CN113980496A - Coating composition, lithium battery ternary cathode material sieving screen and preparation method thereof - Google Patents

Coating composition, lithium battery ternary cathode material sieving screen and preparation method thereof Download PDF

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Publication number
CN113980496A
CN113980496A CN202111058346.3A CN202111058346A CN113980496A CN 113980496 A CN113980496 A CN 113980496A CN 202111058346 A CN202111058346 A CN 202111058346A CN 113980496 A CN113980496 A CN 113980496A
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screen
lithium battery
coating
cathode material
coating composition
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丘吉祥
张军
李鹏飞
李洪伟
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Ruyuan Dongyangguang New Energy Material Co ltd
Shaoguan East Sunshine Technology R&D Co Ltd
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Ruyuan Dong Yang Guang Materials Co ltd
Shaoguan East Sunshine Technology R&D Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
    • B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
    • B07B1/00—Sieving, screening, sifting, or sorting solid materials using networks, gratings, grids, or the like
    • B07B1/46—Constructional details of screens in general; Cleaning or heating of screens
    • B07B1/4609—Constructional details of screens in general; Cleaning or heating of screens constructional details of screening surfaces or meshes
    • B07B1/4618—Manufacturing of screening surfaces
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic

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Abstract

The invention discloses a coating composition, a lithium battery ternary cathode material sieving screen and a preparation method thereof, wherein the coating composition comprises the following components in percentage by mass: ZrO (ZrO)230％～45％；LiAlO230％～45％；TiO25％～20％；MgO 5％～20％；SiO22 to 15 percent. The coating can reduce the friction between the lithium battery ternary cathode material and stainless steel screen meshes in the screening process, further effectively control the mixing of strong magnetic metals such as Ni and Cr in the original screen mesh material, reduce the content of magnetic foreign matters in the ternary cathode material, and improve the cycle stability and safety performance of products. Meanwhile, the formed screen coating can effectively isolate alkaline corrosion of the ternary positive electrode material of the lithium battery to the screen wires, reduce the risk of breaking the screen wires and improve the screenRetention of mesh size and screen life.

