve the problem of lithium dendrite growth, i.e., which inhibits the lithium dendrite growth inside a battery, to improve the safety and electrochemical performance of the battery.
Disclosure of Invention
The object of the present invention is to provide a metal compound separator comprising a base film and a coating layer formed on at least one side of the base film, the coating layer comprising at least heat-resistant particles and metal oxide particles.
Preferably, the base film has a thickness of 5 to 16 μm and the coating has a thickness of 2 to 4 μm.
Preferably, the heat-resistant particles are mixed with the metal oxide particles to form a layered structure on one side of the base film as a coating layer.
Preferably, the heat-resistant particles form a first layer structure on one side of the base film, and the metal oxide particles form a second layer structure on the same side of the base film, so that the first layer structure and the second layer structure together serve as a coating.
Preferably, under the condition that the first layer structure and the second layer structure are located on the same side of the base film, the second layer structure is located on the side of the first layer structure far away from the base film.
Preferably, the heat-resistant particles form a first layer structure on one side of the base film, and the metal oxide particles form a second layer structure on the other side of the base film, so that the first layer structure and the second layer structure together serve as a coating.
Preferably, the base film is one or more of polyethylene and polypropylene.
Preferably, the heat-resistant particles are one or more of alumina, boehmite, and barium sulfate.
Preferably, the heat-resistant particles have a particle size of 50 to 500 nm.
Preferably, the metal oxide particles are one or more of transition metal oxides, group IVA metal oxides.
Preferably, the metal oxide particles are one or more of manganese oxide, tin oxide, ferric oxide and ferroferric oxide.
Preferably, the metal oxide particles have a particle size of 20 to 100 nm.
Preferably, the ratio of the particle size of the metal oxide particles to that of the heat-resistant particles is 1: (2 to 25).
Preferably, the coating further comprises a binder.
Preferably, the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polypropylene, polyethylene and sodium hydroxymethyl cellulose.
Preferably, the heat-resistant particles, the metal oxide particles and the binder are mixed to form a layered structure.
Preferably, the heat-resistant particles are mixed with a binder to form a first layer structure, and the metal oxide particles are mixed with a binder to form a second layer structure.
It is another object of the present invention to provide a lithium battery comprising the metal compound separator as described above, a positive electrode and a negative electrode, the metal compound separator being located between the positive electrode and the negative electrode.
Preferably, the negative electrode is located on the side of the metal compound separator on which the layer structure is formed, under the condition that the heat-resistant particles and the metal oxide particles are mixed to form the layer structure.
Preferably, the negative electrode is located on a side of the metal compound separator where the first layer structure and the second layer structure are formed, under the condition that the first layer structure and the second layer structure are located on the same side of the base film.
Preferably, the negative electrode is located on the side of the metal compound separator where the second layer structure is formed, under the condition that the heat-resistant particles form the first layer structure on one side of the base film and the metal oxide particles form the second layer structure on the other side of the base film.
Another object of the present invention is to provide a method for preparing a metal compound separator, which comprises the following steps: mixing materials: mixing the heat-resistant particles, the metal oxide particles and a solvent to obtain a dispersion liquid; and dry coating: and coating the dispersion liquid on at least one side of the base film, and drying to obtain the metal compound diaphragm.
Preferably, the dry coating comprises: and coating the dispersion liquid on at least one side of the base film to enable the metal oxide particles to be distributed to the side, away from the base film, of the dispersion liquid, and drying to obtain the metal compound diaphragm.
Preferably, the solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol and isopropanol.
Preferably, the dispersion further comprises a binder.
Another object of the present invention is to provide a method for preparing a metal compound separator, which comprises the following steps: mixing materials: mixing the heat-resistant particles with a solvent to obtain a first dispersion liquid, and mixing the metal oxide particles with the solvent to obtain a second dispersion liquid; and dry coating: and coating the first dispersion liquid and the second dispersion liquid on the same side of the base film, and drying to obtain the metal compound diaphragm.
Preferably, the solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol and isopropanol.
Preferably, the first dispersion further comprises a binder, and the second dispersion further comprises a binder.
