CN211556020U - Ceramic diaphragm with good bonding property and lithium ion battery comprising ceramic diaphragm - Google Patents
Ceramic diaphragm with good bonding property and lithium ion battery comprising ceramic diaphragm Download PDFInfo
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- CN211556020U CN211556020U CN202020420788.2U CN202020420788U CN211556020U CN 211556020 U CN211556020 U CN 211556020U CN 202020420788 U CN202020420788 U CN 202020420788U CN 211556020 U CN211556020 U CN 211556020U
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Abstract
The utility model discloses a ceramic diaphragm has first aqueous slurry coating on the diaphragm substrate, first aqueous slurry coating surface coating has second aqueous slurry coating. The thickness of the second aqueous slurry coating is larger than that of the first aqueous slurry coating, and the compactness of the first aqueous slurry coating is larger than that of the second aqueous slurry coating; the utility model discloses simultaneously disclose the lithium ion battery who contains this ceramic diaphragm. The ceramic diaphragm of the utility model has the characteristics of strong cohesiveness, good drying effect and excellent electrochemical performance.
Description
Technical Field
The utility model relates to a lithium ion battery technical field, especially a ceramic diaphragm that associativity is good and contain the lithium ion battery of this ceramic diaphragm.
Background
Lithium ion batteries are widely used as energy storage materials in the fields of portable electronic devices, electric vehicles, electronic storage systems and the like by virtue of the advantages of high energy density, long cycle life and the like.
The diaphragm in the lithium ion battery system is taken as an important component part and plays an important role in the electrochemical performance and safety of the lithium battery.
However, as the energy density of the lithium ion battery is continuously improved, the battery voltage is continuously improved, the traditional polyolefin diaphragm can not meet the requirements of the existing high-voltage and high-safety lithium ion battery in terms of high voltage resistance and high temperature resistance, and the inorganic coating polyolefin diaphragm subjected to ceramic treatment has greatly improved oxidation resistance, high temperature resistance and safety, and becomes the mainstream of the existing lithium ion battery technology.
In view of the above, chinese patent application CN109802077A discloses a method for preparing a ceramic diaphragm with low water content, comprising the following steps: the method comprises the following steps: (1) and preparing an aqueous solution: preparing a 4% aqueous solution from a thickening agent and deionized water; (2) and preparing aqueous slurry: adding alumina ceramic powder, glue solution and surfactant into the aqueous solution prepared in the step (1) to prepare aqueous slurry; (3) and preparing a ceramic diaphragm: and (3) coating the water-based slurry obtained in the step (2) on a diaphragm by using a conventional diaphragm as a substrate, and drying to obtain the low-water-content ceramic diaphragm. The utility model discloses a guarantee ceramic diaphragm is in lower moisture content state in lithium cell preparation use, reduces and toasts the cost, guarantee lithium ion battery's electrical property and security performance.
However, in this ceramic separator, a binder such as LA133 or epoxy resin is mainly used as the binder, and there are the following problems in practical use: 1. the bonding strength is low, the prepared ceramic diaphragm is powder-falling in the use process, the heat resistance of the ceramic diaphragm is reduced and the internal resistance of the battery is increased when a large amount of the ceramic diaphragm is added, and the cycle rate performance of the battery is not facilitated; 2. the prepared ceramic slurry has high viscosity, the solid content can only reach 25 percent, the drying energy consumption cost of the ceramic diaphragm is high, and the production efficiency is low.
SUMMERY OF THE UTILITY MODEL
The utility model mainly aims to provide a preparation method of a ceramic diaphragm with good bonding performance, which has the characteristics of strong bonding performance, good drying effect and excellent electrochemical performance.
The utility model discloses can realize through following technical scheme:
a ceramic diaphragm with good bonding performance comprises a diaphragm base material, wherein a first water-based slurry coating is coated on the diaphragm base material, and a second water-based slurry coating is coated on the surface of the first water-based slurry coating. The thickness of the second aqueous slurry coating is larger than that of the first aqueous slurry coating, and the compactness of the first aqueous slurry coating is larger than that of the second aqueous slurry coating.
