CN114243215A - Coating slurry, preparation method thereof, composite diaphragm and lithium ion battery - Google Patents
Coating slurry, preparation method thereof, composite diaphragm and lithium ion battery Download PDFInfo
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- CN114243215A CN114243215A CN202111554436.1A CN202111554436A CN114243215A CN 114243215 A CN114243215 A CN 114243215A CN 202111554436 A CN202111554436 A CN 202111554436A CN 114243215 A CN114243215 A CN 114243215A
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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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
- 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
- H01M50/434—Ceramics
Abstract
The invention provides coating slurry, a preparation method thereof, a composite diaphragm and a lithium ion battery. The coating slurry comprises the following components in percentage by mass: ceramic particles, double metal hydroxide, a thickening agent, a water-based binder, 0.3-0.7% of a dispersing agent, 0.03-0.04% of a wetting agent and 39-63% of deionized water; the mass ratio of the ceramic particles to the double metal hydroxide is (0.75-2.5) to 1; the mass ratio of the total mass of the ceramic particles and the double metal hydroxide to the thickener is 1 (0.13-0.4); the mass ratio of the total mass of the ceramic particles and the double metal hydroxide to the aqueous binder is 1 (0.11-0.48). The composite diaphragm provided by the invention coats a flame-retardant coating on the surface of the polyolefin base film, and can improve the wettability to electrolyte.
Description
Technical Field
The invention belongs to the field of battery materials, and particularly relates to coating slurry, a preparation method thereof, a composite diaphragm and a lithium ion battery.
Background
With the increasing demand of people on high-performance lithium ion batteries, the safety performance of the lithium ion batteries is concerned more, when the batteries are overcharged, charged and discharged with high rate, internally and externally short-circuited, vibrated, impacted and the like, a series of side reactions occur inside the batteries spontaneously to release a large amount of heat, and when the internal temperature reaches a certain value, the batteries are burnt or exploded and the like. In order to further improve the safety performance of the battery, a coating treatment is mainly performed on the surface of a polyolefin base film from the layer of the separator, for example, a heat-resistant ceramic coating is coated on the surface of the base film, and the heat-resistant performance of the separator is enhanced by using a ceramic material having smaller particles and a high-temperature-resistant binder.
The existing method for improving the safety performance of the diaphragm still has some problems, for example, under the condition of high temperature (more than 150 ℃), the modified diaphragm still has serious shrinkage and even cracks. When the battery is burned, the polyolefin separator is melted and decomposed, resulting in pulverization of the ceramic coating. In addition, the use of ceramic powder with smaller particles is not only costly, but also reduces the lithium ion transport channels.
Therefore, in the art, it is desired to develop a coating layer having good heat-resistant stability and improved battery safety, which not only can increase the transport speed of lithium ions, but also is not easily damaged by combustion.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a coating slurry, a preparation method thereof, a composite diaphragm and a lithium ion battery. Compared with the prior art, the composite diaphragm provided by the invention has the advantages that the flame-retardant coating is coated on the surface of the polyolefin base film, the flame-retardant effect can be achieved under the high-temperature condition (higher than 250 ℃), the safety of the battery is improved, and meanwhile, the wettability of the electrolyte can be improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a coating slurry, which comprises the following components by mass: ceramic particles, double metal hydroxide, a thickening agent, a water-based binder, 0.3-0.7% of a dispersing agent, 0.03-0.04% of a wetting agent and 39-63% of deionized water;
the mass ratio of the ceramic particles to the double metal hydroxide is (0.75-2.5) to 1;
the mass ratio of the total mass of the ceramic particles and the double metal hydroxide to the thickener is 1 (0.13-0.4);
the mass ratio of the total mass of the ceramic particles and the double metal hydroxide to the aqueous binder is 1 (0.11-0.48).
In the present invention, the mass ratio of the ceramic particles to the double metal hydroxide is (0.75-2.5):1, and may be, for example, 0.75:1, 0.77:1, 0.8:1, 0.82:1, 0.85:1, 0.87:1, 0.9:1, 0.92:1, 0.95:1, 0.97:1, 1:1, 1.2:1, 1.5:1, 1.7:1, 2:1, 2.2:1, 2.5: 1.
In the invention, the mass ratio of the ceramic particles to the bimetal hydroxide is adjusted to meet the heat resistance and the processability, the heat resistance is reduced due to the excessively low mass percentage of the ceramic particles, and otherwise, the ceramic particles have high solid content, so that the processing is difficult; too low a mass percentage of the double metal hydroxide results in reduced flame retardancy, which in turn results in a higher solid content of the double metal hydroxide, making processing difficult.
In the present invention, the mass ratio of the total mass of the ceramic particles and the double metal hydroxide to the thickener is 1 (0.13-0.4), and may be, for example, 1:0.13, 1:0.15, 1:0.17, 1:0.2, 1:0.22, 1:0.25, 1:0.27, 1:0.3, 1:0.32, 1:0.35, 1:0.37, 1: 0.4.
