Refractory material sagger, preparation method thereof and application of refractory material sagger in preparation of positive electrode material

Abstract

The invention discloses a refractory material sagger, a preparation method of the refractory material sagger and application of the refractory material sagger in preparation of a positive electrode material, and belongs to the technical field of secondary batteries, and the thermal shock resistant sagger comprises an inner surface working layer and an outer matrix layer from inside to outside; the thickness of the inner surface working layer is 1-3mm; according to the sagger, the inner surface working layer serves as the inner layer, the outer matrix layer serves as the outer layer, the inner layer is resistant to alkali erosion, the outer layer is small in thermal expansion coefficient and resistant to high temperature, and the sagger has the excellent low expansion coefficient and thermal shock resistance, is long in cycle service life and has wide application prospects.

Description

Technical Field

[0001] The invention relates to the technical field of secondary batteries, and in particular to a sagger made of refractory materials, a preparation method thereof, and an application thereof in preparing positive electrode materials. Background Art

[0002] Lithium battery positive electrode materials must be sintered in a high-temperature roller kiln, especially the current high-nickel positive electrode materials, which must be sintered in an environment with an oxygen concentration of >95 parts. Therefore, the sintering process must use a high-temperature resistant sagger to support the firing.

[0003] The sagger materials used in the production of lithium-ion battery positive electrode materials are mainly mullite or mullite-cordierite and corundum mullite. Li2CO3 or LiOH·H2O is used in the production of lithium battery positive electrode materials. They will decompose into Li2O during high-temperature roasting. Since Li2O has strong alkaline corrosion, Li2O will react with Al2O3 to produce LiAlO2. Therefore, the alkaline corrosion of the positive electrode raw materials on the sagger is relatively large, requiring the sagger to have high corrosion resistance.

[0004] In addition, with the downward pressure on costs in the power lithium battery industry, lithium battery positive electrode materials are undergoing a production-enhancing transformation. The high-temperature sintering time has been greatly shortened, from the previous normal sintering time of 20 to 30 hours to 10 to 15 hours. The sagger materials heat up and cool down quickly at high temperatures. As the number of uses increases, the saggers are prone to cracks, which ultimately greatly reduces the service life of the high-temperature resistant saggers.

[0005] In view of this, this application is filed. Summary of the invention

[0006] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a refractory sagger and a preparation method thereof and an application thereof in the preparation of positive electrode materials. The sagger has excellent low expansion coefficient and thermal shock resistance, and the sagger has a high cycle life and has broad application prospects.

[0007] To achieve the above object, the technical solution adopted by the present invention is:

[0008] A sagger made of refractory materials, the sagger comprising an inner surface working layer and an outer matrix layer from inside to outside; the thickness of the inner surface working layer is 1 to 3 mm;

[0009] The inner surface working layer includes the following raw materials in parts by weight: 0-10 parts of kaolin, 0-50 parts of plate-like corundum, 0-50 parts of fused white corundum, 5-15 parts of activated alumina, 0-10 parts of zirconium mullite, 0-5 parts of organic binder, 0-10 parts of spodumene, 0-10 parts of cordierite, 20-80 parts of magnesium-rich spinel, 10-70 parts of fused magnesium-rich spinel, 0-10 parts of light magnesium carbonate, 0-10 parts of magnesite, 0-15 parts of fused zirconium oxide, 0-15 parts of zirconium oxide, 0-15 parts of yttrium-stabilized zirconium oxide, 0-15 parts of zircon, 0-15 parts of lanthanum oxide, 0-15 parts of cerium oxide, 0-15 parts of yttrium oxide, 0-15 parts of periclase, 0-15 parts of forsterite, 0-5 parts of feldspar, and 1-5 parts of water.

[0010] The iron oxide content of the kaolin used in the present invention is less than 1 part, and the particle size D50 is less than 10 μm.

[0011] Among them, the tabular corundum is 200-325 mesh.