Further, the thickness of the first aqueous slurry coating on the diaphragm is 0.5-10 μm, and the thickness of the second aqueous slurry coating on the first aqueous slurry coating is 3-20 μm.
Further, the diaphragm base material is a PP diaphragm, a PE diaphragm or a three-layer composite diaphragm.
Further, the separator is a wet separator or a dry separator.
The utility model discloses an on the other hand lies in protecting a lithium ion battery, including positive plate, negative pole piece and diaphragm, the diaphragm is foretell ceramic diaphragm, and ceramic diaphragm sets up and makes positive plate and negative pole piece insulate from each other between positive plate and negative pole piece.
Further, the lithium ion battery is a cylindrical lithium ion battery or a laminated lithium ion battery.
Further, the lithium ion battery is a lithium iron phosphate lithium ion battery, a lithium cobalt oxide lithium ion battery, a lithium manganese oxide lithium ion battery or a ternary material lithium ion battery.
The ceramic diaphragm with good bonding performance is prepared by the following method:
(1) and preparing an aqueous solution: preparing a 4% aqueous solution from a thickening agent and deionized water, and dividing the obtained aqueous solution into 2 groups for later use;
(2) preparing a first aqueous slurry: adding ceramic powder, graphene, aqueous polyurethane-acrylic resin emulsion, sodium m-carboxybenzenesulfonate and a silane coupling agent into one group of aqueous solution prepared in the step (1) to prepare first aqueous slurry;
(3) and preparing a second aqueous slurry: adding ceramic powder, aqueous polyurethane-acrylic resin emulsion, sodium m-carboxybenzenesulfonate and a silane coupling agent into the other group of aqueous solution prepared in the step (1) to prepare second aqueous slurry;
(4) and preparing a ceramic diaphragm: and (3) taking a conventional separator as a substrate, coating the first aqueous slurry obtained in the step (2) on the separator to form a first aqueous slurry coating, drying, and then coating the second aqueous slurry on the first aqueous slurry coating to form a second aqueous slurry coating, so that the ceramic separator with good bonding property can be obtained.
Further, the average particle size of the ceramic powder in the first aqueous slurry obtained in the step (2) is 0.1 to 2 μm, the average particle size of the ceramic powder in the second aqueous slurry obtained in the step (3) is 1 to 3 μm, and the average particle size of the ceramic powder in the first aqueous slurry is larger than the average particle size of the ceramic powder in the second aqueous slurry. Through the granularity gradient that sets up ceramic powder, form certain space gradient between first aqueous slurry coating and second aqueous slurry coating, make things convenient for volatilizing of moisture in drying process for drying process promotes drying effect, avoids the influence that too much moisture caused to lithium ion battery security.
Further, the thickness of the first aqueous slurry obtained in the step (2) coated on the diaphragm is 0.5-10 μm, the thickness of the second aqueous slurry obtained in the step (3) coated on the first aqueous slurry coating is 3-20 μm, and the thickness of the first aqueous slurry coated on the diaphragm is smaller than that of the second aqueous slurry coated on the diaphragm. The second aqueous slurry coating is thicker than the first aqueous slurry coating, so that the advantage of strong liquid absorption capacity of the second aqueous slurry coating is fully exerted, and the first aqueous slurry coating is thinner than the second aqueous slurry coating, so that the locking capacity of the electrolyte is ensured, the drying is avoided, the influence of over-thickness on the liquid absorption capacity of the diaphragm is avoided, and the membrane is prevented from being damaged,
Further, the ceramic powder is one or more of aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide and barium oxide, can be flexibly selected according to actual needs, and meets different safety performance requirements.