In the invention, the mass ratio of the total mass of the ceramic particles and the bimetal hydroxide to the thickener is adjusted to ensure that the stability and the processability of the slurry are met, the poor stability of the slurry is caused by the excessively low mass percentage of the thickener, and otherwise, the processing is difficult due to the excessively high viscosity.
In the present invention, the mass ratio of the total mass of the ceramic particles and the double metal hydroxide to the aqueous binder is 1 (0.11 to 0.48), and may be, for example, 1:0.11, 1:0.13, 1:0.15, 1:0.17, 1:0.2, 1:0.22, 1:0.25, 1:0.27, 1:0.3, 1:0.32, 1:0.35, 1:0.37, 1:0.4, 1:0.42, 1:0.45, 1: 0.48.
In the invention, the total mass of the ceramic particles and the bimetal hydroxide is adjusted to the mass ratio of the water-based binder, so that the adhesive coating does not fall off and has better heat resistance, the mass percentage of the water-based binder is too low, the adhesive force is insufficient, the coating falls off and the heat resistance is reduced, and otherwise, the prepared diaphragm has poor air permeability.
In the present invention, the mass percentage of the dispersant in the coating slurry may be 0.3% to 0.7%, for example, 0.3%, 0.32%, 0.35%, 0.37%, 0.4%, 0.42%, 0.45%, 0.47%, 0.5%, 0.52%, 0.55%, 0.57%, 0.6%, 0.62%, 0.65%, 0.67%, 0.7%.
In the invention, the mass percent of the dispersing agent is adjusted to ensure that the slurry is uniformly dispersed, and the mass percent of the dispersing agent is too low to cause the slurry to be difficult to agglomerate and disperse, otherwise, the performance of the diaphragm is influenced.
In the present invention, the mass percentage of the wetting agent in the coating slurry is 0.03% to 0.04%, and may be, for example, 0.03%, 0.032%, 0.035%, 0.037%, 0.04%.
In the invention, the slurry and the base material are better infiltrated by adjusting the mass percent of the wetting agent, the slurry is poorly infiltrated to the base material due to the excessively low mass percent of the wetting agent, the phenomenon of coating leakage occurs, and otherwise, the appearance and the performance of the product are influenced by much foaming in the processing process.
In the present invention, the mass percentage of the deionized water in the coating slurry is 39% to 63%, for example, 39%, 42%, 45%, 48%, 51%, 54%, 57%, 60%, 63%.
The invention utilizes the addition of one in the coating slurryA flame-retardant bimetal hydroxide whose surface is treated by sodium tripolyphosphate (Na)5P3O10) The modified double metal hydroxide releases water and flame retardant gas (carbon dioxide) when heated, thereby reducing the surface temperature of the material and isolating oxygen; the surface of the material is modified by sodium tripolyphosphate, and P is added under the high temperature condition (more than 250℃)3O10 5-The phosphorus oxide is formed by thermal decomposition, and the phosphorus oxide further reacts to form polysilicate glass body to cover the surface of the coating, so that the diaphragm is inhibited from continuously oxidizing and burning. In addition, the double metal hydroxide has a certain alkalinity, and can neutralize hydrogen fluoride gas. The interlayer structure of the double metal hydroxide can allow ions to be rapidly transmitted, and the double metal hydroxide has a large specific surface area and can effectively improve the wettability of lithium ions in the electrolyte.
Preferably, the ceramic particles comprise any one or a combination of at least two of alumina particles, magnesia, silica or calcia, such as alumina and magnesia, silica or calcia, but not limited to the listed species, and the same applies to species not listed in the scope of the ceramic particles.
Preferably, the ceramic particles have an average particle size of 0.3 μm to 0.8. mu.m, and may be, for example, 0.3 μm, 0.32. mu.m, 0.35. mu.m, 0.37. mu.m, 0.4. mu.m, 0.42. mu.m, 0.45. mu.m, 0.47. mu.m, 0.5. mu.m, 0.52. mu.m, 0.55. mu.m, 0.57. mu.m, 0.6. mu.m, 0.62. mu.m, 0.65. mu.m, 0.67. mu.m, 0.7. mu.m, 0.72. mu.m, 0.75. mu.m, 0.77. mu.m, 0.8. mu.m.
In the present invention, the average particle size of the ceramic particles is adjusted so that the heat resistance and the processability are good, and the dispersion during the processing is difficult due to the excessively small average particle size of the ceramic particles, and otherwise, the heat resistance is lowered.
Preferably, the double metal hydroxide is a double metal hydroxide with a surface modified by sodium tripolyphosphate.
According to the invention, the surface of the double metal hydroxide modified by the sodium tripolyphosphate is adopted, so that the double metal hydroxide is decomposed to release flame-retardant gas and water under a high-temperature condition to form a layer of protective film, and the sodium tripolyphosphate is decomposed to form a glass state to cover the surface of the material to further retard flame air.
In the invention, the surface of the double metal hydroxide modified by the sodium tripolyphosphate is adopted, compared with the unmodified double metal hydroxide, a layer of protective film can be formed at high temperature, the sodium tripolyphosphate is decomposed to form a glass state, and the glass state covers the surface of the material to further retard the flame of air.
