Stable ionic sieve that is resistant to high temperatures and easy to store, and preparation method and usage method therefor and use thereof

Abstract

The present disclosure belongs to the technical field of ionic sieves for use in the field of the chemical strengthening of glass, and particularly relates to a stable ionic sieve that is resistant to high temperatures and easy to store, and a preparation method and usage method therefor and the use thereof. The ionic sieve comprises the following components at the following contents: 38.0-58.7 mol% of SiO2, 7.0-17.0 mol% of Al2O3, 34.0-45.0 mol% of Na2O, 0.1-3.0 mol% of K2O, 0.1-2.0 mol% of Y2O3, 0.1-3.0 mol% of B2O3, and 0.0-3.0 mol% of ZrO2. The ionic sieve in the present disclosure has good resistance to high temperatures and high humidity; after the ionic sieve is used to absorb lithium ions in a salt bath for a long time, the content of crystals in the ionic sieve is less than 10 wt%; and the ionic sieve is not prone to degrading from corrosion during storage and transportation.

Description

High-temperature-resistant and easy-to-store stable ion sieve, and preparation and use methods and applications thereof

[0001] Cross-reference to Related Applications

[0002] The present disclosure claims priority to Chinese Patent Application No. 202410409960.7, filed on April 7, 2024, entitled “High-temperature-resistant and easy-to-store stable ion sieve, and preparation and use methods and applications thereof,” the entire contents of which are incorporated herein by reference. TECHNICAL FIELD

[0003] The present disclosure belongs to the field of ion sieve technology for glass chemical strengthening, and specifically relates to a high-temperature-resistant and easy-to-store stable ion sieve, and preparation and use methods and applications thereof. BACKGROUND

[0004] As a protective glass for displays of portable terminals such as smartphones, a glass capable of withstanding drop strength is required, and a chemically strengthened glass having a high surface compressive stress value (CS) and a large depth of layer (DOL) is being actively developed.

[0005] In the glass processing industry, by immersing a chemically strengthened glass in a molten salt bath, alkali metal cations with a small ionic radius in the glass are replaced with alkali metal cations with a large ionic radius in the molten salt bath, thereby generating a compressive stress layer on the surface of the glass, and thus obtaining a chemically strengthened glass.

[0006] In industrialized continuous production, as ion exchange proceeds, the amount of ions with a large ionic radius in the molten salt bath decreases, and the amount of ions with a small ionic radius increases, so the number of uses of the molten salt bath is limited.

[0007] In order to increase the number of uses of the molten salt bath, i.e., in order to extend the life of the molten salt bath, ion impurity removal means is often used by the production plant to ensure that the concentration of impurity ions in the molten salt bath meets the requirements of the molten salt bath for glass strengthening.

[0008] Currently, the common impurity ion removal means in the industry mainly includes adding phosphate (sodium phosphate, potassium phosphate), ion sieve, etc. to the molten salt bath as a removal material or adsorption material for impurity ions in the molten salt bath. However, lithium phosphate can cause the molten salt bath to become turbid, and it needs to be clarified for a long time before it can be used, and some lithium phosphate particles will adhere to the surface of the strengthened glass, thereby causing defects in the glass. Thus, the effect of improving the life of the molten salt bath is limited, and the molten salt bath still needs to be replaced frequently in a short period of time, which is not conducive to mass production; at the same time, when the precipitated lithium phosphate is excessive at the bottom of the molten salt bath, it can reduce the effective working area of the molten salt bath and make it difficult to clean.

[0009] However, the ordinary silicon-based ion sieve will cause granular defects on the surface of the strengthened glass product after long-term use in the high-temperature molten salt bath, thereby affecting the surface quality of the product.

[0010] It should be noted that this part of the disclosure only provides background technology related to the disclosure, and does not necessarily constitute prior art or known technology.

[0011] SUMMARY

[0012] A high-temperature-resistant and easy-to-store stable ion sieve, according to the molar percentage, the ion sieve comprises the following components in the following amounts:

[0013] SiO2: 38.0 mol% to 58.7 mol%,

[0014] Al2O3: 7.0 mol% to 17.0 mol%,

[0015] Na2O: 34.0 mol% to 45.0 mol%,

[0016] K2O: 0.1 mol% to 3.0 mol%,

[0017] Y2O3: 0.1 mol% to 2.0 mol%,

[0018] B2O3: 0.1 mol% to 3.0 mol%,

[0019] ZrO2: 0.0 mol% to 3.0 mol%.

[0020] A preparation method of the high-temperature-resistant and easy-to-store stable ion sieve as described above, comprising the following steps: selecting raw material components according to the composition of the ion sieve, melting and forming, and then annealing to obtain the ion sieve.

[0021] A use method of the high-temperature-resistant and easy-to-store stable ion sieve as described above, comprising the following steps:

[0022] Step 1): providing a salt bath to be purified, the salt bath containing lithium ions; wherein the impurity ions are mainly lithium ions;

[0023] Step 2): adding the high-temperature-resistant and easy-to-store stable ion sieve to the salt bath to be purified;

[0024] Step 3): taking out after the high-temperature-resistant and easy-to-store stable ion sieve is reacted in the salt bath to be purified for the required time.

[0025] A chemical strengthening method of lithium-containing microcrystalline glass, comprising the following steps: adding the high-temperature-resistant and easy-to-store stable ion sieve as described above in the salt bath for chemical strengthening of the lithium-containing microcrystalline glass or adding the stable ion sieve prepared by the preparation method of the high-temperature-resistant and easy-to-store stable ion sieve as described above. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the present disclosure, and therefore should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can also be obtained without creative labor on the basis of these drawings.

[0027] FIG. 1 is an initial XRD pattern of the ion sieve corresponding to Example 1, Comparative Example 1, and Comparative Example 4, respectively.

[0028] FIG. 2 is an XRD pattern of the ion sieve corresponding to Example 1, Comparative Example 1, and Comparative Example 4, respectively, after absorbing lithium ions in a 480°C molten salt salt bath for 8h.

[0029] FIG. 3 is a standard example diagram of six different levels of high-temperature and high-humidity erosion resistance of the ion sieve. DETAILED DESCRIPTION

[0030] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The ranges or values should be construed to be approximations that can vary depending on the intended application. For numerical ranges, the endpoints are provided as a separate value from but are included in the range. For values that are less than one, one part per million, or one percent, the endpoints "0" and "one" are combined to form a range that includes values such as "0.1," "0.2," or "0.9."

[0031] Unless otherwise indicated, conventional methods or those described in the literature are employed in the examples. Unless otherwise indicated, the reagents or instruments used are conventional products available on the market.

[0032] In addition, it is worth noting that "and / or" disclosed in the present disclosure includes three cases, for example, A and / or B includes three cases of A alone, B alone, and A and B existing at the same time.

[0033] It is found through research that the ordinary silicon-based ion sieve will have a significant increase in crystal content when used in a high-temperature molten salt salt bath for a long time, which in turn causes a large amount of substances containing silicon components to enter the molten salt salt bath. The substances are easily bonded and crosslinked with the silicon dioxide components in the surface of the glass in the high-temperature molten salt salt bath, thereby causing granular defects to appear on the surface of the strengthened glass product, and further affecting the surface quality of the product.