Further, the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane and 3- (triethoxysilyl) -1-propanethiol. Silane coupling agent is in the utility model discloses in except having surfactant's effect, silane coupling agent can form silica particles gradually in drying process, fills in first aqueous thick liquids and second aqueous thick liquids, has the effect that forms the gradient clearance between first aqueous thick liquids coating and second aqueous thick liquids coating, both promotes imbibition ability, effectively ensures clearance gradient again and accelerates drying effect.
Further, the mass ratio of the thickening agent, the ceramic powder, the aqueous polyurethane-acrylic resin emulsion, the graphene, the sodium m-carboxybenzenesulfonate and the silane coupling agent in the step (2) is (0.05-1): (94.8-95.75): 4: 0.5: 0.01:0.2.
Further, the mass ratio of the thickening agent, the ceramic powder, the aqueous polyurethane-acrylic resin emulsion, the graphene, the sodium m-carboxybenzenesulfonate and the silane coupling agent in the step (3) is (0.05-1): (94.8-95.75): 4: 0.01:0.2.
Further, the solid content of the second aqueous slurry obtained in the step (2) and the step (3) is 30-55 wt%, and the viscosity is 10-150 Mpa.s.
The other aspect of the present invention is to protect the ceramic diaphragm obtained by the above method for preparing a ceramic diaphragm having good bondability.
The utility model discloses a protection scheme is still including the lithium ion battery who contains above-mentioned ceramic diaphragm, and specific lithium ion battery includes but is not limited to cylinder type lithium ion battery, soft packet of lithium ion battery, aluminum hull lithium ion battery.
The utility model discloses the preparation method of the good ceramic diaphragm of associativity has following profitable technological effect:
the adhesive property is strong, the waterborne polyurethane-acrylic resin emulsion is added into the first waterborne slurry to serve as a binder, the silane coupling agent serves as a surfactant, the sodium m-carboxybenzenesulfonate serves as a wetting agent, and the graphene is added at the same time, so that the crosslinking effect of the silane coupling agent is realized, the crosslinking of the polyurethane emulsion and the acrylic monomer is realized, the graphene has the effect of high specific surface area, the polymerization energy of the waterborne slurry and a diaphragm substrate is reduced, and the adhesion difficulty is reduced; the organic group of the m-carboxyl sodium benzenesulfonate is compatible with the polyurethane emulsion and the acrylic monomer similarly, and the sulfonic group is used as an inorganic acid, so that the m-carboxyl sodium benzenesulfonate has good compatibility with water, improves wettability, forms a hydrogen bond binding effect with graphene, reduces a contact angle, and improves the adhesive force of the first aqueous slurry on the diaphragm substrate;
secondly, the drying speed is high, in the coating process of the water-based paint, the layered coating is formed by adopting a mode of combining the layered coating with the layered coating, the graphene is added into the first water-based slurry, the large specific surface area of the graphene is fully utilized, the second water-based slurry without the graphene is coated on the premise that the water-based slurry is bonded with the diaphragm base material, the second water-based slurry has better dispersion uniformity compared with the first water-based slurry without the graphene, the drying gradient is formed on the first water-based slurry coating and the second water-based slurry coating, the drying process is accelerated, and the drying effect is improved;
and thirdly, the electrochemical performance is good, the gaps on the surface of the second aqueous slurry coating layer, which has better dispersibility than the first aqueous slurry coating layer, effectively ensure the permeation of the electrolyte, and the first aqueous slurry coating layer, which is more compact and stronger in binding capacity than the second aqueous slurry coating layer, better limits the loss of the electrolyte after permeation, avoids the dryness of the electrolyte on the surface of the diaphragm, and ensures that the lithium ion battery has excellent electrochemical performance.
Drawings
FIG. 1 is a schematic structural view of a ceramic diaphragm with good bondability;
FIG. 2 is a schematic structural diagram of a laminated lithium ion battery comprising a ceramic diaphragm according to the present invention;
FIG. 3 is a schematic diagram of the structure of a cylindrical lithium ion battery containing a ceramic diaphragm according to the present invention;
the reference numerals include: 100. a ceramic diaphragm 101, a diaphragm base material 102, a first aqueous slurry coating 103 and a second aqueous slurry coating; 200. a positive plate; 300. and a negative plate.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following will explain the product of the present invention in detail with reference to the embodiments.