Preferably, the double hydroxide includes at least one of magnesium aluminum double hydroxide, lithium aluminum double hydroxide, and zinc aluminum double hydroxide.
In the invention, the double metal hydroxide is adopted, so that the coating has flame retardance and a specific interlayer structure, and the ion conduction capability can be improved.
Preferably, the average particle size of the double metal hydroxide is 0.5 μm to 1.0. mu.m, and may be, for example, 0.5 μm, 0.52 μm, 0.55 μm, 0.57 μm, 0.6 μm, 0.62 μm, 0.65 μm, 0.67 μm, 0.7 μm, 0.72 μm, 0.75 μm, 0.77 μm, 0.8 μm, 0.82 μm, 0.85 μm, 0.87 μm, 0.9 μm, 0.92 μm, 0.95 μm, 0.97 μm, 1.0. mu.m.
In the present invention, the average particle size of the double metal hydroxide is adjusted to be suitable, and too small average particle size of the double metal hydroxide causes difficulty in dispersion and causes pore blocking, whereas heat resistance and flame retardancy are adversely affected.
Preferably, the thickener is a carboxymethyl cellulose-based thickener.
Preferably, the carboxymethyl cellulose-based thickener comprises sodium carboxymethyl cellulose.
Preferably, the dispersant is an acrylate-based dispersant.
Preferably, the acrylate-based dispersant comprises sodium acrylate or ammonium acrylate.
Preferably, the lubricant is a fatty alcohol lubricant.
Preferably, the fatty alcohol based lubricant comprises any one of a polyethylene glycol, glycerol or propylene glycol.
In a second aspect, the present invention provides a method of preparing the coating slurry of the first aspect, the method comprising the steps of:
mixing a dispersing agent and deionized water, adding ceramic particles and a bimetal hydroxide for dispersion, then adding a thickening agent for continuous secondary dispersion, and then sequentially adding an aqueous binder and a wetting agent for secondary mixing to obtain the coating slurry.
Preferably, the mixing is carried out under stirring.
Preferably, the stirring rate is 1200r/min-1700r/min, for example 1200r/min, 1250r/min, 1300r/min, 1350r/min, 1400r/min, 1450r/min, 1500r/min, 1550r/min, 1600r/min, 1650r/min, 1700 r/min.
Preferably, the stirring time is 10min-20min, for example, 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min, 20 min.
Preferably, the rate of dispersion is 1700r/min to 2200r/min, and may be 1700r/min, 1750r/min, 1800r/min, 1850r/min, 1900r/min, 1950r/min, 2000r/min, 2050r/min, 2100r/min, 2150r/min, 2200r/min, for example.
Preferably, the dispersing time is 40min-80min, for example, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80 min.
Preferably, the rate of the secondary dispersion is 45r/min to 60r/min, for example 45r/min, 48r/min, 50r/min, 55r/min, 60 r/min.
Preferably, the time of the secondary dispersion is 20min to 40min, for example, 20min, 22min, 25min, 27min, 30min, 32min, 35min, 37min, 40 min.
In a third aspect, the present invention provides a composite separator comprising a base film and a coating layer coated on at least one side of the base film, the coating layer being prepared using the coating slurry according to the first aspect.
Preferably, the coating has a thickness of 2 μm to 4 μm, and may be, for example, 2 μm, 2.2 μm, 2.5 μm, 2.7 μm, 3 μm, 3.2 μm, 3.5 μm, 3.7 μm, 4 μm.
In the present invention, by adjusting the thickness of the coating layer so that the thickness is appropriate, the heat-resistant effect is not achieved due to the excessively thin coating layer, which in turn increases the weight of the battery and increases the internal resistance.
In a fourth aspect, the invention provides a lithium ion battery, which comprises an electrode plate, an electrolyte and a diaphragm, wherein the diaphragm is the composite diaphragm of the third aspect.
The composite diaphragm with the flame retardant effect provided by the invention has high heat resistance and flame retardance under a high-temperature condition (higher than 250 ℃), has good wettability to an electrolyte, and improves the electrochemical performance and safety performance of a battery at high temperature.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a coating slurry, which is characterized in that flame-retardant bimetal hydroxide is added into the coating slurry of a diaphragm, the surface of the coating slurry is modified by sodium tripolyphosphate, and the coating slurry has an interlayer structure, and the modified bimetal hydroxide releases water and flame-retardant gas (carbon dioxide) when heated, so that the surface temperature of the material is reduced and oxygen is isolated; the surface of the diaphragm is modified by sodium tripolyphosphate, and a layer of polysilicate glass body is formed on the surface of the diaphragm under the high-temperature condition (more than 380 ℃), so that oxygen contact is isolated, and the diaphragm is prevented from being continuously oxidized and combusted. In addition, the double metal hydroxide has certain alkalinity, can generate a neutralizing effect on hydrogen fluoride gas, can allow ions to be rapidly transmitted due to the interlayer structure of the double metal hydroxide, has a large specific surface area, and can effectively improve the wettability of lithium ions in the electrolyte.
