CN113233758A - Glass composition, glass raw powder and preparation method thereof, and glass powder and preparation method thereof - Google Patents

Glass composition, glass raw powder and preparation method thereof, and glass powder and preparation method thereof Download PDF

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Publication number
CN113233758A
CN113233758A CN202110715723.XA CN202110715723A CN113233758A CN 113233758 A CN113233758 A CN 113233758A CN 202110715723 A CN202110715723 A CN 202110715723A CN 113233758 A CN113233758 A CN 113233758A
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glass
powder
raw powder
glass raw
preparing
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CN113233758B (en
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仇卫星
秦国斌
郑文彬
乔良
卢克军
张宁
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Shanghai Tongcheng Electronic Materials Co Ltd
Beijing Asashi Electronic Materials Co ltd
Red Avenue New Materials Group Co Ltd
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Shanghai Tongcheng Electronic Materials Co Ltd
Beijing Asashi Electronic Materials Co ltd
Red Avenue New Materials Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The application provides a glass composition, glass raw powder and a preparation method thereof, and glass powder and a preparation method thereof, and belongs to the field of battery sealing materials. The glass composition comprises the following components in percentage by mass: 56-68% SiO210-20% of BaO and 1-6% of B2O36-8% of Na2O, 4-6% of K2O, 3-5% of Al2O3And 0.5 to 1% of Li2And O. The glass powder is prepared from the glass composition, can be well matched and sealed with the metal pole, and has better electrolyte corrosion resistance.