As shown in fig. 1, the utility model discloses a ceramic diaphragm with good bonding performance, which comprises a diaphragm base material 101, wherein a first aqueous slurry coating 102 is coated on the diaphragm base material, and a second aqueous slurry coating 103 is coated on the surface of the first aqueous slurry coating 102. The second aqueous slurry coating 103 has a thickness greater than the first aqueous slurry coating 102, and the first aqueous slurry coating 102 has a compactability greater than the second aqueous slurry coating 103.
Further, the thickness of the first aqueous slurry coating on the diaphragm is 0.5-10 μm, and the thickness of the second aqueous slurry coating on the first aqueous slurry coating is 3-20 μm.
Further, the diaphragm base material is a PP diaphragm, a PE diaphragm or a three-layer composite diaphragm.
Further, the separator is a wet separator or a dry separator.
As shown in fig. 2 and 3, another aspect of the present invention is to protect a lithium ion battery, which includes a positive plate 200, a negative plate 300, and a separator, wherein the separator is the ceramic separator 100 described above, and the ceramic separator 100 is disposed between the positive plate 200 and the negative plate 300 to insulate the positive plate 200 and the negative plate 300 from each other.
Further, the lithium ion battery is a cylindrical lithium ion battery or a laminated lithium ion battery.
Further, the lithium ion battery is a lithium iron phosphate lithium ion battery, a lithium cobalt oxide lithium ion battery, a lithium manganese oxide lithium ion battery or a ternary material lithium ion battery.
The ceramic diaphragm with good bonding performance is prepared by the following method:
(1) and preparing an aqueous solution: preparing a 4% aqueous solution from a thickening agent and deionized water, and dividing the obtained aqueous solution into 2 groups for later use;
(2) preparing a first aqueous slurry: adding ceramic powder, graphene, aqueous polyurethane-acrylic resin emulsion, sodium m-carboxybenzenesulfonate and a silane coupling agent into one group of aqueous solution prepared in the step (1) to prepare first aqueous slurry;
(3) and preparing a second aqueous slurry: adding ceramic powder, aqueous polyurethane-acrylic resin emulsion, sodium m-carboxybenzenesulfonate and a silane coupling agent into the other group of aqueous solution prepared in the step (1) to prepare second aqueous slurry;
(4) and preparing a ceramic diaphragm: and (3) taking a conventional separator as a substrate, coating the first aqueous slurry obtained in the step (2) on the separator to form a first aqueous slurry coating, drying, and then coating the second aqueous slurry on the first aqueous slurry coating to form a second aqueous slurry coating, so that the ceramic separator with good bonding property can be obtained.
Further, the average particle size of the ceramic powder in the first aqueous slurry obtained in the step (2) is 0.1 to 2 μm, the average particle size of the ceramic powder in the second aqueous slurry obtained in the step (3) is 1 to 3 μm, and the average particle size of the ceramic powder in the first aqueous slurry is larger than the average particle size of the ceramic powder in the second aqueous slurry.
Further, the thickness of the first aqueous slurry obtained in the step (2) coated on the diaphragm is 0.5-10 μm, the thickness of the second aqueous slurry obtained in the step (3) coated on the first aqueous slurry coating is 3-20 μm, and the thickness of the first aqueous slurry coated on the diaphragm is smaller than that of the second aqueous slurry coated on the diaphragm.
Further, the ceramic powder is one or more of aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide and barium oxide.
Further, the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane and 3- (triethoxysilyl) -1-propanethiol.
Further, the mass ratio of the thickening agent, the ceramic powder, the aqueous polyurethane-acrylic resin emulsion, the graphene, the sodium m-carboxybenzenesulfonate and the silane coupling agent in the step (2) is (0.05-1): (94.8-95.75): 4: 0.5: 0.01:0.2.