[0034] In addition, it is found through research that the surface of ordinary silicate ion sieve is prone to corrosion during storage and transportation, especially in high-temperature and humid seasons, resulting in defects such as white spots or fog, thereby affecting the product quality of ion sieve and further affecting the surface quality of the product.

[0035] The purpose of the present disclosure is to overcome the defects of ordinary silicate ion sieve in the prior art, such as the appearance of granular defects on the surface of strengthened glass after long-term use in high-temperature molten salt bath, and the corrosion of ion sieve to produce white spots or fog due to poor resistance to high temperature and humidity. A high-temperature-resistant and easy-to-store stable ion sieve that can be used as a molten salt bath purification additive material, a preparation method, a use method and an application thereof are provided. The ion sieve has excellent high-temperature and high-humidity resistance. After long-term use in the salt bath and absorbing lithium ions, the content of crystals in the ion sieve is less than 10wt%, and the ion sieve is not prone to corrosion and deterioration during storage and transportation.

[0036] To achieve the above-mentioned purpose, in a first aspect, the present disclosure provides a high-temperature-resistant and easy-to-store stable ion sieve, which comprises the following components in a molar percentage:

[0037] SiO2: 38.0mol%-58.7mol%,

[0038] Al2O3: 7.0mol%-17.0mol%,

[0039] Na2O: 34.0mol%-45.0mol%,

[0040] K2O: 0.1mol%-3.0mol%,

[0041] Y2O3: 0.1mol%-2.0mol%,

[0042] B2O3: 0.1mol%-3.0mol%,

[0043] ZrO2: 0.0mol%-3.0mol%.

[0044] In one or more optional embodiments of the present disclosure, the ion sieve comprises, in a molar percentage:

[0045] SiO2: 39.0mol%-50.0mol%, and / or,

[0046] Al2O3: 7.0mol%-15.0mol%, preferably 8.0mol%-15.0mol%, and / or,

[0047] Na2O: 35.0mol%-43.0mol%, preferably 37.0mol%-43.0mol%, and / or,

[0048] K2O: 0.5-3.0 mol%, preferably 0.5-2.5 mol%, and / or,

[0049] Y2O3: 0.2-2.0 mol%, preferably 0.5-2.0 mol%.

[0050] In one or more optional embodiments of the present disclosure, in the ion sieve, in terms of mole percentage:

[0051] SiO2: 40.0-45.0 mol%, and / or,

[0052] Al2O3: 13.0-15.0 mol%, and / or,

[0053] Na2O: 40.0-43.0 mol%, and / or,

[0054] K2O: 0.5-2.0 mol%, preferably 0.5-1.0 mol%, and / or,

[0055] Y2O3: 0.5-1.0 mol%, and / or,

[0056] ZrO2: 0.0-2.5 mol%, preferably 0.5-2.5 mol%, more preferably 1.0-2.5 mol%, and / or,

[0057] B2O3: 0.5-1.0 mol%.

[0058] In one or more optional embodiments of the present disclosure, the ion sieve reaches level II or above in resistance to high-temperature and high-humidity erosion.

[0059] In one or more optional embodiments of the present disclosure, after the ion sieve is subjected to lithium ion absorption in a salt bath at a temperature of 350-550°C for 0.5-24 h, the content of crystals in the ion sieve is less than 10 wt%.

[0060] In one or more optional embodiments of the present disclosure, the lithium ion concentration of the salt bath is 50-400 ppm, preferably 50-350 ppm, more preferably 50-200 ppm.

[0061] In one or more optional embodiments of the present disclosure, the ion sieve reaches level I in resistance to high-temperature and high-humidity erosion.

[0062] In one or more optional embodiments of the present disclosure, the ion sieve has one or more of a granular shape, a sheet shape, a porous shape, and a plate shape.

[0063] In one or more optional embodiments of the present disclosure, when the ion sieve has a granular shape, the particle size is 0.5-2.0 mm.

[0064] In one or more optional embodiments of the present disclosure, when the ion sieve has a sheet shape, the size is 1.00-10.00 mm.

[0065] In one or more optional embodiments of the present disclosure, when the ion sieve has a porous shape, the pore size is 1.0-5.0 mm.

[0066] In one or more optional embodiments of the present disclosure, when the ion sieve has a plate shape, the thickness is 0.5-2.0 mm.

[0067] In one or more optional embodiments of the present disclosure, when the ion sieve has a plate shape, the thickness is 0.5-2.0 mm.

[0068] In one or more optional embodiments of the present disclosure, the ion sieve has one or more of a granular shape, a sheet shape, a porous shape, and a plate shape.

[0069] In one or more optional embodiments of the present disclosure, when the ion sieve has a granular shape, the particle size is 0.5-2.0 mm.

[0070] In one or more optional embodiments of the present disclosure, when the ion sieve has a sheet shape, the size is 1.00-10.00 mm.

[0071] In one or more optional embodiments of the present disclosure, when the ion sieve has a porous shape, the pore size is 1.0-5.0 mm.

[0072] In one or more optional embodiments of the present disclosure, when the ion sieve has a plate shape, the thickness is 0.5-2.0 mm. In the preparation method of the present disclosure, the melting temperature is 1300-1650°C, and the melting time is 1-24 h.

[0073] In the preparation method of the present disclosure, the annealing temperature is 400-450°C, and the annealing time is 12-24 h.

[0074] In one or more optional embodiments of the present disclosure, the ion sieve has one or more of a granular shape, a sheet shape, a porous shape, and a plate shape.

[0075] Step 1): providing a salt bath to be purified, wherein the salt bath contains lithium ions; wherein the impurity ions are mainly lithium ions;

[0076] Step 2): adding a high-temperature-resistant and easy-to-store stable ion sieve into the salt bath to be purified;

[0077] Step 3): taking out the high-temperature-resistant and easy-to-store stable ion sieve after the required time for the reaction of the high-temperature-resistant and easy-to-store stable ion sieve in the salt bath to be purified.

[0078] In the method for using the high-temperature-resistant and easy-to-store stable ion sieve according to the present disclosure, the concentration of the lithium ions in step 1) is 50-400 ppm; preferably 50-350 ppm, and more preferably 50-200 ppm.

[0079] In the method for using the high-temperature-resistant and easy-to-store stable ion sieve according to the present disclosure, the salt bath in step 1) further contains sodium salt and / or potassium salt; preferably NaNO3 and / or KNO3.

[0080] In the method for using the high-temperature-resistant and easy-to-store stable ion sieve according to the present disclosure, the temperature of the salt bath in step 1) is 350-550°C; preferably 380-530°C; and more preferably 380-500°C.

[0081] In one or more optional embodiments of the present disclosure, the concentrations of NaNO3 and KNO3 in the salt bath can be balanced according to the composition of the glass material for ion exchange.

[0082] In one or more optional embodiments of the present disclosure, the glass material comprises lithium-containing microcrystalline glass, lithium-aluminum-silicon glass.

[0083] In one or more optional embodiments of the present disclosure, the crystalline phase of the lithium-containing microcrystalline glass comprises one or more of petalite, lithium disilicate, lithium monosilicate, and eucryptite.

[0084] In the method for using the high-temperature-resistant and easy-to-store stable ion sieve according to the present disclosure, the amount of the ion sieve added in step 2) is 0.50-5.00 wt% of the mass of the salt bath to be purified; preferably 1.00-5.00 wt% of the mass of the salt bath to be purified.