Another object of the present invention is to provide a method for preparing a metal compound separator, which comprises the following steps: mixing materials: mixing the heat-resistant particles with a solvent to obtain a first dispersion liquid, and mixing the metal oxide particles with the solvent to obtain a second dispersion liquid; and dry coating: and coating the first dispersion liquid on one side of the base film, coating the second dispersion liquid on the other side of the base film, and drying to obtain the metal compound diaphragm.
Preferably, the solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol and isopropanol.
Preferably, the first dispersion further comprises a binder, and the second dispersion further comprises a binder.
The metal compound diaphragm provided by the invention has the advantages that the heat-resistant particles and the metal oxide particles are coated on the base film, so that the heat-resistant particles and the metal oxide particles play a synergistic effect, and the electrochemical performance of a lithium battery using the diaphragm is improved. In addition, the heat-resistant particles can improve the thermal stability of the diaphragm, reduce the thermal shrinkage rate, improve the ink splashing temperature and enhance the safety performance of the battery under the high-temperature condition. In addition, the metal oxide particles have slight solubility and can be deposited on the surface of the negative electrode along with the discharge process of the lithium battery. The formed lithium dendrite can react with the metal oxide deposited on the surface of the negative electrode to form metal alloy as the cycle number of the battery is increased or the battery operates in special environments such as high temperature or low temperature. Because the formed metal alloy has certain volume expansibility, a protective layer can be formed on the surface of the negative electrode to adjust the electric field on the surface of the negative electrode, so that the Li flux of the negative electrode is uniform, the continuous formation of lithium dendrites of the negative electrode is inhibited, and the cycle stability of the battery is improved. Moreover, the matching of the heat-resistant particles with different particle sizes and the metal oxide particles can also improve the tortuosity of micropores, thereby reducing the micro short circuit of the battery and the self-discharge of the battery. Moreover, the heat-resistant particles can also neutralize free HF in the electrolyte, thereby avoiding battery corrosion.
Drawings
FIG. 1 is a schematic cross-sectional view of a metal compound diaphragm according to a first embodiment of the present invention;
FIG. 2 is a schematic cross-sectional view of a metal compound diaphragm according to a second embodiment of the present invention;
FIG. 3 is a schematic cross-sectional view of a metal compound diaphragm according to a third embodiment of the present invention;
fig. 4 is a graph illustrating the battery capacity retention rates of the separators of all examples and the separators of all comparative examples after different cycles.
Description of component reference numerals
1 … base film
2 … coating
21 … layer structure
22 … first layer Structure
23 … second layer structure
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Referring to fig. 1, a metal compound separator according to a first embodiment of the present invention includes a base film (1) and a coating layer (2), the coating layer (2) is formed on at least one side of the base film (1) and includes heat-resistant particles and metal oxide particles, and the heat-resistant particles and the metal oxide particles are mixed to form a layered structure (21) on one side of the base film (1) as the coating layer (2). Further, the base film (1) may have a thickness of, but not limited to, 5 to 16 μm, and the coating layer (2) may have a thickness of, but not limited to, 2 to 4 μm. In addition, the base film (1) may be, but not limited to, one or more of polyethylene and polypropylene, the heat-resistant particles may be, but not limited to, one or more of alumina, boehmite and barium sulfate, and the metal oxide particles may be, but not limited to, one or more of transition metal oxide and group IVA metal oxide, and specifically may be, but not limited to, one or more of manganese oxide, tin oxide, iron sesquioxide and iron tetroxide.
To improve the adhesion of the coating (2), the coating (2) may further contain a binder, examples of which may be, but are not limited to, one or more of polyvinylidene fluoride, polytetrafluoroethylene, polypropylene, polyethylene, sodium carboxymethylcellulose. That is, the heat-resistant particles, the metal oxide particles and the binder may be mixed to form a layer structure (21) as the coating layer (2).