Further, the mass ratio of the thickening agent, the ceramic powder, the aqueous polyurethane-acrylic resin emulsion, the graphene, the sodium m-carboxybenzenesulfonate and the silane coupling agent in the step (3) is (0.05-1): (94.8-95.75): 4: 0.01:0.2.
Further, the solid content of the second aqueous slurry obtained in the step (2) and the step (3) is 30-55 wt%, and the viscosity is 10-150 Mpa.s.
Example 1
The ceramic diaphragm with good bonding performance is prepared by the following method:
(1) and preparing an aqueous solution: preparing a 4% aqueous solution from a thickening agent and deionized water, and dividing the obtained aqueous solution into 2 groups for later use;
(2) preparing a first aqueous slurry: adding ceramic powder, graphene, aqueous polyurethane-acrylic resin emulsion, sodium m-carboxybenzenesulfonate and a silane coupling agent into one group of aqueous solution prepared in the step (1) to prepare first aqueous slurry;
(3) and preparing a second aqueous slurry: adding ceramic powder, aqueous polyurethane-acrylic resin emulsion, sodium m-carboxybenzenesulfonate and a silane coupling agent into the other group of aqueous solution prepared in the step (1) to prepare second aqueous slurry;
(4) and preparing a ceramic diaphragm: and (3) taking a conventional separator as a substrate, coating the first aqueous slurry obtained in the step (2) on the separator to form a first aqueous slurry coating, drying, and then coating the second aqueous slurry on the first aqueous slurry coating to form a second aqueous slurry coating, so that the ceramic separator with good bonding property can be obtained.
In this example, the average particle size of the ceramic powder in the first aqueous slurry obtained in step (2) was 2 μm, and the average particle size of the ceramic powder in the second aqueous slurry obtained in step (3) was 3 μm. The thickness of the first aqueous slurry coating obtained in the step (2) on the diaphragm is 3 μm, and the thickness of the second aqueous slurry coating obtained in the step (3) on the first aqueous slurry coating is 8 μm.
In this embodiment, the ceramic powder is alumina. The silane coupling agent is gamma-aminopropyl triethoxysilane.
In this embodiment, the mass ratio of the thickener, the ceramic powder, the aqueous polyurethane-acrylic resin emulsion, the graphene, the sodium m-carboxybenzenesulfonate, and the silane coupling agent in step (2) is 1: 95.25: 4: 0.5: 0.01:0.2. The mass ratio of the thickening agent, the ceramic powder, the waterborne polyurethane-acrylic resin emulsion, the graphene, the sodium m-carboxybenzenesulfonate and the silane coupling agent in the step (3) is 1: 95.25: 4: 0.01:0.2.
In this embodiment, the solid content of the second aqueous slurry obtained in step (2) and step (3) is 30 to 55wt%, and the viscosity is 10 to 150 mpa.s, and in practice, the test value is within this range and is not strictly controlled.
Example 2
The ceramic diaphragm with good bonding performance is prepared by the following method:
(1) and preparing an aqueous solution: preparing a 4% aqueous solution from a thickening agent and deionized water, and dividing the obtained aqueous solution into 2 groups for later use;
(2) preparing a first aqueous slurry: adding ceramic powder, graphene, aqueous polyurethane-acrylic resin emulsion, sodium m-carboxybenzenesulfonate and a silane coupling agent into one group of aqueous solution prepared in the step (1) to prepare first aqueous slurry;
(3) and preparing a second aqueous slurry: adding ceramic powder, aqueous polyurethane-acrylic resin emulsion, sodium m-carboxybenzenesulfonate and a silane coupling agent into the other group of aqueous solution prepared in the step (1) to prepare second aqueous slurry;
(4) and preparing a ceramic diaphragm: and (3) taking a conventional separator as a substrate, coating the first aqueous slurry obtained in the step (2) on the separator to form a first aqueous slurry coating, drying, and then coating the second aqueous slurry on the first aqueous slurry coating to form a second aqueous slurry coating, so that the ceramic separator with good bonding property can be obtained.