[0085] In the method for using the high-temperature-resistant and easy-to-store stable ion sieve according to the present disclosure, the reaction time of the ion sieve in the salt bath to be purified in step 3) is 3-24 h; preferably 6-24 h; and more preferably 8-16 h.

[0086] In the method for using the high-temperature-resistant and easy-to-store stable ion sieve according to the present disclosure, when the lithium ion concentration of the salt bath to be purified is 50-400 ppm, the addition amount of the ion sieve is 0.50wt%-5.00wt% of the mass of the salt bath to be purified, and after the reaction in the salt bath to be purified for 3-24 hours, the absorption efficiency of the ion sieve is 50%-95%; preferably, the absorption efficiency of the ion sieve is 53%-95%.

[0087] In a fourth aspect, the present disclosure further provides a chemical strengthening method of lithium-containing microcrystalline glass, comprising the following steps: adding the high-temperature-resistant and easy-to-store stable ion sieve according to the present disclosure or the stable ion sieve prepared by the preparation method of the high-temperature-resistant and easy-to-store stable ion sieve according to the present disclosure into a salt bath for chemical strengthening of the lithium-containing microcrystalline glass.

[0088] The embodiments of the present disclosure can achieve the following beneficial effects.

[0089] The present disclosure can improve the high-temperature and high-humidity corrosion resistance of the ion sieve by adding Y2O3 and / or ZrO2 in a suitable range in the specific components of the ion sieve, and by adjusting the composition of the ion sieve in a respective specific suitable range, the ion sieve has excellent high-temperature and high-humidity corrosion resistance, reaching level II or above, meeting the storage performance requirements of the ion sieve; the surface of the ion sieve is not easily corroded, and the generation of white spots or fog-like defects is reduced; the quality is stable during storage and transportation in the high-temperature and humid season, and the influence of harsh environment on the performance of the ion sieve is reduced.

[0090] The present disclosure adjusts the composition of the ion sieve to ensure that the content of crystals in the ion sieve is less than 10wt% after the ion sieve continuously absorbs lithium ions in a high-temperature salt bath for a long time, the change is small, and the ion sieve has thermal stability; further, no substances containing silicon components are generated, thereby affecting the surface quality of the product; it is beneficial to increase the number of uses of the molten salt bath and prolong the service life of the molten salt bath.

[0091] The ion sieve prepared by the present disclosure has a high adsorption efficiency for lithium ions during long-term continuous lithium ion absorption in a high-temperature salt bath, which can ensure that the concentration of lithium ions in the salt bath during glass strengthening process remains within a reasonable range.

[0092] In a first aspect, the present disclosure provides a high-temperature-resistant and easy-to-store stable ion sieve, which comprises the following components in a molar percentage:

[0093] SiO2: 38.0mol%-58.7mol%,

[0094] Al2O3: 7.0mol%-17.0mol%,

[0095] Na2O: 34.0mol%-45.0mol%,

[0096] K2O: 0.1 mol% - 3.0 mol%,

[0097] Y2O3: 0.1 mol% - 2.0 mol%,

[0098] B2O3: 0.1 mol% - 3.0 mol%,

[0099] ZrO2: 0.0 mol% - 3.0 mol%.

[0100] In the components of the ion sieves described in the present disclosure:

[0101] SiO2, as a network former oxide of glass, serves to form the backbone of the covalently bonded constituent ion sieve network structure. In some embodiments, SiO2is present in an amount of 38.0 mol% - 58.7 mol%, preferably 39.0 mol% - 50.0 mol%, further preferably 40.0 mol% - 50.0 mol%, further preferably 40.0 mol% - 45.0 mol%, calculated as a mole percent.

[0102] In one or more alternative embodiments, the ion sieves can comprise, but are not limited to, 38.0 mol% - 58.7 mol%, 38.0 mol% - 55.0 mol%, 38.0 mol% - 50.0 mol%, 40.0 mol% - 50.0 mol%, 42.0 mol% - 50.0 mol%, 42.0 mol% - 55.0 mol%, 50.0 mol% - 55.0 mol% of SiO2, calculated as a mole percent. In some embodiments, the ion sieves can comprise, but are not limited to, 38.0 mol%, 39.0 mol%, 40.0 mol%, 41.0 mol%, 42.0 mol%, 43.0 mol%, 44.0 mol%, 45.0 mol%, 46.0 mol%, 47.0 mol%, 50.0 mol%, 53.0 mol%, 55.0 mol%, 58.0 mol%, or 58.7 mol% of SiO2, or a range of values between any two of the foregoing specifically named values, as long as the ion sieves of the present disclosure provide the desired properties. It is to be understood that any of the foregoing ranges can be combined with any of the other ranges, as long as the ion sieves of the present disclosure provide the desired properties.

[0103] Al2O3 is a network architecture component and is beneficial to enhance the lithium ion absorption rate during the process of lithium ion absorption by the ion sieve. However, too much alumina can cause difficulty in forming the ion sieve. In one or more alternative embodiments, the content of Al2O3 is 7.0-17.0 mol%, preferably 7.0-15.0 mol%, more preferably 8.0-15.0 mol%, further preferably 13.0-15.0 mol%, calculated in terms of mole percentage.

[0104] In one or more alternative embodiments, the ion sieve can contain, but is not limited to, 7.0-17.0 mol%, 9.0-17.0 mol%, 10.0-17.0 mol%, 12.0-17.0 mol%, 15.0-17.0 mol%, 7.0-15.0 mol%, 7.0-12.0 mol%, 7.0-10.0 mol%, or 8.0-14.0 mol% of Al2O3, calculated in terms of mole percentage. In some embodiments, the ion sieve can contain, but is not limited to, 7.0 mol%, 8.0 mol%, 9.0 mol%, 10.0 mol%, 11.0 mol%, 12.0 mol%, 13.0 mol%, 14.0 mol%, 15.0 mol%, 16.0 mol%, or 17.0 mol% of Al2O3, or Al2O3 within a numerical range formed by any two of the aforementioned specific numerical values as endpoints, as long as an ion sieve with the required performance of the present disclosure can be obtained. It should be understood that in specific embodiments, any of the aforementioned ranges can be combined with any other range, as long as an ion sieve with the required performance of the present disclosure can be obtained.

[0105] Na2O is an extra-network oxide for glass formation, and its content directly affects the ability of the ion sieve to absorb lithium ions. In one or more alternative embodiments, the content of Na2O in the ion sieve is 34.0-45.0 mol%, preferably 35.0-43.0 mol%, further preferably 37.0-43.0 mol%, further preferably 40.0-43.0 mol%, calculated in terms of mole percentage.

[0106] In one or more alternative embodiments, the ion sieve can comprise, in terms of mole percent, 34.0 mol% to 45.0 mol%, 35.0 mol% to 45.0 mol%, 38.0 mol% to 45.0 mol%, 40.0 mol% to 45.0 mol%, 42.0 mol% to 45.0 mol% Na20. In one or more alternative embodiments, the ion sieve can comprise, in terms of mole percent, 34.0 mol%, 35.0 mol%, 37.0 mol%, 39.0 mol%, 40.0 mol%, 41.0 mol%, 42.0 mol%, 43.0 mol%, 44.0 mol%, or 45.0 mol% Na20, or a range of Na20 between any two of the foregoing specific values as endpoints, as long as the ion sieve has the desired properties for the present disclosure. It should be understood that any of the foregoing ranges can be combined with any other range, as long as the ion sieve has the desired properties for the present disclosure.