In addition, the metal oxide particles, through their slight solubility, can deposit on the surface of the negative electrode as the lithium battery discharges. The formed lithium dendrite can react with the metal oxide deposited on the surface of the negative electrode to form metal alloy along with the increase of the cycle number of the battery or the operation of the battery under special environments such as high temperature or low temperature, and the like, and the metal alloy forms a protective layer on the surface of the negative electrode through the volume expansibility of the metal alloy to inhibit the negative electrode lithium dendrite from being continuously formed, so that the cycle stability of the battery is improved. Based on this, in order to improve the slightly solubility of the metal oxide particles, the content distribution of the metal oxide particles in the layer structure (21) may be decreased from the side away from the base film (1) to the side close to the base film (1); alternatively, the particle size of the metal oxide particles may be smaller than that of the heat-resistant particles, so that the metal oxide particles are naturally distributed toward the side of the layer structure (21) away from the base film (1) during film formation, and the content distribution of the metal oxide particles in the layer structure (21) is gradually reduced from the side away from the base film (1) to the side close to the base film (1). In addition, the particle size of the heat-resistant particles may be, but is not limited to, 50 to 500nm, and the particle size of the metal oxide particles may be, but is not limited to, 20 to 100 nm. In addition, the particle size ratio between the metal oxide particles and the heat-resistant particles may be, but is not limited to, 1: (2 to 25).
The metal compound separator according to the first embodiment of the present invention can be used for a lithium battery. More specifically, the lithium battery contains a positive electrode and a negative electrode in addition to a metal compound separator, and the metal compound separator is located between the positive electrode and the negative electrode. In order to facilitate deposition of metal oxide particles on the surface of the negative electrode following the discharge process of the lithium battery, the negative electrode may be located on the side of the metal compound separator on which the layer structure (21) is formed.
The following further illustrates a method for preparing a metal compound separator according to a first embodiment of the present invention, which comprises: a material mixing step; and a drying coating step.
In the mixing, the heat-resistant particles, the metal oxide particles and the solvent are mixed to obtain a dispersion. The use of a solvent, which may be exemplified by, but not limited to, one or more of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol, isopropanol, disperses the heat-resistant particles and metal oxide particles so that they may be subsequently distributed in a desired manner on one side of the base film (1). Furthermore, to improve the adhesion of the coating (2), the dispersion may further comprise a binder. Under these conditions, the use of a solvent is more soluble in the binder.
In the drying coating, the dispersion liquid is coated on one side of the base film (1) and dried to obtain the metal compound separator. Examples of coating means may be, but are not limited to, gravure roll coating, dipping, narrow coating, or spray coating. In addition, under the condition that the content distribution of the metal oxide particles in the layer structure (21) is gradually reduced from the side far away from the base film (1) to the side close to the base film (1), the metal oxide particles can be distributed to the side, far away from the base film (1), of the dispersion liquid after coating; alternatively, the particle size of the metal oxide particles may be smaller than that of the heat-resistant particles, so that the metal oxide particles after coating are naturally distributed toward the side of the dispersion liquid away from the base film (1).
Referring to fig. 2, a metal compound separator according to a second embodiment of the present invention includes a base film (1) and a coating layer (2), the coating layer (2) is formed on at least one side of the base film (1) and includes heat-resistant particles and metal oxide particles, the heat-resistant particles form a first layer structure (22) on one side of the base film (1), and the metal oxide particles form a second layer structure (23) on the same side of the base film (1), such that the first layer structure (22) and the second layer structure (23) together serve as the coating layer (2). Further, the base film (1) may have a thickness of, but not limited to, 5 to 16 μm, and the coating layer (2) may have a thickness of, but not limited to, 2 to 4 μm. In addition, the base film (1) may be, but not limited to, one or more of polyethylene and polypropylene, the heat-resistant particles may be, but not limited to, one or more of alumina, boehmite and barium sulfate, and the metal oxide particles may be, but not limited to, one or more of transition metal oxide and group IVA metal oxide, and specifically may be, but not limited to, one or more of manganese oxide, tin oxide, iron sesquioxide and iron tetroxide.
To improve the adhesion of the coating (2), the coating (2) may further contain a binder, examples of which may be, but are not limited to, one or more of polyvinylidene fluoride, polytetrafluoroethylene, polypropylene, polyethylene, sodium carboxymethylcellulose. That is, the heat-resistant particles and the binder may be mixed to form a first layer structure (22), and the metal oxide particles and the binder may be mixed to form a second layer structure (23), so that the first layer structure (22) and the second layer structure (23) together serve as the coating layer (2).