In this example, the average particle size of the ceramic powder in the first aqueous slurry obtained in step (2) was 1.2 μm, and the average particle size of the ceramic powder in the second aqueous slurry obtained in step (3) was 2 μm. The thickness of the first aqueous slurry coating obtained in the step (2) on the diaphragm is 1 μm, and the thickness of the second aqueous slurry coating obtained in the step (3) on the first aqueous slurry coating is 5 μm.
In this embodiment, the ceramic powder is alumina or silica. The silane coupling agent is gamma-aminopropyl triethoxysilane or gamma-methacryloxypropyl trimethoxysilane.
In this embodiment, the mass ratio of the thickener, the ceramic powder, the aqueous polyurethane-acrylic resin emulsion, the graphene, the sodium m-carboxybenzenesulfonate, and the silane coupling agent in step (2) is 0.5: 94.8: 4: 0.5: 0.01:0.2. The mass ratio of the thickening agent, the ceramic powder, the waterborne polyurethane-acrylic resin emulsion, the graphene, the sodium m-carboxybenzenesulfonate and the silane coupling agent in the step (3) is 0.5: (94.8:4: 0.01:0.2.
In this embodiment, the solid content of the second aqueous slurry obtained in step (2) and step (3) is 30 to 55wt%, and the viscosity is 10 to 150 mpa.s, and in practice, the test value is within this range and is not strictly controlled.
Example 3
The ceramic diaphragm with good bonding performance is prepared by the following method:
(1) and preparing an aqueous solution: preparing a 4% aqueous solution from a thickening agent and deionized water, and dividing the obtained aqueous solution into 2 groups for later use;
(2) preparing a first aqueous slurry: adding ceramic powder, graphene, aqueous polyurethane-acrylic resin emulsion, sodium m-carboxybenzenesulfonate and a silane coupling agent into one group of aqueous solution prepared in the step (1) to prepare first aqueous slurry;
(3) and preparing a second aqueous slurry: adding ceramic powder, aqueous polyurethane-acrylic resin emulsion, sodium m-carboxybenzenesulfonate and a silane coupling agent into the other group of aqueous solution prepared in the step (1) to prepare second aqueous slurry;
(4) and preparing a ceramic diaphragm: and (3) taking a conventional separator as a substrate, coating the first aqueous slurry obtained in the step (2) on the separator to form a first aqueous slurry coating, drying, and then coating the second aqueous slurry on the first aqueous slurry coating to form a second aqueous slurry coating, so that the ceramic separator with good bonding property can be obtained.
In this example, the average particle size of the ceramic powder in the first aqueous slurry obtained in step (2) was 0.3 μm, and the average particle size of the ceramic powder in the second aqueous slurry obtained in step (3) was 1.2 μm. The thickness of the first aqueous slurry coating obtained in the step (2) on the diaphragm is 2 μm, and the thickness of the second aqueous slurry coating obtained in the step (3) on the first aqueous slurry coating is 5 μm.
In this example, the ceramic powder is alumina and barium oxide. The silane coupling agent is 3- (triethoxysilyl) -1-propanethiol.
In this embodiment, the mass ratio of the thickener, the ceramic powder, the aqueous polyurethane-acrylic resin emulsion, the graphene, the sodium m-carboxybenzenesulfonate, and the silane coupling agent in step (2) is 0.05: 95.75: 4: 0.5: 0.01:0.2. The mass ratio of the thickening agent, the ceramic powder, the waterborne polyurethane-acrylic resin emulsion, the graphene, the sodium m-carboxybenzenesulfonate and the silane coupling agent in the step (3) is 0.05: 95.75: 4: 0.01:0.2.
In this embodiment, the solid content of the second aqueous slurry obtained in step (2) and step (3) is 30 to 55wt%, and the viscosity is 10 to 150 mpa.s, and in practice, the test value is within this range and is not strictly controlled.