[0107] K20 can assist Na20 in adsorbing lithium ions in the salt bath. In one or more alternative embodiments, the ion sieve can comprise, in terms of mole percent, 0.1 mol% to 3.0 mol%, preferably 0.5 mol% to 3.0 mol%, more preferably 0.5 mol% to 2.5 mol%, further preferably 0.5 mol% to 2.0 mol%, further preferably 0.5 mol% to 1.0 mol% K20.

[0108] In one or more alternative embodiments, the ion sieve can comprise, but is not limited to, 0.1-3.0 mol%, 0.1-2.5 mol%, 0.1-2.0 mol%, 0.1-1.6 mol%, 0.1-1.0 mol%, 0.5-1.6 mol%, 0.5-2.6 mol%, 0.5-1.0 mol%, 0.1-0.5 mol%, 1.2-1.6 mol%, 1.2-3.0 mol%, or 1.0-2.0 mol% of K2O, calculated as a mole percentage. In one or more alternative embodiments, the ion sieve can comprise, but is not limited to, 0.1 mol%, 0.3 mol%, 0.5 mol%, 0.7 mol%, 0.8 mol%, 0.9 mol%, 1.0 mol%, 1.1 mol%, 1.2 mol%, 1.3 mol%, 1.4 mol%, 1.5 mol%, 1.6 mol%, 1.8 mol%, 2.0 mol%, 2.5 mol%, 2.8 mol%, or 3.0 mol% of K2O, or K2O within a range of any two of the foregoing specific numerical values as endpoints, calculated as a mole percentage, as long as an ion sieve with the desired properties of the present disclosure is obtained. It should be understood that in a particular embodiment, any of the foregoing ranges can be combined with any other range, as long as an ion sieve with the desired properties of the present disclosure is obtained.

[0109] Y2O3 can improve the high temperature and high humidity erosion resistance of the ion sieve, and can also improve the viscosity of the ion sieve, but too much will make it difficult to shape when the ion sieve is melted. In one or more alternative embodiments, the content of Y2O3 is 0.1-2.0 mol%, preferably 0.2-2.0 mol%, preferably 0.5-2.0 mol%, more preferably 0.5-1.0 mol%, calculated as a mole percentage.

[0110] In one or more alternative embodiments, the ion sieve can comprise, but is not limited to, 0.1 mol% to 2.0 mol%, 0.1 mol% to 1.6 mol%, 0.1 mol% to 1.0 mol%, 0.5 mol% to 1.6 mol%, 0.5 mol% to 2.0 mol%, 0.5 mol% to 1.0 mol%, 0.1 mol% to 0.5 mol%, 1.2 mol% to 1.6 mol%, 1.2 mol% to 2.0 mol%, or 1.0 mol% to 2.0 mol% of Y2O3, by mole percent. In one or more alternative embodiments, the ion sieve can comprise, but is not limited to, 0.1 mol%, 0.3 mol%, 0.5 mol%, 0.7 mol%, 0.8 mol%, 0.9 mol%, 1.0 mol%, 1.1 mol%, 1.2 mol%, 1.3 mol%, 1.4 mol%, 1.5 mol%, 1.6 mol%, 1.8 mol%, or 2.0 mol% of Y2O3, or Y2O3 within a range of any two of the foregoing specific values as endpoints, as long as the ion sieve has the desired properties of the present disclosure. It is understood that in specific embodiments, any of the foregoing ranges can be combined with any of the other ranges, as long as the ion sieve has the desired properties of the present disclosure.

[0111] ZrO2can improve the high temperature and high humidity corrosion resistance of the ion sieve, but it also plays a nucleation role, and too much will make the ion sieve tend to nucleate and crystallize. In some alternative embodiments, the content of ZrO2is 0.0 mol% to 3.0 mol%, preferably 0.5 mol% to 3.0 mol%, or preferably 0.0 mol% to 2.5 mol%, further preferably 0.5-2.5 mol%, more preferably 1.0-2.5 mol%, by mole percent.

[0112] In some alternative embodiments, the ion exchange resin can comprise, but not limited to, 0.0-3.0 mol%, 0.1-3.0 mol%, 0.1-2.5 mol%, 0.1-2.0 mol%, 0.1-1.6 mol%, 0.1-1.0 mol%, 0.5-1.6 mol%, 0.5-2.6 mol%, 0.5-1.0 mol%, 0.1-0.5 mol%, 1.2-1.6 mol%, 1.2-3.0 mol%, or 1.0-2.0 mol% of Zr02, in terms of mole percentage. In some alternative embodiments, the ion exchange resin can comprise, but not limited to, 0.0 mol%, 0.1 mol%, 0.3 mol%, 0.5 mol%, 0.7 mol%, 0.8 mol%, 0.9 mol%, 1.0 mol%, 1.1 mol%, 1.2 mol%, 1.3 mol%, 1.4 mol%, 1.5 mol%, 1.6 mol%, 1.8 mol%, 2.0 mol%, 2.5 mol%, 2.8 mol%, or 3.0 mol% of Zr02, or within any two of the foregoing specific values, in terms of mole percentage, as long as the ion exchange resin with desired properties of the present disclosure is obtained. It should be understood that any of the foregoing ranges can be combined with any other range, as long as the ion exchange resin with desired properties of the present disclosure is obtained.

[0113] B2O3 can reduce the high temperature melt viscosity, improve the melting characteristics of the ion exchange resin, and can reduce the micro-cracks of the ion exchange resin during rapid cooling, but too much boron oxide can deteriorate the storage properties of the ion exchange resin. In some embodiments, the B2O3 content is 0.1-3.0 mol%, preferably 0.5-1.0 mol%, in terms of mole percentage.

[0114] In one or more alternative embodiments, the ion sieve can comprise, but is not limited to, 0.1-3.0 mol%, 0.1-2.5 mol%, 0.1-2.0 mol%, 0.1-1.6 mol%, 0.1-1.0 mol%, 0.5-1.6 mol%, 0.5-2.6 mol%, 0.5-1.0 mol%, 0.1-0.5 mol%, 1.2-1.6 mol%, 1.2-3.0 mol%, or 1.0-2.0 mol% B203, calculated as a mole percent. In some alternative embodiments, the ion sieve can comprise, but is not limited to, 0.1 mol%, 0.3 mol%, 0.5 mol%, 0.7 mol%, 0.8 mol%, 0.9 mol%, 1.0 mol%, 1.1 mol%, 1.2 mol%, 1.3 mol%, 1.4 mol%, 1.5 mol%, 1.6 mol%, 1.8 mol%, 2.0 mol%, 2.5 mol%, 2.8 mol%, or 3.0 mol% B203, or a range of values between any two of the foregoing specifically stated values, as the end points of a range, provided that an ion sieve having the desired properties of the present disclosure is obtained. It will be appreciated that in a particular embodiment, any of the above ranges can be combined with any other range, provided that an ion sieve having the desired properties of the present disclosure is obtained.