Description

Coating composition, lithium battery ternary cathode material sieving screen and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a coating composition, a lithium battery ternary anode material sieving screen and a preparation method thereof.
Background
The content of the magnetic foreign matters in the ternary cathode material of the lithium battery is always an important factor influencing the safety performance of the ternary lithium battery, so that how to control the content of the magnetic foreign matters in the ternary cathode material of the lithium battery is a key link in the preparation process of the ternary cathode material of the lithium battery. One of the common methods for removing the magnetic foreign matter content in the preparation process of the tube-controlled lithium battery ternary cathode material in the industry is to remove the magnetic foreign matter by electromagnetic demagnetization after sieving, but in actual production, the method has the following defects: 1) when the content of the magnetic foreign matters is high, the electromagnetic demagnetizer is difficult to control the magnetic foreign matters within a low value range; 2) the electromagnetic demagnetizer has overlong service time, the demagnetizing efficiency is greatly reduced, and the content fluctuation of magnetic foreign matters is larger.
And because the magnetic foreign matters in the lithium battery ternary cathode material mainly come from the friction between the material and the stainless steel woven screen during the screening process, the strong magnetic metal substances such as Ni, Cr and the like in the screen are brought into the material, and finally the content of the magnetic foreign matters in the material is increased. Therefore, the application of a coating sprayed on the surface of the screen mesh to reduce the friction between the material and the screen mesh is a preferred scheme for managing and controlling the content of foreign matters in the screened material from a source at present. Chinese patent CN105431395A discloses a method for preparing a catalyst from MgO and TiO2And Al2O3The coating is a thermal spraying coating with main components, has better high temperature resistance and insulating property, but cannot effectively resist alkaline corrosion of the ternary cathode material of the lithium battery.
Disclosure of Invention
The invention aims to solve the problem that the existing coating can not effectively resist alkaline corrosion of a lithium battery ternary cathode material, and provides a coating composition.
The invention further aims to provide a lithium battery ternary cathode material screening screen prepared from the coating composition.
The invention also aims to provide a preparation method of the lithium battery ternary cathode material sieving screen.
The above object of the present invention is achieved by the following technical solutions:
a coating composition, wherein the coating comprises the following components in percentage by mass:
Figure BDA0003255462550000021
the coating composition of the invention comprises a specific content of ZrO2、LiAlO2、TiO2MgO and SiO2In which ZrO2、LiAlO2MgO and TiO2Can improve the oxidation resistance and high temperature resistance of the coating, and a proper amount of SiO is added2The coating surface after enabling the spraying has the smooth characteristic, reduces the deposit volume of lithium electricity ternary material on the screen cloth, makes coating surface hardness increase simultaneously, and reinforcing coating wearability to reduce the frictional contact of lithium electricity ternary cathode material (basicity) and screen cloth, isolated lithium electricity ternary cathode material (basicity) is to the erosion of net twine, protection screen cloth, extension screen cloth life.
Preferably, the coating composition comprises the following components in percentage by mass:
Figure BDA0003255462550000022
the invention also provides application of the coating composition in preparation of a lithium battery ternary cathode material sieving screen.
The lithium battery ternary cathode material sieving screen comprises a screen mesh wire made of stainless steel and the coating composition sprayed on the screen mesh wire.
Stainless steel, which is conventional in the art, may be used in the present invention. Preferably, the stainless steel is selected from one or more of 316L stainless steel, 306 stainless steel, 304 stainless steel.
Preferably, the thickness of the coating is 10-60 nm. More preferably 25 to 40 nm.
The invention also provides a preparation method of the lithium battery ternary cathode material sieving screen, which comprises the following steps:
s1, weighing the components of the coating in proportion, and mixing and grinding to obtain a powder spraying raw material;
s2, uniformly spraying the prepared spraying raw materials on the front and back sides of the screen mesh edge to cover the original screen mesh edge;
and S3, sintering the sprayed screen to obtain the screen after sintering.
The spraying method is an oxy-ethylene flame spraying method, and the sintering specifically comprises the step of putting the sprayed screen and the net rack into a box furnace for sintering by taking a sintering sagger as a bottom support.
Preferably, in the step S2, the spraying temperature is 1200 to 1500 ℃. More preferably 1350 deg.c.
Preferably, in step S3, the sintering temperature is 600 to 800 ℃.
Preferably, in the step S3, the sintering time is 2.5 to 3.5 hours.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a coating composition, and the coating prepared from the coating composition can reduce the friction between a lithium battery ternary positive electrode material and a stainless steel screen mesh in the screening process, effectively control the mixing of strong magnetic metals such as Ni and Cr in the original screen mesh material, reduce the content of magnetic foreign matters in the ternary positive electrode material, and improve the cycle stability and safety performance of a product. Meanwhile, the formed screen coating can effectively isolate alkaline corrosion of the lithium battery ternary positive electrode material to the screen wires, reduce the risk of breaking the screen wires, improve the aperture retention rate of the screen mesh and prolong the service life of the screen mesh.
Drawings
FIG. 1 is a schematic representation of a screen according to the present invention.
Detailed Description
In order to more clearly and completely describe the technical scheme of the invention, the invention is further described in detail by the specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the invention, and are not used for limiting the invention, and various changes can be made within the scope defined by the claims of the invention.
The manufacturers and particle size distributions of the raw materials used in the following examples and comparative examples are as follows:
ZrO2: attes optical, particle size distribution D100<50um，D50：20～30um；
LiAlO2: beijing, Ingaku, Loop science, Inc., particle size distribution: d100<50um，D50：20～30um；
TiO2: attes optical, particle size distribution D100<30um；D50：10～12um；
MgO: magical science and technology, ltd, particle size distribution: d100<30um, D50: 10-12 um;
SiO2: estes optics, particle size distribution: d90<16um，D50：7～8um。
Example 1
A coating composition, wherein the coating comprises the following components in percentage by mass: ZrO (ZrO)2 40％；LiAlO235％；TiO2 10％；MgO 10％；SiO2 5％。
The method for preparing the lithium battery ternary cathode material sieving screen by using the coating composition comprises the following steps:
s1, weighing the components according to the mass percentage, mixing and grinding to obtain a powder spraying raw material with a nanoscale particle size;
s2, uniformly spraying the prepared spraying raw material on the front side and the back side of the screen mesh edge by an ethylene oxide flame spraying method, covering the original screen mesh edge, wherein the spraying temperature is 1350 ℃, and the thickness of the spraying coating is 30 nm;
and S3, placing the sprayed screen into a box furnace for sintering by taking a sintering sagger as a bottom support, wherein the sintering temperature is 750 ℃, the sintering time is 3 hours, testing the tension of the screen after the screen is discharged from the box for sintering, and storing the screen to a standby screen storage room for standby application according to requirements.
Example 2
Unlike example 1, the coating described in this example comprises the following components in mass percent: ZrO (ZrO)235％；LiAlO2 40％；TiO2 10％；MgO 10％；SiO2 5％。
Example 3