[0012] Among them, the α-alumina is a corundum phase>90%.

[0013] The zirconium mullite has a zirconium oxide content of more than 30% and a mesh size of 200 to 325.

[0014] The spodumene is a powder with a lithium oxide content of more than 6% and less than 325 mesh.

[0015] Among them, cordierite is cordierite phase>90%; 200~325 mesh.

[0016] Among them, the magnesium-rich spinel has a magnesium oxide content of more than 30% and a mesh size of 200 to 325.

[0017] Among them, the magnesium-rich spinel has a magnesium oxide content of more than 22% and a mesh size of 200 to 325.

[0018] Among them, light magnesium carbonate is industrial grade, magnesium oxide content>45%, powder.

[0019] Among them, the magnesite has a magnesium carbonate content of >96% and a mesh size of 200 to 325.

[0020] The fused zirconia has a zirconium oxide content of more than 98% and a mesh size of 325 to 800.

[0021] The zirconium oxide has a zirconium oxide content of more than 99% and a mesh size of 325 to 800.

[0022] The yttrium stabilized zirconia has a zirconia content of more than 99% and a mesh size of 325 to 800.

[0023] The zircon has a zirconium oxide content of more than 65% and a mesh size of 325 to 800.

[0024] The lanthanum oxide has a lanthanum oxide content of more than 95% and a mesh size of 325 to 800.

[0025] The cerium oxide has a cerium oxide content of more than 98% and a mesh size of 325 to 800.

[0026] The yttrium oxide has an yttrium oxide content of more than 99% and a mesh size of 325 to 800.

[0027] Among them, periclase has a magnesium oxide content of more than 95% and a mesh size of 325 to 800.

[0028] Among them, forsterite has a magnesium oxide content of more than 50%, an iron oxide content of less than 1%, and a mesh size of 200 to 800.

[0029] Among them, the feldspar is potassium feldspar or sodium feldspar, and the iron oxide content is less than 1%.

[0030] As a preferred embodiment of the present invention, the inner surface working layer includes the following preparation raw materials in parts by weight: including the following components in parts by weight: 5-7 parts of kaolin, 0-19 parts of plate-like corundum, 15-35 parts of fused white corundum, 6-12 parts of activated alumina, 0-8 parts of zircon mullite, 1-4 parts of organic binder, 0-5 parts of spodumene, 0-2 parts of cordierite, 34-70 parts of magnesium-rich spinel, 0-8 parts of light magnesium carbonate, 3-10 parts of zirconium oxide, 0-4 parts of zircon, 0-3 parts of yttrium oxide, 0-1.5 parts of feldspar, and 1-5 parts of water.

[0031] As a preferred embodiment of the present invention, the fused white corundum is composed of 800 mesh fused white corundum and 200-325 mesh fused white corundum in a weight ratio of 1:(0.5-2).

[0032] As a preferred embodiment of the present invention, the organic binder is at least one of sodium lignin sulfonate, calcium lignin sulfonate, peach gum, yellow dextrin, white dextrin, polyvinyl alcohol, polyethylene glycol, 801 glue powder, carboxymethyl cellulose, and hydroxypropyl methyl cellulose.

[0033] As a preferred embodiment of the present invention, the outer matrix layer includes the following raw materials in parts by weight: 5 to 40 parts of M45 sintered mullite, 5 to 40 parts of M70 sintered mullite, 0 to 40 parts of roller stock, 10 to 20 parts of kaolin, 5 to 20 parts of α-alumina, 10 to 50 parts of cordierite, 1 to 10 parts of talc, 0 to 20 parts of magnesium aluminum spinel, 0 to 20 parts of andalusite, 0 to 15 parts of sillimanite, 0 to 15 parts of kyanite, 1 to 5 parts of binder, 1 to 5 parts of feldspar, 10 to 30 parts of fused quartz, and 1 to 5 parts of water.

