CN111792950B - Garnet solid electrolyte powder sintering container - Google Patents

Garnet solid electrolyte powder sintering container Download PDF

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Publication number
CN111792950B
CN111792950B CN202010666474.5A CN202010666474A CN111792950B CN 111792950 B CN111792950 B CN 111792950B CN 202010666474 A CN202010666474 A CN 202010666474A CN 111792950 B CN111792950 B CN 111792950B
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slurry
container
sintering
sintering container
surface layer
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CN111792950A (en
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罗林君
谢龙巍
魏远航
黄祯
林久
许晓雄
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Zhejiang Funlithium New Energy Tech Co Ltd
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Zhejiang Funlithium New Energy Tech Co Ltd
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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
    • 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
    • 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

Abstract

The invention discloses a garnetA solid electrolyte powder sintering container relates to the electrolyte powder preparation field, mainly comprising an inner surface layer comprising a bottom layer and a surface layer, wherein the bottom layer comprises MgO-SiO 2 ‑B 2 O 3 The 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

Garnet solid electrolyte powder sintering container
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 been unable to meet the requirements of long-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 solid electrolyte has good thermal stability and chemical stability, is stable to a lithium metal cathode, and has room temperature lithium ion conductivity of 10 -3 S/cm, and has potential application value. At present, 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 reuse of solvent and contribution 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 containers are suitable for the production of garnet electrolyte materials, the cost of manufacturing a sintering container using a single magnesia component is high.
For this reason, this application is through in sintering container top layer and the partial coating protective coating of material direct contact to use in garnet electrolyte powder's preparation, thereby reduce sintering container's surface by the corruption, take place cracked risk, the nonstick alms bowl of material, the life of extension sintering container can reduce the production that lacks the lithium phase simultaneously, avoids garnet electrolyte powder material to receive the pollution.
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-SiO 2 -B 2 O 3 The 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 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 rise rate is 5 ℃/min and the temperature drop 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 can be directly improved 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 summary, the beneficial technical effects of the invention are as follows: on one hand, the corrosion and the cracking of the surface of the sintering container in the sintering process can be reduced, on the other hand, the problem that lithium-deficient mixed phases occur in electrolyte powder can be reduced, 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 2000cm 2 。
Comparative example 2
A commercially available sagger with a molded inlet, the net weight of 5.2kg and the total area of the part contacted with the sintering material of 2000cm 2 。
Comparative example 3
Slurry B was applied to the sagger used in comparative example 2: dispersing 50g of magnesium oxide (with a spherical shape of 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 (with a spherical shape of 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:
coated on a sagger as 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 (with a spherical shape of 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, maintaining 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 cases of effects of comparative examples 1 to 4 and examples 1 to 4
Figure BDA0002580241410000041
As can be seen from the comparison of examples 1 to 4 with comparative examples 1 to 4, only when MgO-SiO is contained 2 -B 2 O 3 When the bottom layer and the surface layer containing MgO exist at the same 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 (3)

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-SiO 2 -B 2 O 3 The 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;
s5, raising the sintering temperature to 1100-1400 ℃, carrying out sintering heat preservation for 3h, and then cooling to normal temperature, thereby obtaining a sintering container with a protective layer;
wherein, 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.
2. The sintering container of garnet solid electrolyte powder according to 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.
CN202010666474.5A 2020-07-11 2020-07-11 Garnet solid electrolyte powder sintering container Active CN111792950B (en)

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JP5438345B2 (en) * 2009-03-23 2014-03-12 日本碍子株式会社 Firing jig
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Patent Citations (3)

* Cited by examiner, † Cited by third party
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
CN103936465A (en) * 2014-03-27 2014-07-23 中南大学 Anti-oxidation coating of carbon/carbon composite material and preparation method of anti-oxidation coating

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