[0115] In one or more optional embodiments, the content of crystals in the ion sieve is less than 10 wt% after the lithium ion absorption in the salt bath. The temperature of the salt bath is 350-550 °C, the time of the lithium ion absorption is 0.5-24 h, and the concentration of lithium ions in the salt bath is 50-400 ppm. In one or more optional embodiments, the temperature of the salt bath can be, but is not limited to, 350 °C, 360 °C, 370 °C, 380 °C, 400 °C, 410 °C, 420 °C, 430 °C, 440 °C, 450 °C, 460 °C, 470 °C, 480 °C, 490 °C, 500 °C, 510 °C, 520 °C, 530 °C, 540 °C, 550 °C, or a value within a range formed by any two of the above values as endpoints. In one or more optional embodiments, the time of the lithium ion absorption can be, but is not limited to, 0.5 h, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 12 h, 16 h, 14 h, 18 h, 20 h, 22 h, 24 h, or a value within a range formed by any two of the above values as endpoints. In one or more optional embodiments, the concentration of lithium ions in the salt bath can be, but is not limited to, 50 ppm, 60 ppm, 70 ppm, 80 ppm, 90 ppm, 100 ppm, 120 ppm, 140 ppm, 150 ppm, 160 ppm, 170 ppm, 180 ppm, 190 ppm, 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, or a value within a range formed by any two of the above values as endpoints. It should be understood that in specific embodiments, any of the above ranges can be combined with any other range, as long as an ion sieve with the desired performance of the present disclosure is obtained. The present disclosure does not have a particular limitation on the type of the salt bath, as long as it contains lithium ions, and the impurity ions therein are mainly lithium ions; for example, it can be a salt bath containing NaNCb, a salt bath containing KNCb, or a mixed salt bath containing NaNCb and KNCb.

[0116] In one or more optional embodiments, the ion exchange resin achieves a rating of Class II or higher in resistance to high temperature and high humidity erosion. In some embodiments, the ion exchange resin achieves a rating of Class I in resistance to high temperature and high humidity erosion. In the present disclosure, the resistance to high temperature and high humidity erosion test is as follows: a plate-shaped ion exchange resin having a polished surface with a surface area of 50 mm x 50 mm is placed in a temperature and humidity alternating test chamber at a temperature of 85°C and a relative humidity of 85% for 48 hours, then taken out and the state of the surface of the ion exchange resin is observed; and the judgment is made according to the resistance to high temperature and high humidity erosion standard shown in Table 1. The temperature and humidity alternating test chamber is not particularly limited, as long as it can be used for double 85 test, such as QTH-80C and the like. The plate-shaped ion exchange resin does not have a particular thickness requirement, and can be, but is not limited to, 0.50-2.00 mm; for example, 0.50 mm, 0.60 mm, 0.70 mm, 0.80 mm, 0.90 mm, 1.00 mm, 1.10 mm, 1.20 mm, 1.30 mm, 1.40 mm, 1.50 mm, 1.60 mm, 1.70 mm, 1.80 mm, 1.90 mm, 2.00 mm, or a value within a range formed by any two of the above values as endpoints. It should be understood that in specific embodiments, any of the above ranges can be combined with any other range, as long as the ion exchange resin with the required performance of the present disclosure can be obtained.

[0117] In one or more optional embodiments, the ion exchange resin has one or more of a granular shape, a sheet shape, a porous shape, and a plate shape.

[0118] In one or more optional embodiments, when the ion exchange resin has a granular shape, the particle size is 0.50-2.00 mm, for example, can be, but is not limited to, 0.50 mm, 0.60 mm, 0.70 mm, 0.80 mm, 0.90 mm, 1.00 mm, 1.10 mm, 1.20 mm, 1.30 mm, 1.40 mm, 1.50 mm, 1.60 mm, 1.70 mm, 1.80 mm, 1.90 mm, 2.00 mm, or a value within a range formed by any two of the above values as endpoints. It should be understood that in specific embodiments, any of the above ranges can be combined with any other range, as long as the ion exchange resin with the required performance of the present disclosure can be obtained.

[0119] Preferably, when the ion sieve is in the shape of a sheet, its size is 1.00-10.00 mm, for example, but not limited to, 1.00 mm, 1.50 mm, 2.00 mm, 2.50 mm, 3.00 mm, 3.50 mm, 4.00 mm, 5.00 mm, 6.00 mm, 7.00 mm, 8.00 mm, 9.00 mm, 10.00 mm, or a value within a range formed by any two of the above values as endpoints. It should be understood that in specific embodiments, any of the above ranges can be combined with any other range, as long as the ion sieve with the desired performance of the present disclosure can be obtained.

[0120] Further preferably, when the ion sieve is in the shape of a porous shape, its pore size is 1.00-5.00 mm, for example, but not limited to, 1.00 mm, 1.50 mm, 2.00 mm, 2.50 mm, 3.00 mm, 3.50 mm, 4.00 mm, 5.00 mm, or a value within a range formed by any two of the above values as endpoints. It should be understood that in specific embodiments, any of the above ranges can be combined with any other range, as long as the ion sieve with the desired performance of the present disclosure can be obtained.

[0121] More preferably, when the ion sieve is in the shape of a plate, its thickness is 0.50-2.00 mm, for example, but not limited to, 0.50 mm, 0.60 mm, 0.70 mm, 0.80 mm, 0.90 mm, 1.00 mm, 1.10 mm, 1.20 mm, 1.30 mm, 1.40 mm, 1.50 mm, 1.60 mm, 1.70 mm, 1.80 mm, 1.90 mm, 2.00 mm, or a value within a range formed by any two of the above values as endpoints. It should be understood that in specific embodiments, any of the above ranges can be combined with any other range, as long as the ion sieve with the desired performance of the present disclosure can be obtained. In the present disclosure, when the ion sieve is in the shape of a plate, there is no specific limit to its surface area, which can be selected according to actual use needs, for example, it can be 50 mm x 50 mm, 50 mm x 70 mm, etc. In some embodiments, the ion sieve in the present disclosure can contain a polished surface or not, as long as the ion sieve with the desired performance of the present disclosure can be obtained.

[0122] In a second aspect, the present disclosure provides a method for preparing the high-temperature-resistant and easy-to-store stable ion sieve, comprising: selecting raw material components according to the composition of the high-temperature-resistant and easy-to-store stable ion sieve, mixing, melting and forming, and then annealing to obtain the ion sieve.

[0123] The molding method is not particularly limited in the present disclosure, for example, the molten liquid can be injected into a mold or a platform of cast iron for molding. After the annealing treatment of the present disclosure, post-treatment such as cutting and polishing can be performed to process the ion sieve into a shape common in the field, for example, one or more of granular, flaky, porous, and plate-like. The size of the shape of the ion sieve processed in the present disclosure is not particularly limited, for example, the size of the cutting can be 50 mm x 50 mm x 0.7 mm.

[0124] In the method for preparing the ion sieve of the present disclosure, the melting temperature is 1300℃-1650℃, and the melting time is 1h-24h. In the method for preparing the ion sieve of the present disclosure, the melting temperature can be 1300℃, 1350℃, 1400℃, 1450℃, 1500℃, 1550℃, 1600℃, 1650℃, or a value within a range formed by any two of the above values as endpoints. In the method for preparing the ion sieve of the present disclosure, the melting time can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 12h, 15h, 17h, 20h, 21h, 24h, or a value within a range formed by any two of the above values as endpoints.