The preparation method of the composite diaphragm provided by the invention is simple and effective, and meanwhile, the preparation method of the flame-retardant material of the bimetal hydroxide is simple, environment-friendly and low in cost.
Drawings
Fig. 1 is a flow chart of a coating process of the composite membrane provided in examples 1 to 6, including 1-an unreeling device, 2-a preheating oven, 3-a substrate, 4-a gravure roll, 5-a trough, 6-a filter, 7-a transfer pump, 8-a feeding pump, 9-a heating oven, and 10-a reeling device.
Detailed Description
The technical solution of the present invention is further explained by combining the drawings and the detailed description. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The purity of all the raw materials in the examples and comparative examples of the present invention was more than 99.9%.
Example 1
The embodiment provides a coating slurry, which comprises the following components in percentage by mass: 20% of aluminum oxide particles (the average particle size is 0.3 mu m), magnesium aluminum hydroxide (the average particle size is 0.5 mu m) with a surface modified by sodium tripolyphosphate, a sodium carboxymethyl cellulose thickener, a polyethyl acrylate aqueous binder, a sodium acrylate dispersant 0.3%, a polyvinyl alcohol wetting agent 0.03% and deionized water 42.67%, wherein the mass ratio of the aluminum oxide particles to the magnesium aluminum metal hydroxide with a surface modified by sodium tripolyphosphate is 1.176:1, the mass ratio of the total mass of the aluminum oxide particles to the magnesium aluminum metal hydroxide with a surface modified by sodium tripolyphosphate to the sodium carboxymethyl cellulose thickener is 1:0.243, and the mass ratio of the total mass of the aluminum oxide particles to the magnesium aluminum metal hydroxide with a surface modified by sodium tripolyphosphate to the polyethyl acrylate aqueous binder is 1: 0.297.
Taking the total mass of the coating slurry as 100 percent, mixing 0.3 percent of sodium acrylate dispersant and 42.67 percent of deionized water in percentage by mass, dispersing at high speed for 15min in a double-planet mixer under the condition of the stirring speed of 1500r/min, then adding 20 percent of alumina particles and magnesium aluminum hydroxide with the surface modified by sodium tripolyphosphate for dispersion, wherein the dispersing speed is 2000r/min, the dispersing time is 60min, transferring the mixture into a sand mill for sand grinding dispersion under the condition that the rotating speed is 1200r/min and the time is 30min, after the dispersion is finished, entering a stirring tank through a magnetic filter, slowly adding sodium carboxymethyl cellulose thickener for continuous secondary dispersion, dispersing for 30min at the rotating speed of 60r/min, sequentially adding polyethylacrylate aqueous binder and 0.03 percent of polyethylene glycol wetting agent in percentage by mass for secondary mixing after the stirring is finished, and continuously stirring for 20min to form coating slurry, coating the coating slurry on two sides of a polyethylene base film with the thickness of 9 mu m in a gravure transfer coating mode, wherein the thickness of the coating is 2 mu m, and baking for 5min at the temperature of 60 ℃ to obtain the composite diaphragm.
Example 2
The embodiment provides a coating slurry, which comprises the following components in percentage by mass: 20% of aluminum oxide particles (the average particle size is 0.5 mu m), lithium aluminum hydroxide (the average particle size is 0.7 mu m) with a surface modified by sodium tripolyphosphate, a sodium carboxymethyl cellulose thickener, a polymethyl methacrylate aqueous binder, a sodium acrylate dispersant 0.5%, 0.035% of a propylene glycol wetting agent and 48.465% of deionized water, wherein the mass ratio of the aluminum oxide particles to the lithium aluminum metal hydroxide with a surface modified by sodium tripolyphosphate is 1.333:1, the mass ratio of the total mass of the aluminum oxide particles to the lithium aluminum metal hydroxide with a surface modified by sodium tripolyphosphate to the sodium carboxymethyl cellulose thickener is 1:0.228, and the mass ratio of the total mass of the aluminum oxide particles to the lithium aluminum metal hydroxide with a surface modified by sodium tripolyphosphate to the polymethyl methacrylate aqueous binder is 1: 0.228.
Taking the total mass of the coating slurry as 100 percent, mixing 0.5 percent of sodium acrylate dispersant and 48.465 percent of deionized water in percentage by mass, dispersing the mixture in a double-planet mixer at a high speed for 15min under the condition of a stirring speed of 1500r/min, then adding 20 percent of alumina particles in percentage by mass and lithium aluminum hydroxide with the surface modified by sodium tripolyphosphate for dispersion, wherein the dispersing speed is 2000r/min, the dispersing time is 60min, transferring the mixture to a sand mill for sand grinding dispersion under the condition that the rotating speed is 1200r/min and the time is 30min, after the dispersion is finished, entering a stirring tank through a magnetic filter, slowly adding sodium carboxymethyl cellulose thickener for continuous secondary dispersion, dispersing the mixture for 30min at the rotating speed of 60r/min, and after the stirring is finished, sequentially adding a polymethyl methacrylate aqueous binder and 0.035 percent of propylene glycol wetting agent in percentage by mass for secondary mixing, and continuously stirring for 20min to form coating slurry, coating the coating slurry on two sides of a polyethylene base film with the thickness of 9 mu m in a gravure transfer coating mode, wherein the thickness of the coating is 3 mu m, and baking for 5min at the temperature of 60 ℃ to obtain the composite diaphragm.