In addition, the metal oxide particles, through their slight solubility, can deposit on the surface of the negative electrode as the lithium battery discharges. The formed lithium dendrite can react with the metal oxide deposited on the surface of the negative electrode to form metal alloy along with the increase of the cycle number of the battery or the operation of the battery under special environments such as high temperature or low temperature, and the like, and the metal alloy forms a protective layer on the surface of the negative electrode through the volume expansibility of the metal alloy to inhibit the negative electrode lithium dendrite from being continuously formed, so that the cycle stability of the battery is improved. On the basis of this, in order to increase the sparingly solubility of the metal oxide particles, the second layer structure (23) is located on the side of the first layer structure (22) remote from the base film (1). In addition, the particle size of the heat-resistant particles may be, but is not limited to, 50 to 500nm, and the particle size of the metal oxide particles may be, but is not limited to, 20 to 100 nm. In addition, the ratio of the particle diameters between the metal oxide particles and the heat-resistant particles may be, but is not limited to, 1: (2 to 25).
The metal compound separator according to the second embodiment of the present invention can be used for a lithium battery. More specifically, the lithium battery includes a positive electrode and a negative electrode in addition to the metal compound separator, and the metal compound separator is disposed between the positive electrode and the negative electrode. In order to facilitate deposition of metal oxide particles on the surface of the negative electrode following the discharge process of the lithium battery, the negative electrode may be located at a side of the metal compound separator where the first layer structure (22) and the second layer structure (23) are formed.
The following further illustrates a method for preparing a metal compound separator according to a second embodiment of the present invention, which comprises: a material mixing step; and a drying coating step.
When mixing materials, the heat-resistant particles are mixed with a solvent to obtain a first dispersion liquid, and the metal oxide particles are mixed with the solvent to obtain a second dispersion liquid. The use of a solvent, which may be, but is not limited to, one or more of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol, isopropanol, disperses the heat-resistant particles and metal oxide particles such that they may be subsequently distributed in a desired manner on the same side of the base film (1). Furthermore, to improve the adhesion of the coating (2), the first dispersion may further comprise a binder and the second dispersion may further comprise a binder. Under these conditions, the use of a solvent is more soluble in the binder.
And during drying and coating, coating the first dispersion liquid and the second dispersion liquid on the same side of the base film (1), and drying to obtain the metal compound diaphragm. Examples of coating means may be, but are not limited to, gravure roll coating, dipping, narrow coating, or spray coating.
Referring to fig. 3, a metal compound separator according to a third embodiment of the present invention includes a base film (1) and a coating layer (2), the coating layer (2) is formed on at least one side of the base film (1) and includes heat-resistant particles and metal oxide particles, the heat-resistant particles form a first layer structure (22) on one side of the base film (1), and the metal oxide particles form a second layer structure (23) on the other side of the base film (1), such that the first layer structure (22) and the second layer structure (23) together serve as the coating layer (2). Further, the base film (1) may have a thickness of, but not limited to, 5 to 16 μm, and the coating layer (2) may have a thickness of, but not limited to, 2 to 4 μm. In addition, the base film (1) may be, but not limited to, one or more of polyethylene and polypropylene, the heat-resistant particles may be, but not limited to, one or more of alumina, boehmite and barium sulfate, and the metal oxide particles may be, but not limited to, one or more of transition metal oxide and group IVA metal oxide, and specifically may be, but not limited to, one or more of manganese oxide, tin oxide, iron sesquioxide and iron tetroxide.
To improve the adhesion of the coating (2), the coating (2) may further contain a binder, examples of which may be, but are not limited to, one or more of polyvinylidene fluoride, polytetrafluoroethylene, polypropylene, polyethylene, sodium carboxymethylcellulose. That is, the heat-resistant particles and the binder may be mixed to form a first layer structure (22), and the metal oxide particles and the binder may be mixed to form a second layer structure (23), so that the first layer structure (22) and the second layer structure (23) together serve as the coating layer (2).