Example 4
The ceramic diaphragm with good bonding performance is prepared by the following method:
(1) and preparing an aqueous solution: preparing a 4% aqueous solution from a thickening agent and deionized water, and dividing the obtained aqueous solution into 2 groups for later use;
(2) preparing a first aqueous slurry: adding ceramic powder, graphene, aqueous polyurethane-acrylic resin emulsion, sodium m-carboxybenzenesulfonate and a silane coupling agent into one group of aqueous solution prepared in the step (1) to prepare first aqueous slurry;
(3) and preparing a second aqueous slurry: adding ceramic powder, aqueous polyurethane-acrylic resin emulsion, sodium m-carboxybenzenesulfonate and a silane coupling agent into the other group of aqueous solution prepared in the step (1) to prepare second aqueous slurry;
(4) and preparing a ceramic diaphragm: and (3) taking a conventional separator as a substrate, coating the first aqueous slurry obtained in the step (2) on the separator to form a first aqueous slurry coating, drying, and then coating the second aqueous slurry on the first aqueous slurry coating to form a second aqueous slurry coating, so that the ceramic separator with good bonding property can be obtained.
In this example, the average particle size of the ceramic powder in the first aqueous slurry obtained in step (2) was 1.5 μm, and the average particle size of the ceramic powder in the second aqueous slurry obtained in step (3) was 2.5 μm. The thickness of the first aqueous slurry obtained in the step (2) coated on the diaphragm is 10 μm, and the thickness of the second aqueous slurry obtained in the step (3) coated on the first aqueous slurry coating is 20 μm
In this embodiment, the ceramic powder is alumina, zirconia, or magnesia. The silane coupling agent is gamma-aminopropyl triethoxysilane and 3- (triethoxysilyl) -1-propanethiol.
In this embodiment, the mass ratio of the thickener, the ceramic powder, the aqueous polyurethane-acrylic resin emulsion, the graphene, the sodium m-carboxybenzenesulfonate, and the silane coupling agent in step (2) is 0.2: 95: 4: 0.5: 0.01:0.2. The mass ratio of the thickening agent, the ceramic powder, the waterborne polyurethane-acrylic resin emulsion, the graphene, the sodium m-carboxybenzenesulfonate and the silane coupling agent in the step (3) is 0.2: 95: 4: 0.01:0.2.
In this embodiment, the solid content of the second aqueous slurry obtained in step (2) and step (3) is 30 to 55wt%, and the viscosity is 10 to 150 mpa.s, and in practice, the test value is within this range and is not strictly controlled.
Example 5
The ceramic diaphragm with good bonding performance is prepared by the following method:
(1) and preparing an aqueous solution: preparing a 4% aqueous solution from a thickening agent and deionized water, and dividing the obtained aqueous solution into 2 groups for later use;
(2) preparing a first aqueous slurry: adding ceramic powder, graphene, aqueous polyurethane-acrylic resin emulsion, sodium m-carboxybenzenesulfonate and a silane coupling agent into one group of aqueous solution prepared in the step (1) to prepare first aqueous slurry;
(3) and preparing a second aqueous slurry: adding ceramic powder, aqueous polyurethane-acrylic resin emulsion, sodium m-carboxybenzenesulfonate and a silane coupling agent into the other group of aqueous solution prepared in the step (1) to prepare second aqueous slurry;
(4) and preparing a ceramic diaphragm: and (3) taking a conventional separator as a substrate, coating the first aqueous slurry obtained in the step (2) on the separator to form a first aqueous slurry coating, drying, and then coating the second aqueous slurry on the first aqueous slurry coating to form a second aqueous slurry coating, so that the ceramic separator with good bonding property can be obtained.
In this example, the average particle size of the ceramic powder in the first aqueous slurry obtained in step (2) was 1 μm, and the average particle size of the ceramic powder in the second aqueous slurry obtained in step (3) was 2.3 μm. The thickness of the first aqueous slurry coating obtained in the step (2) on the diaphragm is 2 μm, and the thickness of the second aqueous slurry coating obtained in the step (3) on the first aqueous slurry coating is 8 μm.
