CN111792950A - Garnet solid electrolyte powder sintering container - Google Patents
Garnet solid electrolyte powder sintering container Download PDFInfo
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- CN111792950A CN111792950A CN202010666474.5A CN202010666474A CN111792950A CN 111792950 A CN111792950 A CN 111792950A CN 202010666474 A CN202010666474 A CN 202010666474A CN 111792950 A CN111792950 A CN 111792950A
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- slurry
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- surface layer
- sintering container
- electrolyte powder
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a garnet solid electrolyte powder sintering container, which relates to the field of electrolyte powder preparation, and mainly comprises an inner surface layer and a surface layer, wherein the inner surface layer comprises a bottom layer and a surface layer, and the bottom layer comprises MgO-SiO2‑B2O3The surface layer comprises MgO; the preparation method of the inner surface layer comprises the following steps: s1, preparing slurry A; s2, preparing slurry B; s3, uniformly coating the slurry A on the surface of a sintering container which is in direct contact with the material, and baking to form a bottom layer; s4, spraying the slurry B on the bottom layer, and baking the sintering container to form a surface layer; and S5, keeping the temperature after rising, and cooling to normal temperature to obtain the sintering container with the protective layer. The slurry A and the slurry B are coated on the surface of the container to form a bottom layer and a surface layer of the protective container, so that the container has corrosion resistance and the service life of the container is prolonged. On the other hand, impurities can be prevented from being introduced in the preparation of the garnet solid electrolyte powder.
Description
Technical Field
The invention relates to the field of electrolyte powder preparation, in particular to a garnet solid electrolyte powder sintering container.
Background
With the rapid development of consumer electronics, electric vehicles and other technologies, conventional liquid lithium ion batteries have not been availableCan meet the requirements of long-endurance, long-service-life and high-safety power batteries. The all-solid-state lithium ion battery uses the solid electrolyte to replace the traditional liquid electrolyte, has the advantages of high safety performance, wide working temperature range, high energy density and the like, and has wide application prospect in the fields of new energy automobiles, smart power grids and the like as an energy storage device. The garnet-structured solid electrolyte has good thermal stability and chemical stability, is stable to a lithium metal cathode, and has the room-temperature lithium ion conductivity of 10-3S/cm, and has potential application value. The current common preparation methods of garnet electrolyte powder comprise a solid phase method and a wet chemical method, wherein the solid phase method has the advantages of wide raw material source, good stability, simple process, high safety, good environmental compatibility, easy recovery and reutilization of solvent, and is beneficial to large-scale preparation.
However, garnet electrolyte powders produced by mass production by the solid phase method tend to have lithium-deficient mixed phases, which are largely caused by the reaction of lithium with the sintering container. On one hand, in an alkaline environment, lithium element and water vapor easily enter the container through pores on the surface layer of the sintering container and react with a base material in the container, so that the corrosion and the breakage of the sintering container are caused, the service life of the sintering container is seriously influenced, and meanwhile, the loss of the lithium element in electrolyte is easily caused; on the other hand, part of elements in the base material of the sintering container enter the material structure, and the performance stability is influenced. Although pure magnesia vessels are suitable for the production of garnet electrolyte materials, the cost of using a single magnesia component to make a sintering vessel is relatively high.
Therefore, the protective coating is coated on the surface layer of the sintering container and the part of the surface layer of the sintering container, which is in direct contact with the material, so that the protective coating is applied to the preparation of the garnet electrolyte powder, the risks that the surface of the sintering container is corroded and cracked are reduced, the material does not stick to a bowl, the service life of the sintering container is prolonged, the generation of a lithium-deficient phase can be reduced, and the pollution to the garnet electrolyte powder material is avoided.
Disclosure of Invention
The present invention has an object to provide a garnet solid electrolyte powder sintering container which has good corrosion resistance and is less likely to cause problems of a lithium-deficient phase and a multi-impurity phase.