In addition, the metal oxide particles, through their slight solubility, can deposit on the surface of the negative electrode as the lithium battery discharges. The formed lithium dendrite can react with the metal oxide deposited on the surface of the negative electrode to form metal alloy along with the increase of the cycle number of the battery or the operation of the battery under special environments such as high temperature or low temperature, and the like, and the metal alloy forms a protective layer on the surface of the negative electrode through the volume expansibility of the metal alloy to inhibit the negative electrode lithium dendrite from being continuously formed, so that the cycle stability of the battery is improved. Based on this, in order to improve the slightly solubility of the metal oxide particles, the content distribution of the metal oxide particles in the second layer structure (23) may be decreased from the side away from the base film (1) toward the side close to the base film (1). In addition, the particle size of the heat-resistant particles may be, but is not limited to, 50 to 500nm, and the particle size of the metal oxide particles may be, but is not limited to, 20 to 100 nm. In addition, the ratio of the particle diameters between the metal oxide particles and the heat-resistant particles may be, but is not limited to, 1: (2 to 25).
The metal compound separator according to the third embodiment of the present invention can be used for a lithium battery. More specifically, the lithium battery includes a positive electrode and a negative electrode in addition to the metal compound separator, and the metal compound separator is disposed between the positive electrode and the negative electrode. In order to facilitate deposition of metal oxide particles on the surface of the negative electrode following the discharge process of the lithium battery, the negative electrode may be located on the side of the metal compound separator where the second layer structure (23) is formed.
The following further illustrates a method for preparing a metal compound separator according to a third embodiment of the present invention, which comprises: a material mixing step; and a drying coating step.
When mixing materials, the heat-resistant particles are mixed with a solvent to obtain a first dispersion liquid, and the metal oxide particles are mixed with the solvent to obtain a second dispersion liquid. The use of a solvent, which may be exemplified by, but not limited to, one or more of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol, isopropanol, disperses the heat-resistant particles and metal oxide particles so that they may be subsequently distributed in a desired manner on both sides of the base film (1). Furthermore, to improve the adhesion of the coating (2), the first dispersion may further comprise a binder and the second dispersion may further comprise a binder. Under these conditions, the use of a solvent is more soluble in the binder.
And in the process of drying coating, the first dispersion liquid is coated on one side of the base film (1), the second dispersion liquid is coated on the other side of the base film (1), and the metal compound diaphragm is obtained after drying. Examples of coating means may be, but are not limited to, gravure roll coating, dipping, narrow coating, or spray coating.
The above-described embodiments of the invention are now illustrated by the following examples:
example 1
The thickness of the base film of the separator of this example was 9 μm, and the thickness of the coating layer was 2 μm.
Firstly, mixing alumina heat-resistant particles with the particle size of 100nm, manganese oxide metal oxide particles with the particle size of 50nm, PVDF (polyvinylidene fluoride) binder and a solvent to obtain a dispersion, wherein the solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol and isopropanol.
Next, the dispersion was coated on one side of the polyethylene-based film and dried to obtain a separator.
Example 2
The thickness of the base film of the separator of this example was 9 μm, and the thickness of the coating layer was 4 μm.
Firstly, mixing alumina heat-resistant particles with the particle size of 100nm, PVDF (polyvinylidene fluoride) binder and solvent to obtain a first dispersion solution, and mixing manganese oxide metal oxide particles with the particle size of 50nm, PVDF binder and solvent to obtain a second dispersion solution. The solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol and isopropanol.
And then coating the first dispersion liquid on one side of a polyethylene base film and drying, and coating the second dispersion liquid on the same side of the polyethylene base film and drying to obtain the diaphragm.
Example 3
The thickness of the base film of the separator of this example was 9 μm, and the thickness of the coating layer was 3 μm.
Firstly, mixing alumina heat-resistant particles with the particle size of 500nm, manganese oxide metal oxide particles with the particle size of 100nm, PVDF (polyvinylidene fluoride) binder and a solvent to obtain a dispersion, wherein the solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol and isopropanol.