[0125] In the method for preparing the ion sieve of the present disclosure, the annealing treatment temperature is 400℃-450℃, and the annealing treatment time is 12h-24h. In the method for preparing the ion sieve of the present disclosure, the annealing treatment temperature can be 400℃, 410℃, 420℃, 430℃, 440℃, 450℃, or a value within a range formed by any two of the above values as endpoints. In the method for preparing the ion sieve of the present disclosure, the annealing treatment time can be 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, or a value within a range formed by any two of the above values as endpoints. It should be understood that in the specific embodiments, any of the above ranges can be combined with any other range, as long as an ion sieve with the desired performance of the present disclosure can be obtained.

[0126] In a third aspect, the present disclosure also provides a method for using the high-temperature-resistant and easy-to-store stable ion sieve as described above or prepared by the method for preparing the ion sieve described above, comprising the following steps:

[0127] Step 1): providing a salt bath to be purified, wherein the salt bath contains lithium ions; wherein the impurity ions are mainly lithium ions;

[0128] Step 2): adding the high-temperature-resistant and easy-to-store stable ion sieve to the salt bath to be purified;

[0129] Step 3): The high-temperature-resistant and easy-to-store stable ion-sieve is taken out after the required time in the salt bath to be purified.

[0130] In the method of using the high-temperature-resistant and easy-to-store stable ion-sieve of the present disclosure, the concentration of lithium ions in step 1) is 50-400 ppm; preferably 50-200 ppm; more preferably 50-100 ppm, for example, the concentration of lithium ions can be but not limited to 50 ppm, 60 ppm, 70 ppm, 80 ppm, 90 ppm, 100 ppm, 120 ppm, 140 ppm, 150 ppm, 160 ppm, 170 ppm, 180 ppm, 190 ppm, 200 ppm, 300 ppm, 400 ppm, etc., and all ranges and sub-ranges between the above-mentioned values. It should be understood that in specific embodiments, any of the above-mentioned ranges can be combined with any other range, as long as an ion-sieve with the required performance of the present disclosure can be obtained.

[0131] In the method of using the high-temperature-resistant and easy-to-store stable ion-sieve of the present disclosure, the salt bath in step 1) also contains sodium and / or potassium salts; preferably NaNO3 and / or KNO3. In some embodiments, the salt bath can contain a combination of NaNO3 and KNO3, or it can be NaNO3 or KNO3 alone. Among them, the combination of NaNO3 and KNO3 can be selected according to the required application, and the concentration of NaNO3 and KNO3 in the salt bath can be balanced according to the composition of the glass material for ion exchange, thereby providing sufficient CS and DOL for the glass material; the glass material includes lithium-containing microcrystalline glass, lithium-aluminum-silicon glass; further, the crystalline phase of the lithium-containing microcrystalline glass includes one or more of petalite, lithium disilicate, lithium monosilicate, and eucryptite.

[0132] In the method of using the high-temperature-resistant and easy-to-store stable ion-sieve of the present disclosure, the temperature of the salt bath in step 1) is 350-550°C; preferably 380-530°C; more preferably 380-500°C, for example, the temperature of the salt bath can be but not limited to 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, etc., or a value within a range formed by any two of the above-mentioned values as endpoints. It should be understood that in specific embodiments, any of the above-mentioned ranges can be combined with any other range, as long as an ion-sieve with the required performance of the present disclosure can be obtained.

[0133] In the method of using the high-temperature-resistant and easily-stored stable ion sieve of the present disclosure, the amount of ion sieve added in step 2) is 0.50wt%-5.00wt% of the mass of the salt bath to be purified; preferably 1.00wt%-5.00wt% of the mass of the salt bath to be purified, for example, the amount of ion sieve added can be 0.50wt%, 0.60wt%, 0.70wt%, 0.80wt%, 0.90wt%, 1.00wt%, 1.30wt%, 1.50wt%, 1.60wt%, 1.80wt%, 2.00wt%, 2.30wt%, 2.50wt%, 2.70wt%, 3.00wt%, 3.50wt%, 4.00wt%, 4.50wt%, 5.00wt% of the mass of the salt bath to be purified, or a value within a range formed by any two of the above values as endpoints. It should be understood that in specific embodiments, any of the above ranges can be combined with any other range, as long as the ion sieve with the desired performance of the present disclosure can be obtained.

[0134] In the method of using the high-temperature-resistant and easily-stored stable ion sieve of the present disclosure, the reaction time of the ion sieve in the salt bath to be purified in step 3) is 3-24h; preferably 6-24h; more preferably 8-16h, for example, the reaction time of the ion sieve in the salt bath to be purified can be but not limited to 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 12h, 14h, 16h, 18h, 20h, 21h, 22h, 23h, 24h, or a value within a range formed by any two of the above values as endpoints. It should be understood that in specific embodiments, any of the above ranges can be combined with any other range, as long as the ion sieve with the desired performance of the present disclosure can be obtained.

[0135] In the method of using the high-temperature-resistant and easily-stored stable ion sieve of the present disclosure, when the lithium ion concentration of the salt bath to be purified is 50-400ppm, the amount of ion sieve added is 0.50wt%-5.00wt% of the mass of the salt bath to be purified, and after the reaction time of 3-24h in the salt bath to be purified, the absorption efficiency of the ion sieve is 50%-95%; preferably the absorption efficiency of the ion sieve is 53%-95%, for example, the absorption rate of the ion sieve can be but not limited to 50%, 53%, 56%, 58%, 60%, 65%, 70%, 75%, 78%, 80%, 88%, 90%, 95%, etc., and all ranges and sub-ranges between the above values; it should be understood that in embodiments, any of the above ranges can be combined with any other range.

[0136] In a fourth aspect, the present disclosure also provides a chemical strengthening method of lithium-containing microcrystalline glass, which comprises the following steps: adding the high-temperature-resistant and easy-to-store stable ion sieve or the ion sieve prepared by the above-mentioned method for preparing the high-temperature-resistant and easy-to-store stable ion sieve into a salt bath for chemical strengthening of the lithium-containing microcrystalline glass.

[0137] The related measurement method involved in the present disclosure is explained as follows:

[0138] 1. Stability determination of ion sieve: compare the crystal content in the ion sieve after absorbing lithium ions in the salt bath containing lithium ions for a long time with the crystal content in the ion sieve before absorbing lithium ions. If the crystal content in the ion sieve after absorbing lithium ions is less than 10 wt%, the ion sieve is considered stable; otherwise, if the crystal content in the ion sieve after absorbing lithium ions is greater than 10 wt%, the ion sieve is considered unstable.

[0139] The crystal content of the specific ion sieve is tested by XRD. The test method of XRD is as follows: the initial ion sieve and the ion sieve obtained after reacting in the molten salt salt bath for a certain time are ground into fine powder by a powder mill so that the particle size is less than 75 μm, and then the X-ray diffractometer is used for testing to obtain the XRD diffraction peak curve. The XRD diffraction data are analyzed by using JADE software, and then the crystal content of the ion sieve is analyzed.

[0140] The X-ray diffractometer (Shimadzu XRD_6100) used in the present disclosure has a test incident angle range of 2θ = 10-80°, a scanning speed of 6° / min, a working voltage of 40KV, and a working current of 30mA.