[0034] Among them, M45 sintered mullite has an alumina content of more than 42% and a mesh size of 200 to 325.

[0035] Among them, the M70 sintered mullite has an alumina content of more than 68% and a mesh size of 200 to 325.

[0036] The roller rod material has an aluminum oxide content of more than 70%, a zirconium oxide content of 1-10%, and a mesh size of 200-325.

[0037] It should be noted that the roller rod material is an alumina roller rod, which is a roller rod that is a defective product of a kiln or is dismantled from a scrapped kiln, is obtained by crushing, and is conventionally available on the market.

[0038] Wherein, talc is powder with particle size less than 325 mesh.

[0039] The magnesium-aluminum spinel has an aluminum oxide content of more than 70% and a mesh size of 200 to 325.

[0040] Among them, the andalusite has an alumina content of >57% and a mesh size of 200 to 325.

[0041] Among them, the sillimanite has an aluminum oxide content of more than 45% and a mesh size of 200 to 325.

[0042] Among them, the kyanite has an aluminum oxide content of more than 45% and a mesh size of 200 to 325.

[0043] Among them, the fused quartz has a silicon oxide content of more than 98% and a mesh size of 200 to 325.

[0044] As a preferred embodiment of the present invention, the outer matrix layer includes the following raw materials in parts by weight: 0 to 13 parts of M70 sintered mullite, 10 to 21 parts of roller material, 13 to 16 parts of kaolin, 8 to 17 parts of α-alumina, 20 to 33 parts of cordierite, 1 to 2 parts of talc, 1 to 5 parts of binder, 2 to 5 parts of feldspar, 7 to 27 parts of fused quartz, and 1 to 5 parts of water.

[0045] As a preferred embodiment of the present invention, the binder is at least one of sodium lignin sulfonate, calcium lignin sulfonate, peach gum, yellow dextrin, white dextrin, polyvinyl alcohol, polyethylene glycol, 801 glue powder, carboxymethyl cellulose, and hydroxypropyl methyl cellulose.

[0046] The present invention also provides a method for preparing a refractory sagger, comprising the following steps:

[0047] (1) weighing the raw materials of the inner surface working layer according to the ratio, mixing water and an organic binder evenly to obtain an organic binder solution, premixing the remaining materials evenly to obtain a premix, mixing the premix with the organic binder evenly, aging, and passing through a 2-3 mesh sieve to obtain a material body of the inner surface working layer;

[0048] (2) Weighing the raw materials of the outer matrix layer according to the ratio, mixing water and the binder evenly to obtain a binder solution, premixing the remaining materials evenly, and then mixing them evenly with the binder solution, aging, and passing through a 2-3 mesh sieve to obtain the outer matrix layer material;

[0049] (3) Add the inner surface working layer material and the outer matrix layer material into the mold respectively, press, dry and sinter to obtain a refractory sagger.

[0050] As a preferred embodiment of the present invention, Figure 1 As shown, the present invention does not limit the size of the sagger, and the lower part of the sagger of the present invention can be flat or uneven, that is, it can have a certain height difference.

[0051] like Figure 2 As shown, the present invention uses the inner surface working layer as the inner layer, and its thickness is 1 to 3 mm, preferably 1 to 2 mm, and uses the outer substrate layer as the outer layer. The inner layer is resistant to alkali corrosion, and the outer layer has a small thermal expansion coefficient and is resistant to high temperatures. The sagger has excellent low expansion coefficient and thermal shock resistance. The sagger has a high cycle service life and has broad application prospects.

[0052] As a preferred embodiment of the present invention, the sintering temperature is 1300-1400° C., and the sintering time is 1-10 hours.

[0053] As a preferred embodiment of the present invention, the drying temperature is 50-120° C., and the drying time is greater than 2 hours.

[0054] The present invention also provides an application of a heat shock resistant sagger in preparing positive electrode materials.