The above object of the present invention is achieved by the following technical solutions:
a garnet solid electrolyte powder sintering container, wherein the inner surface layer directly contacting with the material comprises a bottom layer and a surface layer, the bottom layer comprises MgO-SiO2-B2O3The surface layer comprises MgO;
the preparation method of the inner surface layer comprises the following steps:
s1, preparation of slurry A:
weighing 32.3-40.0% of magnesium oxide, 21.5-30.0% of magnesium hydroxide, 25.0-37.6% of silicon dioxide and 3.0-8.6% of boron trioxide according to mass percentage, uniformly mixing with deionized water, ball-milling for 4 hours at a rotation speed of 200rpm, and thus forming slurry A with a solid content of 70-85 wt%;
s2, preparation of slurry B:
dispersing MgO particles in absolute ethyl alcohol to form slurry B with the solid content of 70-85 wt%;
s3, uniformly coating the slurry A on the surface of a sintering container in direct contact with the material, keeping for 2h, and then baking the sintering container at the temperature of 110 ℃ until deionized water is completely volatilized, thereby forming a bottom layer;
s4, spraying the slurry B on the bottom layer, and baking the sintering container at the temperature of 60 ℃ until the absolute ethyl alcohol is completely volatilized, so that a surface layer is formed;
and S5, raising the sintering temperature to 1100-1400 ℃, carrying out sintering heat preservation for 3h, and then cooling to normal temperature, thereby obtaining the finished sintering container with the protective layer.
The surface of the container is coated with slurry A and slurry B to form a bottom layer and a surface layer of the protective container, wherein the surface layer is in contact with the garnet solid electrolyte powder, and has corrosion resistance on one hand, and on the other hand, the elements in the base material of the container are prevented from reacting with the garnet solid electrolyte powder to influence the purity of the garnet solid electrolyte powder.
Secondly, the bottom layer plays a transitional role here, and the surface layer can be firmly attached to the base material of the container and is not easy to fall off, so that the service life of the container is prolonged.
Preferably, the use amount of the magnesium oxide in the slurry B is 25-200% of the total solid mass of the slurry A.
Preferably, in S5, the temperature rising rate is 5 ℃/min, and the temperature lowering rate is 3 ℃/min.
Preferably, the magnesium oxide, the magnesium hydroxide, the silicon dioxide and the boron trioxide in the S1 are sieved by a 40-mesh sieve, and the MgO particles in the S2 are spherical and have the particle size of 30-40 nm.
By adopting the technical scheme, the coating improvement can be directly carried out on the purchased sintering container, the mechanical property of the original sintering container can not be damaged, the sintering container is not easy to corrode and damage, and the coating is tightly combined with the surface of the original container and is not easy to fall off.
In conclusion, the beneficial technical effects of the invention are as follows: on one hand, the surface of the sintering container can be prevented from being corroded and cracked in the sintering process, on the other hand, the problem that lithium-deficient mixed phases occur in electrolyte powder can be solved, and the garnet solid electrolyte with pure phases can be obtained.
Detailed Description
Comparative example 1
A commercially available, domestic formed sagger having a net weight of 4.9kg and a total area of a portion in contact with the sintering material of 2000cm2。
Comparative example 2
A commercially available sagger with a net weight of 5.2kg and a total area of a part contacting with a sintering material of 2000cm2。
Comparative example 3
Slurry B was applied to the sagger used in comparative example 2: dispersing 50g of magnesium oxide (spherical 30-40 nm) in 12.5g of absolute ethyl alcohol to form slurry B, uniformly spraying the slurry B on the bottom layer and the four walls in a sagger, and baking at 60 ℃ until the absolute ethyl alcohol is completely volatilized; heating to 1200 ℃ at the temperature of 5 ℃/min, preserving heat for 3h for forming, and cooling to room temperature at the temperature of 3 ℃/min.
Comparative example 4
The sagger used in comparative example 2 was coated with slurry a only: mixing 66g of silicon dioxide, 72g of magnesium oxide, 56g of magnesium hydroxide, 6g of boron trioxide and 50g of deionized water, and carrying out ball milling at 200rpm for 4 hours to form slurry A; uniformly coating the slurry A on the bottom layer and the four walls in the sagger, keeping for 2 hours, and then baking at 110 ℃ until deionized water is completely volatilized; heating to 1300 deg.C at 5 deg.C/min, holding for 3h, molding, and cooling to room temperature at 3 deg.C/min.