[0141] 2. Test method of lithium ion absorption rate:

[0142] The concentration of lithium ions in the initial molten salt salt bath is detected by using an atomic absorption spectrophotometer and is recorded as C1; after the ion sieve is added into the molten salt salt bath to absorb lithium ions, the concentration of lithium ions in the molten salt salt bath after absorbing lithium ions is detected by using an atomic absorption spectrophotometer and is recorded as C2.

[0143] The specific test method of the concentration of lithium ions in the molten salt salt bath is as follows: take an appropriate amount of molten salt salt bath to be tested for lithium ion concentration, accurately weigh 0.25 g of the cooled solid molten salt salt bath in a 100 ml glass beaker, dissolve with an appropriate amount of deionized water, filter with slow filter paper into a 100 mL volumetric flask, add 1 mL of 18 wt% hydrochloric acid aqueous solution to the volumetric flask, and then add deionized water to the volumetric flask, shake well, and then test the concentration of lithium ions in the molten salt salt bath by using the corresponding standard curve by using an atomic absorption spectrophotometer (AA-6880).

[0144] 3. High temperature and high humidity erosion resistance test: the ion exchange resin with a size of 50mm x 50mm x 0.7mm containing a polished surface was placed in a temperature and humidity alternating test chamber (QTH-80C) at a temperature of 85°C and a relative humidity of 85% for 48h, then taken out, the surface state of the ion exchange resin was observed, and the level of the ion exchange resin resistance to high temperature and high humidity erosion was judged according to the different grade standards in Table 1. The example diagram of each grade in Table 1 is shown in Figure 3.

[0145] Table 1

[0146] The following detailed description of the embodiments of the present disclosure is exemplary and is only used to explain the present disclosure, and cannot be understood as a limitation of the present disclosure.

[0147] Example 1

[0148] The raw material components of Example 1 were mixed according to Table 2, the total mass of the above raw material components was 1kg, then melted at 1450°C for 5h to form a liquid precursor; the above liquid precursor was injected into a mold for molding, then annealed, and then cut and polished to obtain an ion exchange resin with a size of 50mm x 50mm x 0.7mm containing a polished surface; the annealing temperature was 400°C, and the annealing time was 14h.

[0149] The above obtained plate-shaped ion exchange resins were subjected to high temperature and high humidity erosion resistance test, and the results are shown in Table 2.

[0150] In addition, the obtained plate-shaped ion exchange resins were added to a salt bath to be purified, the addition amount of the plate-shaped ion exchange resins was 1.0wt% of the mass of the salt bath to be purified, the salt bath was a salt bath of 700g KNO3, 300g NaNO3 and 1g LiNO3, and the concentration of lithium ions was about 100ppm; after reaction at 480°C for 8h, it was taken out. And the stability and absorption rate of lithium ions of the ion exchange resins were tested respectively; the results are shown in Table 2.

[0151] Examples 2-7

[0152] Respectively according to the method of Example 1, except that the composition of the ion exchange resin was different, as shown in Table 2; and the corresponding test was carried out, and the results are shown in Table 2.

[0153] Comparative Examples 1-5

[0154] According to the method of Example 1, except that the composition of the ion exchange resin was different, as shown in Table 3; and the corresponding test was carried out, and the results are shown in Table 3.

[0155] In addition, the plate-shaped ion sieve prepared in Example 2 was subjected to the high-temperature and high-humidity erosion test, and then was subjected to the same use process as that in Example 2, and the stability and the lithium ion absorption rate of the ion sieve were tested; the results are shown in Table 4.

[0156] Table 2. Ion sieve composition, lithium ion absorption rate, stability and high-temperature and high-humidity erosion resistance of Examples 1-7

[0157] Table 3. Ion sieve composition, lithium ion absorption rate, stability and high-temperature and high-humidity erosion resistance of Comparative Examples 1-5

[0158] Table 4. Lithium ion absorption rate and stability of Example 2 before and after the high-temperature and high-humidity erosion test

[0159] Note: The ion sieve of Example 2 before and after the high-temperature and high-humidity erosion test was subjected to the stability judgment as described above, respectively.

[0160] (1) The ion sieve prepared by the examples of the present disclosure is compared with the ion sieve prepared by the comparative examples. The ion sieve prepared by the examples has a high-temperature and high-humidity erosion resistance of grade II or above, and the content of crystals in the ion sieve is less than 10 wt% after continuously absorbing lithium ions in a high-temperature salt bath; has good storage resistance and high-temperature stability; and has a high lithium ion absorption efficiency of more than 50%. In addition, it can be proved from FIG. 1 and FIG. 2 that the ion sieve of Example 1 is very stable, while the content of crystals in the ion sieve of Comparative Example 4 is 72.73 wt% after absorbing lithium ions, which is unstable.

[0161] (2) By comparing Example 3 and Comparative Example 1, it can be known that the ion sieve of Comparative Example 1 does not add Y2O3, and has a high-temperature and high-humidity erosion resistance of grade III, and the surface of the ion sieve has been eroded very obviously, which indicates that the ion sieve of Comparative Example 1 is difficult to resist the erosion of the ion sieve in a high-temperature and humid environment, and cannot be stored and transported for a long time.

[0162] (3) By comparing the ion sieve of the examples with the ion sieves of Comparative Examples 2 and 4, it can be known that when the composition of the ion sieve is not within the range of the present disclosure, the stability and the high-temperature and high-humidity erosion resistance of the ion sieve are obviously deteriorated.

[0163] (4) It can be known from Comparative Example 5 that adding excessive B2O3 can obviously reduce the high-temperature and high-humidity erosion resistance of the ion sieve.

[0164] The preferred embodiments of the present disclosure are described in detail above, but the present disclosure is not limited thereto. Within the technical concept of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure, including various technical features being combined in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present disclosure and fall within the protection scope of the present disclosure. Industrial applicability

[0165] The present disclosure can improve the high-temperature and high-humidity corrosion resistance of ion exchange by adding Y2O3 and / or ZrO2 in a suitable range in specific components of ion exchange, and by adjusting the composition of ion exchange in a respective specific suitable range, the ion exchange has excellent high-temperature and high-humidity corrosion resistance, reaching level II or above, meeting the storage performance requirements of ion exchange; the surface of the ion exchange is not easily corroded, and the generation of white spots or mist-like defects is reduced; the quality is stable during storage and transportation in high-temperature and humid seasons, and the influence of harsh environments on the performance of ion exchange is reduced.

[0166] The present disclosure adjusts the composition of ion exchange to ensure that the content of crystals in the ion exchange is less than 10wt% after long-term and continuous absorption of lithium ions in a salt bath high-temperature environment, with a small change and thermal stability; further, it will not produce substances containing silicon components, thereby affecting the surface quality of the product; it is beneficial to increase the number of use of the molten salt salt bath and prolong the service life of the molten salt salt bath.

[0167] The ion exchange prepared by the present disclosure has high adsorption efficiency for lithium ions during long-term and continuous absorption of lithium ions in a high-temperature salt bath, which can ensure that the concentration of lithium ions in the salt bath during the glass strengthening process remains within a reasonable range.

[0168] In addition, it can be understood that the high-temperature-resistant and easy-to-store stable ion exchange prepared by the embodiments of the present disclosure, as well as the preparation, use method and application thereof, are reproducible and can be used in various industrial applications. For example, the high-temperature-resistant and easy-to-store stable ion exchange prepared by the embodiments of the present disclosure, as well as the preparation, use method and application thereof, can be used in the field of ion exchange technology related to glass chemical strengthening.