[0055] The beneficial effects of the present invention are as follows: the present invention uses the inner surface working layer as the inner layer and the outer substrate layer as the outer layer, the inner layer is resistant to alkali corrosion, the outer layer has a small thermal expansion coefficient and is resistant to high temperatures, the sagger has excellent low expansion coefficient and thermal shock resistance, the sagger has a high cycle service life, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 It is the dimension diagram and the physical diagram of the sagger of the present invention.

[0057] Figure 2 This is the distribution diagram of the inner layer and the outer layer of the present invention.

[0058] Figure 3 This is a diagram for evaluating the thermal shock resistance of saggers.

[0059] Figure 4 This is a service life test chart. DETAILED DESCRIPTION

[0060] In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application are described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

[0061] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0062] In this application, when it comes to numerical ranges, unless otherwise specified, the above numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0063] In the present application, there is no particular limitation on the specific dispersion and stirring treatment methods.

[0064] Unless otherwise specified, the components, raw materials or instruments used in the embodiments and comparative examples of the present invention are all commercially available raw materials or instruments, and the components and raw materials used in each parallel experiment are all of the same kind.

[0065] The following examples are provided to facilitate understanding of the present invention. These examples are not provided to limit the scope of the claims.

[0066] Example 1

[0067] This embodiment provides five inner surface working layer materials B1 to B5 and corresponding five outer substrate layer materials A1 to A5, and the specific formulations are shown in Table 1 and Table 2 (all in the tables are parts by weight).

[0068] Table 1

[0069]

[0070]

[0071] Table 2

[0072]

[0073] The above-mentioned method for preparing the refractory sagger comprises the following steps:

[0074] (1) Weighing the raw materials of the inner surface working layer according to the ratio, mixing water and organic binder evenly to obtain an organic binder solution, premixing the remaining materials evenly to obtain a premix, mixing the premix with the organic binder evenly, aging (also known as trapped material) for 24 hours, and passing through a 2-3 mesh sieve to obtain an inner surface working layer material body;

[0075] (2) Weighing the raw materials of the outer matrix layer according to the ratio, mixing water and the binder evenly to obtain a binder solution, premixing the remaining materials evenly, and then mixing them evenly with the binder solution, aging for 24 hours, and passing through a 2-3 mesh sieve to obtain the outer matrix layer material;

[0076] (3) The inner surface working layer material and the outer matrix layer material are added into the mold respectively, and the semi-finished product is obtained by pressing with a bidirectional 1500T hydraulic press, which is then dried at 80°C for 4h and sintered at 1350°C for 5h to obtain a refractory sagger.

[0077] Among them, the performance of the sagger is shown in Table 3.

[0078] The thermal shock test process is as follows: Figure 3 shown.

[0079] Life test such as Figure 4 .

[0080] Table 3

[0081]

[0082] It can be seen from Table 3 that the sagger described in the present invention has a low expansion coefficient and high thermal shock resistance and a long service life.

[0083] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A refractory sagger, characterized in that: The sagger comprises an inner surface working layer and an outer matrix layer from inside to outside; the thickness of the inner surface working layer is 1 to 3 mm; The inner surface working layer includes the following raw materials in parts by weight: 0-10 parts of kaolin, 0-50 parts of plate-like corundum, 0-50 parts of fused white corundum, 5-15 parts of activated alumina, 0-10 parts of zirconium mullite, 0-5 parts of organic binder, 0-10 parts of spodumene, 0-10 parts of cordierite, 20-80 parts of magnesium-rich spinel, 10-70 parts of fused magnesium-rich spinel, 0-10 parts of light magnesium carbonate, 0-10 parts of magnesite, 0-15 parts of fused zirconium oxide, 0-15 parts of zirconium oxide, 0-15 parts of yttrium-stabilized zirconium oxide, 0-15 parts of zircon, 0-15 parts of lanthanum oxide, 0-15 parts of cerium oxide, 0-15 parts of yttrium oxide, 0-15 parts of periclase, 0-15 parts of forsterite, 0-5 parts of feldspar, and 1-5 parts of water.