And then, coating the dispersion liquid on the two sides of the polyethylene base film and drying to obtain the diaphragm. Because the particle size of the alumina heat-resistant particles is far larger than that of the manganese oxide metal oxide particles, the manganese oxide metal oxide particles are distributed to one side far away from the polyethylene base film during coating and drying and float on one surface of the coating far away from the polyethylene base film.
Example 4
The thickness of the base film of the separator of this example was 9 μm, and the thickness of the coating layer was 3 μm.
Firstly, mixing alumina heat-resistant particles with the particle size of 500nm, manganese oxide metal oxide particles with the particle size of 20nm, PVDF (polyvinylidene fluoride) binder and a solvent to obtain a dispersion, wherein the solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol and isopropanol.
And then, coating the dispersion liquid on the two sides of the polyethylene base film and drying to obtain the diaphragm. Because the particle size of the alumina heat-resistant particles is far larger than that of the manganese oxide metal oxide particles, the manganese oxide metal oxide particles are distributed to one side far away from the polyethylene base film during coating and drying and float on one surface of the coating far away from the polyethylene base film.
Example 5
The thickness of the base film of the separator of this example was 9 μm, and the thickness of the coating layer was 3 μm.
Firstly, mixing alumina heat-resistant particles with the particle size of 50nm, manganese oxide metal oxide particles with the particle size of 20nm, PVDF (polyvinylidene fluoride) binder and a solvent to obtain a dispersion, wherein the solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol and isopropanol.
And then, coating the dispersion liquid on the two sides of the polyethylene base film and drying to obtain the diaphragm. Because the particle size of the alumina heat-resistant particles is far larger than that of the manganese oxide metal oxide particles, the manganese oxide metal oxide particles are distributed to one side far away from the polyethylene base film during coating and drying and float on one surface of the coating far away from the polyethylene base film.
Comparative example 1
The separator of this comparative example had a base film thickness of 9 μm and a coating thickness of 2 μm.
Firstly, mixing alumina heat-resistant particles with the particle size of 100nm, PVDF binder and a solvent to obtain a dispersion, wherein the solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol and isopropanol.
Next, the dispersion was coated on one side of the polyethylene-based film and dried to obtain a separator.
Comparative example 2
The separator of this comparative example had a base film thickness of 9 μm and a coating thickness of 2 μm.
Firstly, manganese oxide metal oxide particles with the particle size of 50nm, PVDF (polyvinylidene fluoride) binder and a solvent are mixed to obtain a dispersion liquid, wherein the solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol and isopropanol.
Next, the dispersion was coated on one side of the polyethylene-based film and dried to obtain a separator.
Comparative example 3
The separator of this comparative example had a base film thickness of 9 μm and a coating thickness of 3 μm.
Firstly, mixing alumina heat-resistant particles with the particle size of 100nm, manganese oxide metal oxide particles with the particle size of 100nm, PVDF (polyvinylidene fluoride) binder and a solvent to obtain a dispersion, wherein the solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol and isopropanol.
And then, coating the dispersion liquid on the two sides of the polyethylene base film and drying to obtain the diaphragm.
Comparative example 4
The separator of this comparative example had a base film thickness of 9 μm and a coating thickness of 3 μm.
Firstly, mixing alumina heat-resistant particles with the particle size of 50nm, manganese oxide metal oxide particles with the particle size of 100nm, PVDF (polyvinylidene fluoride) binder and a solvent to obtain a dispersion, wherein the solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol and isopropanol.
And then, coating the dispersion liquid on the two sides of the polyethylene base film and drying to obtain the diaphragm.
Comparative example 5
The separator of this comparative example had a base film thickness of 9 μm and was a polyethylene base film only.
The test method comprises the following steps:
the thermal shrinkage was measured by high-temperature baking under the specific test condition of 130 ℃ for 1 hour, while TD and MD represent the longitudinal thermal shrinkage and the transverse thermal shrinkage, respectively, and the greater the thermal shrinkage, the worse the thermal shrinkage of the separator.
The peel strength was measured by an electronic universal tester under the specific test conditions of an effective length of 200mm and an effective width of 30 mm.