In this embodiment, the ceramic powder is alumina or silica. The silane coupling agent is gamma-methacryloxypropyl trimethoxy silane.
In this embodiment, the mass ratio of the thickener, the ceramic powder, the aqueous polyurethane-acrylic resin emulsion, the graphene, the sodium m-carboxybenzenesulfonate, and the silane coupling agent in step (2) is 0.4: 95.2: 4: 0.5: 0.01:0.2. The mass ratio of the thickening agent, the ceramic powder, the waterborne polyurethane-acrylic resin emulsion, the graphene, the sodium m-carboxybenzenesulfonate and the silane coupling agent in the step (3) is 0.4: 95.2: 4: 0.01:0.2.
In this embodiment, the solid content of the second aqueous slurry obtained in step (2) and step (3) is 30 to 55wt%, and the viscosity is 10 to 150 mpa.s, and in practice, the test value is within this range and is not strictly controlled.
Comparative example 1
The only difference between comparative example 1 and example 1 is that: the coating is coated on the diaphragm by adopting the proportion and the method of the Chinese invention patent application CN 109802077A.
In order to evaluate the technical effects of the present invention, the ceramic slurry prepared in examples 1 to 5 and comparative example 1 was coated on a 16 μm polyolefin separator (blank example) with a coating thickness controlled at 4.0 ± 0.5 μm, and then subjected to a performance test, with the specific results as shown in the table:
meanwhile, for the cells of example 1 and comparative example 1 after 500 weeks of 1C charge-discharge cycle, respectively, it was found that the ceramic powder of example 1 still adhered closely to the separator, while the ceramic powder of comparative example 1 had a significant falling-off phenomenon.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way; the utility model can be smoothly implemented by the ordinary technicians in the industry according to the instruction book and the instruction book; however, those skilled in the art should understand that changes, modifications and variations that are equivalent to those of the above-described embodiments may be made without departing from the scope of the present invention; meanwhile, any changes, modifications, evolutions, etc. of the above embodiments, which are equivalent to the actual techniques of the present invention, still belong to the protection scope of the technical solution of the present invention.
Claims (7)
1. A ceramic diaphragm with good bonding performance comprises a diaphragm base material and is characterized in that: coating a first aqueous slurry coating on a diaphragm base material, wherein the surface of the first aqueous slurry coating is coated with a second aqueous slurry coating; the thickness of the second aqueous slurry coating is larger than that of the first aqueous slurry coating, and the compactness of the first aqueous slurry coating is larger than that of the second aqueous slurry coating.
2. The ceramic separator according to claim 1, wherein: the thickness of the first water-based slurry coating on the diaphragm is 0.5-10 mu m, and the thickness of the second water-based slurry coating on the first water-based slurry coating is 3-20 mu m.
3. The ceramic separator having good bondability according to claim 2, wherein: the diaphragm base material is a PP diaphragm, a PE diaphragm or a three-layer composite diaphragm.
4. The ceramic separator according to claim 3, wherein: the diaphragm is a wet diaphragm or a dry diaphragm.
5. A lithium ion battery comprises a positive plate, a negative plate and a diaphragm, and is characterized in that: the separator is the ceramic separator according to any one of claims 1 to 4, which is disposed between the positive electrode sheet and the negative electrode sheet to insulate the positive electrode sheet and the negative electrode sheet from each other.
6. The lithium ion battery of claim 5, wherein: the lithium ion battery is a cylindrical lithium ion battery or a laminated lithium ion battery.
7. The lithium ion battery of claim 6, wherein: the lithium ion battery is a lithium iron phosphate lithium ion battery, a lithium cobalt oxide lithium ion battery, a lithium manganate lithium ion battery or a ternary material lithium ion battery.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202020420788.2U CN211556020U (en) | 2020-03-28 | 2020-03-28 | Ceramic diaphragm with good bonding property and lithium ion battery comprising ceramic diaphragm |
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