Unlike example 1, the coating described in this example comprises the following components in mass percent: ZrO (ZrO)235％；LiAlO2 35％；TiO2 10％；MgO 10％；SiO2 10％。
Example 4
Unlike example 1, the coating described in this example comprises the following components in mass percent: ZrO (ZrO)235％；LiAlO2 35％；TiO2 15％；MgO 10％；SiO2 5％。
Example 5
Unlike example 1, the coating described in this example comprises the following components in mass percent: ZrO (ZrO)235％；LiAlO2 35％；TiO2 10％；MgO 15％；SiO2 5％。
Example 6
Unlike example 1, the coating described in this example comprises the following components in mass percent: ZrO (ZrO)245％；LiAlO2 30％；TiO2 5％；MgO 5％；SiO2 15％。
Example 7
Unlike example 1, the coating described in this example comprises the following components in mass percent: ZrO (ZrO)230％；LiAlO2 45％；TiO2 5％；MgO 5％；SiO2 15％。
Example 8
Unlike example 1, the coating described in this example comprises the following components in mass percent: ZrO (ZrO)230％；LiAlO2 30％；TiO2 15％；MgO 15％；SiO2 10％。
Example 9
Unlike example 1, the coating described in this example comprises the following components in mass percent: ZrO (ZrO)230％；LiAlO2 30％；TiO2 20％；MgO 20％；SiO2 2％。
Example 10
In contrast to example 1, the coating thickness described in this example was 25 nm.
Example 11
In contrast to example 1, the coating thickness in this example was 40 nm.
Example 12
In contrast to example 1, the coating thickness described in this example was 10 nm.
Example 13
In contrast to example 1, the coating thickness described in this example was 60 nm.
Example 14
Unlike example 1, in the preparation method of the lithium battery ternary cathode material sieving screen mesh of the present example, the spraying temperature is 1200 ℃ in step S2.
Example 15
Unlike example 1, in the preparation method of the lithium battery ternary cathode material sieving screen mesh of the present embodiment, the spraying temperature is 1500 ℃ in step S2.
Example 16
Different from example 1, in the preparation method of the lithium battery ternary cathode material sieving screen mesh of the present embodiment, in step S3, the sintering temperature is 800 ℃, and the sintering time is 2.5 h.
Example 17
Different from example 1, in the preparation method of the lithium battery ternary cathode material sieving screen mesh of the present embodiment, in step S3, the sintering temperature is 600 ℃, and the sintering time is 3.5 h.
Comparative example 1
The screen of comparative example 1 was a conventional screen made of 316L stainless steel.
Comparative example 2
Unlike example 1, this example was carried outExamples the coating compositions described do not contain SiO2。
Comparative example 3
Unlike example 1, the coating composition described in this example does not contain LiAlO2。
Comparative example 4
Unlike example 1, the coating composition described in this example does not contain MgO.
Characterization of the test
The screens of examples 1 to 17 and comparative examples 1 to 3 were loaded into a vibrating sifter, and the magnetic 20t ternary positive electrode material (LiNi) was quantitatively sifted and removed0.8Co0.1Mn0.1O). And (3) measuring the magnetic foreign matter index of the material by adopting a chemical weight adsorption method after the 20t ternary cathode material is sieved, counting the weight of oversize materials, cutting the screen after the screen is disassembled, and analyzing the aperture size retention rate and the appearance size of the screen by using an electron microscope. The test results are shown in table 1 below.
TABLE 1
Figure BDA0003255462550000061
Figure BDA0003255462550000071
Figure BDA0003255462550000081
From examples 1 to 17, it can be seen that the coating composition provided by the invention is sprayed on the surface of a stainless steel screen mesh, so that the content of magnetic foreign matters in a screened ternary positive electrode material can be reduced, the content of the magnetic foreign matters is controlled to be below 30/ppb, and the product cycle stability is improved.
The conventional screen cloth is used for quantitatively sieving the ternary cathode material for 20t, the content of the magnetic foreign matters in the sieved ternary cathode material is high, the content of the magnetic foreign matters is gradually increased along with the increase of the sieving times, meanwhile, part of screen wires are deformed, and the width of the screen wires is reduced to 3-5 mu m.
The coating composition of comparative example 2, since it does not contain SiO2After the obtained screen quantitatively sieves 20t of the ternary cathode material, more oversize materials are obtained, the content of magnetic foreign matters is higher after sieving, the aperture retention rate of the screen is smaller, and the screen wire is deformed and reduced in width because the coating component does not contain SiO2The surface texture of the mesh coating is rough, not hard and smooth, so that oversize materials are easy to deposit and cannot effectively isolate the erosion of the ternary positive electrode material (alkaline) of the lithium battery to the mesh, the content of magnetic foreign matters after sieving is high, the pore diameter of the material is extruded, and the mesh is deformed.
Comparative example 3 coating composition without LiAlO2When the original 316L metal mesh is sieved, the mesh is directly rubbed with a positive electrode material, and more Ni and Cr strong magnetic metal elements in the original mesh are mixed in the material, so that the foreign matter content of the material is higher, the mesh is easy to deform, the width is reduced, and the aperture retention rate of the screen is reduced.
The coating component contains MgO, so that the porosity of the coating surface after spraying can be reduced, the coating is attached to the screen wires more uniformly, the coating does not contain MgO in comparative example 4, the thickness of the coating of the screen wire after spraying can become non-uniform, part of the coating has pores, and the thinner part of the coating surface is easily abraded by friction with a positive material during sieving, so that the protective effect of the coating is lost, the screen wires are further eroded, the friction extrusion deformation of the screen wires is caused, and the width of the screen wires is reduced.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. A coating composition, characterized in that the coating composition comprises the following components in percentage by mass:
Figure FDA0003255462540000011
2. the coating composition of claim 1, comprising the following components in percentage by mass
Figure FDA0003255462540000012
3. Use of a coating composition according to claim 1 or 2 for the preparation of a screen for the ternary positive electrode material for lithium batteries.
4. A lithium battery ternary positive electrode material sieving screen is characterized in that the screen comprises a screen mesh wire made of stainless steel and a coating sprayed on the screen mesh wire, wherein the coating is prepared from the coating composition of claim 1 or 2.
5. The lithium battery ternary positive electrode material sieve screen of claim 4, wherein the stainless steel is selected from one or more of 316L stainless steel, 306 stainless steel and 304 stainless steel.
6. The lithium battery ternary cathode material sieve screen of claim 4, wherein the coating thickness is 10-60 nm.
7. The preparation method of the lithium battery ternary cathode material sieving screen mesh disclosed by any one of claims 4 to 6 is characterized by comprising the following steps of:
s1, weighing the components of the coating in proportion, and mixing and grinding to obtain a powder spraying raw material;
s2, uniformly spraying the prepared spraying raw materials on the front and back sides of the screen mesh edge to cover the original screen mesh edge;
and S3, sintering the sprayed screen to obtain the screen after sintering.
8. The method for preparing the lithium battery ternary cathode material sieving screen mesh according to claim 7, wherein in the step S2, the spraying temperature is 1200-1500 ℃.
9. The method for preparing the lithium battery ternary cathode material sieving screen mesh according to claim 7, wherein in the step S3, the sintering temperature is 600-800 ℃.
10. The method for preparing the lithium battery ternary cathode material sieving screen mesh according to claim 7, wherein in the step S3, the sintering time is 2.5-3.5 h.
CN202111058346.3A 2021-09-09 2021-09-09 Coating composition, lithium battery ternary cathode material sieving screen and preparation method thereof Pending CN113980496A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115138560A (en) * 2022-06-28 2022-10-04 山推建友机械股份有限公司 Coarse sand recycling system and method for dry powder mortar production line