Example 3
The embodiment provides a coating slurry, which comprises the following components in percentage by mass: 17% of aluminum oxide particles (the average particle size is 0.4 mu m), magnesium aluminum hydroxide (the average particle size is 0.6 mu m) with a surface modified by sodium tripolyphosphate, a sodium carboxymethyl cellulose thickener, a polyethyl acrylate aqueous binder, a sodium acrylate dispersant 0.4%, 0.032% of a glycerin wetting agent and 56.568% of deionized water, wherein the mass ratio of the aluminum oxide particles to the magnesium aluminum metal hydroxide with a surface modified by sodium tripolyphosphate is 1.308:1, the mass ratio of the total mass of the aluminum oxide particles to the magnesium aluminum metal hydroxide with a surface modified by sodium tripolyphosphate to the sodium carboxymethyl cellulose thickener is 1:0.233, and the mass ratio of the total mass of the aluminum oxide particles to the magnesium aluminum metal hydroxide with a surface modified by sodium tripolyphosphate to the polyethyl acrylate aqueous binder is 1: 0.2.
Taking the total mass of the coating slurry as 100 percent, mixing 0.4 percent of sodium acrylate dispersant and 56.568 percent of deionized water in percentage by mass, dispersing the mixture in a double-planet stirrer at a high speed for 15min under the condition of a stirring speed of 1500r/min, then adding 17 percent of alumina particles and magnesium-aluminum hydroxide with the surface modified by sodium tripolyphosphate for dispersion, wherein the dispersion speed is 2000r/min, the dispersion time is 60min, transferring the mixture to a sand mill for sand grinding dispersion after the dispersion is finished, the rotation speed is 1200r/min, the time is 30min, then entering a stirring tank through a magnetic filter, slowly adding sodium carboxymethyl cellulose thickener for continuous secondary dispersion, dispersing the mixture for 30min at the rotation speed of 60r/min, sequentially adding ethyl polyacrylate water-based binder and 0.032 percent of glycerol wetting agent for secondary mixing after the stirring is finished, and continuously stirring for 20min to form coating slurry, coating the coating slurry on two sides of a polyethylene base film with the thickness of 9 mu m in a gravure transfer coating mode, wherein the thickness of the coating is 2.5 mu m, and baking for 5min at the temperature of 60 ℃ to obtain the composite diaphragm.
Example 4
The embodiment provides a coating slurry, which comprises the following components in percentage by mass: 22% of aluminum oxide particles (the average particle size is 0.6 mu m), zinc-aluminum hydroxide (the average particle size is 0.8 mu m) with the surface modified by sodium tripolyphosphate, a sodium carboxymethyl cellulose thickener, a polyethylacrylate aqueous binder, 0.6% of a sodium acrylate dispersant, 0.038% of a propylene glycol wetting agent and 40.362% of deionized water, wherein the mass ratio of the aluminum oxide particles to the zinc-aluminum metal hydroxide with the surface modified by sodium tripolyphosphate is 1.222:1, the mass ratio of the total mass of the aluminum oxide particles to the zinc-aluminum metal hydroxide with the surface modified by sodium tripolyphosphate to the sodium carboxymethyl cellulose thickener is 1:0.225, and the mass ratio of the total mass of the aluminum oxide particles to the zinc-aluminum metal hydroxide with the surface modified by sodium tripolyphosphate to the polyethylacrylate aqueous binder is 1: 0.25.
Taking the total mass of the coating slurry as 100 percent, mixing 0.6 percent of sodium acrylate dispersant and 40.362 percent of deionized water in percentage by mass, dispersing for 15min at a high speed in a double-planet mixer under the condition of a stirring speed of 1500r/min, then adding 22 percent of alumina particles and zinc-aluminum hydroxide with the surface modified by sodium tripolyphosphate for dispersion, wherein the dispersion speed is 2000r/min, the dispersion time is 60min, transferring the mixture into a sand mill for sand grinding dispersion after the dispersion is finished, the rotation speed is 1200r/min, the time is 30min, entering a stirring tank through a magnetic filter after the dispersion is finished, slowly adding sodium carboxymethyl cellulose thickener for continuous secondary dispersion, dispersing for 30min at the rotation speed of 60r/min, sequentially adding polyethylacrylate aqueous binder and 0.038 percent of propylene glycol wetting agent for secondary mixing after the stirring is finished, and continuously stirring for 20min to form coating slurry, coating the coating slurry on two sides of a polyethylene base film with the thickness of 9 mu m in a gravure transfer coating mode, wherein the thickness of the coating is 3.5 mu m, and baking for 5min at the temperature of 60 ℃ to obtain the composite diaphragm.