Claims

1. A stable ion sieve that is resistant to high temperatures and easy to store, characterized in that: Calculated by mole percentage, the ion sieve includes the following components: SiO2: 38.0mol%-58.7mol%, Al2O3: 7.0mol%-17.0mol%, Na2O: 34.0mol%-45.0mol%, K2O: 0.1mol%-3.0mol%, Y2O3: 0.1mol%-2.0mol%, B2O3: 0.1mol%-3.0mol%, ZrO2: 0.0mol%-3.0mol%.

2. The high temperature resistant and easy to store stable ion sieve according to claim 1, characterized in that: Calculated by mole percentage, in the ion sieve: SiO2: 39.0 mol% - 50.0 mol%, and / or, Al2O3: 7.0 mol% - 15.0 mol%, preferably 8.0 mol% - 15.0 mol%, and / or, Na2O: 35.0 mol% to 43.0 mol%, more preferably 37.0 mol% to 43.0 mol%, and / or K2O: 0.5 mol% to 3.0 mol%, preferably 0.5 mol% to 2.5 mol%, and / or Y2O3: 0.2 mol%-2.0 mol%, preferably 0.5 mol%-2.0 mol%.

3. The high temperature resistant and easy to store stable ion sieve according to claim 2, characterized in that: Calculated by mole percentage, in the ion sieve: SiO2: 40.0 mol% - 45.0 mol%, and / or Al2O3: 13.0 mol% - 15.0 mol%, and / or, Na2O: 40.0 mol% - 43.0 mol%, and / or K2O: 0.5 mol% to 2.0 mol%, preferably 0.5 mol% to 1.0 mol%, and / or Y2O3: 0.5 mol% - 1.0 mol%, and / or ZrO2: 0.0-2.5 mol%, preferably 0.5-2.5 mol%, more preferably 1.0-2.5 mol%, and / or, B2O3: 0.5-1.0 mol%.

4. The high temperature resistant and easy to store stable ion sieve according to any one of claims 1 to 3, characterized in that: After the ion sieve absorbs lithium ions for 0.5 h to 24 h in a salt bath at a temperature of 350° C. to 550° C., the content of crystals in the ion sieve is less than 10 wt %, and the lithium ion concentration of the salt bath is 50 ppm to 400 ppm; and / or, The ion sieve has a high temperature and high humidity corrosion resistance reaching level II or above.

5. The high temperature resistant and easy to store stable ion sieve according to claim 4, characterized in that: The ion sieve reaches level I in terms of resistance to high temperature and high humidity corrosion.

6. The high temperature resistant and easy to store stable ion sieve according to any one of claims 1 to 5, characterized in that: The ion sieve is in the shape of one or more of granular, sheet, porous and plate.

7. The high temperature resistant and easy to store stable ion sieve according to claim 6, characterized in that: When the ion sieve is in granular form, its particle size is 0.5-2.0 mm; When the ion sieve is in the shape of a sheet, its size is 1.00-10.00 mm; When the ion sieve is porous, its pore size is 1.0-5.0 mm; When the ion sieve is in the shape of a plate, its thickness is 0.5-2.0 mm.

8. A method for preparing a high-temperature resistant and easily storable stable ion sieve according to any one of claims 1 to 7, characterized in that: include: According to the composition of the stable ion sieve which is resistant to high temperature and easy to store, the raw material components are selected and mixed, melted and formed, and then annealed to obtain the ion sieve.

9. The method for preparing a high-temperature resistant and easily storable stable ion sieve according to claim 8, characterized in that: The ion sieve is in the shape of one or more of granular, sheet, porous and plate.

10. The method for preparing a high temperature resistant and easily storable stable ion sieve according to claim 9, characterized in that: When the ion sieve is in granular form, the particle size thereof is 0.5-2.0 mm; and / or When the ion sieve is in the shape of a sheet, its size is 1.00-10.00 mm; and / or When the ion sieve is porous, the pore size is 1.0-5.0 mm; and / or When the ion sieve is in the shape of a plate, its thickness is 0.5-2.0 mm.

11. The method for preparing a high temperature resistant and easily storable stable ion sieve according to claim 8, characterized in that: The melting temperature is 1300°C-1650°C, and the melting time is 1h-24h; and / or, The annealing treatment temperature is 400° C.-450° C., and the annealing treatment time is 12 hours-24 hours.

12. A method for using the high temperature resistant and easily storable stable ion sieve according to any one of claims 1 to 7, characterized in that: include: Step 1): providing a salt bath to be purified, wherein the salt bath contains lithium ions; wherein the impurity ions are mainly lithium ions; Step 2): adding a high temperature resistant and easy to store stable ion sieve to the salt bath to be purified; Step 3): After the high-temperature-resistant and easy-to-store stable ion sieve has reacted for a required time in the salt bath to be purified, it is taken out.

13. The method for using the high temperature resistant and easy to store stable ion sieve according to claim 12, characterized in that: In step 1), the concentration of lithium ions is 50-400 ppm; preferably 50-200 ppm; more preferably 50-100 ppm.

14. The method for using the high temperature resistant and easy to store stable ion sieve according to claim 12, characterized in that: In step 1), the salt bath further contains sodium salt and / or potassium salt, preferably NaNO3 and / or KNO3; and / or, The temperature of the salt bath is 350°C-550°C, preferably 380°C-530°C, more preferably 380°C-500°C.

15. The method for using the high temperature resistant and easy to store stable ion sieve according to claim 12 or 14, characterized in that: The concentrations of NaNO3 and KNO3 in the salt bath can be balanced according to the composition of the glass material being ion exchanged.

16. The method for using the high temperature resistant and easy to store stable ion sieve according to claim 15, characterized in that: The glass material includes lithium-containing glass-ceramics and lithium aluminosilicate glass.

17. The method for using the high temperature resistant and easily storable stable ion sieve according to claim 16, characterized in that: The crystal phase of the lithium-containing glass-ceramics includes one or more of petalite, lithium disilicate, lithium monosilicate, and eucryptite.

18. The method for using the high temperature resistant and easily storable stable ion sieve according to claim 12, characterized in that: In step 2), the amount of the ion sieve added is 0.50wt%-5.00wt% of the mass of the salt bath to be purified; preferably 1.00wt%-5.00wt% of the mass of the salt bath to be purified; and / or, In step 3), the ion sieve reacts in the salt bath to be purified for 3-24 hours, preferably 6-24 hours, and more preferably 8-16 hours.

19. The method for using the high temperature resistant and easy to store stable ion sieve according to claim 12, characterized in that: When the lithium ion concentration of the salt bath to be purified is 50-400 ppm, the amount of ion sieve added is 0.50wt%-5.00wt% of the mass of the salt bath to be purified, and after the reaction time in the salt bath to be purified is 3-24 hours, the absorption efficiency of the ion sieve is 50%-95%; preferably, the absorption efficiency of the ion sieve is 53%-95%.

20. A method for chemically strengthening lithium-containing glass-ceramics, comprising: A stable ion sieve prepared by the preparation method of the high-temperature resistant and easy-to-store stable ion sieve as described in any one of claims 1 to 7 or the high-temperature resistant and easy-to-store stable ion sieve as described in any one of claims 8 to 11 is added to a salt bath for chemically strengthening lithium-containing microcrystalline glass.

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