Example 1:
the coating was carried out on a sagger used in comparative example 1.
Mixing 66g of silicon dioxide, 72g of magnesium oxide, 56g of magnesium hydroxide, 6g of boron trioxide and 85.7g of deionized water, and ball-milling the mixture at 200rpm for 4 hours to obtain slurry A; uniformly coating the slurry A on the bottom layer and the four walls in the sagger, keeping for 2 hours, and then baking at 110 ℃ until deionized water is completely volatilized to form a coating A; dispersing 50g of magnesium oxide (spherical 30-40 nm) in 12.5g of absolute ethyl alcohol to form slurry B, spraying the slurry B on the coating A, and baking at 60 ℃ until the absolute ethyl alcohol is completely volatilized; heating to 1400 deg.C at 5 deg.C/min, holding for 3 hr, and cooling to room temperature at 3 deg.C/min.
Example 2:
the coating was carried out on a sagger used in comparative example 1.
Mixing 52.5g of silicon dioxide, 45g of magnesium oxide, 30g of magnesium hydroxide, 12g of boron trioxide and 35g of deionized water, and ball-milling at 200rpm for 4 hours to obtain slurry A; uniformly coating the slurry A on the bottom layer and the four walls in the sagger, keeping for 2 hours, and then baking at 110 ℃ until deionized water is completely volatilized to form a coating A; dispersing 50g of magnesium oxide (spherical 30-40 nm) in 18.8g of absolute ethyl alcohol to obtain slurry B, spraying the slurry B on the coating A, and baking at 60 ℃ until the absolute ethyl alcohol is completely volatilized; heating to 1300 deg.C at 5 deg.C/min, holding for 3h, molding, and cooling to room temperature at 3 deg.C/min.
Example 3:
the coating was carried out on a sagger used in comparative example 2.
Mixing 33g of silicon dioxide, 36g of magnesium oxide, 28g of magnesium hydroxide, 3g of boron trioxide and 17.7g of deionized water, and carrying out ball milling at 200rpm for 4h of slurry A; uniformly coating the slurry A on the bottom layer and the four walls in the sagger, keeping for 2 hours, and then baking at 110 ℃ until deionized water is completely volatilized to form a coating A; dispersing 25g of magnesium oxide (spherical 30-40 nm) in 10.7g of absolute ethyl alcohol to obtain slurry B, spraying the slurry B on the coating A, and baking at 60 ℃ until the absolute ethyl alcohol is completely volatilized; heating to 1100 deg.C at 5 deg.C/min, holding for 3 hr, and cooling to room temperature at 3 deg.C/min.
Example 4:
the coating was carried out on a sagger used in comparative example 2.
Mixing 12.5g of silicon dioxide, 20g of magnesium oxide, 15g of magnesium hydroxide, 2.5g of boron trioxide and 12.5g of deionized water, and ball-milling at 200rpm for 4h to obtain slurry A; uniformly coating the slurry A on the bottom layer and the four walls in the sagger, keeping for 2 hours, and then baking at 110 ℃ until deionized water is completely volatilized to form a coating A; dispersing 100g of magnesium oxide (spherical 30-40 nm) in 17.7g of absolute ethyl alcohol to obtain slurry B, spraying the slurry B on the coating A, and baking at 60 ℃ until the absolute ethyl alcohol is completely volatilized; heating to 1200 ℃ at the temperature of 5 ℃/min, preserving heat for 3h for forming, and cooling to room temperature at the temperature of 3 ℃/min.
All solid powders in the examples were sieved through a 40 mesh sieve.
The actual effect and service life of the modified sintered vessel were evaluated by: adding garnet electrolyte to-be-sintered material accounting for 60% of the container volume into the improved sintering container, keeping the mixture at 950 ℃ for 10h, and taking out the sintered material. And inspecting the erosion degree of the sintering container, whether the sintered material has heterogeneous impurity particles, and whether the sintered material has impurity phases or not and the coating damage condition in the phase test of the sintered material. The test is evaluated by 20 practical use cases (if the conditions which obviously affect the service life, such as peeling crack, foreign impurities, lithium-deficient phases or corrosion conditions, appear in repeated sintering tests within 20 times, the test is not continued by using the container).