Example 5
The embodiment provides a coating slurry, which comprises the following components in percentage by mass: 15% of aluminum oxide particles (the average particle size is 0.3 mu m), magnesium aluminum hydroxide (the average particle size is 0.5 mu m) with a surface modified by sodium tripolyphosphate, a sodium carboxymethyl cellulose thickener, a polyethyl methacrylate aqueous binder, 0.3% of a sodium acrylate dispersant, 0.03% of a glycerol wetting agent and 63.67% of deionized water, wherein the mass ratio of the aluminum oxide particles to the magnesium aluminum metal hydroxide with a surface modified by sodium tripolyphosphate is 1.5:1, the mass ratio of the total mass of the aluminum oxide particles to the magnesium aluminum metal hydroxide with a surface modified by sodium tripolyphosphate to the sodium carboxymethyl cellulose thickener is 1:0.24, and the mass ratio of the total mass of the aluminum oxide particles to the magnesium aluminum metal hydroxide with a surface modified by sodium tripolyphosphate to the polyethyl methacrylate aqueous binder is 1: 0.2.
Taking the total mass of the coating slurry as 100 percent, mixing 0.3 percent of sodium acrylate dispersant and 63.67 percent of deionized water in percentage by mass, dispersing for 15min at high speed in a double-planet stirrer under the condition of the stirring speed of 1500r/min, then adding 15 percent of alumina particles and magnesium aluminum hydroxide with the surface modified by sodium tripolyphosphate for dispersion, wherein the dispersing speed is 2000r/min, the dispersing time is 60min, transferring the mixture to a sand mill for sand grinding dispersion under the condition that the rotating speed is 1200r/min and the time is 30min, after the dispersion is finished, entering a stirring tank through a magnetic filter, slowly adding sodium carboxymethyl cellulose thickener for continuous secondary dispersion, dispersing for 30min at the rotating speed of 60r/min, sequentially adding a polyethyl methacrylate aqueous binder and a glycerol wetting agent with the mass percent of 0.03 percent for secondary mixing after the stirring is finished, and continuously stirring for 20min to form coating slurry, coating the coating slurry on two sides of a polyethylene base film with the thickness of 9 mu m in a gravure transfer coating mode, wherein the thickness of the coating is 2 mu m, and baking for 5min at the temperature of 60 ℃ to obtain the composite diaphragm.
Example 6
The embodiment provides a coating slurry, which comprises the following components in percentage by mass: 25% of aluminum oxide particles (the average particle size is 0.8 mu m), magnesium aluminum hydroxide (the average particle size is 1.0 mu m) with the surface modified by sodium tripolyphosphate, a sodium carboxymethyl cellulose thickener, a polyethyl methacrylate aqueous binder, 0.7% of a sodium acrylate dispersant, 0.04% of a glycerol wetting agent and 32.26% of deionized water, wherein the mass ratio of the aluminum oxide particles to the magnesium aluminum metal hydroxide with the surface modified by sodium tripolyphosphate is 1.25:1, the mass ratio of the total mass of the aluminum oxide particles to the magnesium aluminum metal hydroxide with the surface modified by sodium tripolyphosphate to the sodium carboxymethyl cellulose thickener is 1:0.222, and the mass ratio of the total mass of the aluminum oxide particles to the magnesium aluminum metal hydroxide with the surface modified by sodium tripolyphosphate to the polyethyl methacrylate aqueous binder is 1: 0.267.
Taking the total mass of the coating slurry as 100 percent, mixing 0.7 percent by mass of sodium acrylate dispersant and 32.26 percent by mass of deionized water, dispersing at high speed for 15min in a double-planet mixer under the condition of the stirring speed of 1500r/min, then adding 25 percent by mass of alumina particles and magnesium aluminum hydroxide with the surface modified by sodium tripolyphosphate for dispersing at the speed of 2000r/min for 60min, transferring the mixture to a sand mill for sand grinding dispersion under the condition of the rotating speed of 1200r/min for 30min, after the dispersion is finished, entering a stirring tank through a magnetic filter, slowly adding sodium carboxymethyl cellulose thickener for continuous secondary dispersion, dispersing at the rotating speed of 60r/min for 30min, sequentially adding a polyethyl methacrylate aqueous binder and a glycerol wetting agent with the mass percent of 0.04 percent for secondary mixing after the stirring is finished, and continuously stirring for 20min to form coating slurry, coating the coating slurry on two sides of a polyethylene base film with the thickness of 9 mu m in a gravure transfer coating mode, wherein the thickness of the coating is 4 mu m, and baking for 5min at the temperature of 60 ℃ to obtain the composite diaphragm.
Fig. 1 is a flow chart of a coating process of the composite separator provided in embodiments 1 to 6, and as can be seen from fig. 1, the final composite separator is obtained after the slurry is coated on the surface of the base film, dried and rolled in the processes of preparing the slurry in embodiments 1 to 6.