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60182656A (en) * 1984-02-29 1985-09-18 Kawaguchiko Seimitsu Kk Sealed type alkaline battery
CN101689621A (en) * 2007-06-29 2010-03-31 永备电池有限公司 The anti-steam permeability potted component that is used for non-aqueous electrochemical cells
CN109081687A (en) * 2018-09-26 2018-12-25 景德镇陶瓷大学 A kind of highly heatproof and shockproof ceramic crucible and preparation method thereof suitable for calcining anode material of lithium battery
CN109956760A (en) * 2019-03-13 2019-07-02 乳源东阳光磁性材料有限公司 A kind of nickelic ternary material sintering saggar and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60182656A (en) * 1984-02-29 1985-09-18 Kawaguchiko Seimitsu Kk Sealed type alkaline battery
CN101689621A (en) * 2007-06-29 2010-03-31 永备电池有限公司 The anti-steam permeability potted component that is used for non-aqueous electrochemical cells
CN109081687A (en) * 2018-09-26 2018-12-25 景德镇陶瓷大学 A kind of highly heatproof and shockproof ceramic crucible and preparation method thereof suitable for calcining anode material of lithium battery
CN109956760A (en) * 2019-03-13 2019-07-02 乳源东阳光磁性材料有限公司 A kind of nickelic ternary material sintering saggar and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115138560A (en) * 2022-06-28 2022-10-04 山推建友机械股份有限公司 Coarse sand recycling system and method for dry powder mortar production line

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