2. The refractory sagger according to claim 1, characterized in that: The invention comprises the following components in parts by weight: 5-7 parts of kaolin, 0-19 parts of plate-like corundum, 15-35 parts of fused white corundum, 6-12 parts of activated alumina, 0-8 parts of zirconium mullite, 1-4 parts of organic binder, 0-5 parts of spodumene, 0-2 parts of cordierite, 34-70 parts of magnesium-rich spinel, 0-8 parts of light magnesium carbonate, 3-10 parts of zirconium oxide, 0-4 parts of zircon, 0-3 parts of yttrium oxide, 0-1.5 parts of feldspar and 1-5 parts of water.

3. The refractory sagger according to claim 1, characterized in that: The fused white corundum is composed of 800 mesh fused white corundum and 200-325 mesh fused white corundum in a weight ratio of 1:(0.5-2).

4. The refractory sagger according to claim 1, characterized in that: The organic binder is at least one of sodium lignin sulfonate, calcium lignin sulfonate, peach gum, yellow dextrin, white dextrin, polyvinyl alcohol, polyethylene glycol, 801 glue powder, carboxymethyl cellulose, and hydroxypropyl methyl cellulose.

5. The refractory sagger according to claim 1, characterized in that: The outer matrix layer includes the following raw materials in parts by weight: 5 to 40 parts of M45 sintered mullite, 5 to 40 parts of M70 sintered mullite, 0 to 40 parts of roller stock, 10 to 20 parts of kaolin, 5 to 20 parts of α-alumina, 10 to 50 parts of cordierite, 1 to 10 parts of talc, 0 to 20 parts of magnesia aluminum spinel, 0 to 20 parts of andalusite, 0 to 15 parts of sillimanite, 0 to 15 parts of kyanite, 1 to 5 parts of binder, 1 to 5 parts of feldspar, 10 to 30 parts of fused quartz, and 1 to 5 parts of water.

6. The refractory sagger according to claim 1, characterized in that: The outer matrix layer includes the following raw materials in parts by weight: 0-13 parts of M70 sintered mullite, 10-21 parts of roller material, 13-16 parts of kaolin, 8-17 parts of α-alumina, 20-33 parts of cordierite, 1-2 parts of talc, 1-5 parts of binder, 2-5 parts of feldspar, 7-27 parts of fused quartz, and 1-5 parts of water.

7. The refractory sagger according to claim 5, characterized in that: The binder is at least one of sodium lignin sulfonate, calcium lignin sulfonate, peach gum, yellow dextrin, white dextrin, polyvinyl alcohol, polyethylene glycol, 801 glue powder, carboxymethyl cellulose, and hydroxypropyl methyl cellulose.

8. The method for preparing a refractory sagger according to any one of claims 1 to 7, characterized in that: The following steps are involved: (1) weighing the raw materials of the inner surface working layer according to the ratio, mixing water and an organic binder evenly to obtain an organic binder solution, premixing the remaining materials evenly to obtain a premix, mixing the premix with the organic binder evenly, aging, and passing through a 2-3 mesh sieve to obtain a material body of the inner surface working layer; (2) Weighing the raw materials of the outer matrix layer according to the ratio, mixing water and the binder evenly to obtain a binder solution, premixing the remaining materials evenly, and then mixing them evenly with the binder solution, aging, and passing through a 2-3 mesh sieve to obtain the outer matrix layer material; (3) Add the inner surface working layer material and the outer matrix layer material into the mold respectively, press, dry and sinter to obtain a refractory sagger.

9. The method for preparing a refractory sagger according to claim 8, characterized in that: The sintering temperature is 1300-1400° C., and the sintering time is 1-10 hours.

10. Use of the refractory sagger according to any one of claims 1 to 7 in the preparation of positive electrode materials.

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