The amount of gas permeability was measured by a Gurley4320 permeameter, which measures the time for 100ml of gas to pass through the membrane, with a greater increase in gas permeability representing a poorer permeability of the membrane.
The closed pore/rupture temperature is measured by a Q400 thermal mechanical analyzer of the American TA company, and the specific test method is that a diaphragm sample strip cut in the MD and TD directions is pulled by constant force, and simultaneously, the temperature of a sample cabin is increased at the rate of 5 ℃/min to obtain the closed pore temperature and the rupture temperature.
The particle size distribution of the heat-resistant particles and the metal oxide particles is measured by a Mastersizer 2000 laser particle size analyzer, the specific test method is that a sample is added into test equipment, the brightness of the sample reaches the test range, the particle size of the sample is tested after ultrasonic treatment for 60 seconds, and the particle size result D of the sample is recorded 10 、D 50 And D 90 。
And (3) configuring the diaphragm with a positive electrode and a negative electrode to prepare a soft package battery cell, and testing the retention rate of the circulating capacity at 1C/25 ℃.
Configuring a positive electrode and a negative electrode of a diaphragm to prepare a soft package battery core, using a high-temperature-resistant steel needle with the diameter of 5mm and the needle point angle of 50 degrees to penetrate through the battery plate at the speed of 25 +/-2 mm/s in the direction vertical to the battery plate after the battery is charged according to requirements (4.2VCC-CV), and pulling out the steel needle after the steel needle stays in the battery for 10 minutes to observe the phenomenon. Testing two batteries in each group, and if the two batteries do not generate the fire explosion phenomenon, judging that the acupuncture safety test of the battery in the experimental group passes (OK); if one battery has the fire and explosion phenomena, the battery needling safety test of the test set is judged to fail (NG).
All test results are shown in table 1.
TABLE 1 test results
As can be seen from table 1, all examples are superior to all comparative examples in heat shrinkage characteristics in MD direction and TD direction, peel strength, difference in closed cell and rupture temperature, cell capacity retention characteristics, puncture resistance, and the like. As can be seen from fig. 4, the battery capacity retention rate was maintained at 89% or more after 1000 cycles in all examples.
Comparing comparative examples 1, 2, and 5, it can be seen that the use of only alumina refractory particles in the coating increases the gas permeability for 32 seconds, the use of only manganese oxide metal oxide particles in the coating increases the gas permeability for 37 seconds, and theoretically, the use of both alumina refractory particles and manganese oxide metal oxide particles in the coating increases the gas permeability for between 32 and 37 seconds. However, comparing example 1 with comparative example 5, it can be seen that the use of both alumina heat-resistant particles and manganese oxide metal oxide particles in the coating layer increased the gas permeability number by 4 seconds, indicating that the alumina heat-resistant particles and manganese oxide metal oxide particles had a synergistic effect on the gas permeability properties of the separator.
Comparing comparative examples 1, 2, and 5, it can be seen that the use of only alumina heat-resistant particles in the coating increases the battery capacity retention by 6%, the use of only manganese oxide metal oxide particles in the coating increases the battery capacity retention by 6%, and theoretically, the use of both alumina heat-resistant particles and manganese oxide metal oxide particles in the coating increases the battery capacity retention by 6%. However, comparing example 1 with comparative example 5, it can be seen that the simultaneous use of the heat-resistant alumina particles and the manganese oxide metal oxide particles in the coating layer increases the battery capacity retention rate by 18%, indicating that the heat-resistant alumina particles and the manganese oxide metal oxide particles produce a synergistic effect on the capacity retention property of the separator battery.
Comparing examples 3 to 5 with comparative examples 3 and 4, it can be seen that the alumina heat-resistant particles and the manganese oxide metal oxide particles can prevent pores from being plugged to the base film through proper particle sizes, so as to enhance the air permeability of the separator. Moreover, the aluminum oxide heat-resistant particles and the manganese oxide metal oxide particles can increase the peeling strength and the difference between the closed pore temperature and the film breaking temperature through proper particle sizes, and the safety of the battery is improved. In addition, as shown in fig. 4, the heat-resistant alumina particles and the manganese oxide metal oxide particles pass through appropriate particle sizes, so that the battery capacity retention rate is maintained at 89% or more after 1000 cycles of the separator, which indicates that the appropriate particle sizes can exert an effect of inhibiting the growth of lithium dendrites.