The effects of comparative examples 1 to 4 and examples 1 to 4 are shown in Table 1.
TABLE 1 comparative examples 1 to 4 and examples 1 to 4
As can be seen from the comparison of examples 1 to 4 with comparative examples 1 to 4, only when MgO-SiO is contained2-B2O3With both a bottom layer and a surface layer comprising MgOIn time, the improvement effect can be effectively improved.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (4)
1. A garnet solid electrolyte powder sintering container, characterized in that: the inner surface layer in direct contact with the material comprises a bottom layer and a surface layer, wherein the bottom layer comprises MgO-SiO2-B2O3The surface layer comprises MgO;
the preparation method of the inner surface layer comprises the following steps:
s1, preparation of slurry A:
weighing 32.3-40.0% of magnesium oxide, 21.5-30.0% of magnesium hydroxide, 25.0-37.6% of silicon dioxide and 3.0-8.6% of boron trioxide according to mass percentage, uniformly mixing with deionized water, ball-milling for 4 hours at a rotation speed of 200rpm, and thus forming slurry A with a solid content of 70-85 wt%;
s2, preparation of slurry B:
uniformly dispersing MgO particles in absolute ethyl alcohol to form slurry B with the solid content of 70-85 wt%;
s3, uniformly coating the slurry A on the surface of a sintering container in direct contact with the material, keeping for 2h, and then baking the sintering container at the temperature of 110 ℃ until deionized water is completely volatilized, thereby forming a bottom layer;
s4, spraying the slurry B on the bottom layer, and baking the sintering container at the temperature of 60 ℃ until the absolute ethyl alcohol is completely volatilized, so that a surface layer is formed;
and S5, raising the sintering temperature to 1100-1400 ℃, carrying out sintering heat preservation for 3h, and then cooling to normal temperature, thereby obtaining the sintering container with the protective layer.
2. The garnet solid electrolyte powder sintering container as set forth in claim 1, wherein: the usage amount of the magnesium oxide in the slurry B is 25-200% of the total solid mass of the slurry A.
3. The garnet solid electrolyte powder sintering container as set forth in claim 1, wherein: in S5, the temperature rising rate is 5 ℃/min, and the temperature reducing rate is 3 ℃/min.
4. The garnet solid electrolyte powder sintering container as set forth in claim 1, wherein: and in the S1, the magnesium oxide, the magnesium hydroxide, the silicon dioxide and the boron trioxide are sieved by a 40-mesh sieve, and in the S2, MgO particles are spherical and have the particle size of 30-40 nm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010666474.5A CN111792950B (en) | 2020-07-11 | 2020-07-11 | Garnet solid electrolyte powder sintering container |
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| CN202010666474.5A CN111792950B (en) | 2020-07-11 | 2020-07-11 | Garnet solid electrolyte powder sintering container |
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| CN111792950B CN111792950B (en) | 2022-09-06 |
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| CN110451984A (en) * | 2019-05-21 | 2019-11-15 | 湖南太子新材料科技有限公司 | A kind of preparation method of coat of silicon carbide and the saggar with coat of silicon carbide |
| CN111233482A (en) * | 2020-01-19 | 2020-06-05 | 湖南太子新材料科技有限公司 | High-temperature-resistant sagger and preparation method thereof |
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2020
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5364513A (en) * | 1992-06-12 | 1994-11-15 | Moltech Invent S.A. | Electrochemical cell component or other material having oxidation preventive coating |
| CN1796336A (en) * | 2004-12-28 | 2006-07-05 | 日本碍子株式会社 | Clamp for electron component |
| US20080187767A1 (en) * | 2006-11-21 | 2008-08-07 | United Technologies Corporation | Oxidation resistant coatings, processes for coating articles, and their coated articles |
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