Comparative example 1
This comparative example differs from example 1 in that the coating slurry has 10 mass percent alumina particles and an appropriate adjusted mass percent of deionized water of 52.67 mass percent, all other things being equal to example 1.
Comparative example 2
This comparative example differs from example 1 in that the coating slurry had a mass percent of alumina particles of 30% and an adjusted mass percent of deionized water of 32.67% was used, all other things being equal to example 1.
Comparative example 3
The comparative example is different from example 1 in that the mass ratio of the alumina particles to the magnesium aluminum metal hydroxide with the surface modified by sodium tripolyphosphate is 4:1, the mass percentage of the adaptive deionized water is adjusted to be 54.67%, and the rest is the same as example 1.
Comparative example 4
The comparative example is different from example 1 in that the mass ratio of the alumina particles to the magnesium aluminum hydroxide with the surface modified by sodium tripolyphosphate is 0.67:1, the mass percentage of the deionized water is adjusted to be 29.67, and the rest is the same as example 1.
Comparative example 5
The comparative example differs from example 1 in that the magnesium aluminum hydroxide modified with sodium tripolyphosphate in the coating slurry is replaced with magnesium aluminum hydroxide not modified with sodium tripolyphosphate in the preparation process, and the rest is the same as example 1.
Comparative example 6
The comparative example differs from example 1 in that the magnesium aluminum hydroxide in the coating slurry, which is surface modified with sodium tripolyphosphate, is replaced with aluminum hydroxide which is not surface modified with sodium tripolyphosphate during the preparation process, and the rest is the same as example 1.
The lithium ion batteries were prepared by using the composite separators provided in examples 1 to 6 and comparative examples 1 to 6, and the preparation method was as follows:
preparing a positive plate: adding a positive electrode material nickel cobalt lithium manganate, a conductive agent Super P and a binder PVDF into a solvent according to the mass ratio of 96.5:1.8:1.7, fully stirring to obtain a mixed slurry, uniformly coating the mixed slurry on an aluminum foil, and drying, rolling and cutting to obtain a required positive plate;
preparing a negative plate: adding graphite serving as a negative electrode active material, a conductive agent Super P and a binder SBR into a solvent according to the mass ratio of 96.2:1.5:2.3, fully stirring to obtain mixed slurry, uniformly coating the mixed slurry on a copper foil, and drying, rolling and cutting into pieces to obtain a required negative electrode;
the electrolyte is selected from the conventional ternary system electrolyte on the market: wherein LiPF is calculated by taking the total mass of the electrolyte as 100 percent6The concentration of (a) is 1.1mol/L, and the components and the mass ratio of Ethylene Carbonate (EC), methylethyl carbonate (EMC), diethyl carbonate (DEC) are 3:5:2 in the mixed solvent.
Preparing a lithium ion battery: and assembling the prepared negative plate, the prepared positive plate and the electrolyte, and then testing the electrochemical performance.
Test conditions
The composite separators provided in examples 1 to 6 and comparative examples 1 to 6 were subjected to a performance test by the following method:
(1) heat shrinkage ratio: measuring the size change of the diaphragm before and after heating to 150 ℃ by using a steel ruler, calculating the shrinkage rate, and referring to GB/T36363-2018
(2) And (3) flame retardant test: the diaphragm is ignited by an open flame and the time for the diaphragm to start burning is calculated, and in the present invention, the burning time refers to the time required to ignite the diaphragm.
(3) Liquid suction speed: the same width 10mm diaphragm, perpendicular to the electrolyte contact, and the time at which the imbibition rises 10mm was calculated
The test results are shown in table 1:
the lithium ion batteries prepared by the composite diaphragms provided in the application examples 1-6 and the comparative application examples 1-6 are subjected to electrochemical performance test, and the test method comprises the following steps:
(1) and (3) cycle testing: charging to 4.35V at 25 deg.C under 1C constant current, charging to 0.05C under constant voltage, and discharging to 2.8V under 1C constant current, wherein the cycle number is 500 times.
The test results are shown in table 2:
TABLE 1
TABLE 2
| Capacity retention after 500 cycles at a current density of 1C (%) | |
| Application example 1 | 97.1 |
| Application example 2 | 96.89 |
| Application example 3 | 95.98 |
| Application example 4 | 97.3 |
| Application example 5 | 95.81 |
| Application example 6 | 97.6 |
| Comparative application example 1 | 96.9 |
| Comparative application example 2 | 97.01 |
| Comparative application example 3 | 94.5 |
| Comparative application example 4 | 98.1 |
| Comparative application example 5 | 97.35 |
| Comparative application example 6 | 96.85 |
As can be seen from the data of table 1, the composite separators provided in examples 1 to 6 of the present invention have a thickness in the range of 12.98 μm to 17 μm, an MD heat shrinkage of not more than 2.89% at 150 ℃/h while a TD heat shrinkage of not more than 1.9%, a time required for igniting the separator of not less than 2.8s, and a liquid absorption rate of not more than 7.2s/10mm, indicating that the composite separators provided by the present invention have good heat resistance, flame retardancy, and liquid absorption rate.