The above matters related to the common general knowledge are not described in detail and can be understood by those skilled in the art.
The present invention is not intended to be limited to the particular embodiments shown and described, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (14)
1. A metal compound membrane comprising:
a base film and a coating layer formed on at least one side of the base film and including at least heat-resistant particles and metal oxide particles.
2. The metal compound separator according to claim 1, wherein:
the heat-resistant particles are mixed with the metal oxide particles to form a layer structure on one side of the base film as the coating layer;
the heat-resistant particles form a first layer structure on one side of the base film, and the metal oxide particles form a second layer structure on the same side of the base film, so that the first layer structure and the second layer structure are jointly used as the coating; or
The heat-resistant particles form a first layer structure on one side of the base film, and the metal oxide particles form a second layer structure on the other side of the base film, so that the first layer structure and the second layer structure are jointly used as the coating.
3. The metal compound separator according to claim 2, wherein:
and under the condition that the first layer structure and the second layer structure are positioned on the same side of the base film, the second layer structure is positioned on the side, away from the base film, of the first layer structure.
4. The metal compound separator according to claim 1, wherein:
the base film is one or more of polyethylene and polypropylene;
the heat-resistant particles are one or more of alumina, boehmite and barium sulfate; and/or
The metal oxide particles are one or more of transition metal oxides, group IVA metal oxides.
5. The metal compound separator according to claim 2, wherein:
under the condition that the heat-resistant particles are mixed with the metal oxide particles to form the layer structure, the particle diameter of the metal oxide particles is smaller than that of the heat-resistant particles.
6. The metal compound separator according to claim 5, wherein:
the ratio of the metal oxide particles to the heat-resistant particles is 1: (2 to 25);
the heat-resistant particles have a particle size of 50 to 500nm, and the metal oxide particles have a particle size of 20 to 100 nm; and/or
The base film has a thickness of 5 to 16 μm and the coating has a thickness of 2 to 4 μm.
7. The metal compound separator according to claim 1, wherein:
the coating further includes a binder.
8. The metal compound separator according to claim 7, wherein:
the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polypropylene, polyethylene and sodium hydroxymethyl cellulose.
9. A lithium battery, comprising:
the metal compound separator according to claim 2, a positive electrode, and a negative electrode, the metal compound separator being located between the positive electrode and the negative electrode.
10. A lithium battery as in claim 9, wherein:
the negative electrode is located on the side of the metal compound separator on which the layer structure is formed, under the condition that the heat-resistant particles and the metal oxide particles are mixed to form the layer structure.
11. A lithium battery as in claim 9, wherein:
the negative electrode is located on the side of the metal compound separator where the first layer structure and the second layer structure are formed, under the condition that the first layer structure and the second layer structure are located on the same side of the base film.
12. A lithium battery as in claim 9, wherein:
the negative electrode is positioned on the side of the metal compound separator where the second layer structure is formed, under the condition that the heat-resistant particles form the first layer structure on one side of the base film and the metal oxide particles form the second layer structure on the other side of the base film.
13. A method of making a metal compound separator comprising the steps of:
mixing materials: mixing the heat-resistant particles, the metal oxide particles and a solvent to obtain a dispersion liquid; and
drying and coating: and coating the dispersion liquid on at least one side of the base film, and drying to obtain the metal compound diaphragm.
14. The method of claim 13, wherein:
the dry coating comprises: coating the dispersion liquid on at least one side of the base film to enable the metal oxide particles to be distributed to the side, away from the base film, of the dispersion liquid, and drying to obtain the metal compound diaphragm.
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| CN202210536146.2A CN114843702B (en) | 2022-05-09 | 2022-05-09 | Metal compound diaphragm and preparation method and application thereof |
| PCT/CN2022/100732 WO2023216376A1 (en) | 2022-05-09 | 2022-06-23 | Metal compound separator, preparation method therefor and use thereof |
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