Compared with example 1, comparative example 1 shows that too low mass percentage of alumina ceramic particles results in a decrease, increasing MD and TD heat shrinkage of the separator; comparative example 2 shows that the mass percentage of alumina ceramic particles is too high, and although the heat resistance of the separator is enhanced, the burning time of the separator becomes short and the liquid absorption speed becomes slow; the comparative example 3 shows that the combustion time of the diaphragm is shortened and the liquid absorption speed is slowed due to the excessively low mass percentage of the magnesium aluminum hydroxide modified by the sodium tripolyphosphate, so that the flame retardant property and the infiltration property of the diaphragm to the electrolyte are reduced; comparative example 4 shows that the magnesium aluminum hydroxide with the surface modified by sodium tripolyphosphate has higher mass percentage content, which is more beneficial to improving the flame retardant property and the liquid absorption rate of the diaphragm, but the processing of the diaphragm is difficult; comparative examples 5 and 6 show that the flame retardant property and the liquid absorption rate of the separator can be improved by using the sodium tripolyphosphate-modified double hydroxide as compared with the unmodified double hydroxide.
As can be seen from the data in table 2, the capacity retention rate of the lithium ion battery provided in application examples 1 to 6 is not lower than 95.81% after the lithium ion battery is cycled for 500 times at a current density of 1C, which indicates that the lithium ion battery prepared by the composite separator provided in the invention has good cycling stability.
Compared with application example 1, although the capacity retention rates of the lithium ion batteries of the comparative application example 4 and the comparative application example 5 after 500 cycles at a current density of 1C are slightly higher than that of the application example 1, the performance of the diaphragms is inferior to that of the composite diaphragm provided in example 1, and the capacity retention rates of other comparative application examples are lower than that of the application example 1, which indicates that the composite diaphragm prepared by providing components with specific content has a higher infiltration speed and is beneficial to improving the capacity retention rate after cycles.
The applicant states that the present invention is illustrated by the above examples of the process of the present invention, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. The coating slurry is characterized by comprising the following components in percentage by mass: ceramic particles, double metal hydroxide, a thickening agent, a water-based binder, 0.3-0.7% of a dispersing agent, 0.03-0.04% of a wetting agent and 39-63% of deionized water;
the mass ratio of the ceramic particles to the double metal hydroxide is (0.75-2.5) to 1;
the mass ratio of the total mass of the ceramic particles and the double metal hydroxide to the thickener is 1 (0.13-0.4);
the mass ratio of the total mass of the ceramic particles and the double metal hydroxide to the aqueous binder is 1 (0.11-0.48).
2. The coating slurry of claim 1, wherein the ceramic particles comprise any one of, or a combination of at least two of, alumina particles, magnesia, silica, or calcia;
preferably, the ceramic particles have an average particle size of 0.3 μm to 0.8 μm.
3. The coating slurry according to claim 1 or 2, wherein the double metal hydroxide is a double metal hydroxide whose surface is modified with sodium tripolyphosphate;
preferably, the double hydroxide includes at least one of magnesium aluminum double hydroxide, lithium aluminum double hydroxide, and zinc aluminum double hydroxide.
4. The coating slurry according to any one of claims 1 to 3, wherein the average particle size of the double metal hydroxide is 0.5 μm to 1.0 μm.
5. The coating slurry of any one of claims 1 to 4, wherein the thickener is a carboxymethyl cellulose-based thickener;
preferably, the carboxymethyl cellulose-based thickener comprises sodium carboxymethyl cellulose.
6. The coating syrup according to any of claims 1 to 5, characterized in that the dispersant is an acrylate-based dispersant;
preferably, the acrylate-based dispersant comprises sodium acrylate or ammonium acrylate.
7. The coating slip of any one of claims 1-6, wherein the lubricant is a fatty alcohol based lubricant;
preferably, the fatty alcohol based lubricant comprises any one of a polyethylene glycol, glycerol or propylene glycol.
8. A method of preparing the coating slip of any one of claims 1-7, characterized in that the method comprises the steps of:
mixing a dispersing agent and deionized water, adding ceramic particles and a double-metal hydroxide for dispersion, then adding a thickening agent for continuous secondary dispersion, and then sequentially adding an aqueous binder and a wetting agent for secondary mixing to obtain the coating slurry;
preferably, the mixing is carried out under stirring;
preferably, the stirring speed is 1200r/min-1700 r/min;
preferably, the stirring time is 10min-20 min;
preferably, the rate of dispersion is 1700r/min to 2200 r/min;
preferably, the dispersing time is 40min-80 min;
preferably, the rate of the secondary dispersion is 45r/min-60 r/min;
preferably, the time of the secondary dispersion is 20min to 40 min.
9. A composite separator comprising a base film and a coating layer coated on at least one side of the base film, the coating layer being prepared using the coating slurry according to any one of claims 1 to 7;
preferably, the thickness of the coating is 2 μm to 4 μm.
10. A lithium ion battery, characterized in that the lithium ion battery comprises an electrode sheet, an electrolyte and a separator, wherein the separator is the composite separator according to claim 9.
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