Description

Glass composition, glass raw powder and preparation method thereof, and glass powder and preparation method thereof
Technical Field
The application relates to the field of battery sealing materials, in particular to a glass composition, glass raw powder and a preparation method thereof, and glass powder and a preparation method thereof.
Background
The insulating terminal is a key component of a power battery such as a primary lithium battery, and is generally formed by sintering a metal shell (also called a battery cover plate), a current collector (namely a core column) and a sealing material, wherein the sealing material sealed between the inner wall of a through hole of the battery cover plate and the core column is a weak link. The electrolyte of the lithium ion battery contains salt substances containing lithium ions, hydrofluoric acid and an organic solvent, has strong corrosivity, is easy to leak to influence the service life of the battery and generate potential safety hazards, and therefore, the sealing material needs to have sufficient chemical stability.
The sealing technology of the battery electrode pole at the present stage mainly comprises the following steps: plastic sealing techniques, ceramic metallization sealing techniques and glass sealing techniques. Among them, plastic seals generally have problems of short life and poor safety; ceramic metallization sealing involves the use of solder, resulting in a multilayer interface between the ceramic insulator and the metal substrate being sealed, which is susceptible to cracking due to mismatch in thermal expansion coefficients, and this interface risks damage by stress and corrosion, thereby affecting the life and reliability of the cell; the glass and the oxide film on the metal surface can form chemical bond combination, thus being beneficial to realizing the air tightness of the sealing of the components, and the sealing glass also has relatively excellent electrical insulation and chemical stability. Therefore, in some applications, the sealing of the electrode terminal of the battery is mostly performed by using a glass sealing technology.
At present, DM305, DM308, Elan13 and Elan19 glass powder are mostly adopted as sealing materials for a metal glass sealing cover group of a primary lithium battery, and positive posts matched with the sealing materials are mostly kovar alloy posts and molybdenum posts such as 4J28, 4J29 and 4J 52. In the above applications, the following problems mainly exist: firstly, the packaging glass and the pole are not easy to weld; and secondly, the sealing material is easily corroded by electrolyte and metal lithium when a primary lithium battery is stored for a long time, so that the leakage of the battery is invalid.
Disclosure of Invention
The application aims to provide a glass composition, glass raw powder and a preparation method thereof, and glass powder and a preparation method thereof, wherein the provided glass powder can be well matched and sealed with a metal pole and has better electrolyte corrosion resistance.
The embodiment of the application is realized as follows:
in a first aspect, embodiments herein provide a glass composition comprising, by mass percent: 56-68% SiO210-20% of BaO and 1-6% of B2O36-8% of Na2O, 4-6% of K2O, 3-5% of Al2O3And 0.5 to 1% of Li2O。
In a second aspect, an embodiment of the present application provides a method for preparing glass raw powder, including: heating and melting the glass composition provided in the first aspect to obtain a molten liquid material; then, preparing the molten liquid material into tabletting glass; and then ball-milling and crushing the tabletting glass to obtain glass raw powder.
In a third aspect, embodiments of the present application provide a glass raw powder, the raw materials of which include the glass composition provided in the embodiments of the first aspect, or are obtained by the method for preparing the glass raw powder provided in the embodiments of the second aspect; the expansion coefficient of the glass raw powder at 50-300 ℃ is 85 multiplied by 10-7～110×10-7/° c; the softening temperature of the glass raw powder is 540-590 ℃; the transition temperature Tg of the glass raw powder is 740-790 ℃; and the sealing temperature of the glass raw powder is 930-1000 ℃.
In a fourth aspect, an embodiment of the present application provides a method for preparing glass frit, including: preparing glass raw powder provided by the embodiment of the third aspect; preparing a viscous colloidal transparent solvent, wherein the viscous colloidal transparent solvent comprises an organic binder and a preparation solvent, and the preparation solvent is water or alcohol; mixing the glass raw powder with a viscous colloidal transparent solvent, and then stirring to form the granular powder glass powder.
In a fifth aspect, embodiments of the present application provide a glass frit, raw materials of which include an organic binder and the glass raw frit as provided in the embodiments of the third aspect, or are obtained by the method for preparing the glass frit as provided in the embodiments of the fourth aspect.
The glass composition, the glass raw powder and the preparation method thereof, and the glass powder and the preparation method thereof provided by the embodiment of the application have the beneficial effects that:
glass composition of the present application, BaO and B2O3And adjusting to a specific mass percentage so that the glass has a proper expansion coefficient, a proper softening temperature and a proper transition temperature Tg, and the glass can be well matched and sealed with the metal pole and the shell. The reasonable control of the BaO and the alkali metal oxide can effectively improve the fluidity and the chemical stability of the glass, and can improve the wetting capacity and the sealing performance to the metal, so that the glass has good air tightness and electrolyte corrosion resistance.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
It should be noted that "and/or" in the present application, such as "feature 1 and/or feature 2" refers to "feature 1" alone, "feature 2" alone, and "feature 1" plus "feature 2" alone.
In addition, in the description of the present application, the meaning of "a plurality" of "one or more" means two or more unless otherwise specified; the range of "numerical value a to numerical value b" includes both values "a" and "b", and "unit of measure" in "numerical value a to numerical value b + unit of measure" represents both "unit of measure" of "numerical value a" and "numerical value b".
The glass composition, the glass raw powder and the method for producing the same, and the glass powder and the method for producing the same according to the examples of the present application will be specifically described below.
In a first aspect, embodiments herein provide a glass composition comprising, by mass percent: 56-68% SiO210-20% of BaO and 1-6% of B2O36-8% of Na2O, 4-6% of K2O, 3-5% of Al2O3And 0.5 to 1% of Li2O。
Alternatively, SiO256-67% of BaO, 12-18% of BaO and B2O3The mass percentage of the glass composition is 2-4%.
The inventor researches and discovers that the expansion coefficient of the glass can be remarkably improved by increasing the content of BaO, and the glass can have a proper expansion coefficient (the expansion coefficient at 50-300 ℃ is 85 multiplied by 10) by increasing the content of BaO to a specific mass percentage-7～110-7/° C), the coefficient of expansion is compared with 4J28 (the coefficient of expansion is about 102 x 10 at 50-300℃)-7/° C) and 4J52 (expansion coefficient of about 98X 10 at 50-300 ℃)-7/° c) and the like. Meanwhile, BaO can loosen the structure of the glass and reduce the viscosity, the content of BaO is increased, the fluidity and the chemical stability of the glass can be effectively improved, and the infiltration capacity of the glass to metal is improved.
The inventors have also found that in the glass composition system of the present application, when B is present2O3When the content of (A) is higher, B is increased2O3In such an amount that the softening temperature of the glass is lowered; when B is2O3At lower levels, boron anomaly, expressed as a decrease in B, occurs2O3The content of (a) may lower the softening temperature of the glass. The "boron anomaly" phenomenon occurs because of B2O3In contact with SiO2、Al2O3The glass is high in content while forming a network structure of the glass together to enhance the stability of the glassThe BaO is used as the external oxide of the network, and free oxygen formed by the fracture of Ba-O bonds enters the network to play a role in breaking the network and depolymerizing; at the same time, Ba2+The electrovalence is high, the radius is small, the ionic potential is large, and the polymerization of silicon oxygen anion groups is promoted, so that a new grid structure is formed.
Considering that when the glass powder is applied to sealing batteries, in order to facilitate the binder removal of the granulated powder, the glass is required to have a higher glass transition temperature Tg and a lower softening temperature Tg, and the glass transition temperature Tg is along with B2O3Is increased by a decrease in the content of (b). Therefore, the content of BaO is reduced to a specific mass percentage, and the glass formed by the glass composition has a proper softening temperature (540-590 ℃) and a transition temperature Tg (740-790 ℃).
The inventors have also discovered that in the glass composition system of the present application, reducing the Na content is effective in reducing the glass expansion coefficient without changing the total alkali metal content; an excessively high content of Li leads to a decrease in the glass transition temperature Tg and the sealing temperature, and also to a marked decrease in the corrosion resistance of the glass. The independent dosage of each alkali metal and the total amount of the alkali metal are controlled under certain conditions, so that the fluidity and the chemical stability of the glass can be effectively improved, and the sealing property of the glass is better.
The glass composition provided by the application is SiO2-BaO-Al2O3-B2O3As a base glass system, BaO and B2O3The mass percentage is adjusted to be specific, so that the glass has proper expansion coefficient, softening temperature and transition temperature Tg, and can be well matched with the mainstream alloy pole and the shell such as 4J28 and 4J52 for sealing. The reasonable control of the BaO and the alkali metal oxide can effectively improve the fluidity and the chemical stability of the glass, and can improve the wetting capacity and the sealing performance to the metal, so that the glass has good air tightness and electrolyte corrosion resistance.
In the glass composition of the present application, each component is not limited to be added only in the form of a substance corresponding to its chemical formula, and for example, may be added in the form of a substance that can be thermally decomposed to obtain the corresponding component.
Considering that some oxides are expensive and easily react during long-term storage due to poor stability, in some alternative embodiments, BaO, Na2O、K2O and Li2O is introduced in the form of its corresponding carbonate. Compared with the method of directly introducing the raw materials in the form of oxides, the method has the advantages that the cost can be effectively reduced, and the stability of the raw materials in the long-term storage process is improved.
In the glass composition of the present application, when the corresponding compound component is introduced in the form of another substance, the mass of the added material is based on the mass of the corresponding compound. For example, 106g of sodium carbonate corresponds to 62g of sodium oxide, and when 106g of sodium carbonate is added to the glass composition, the mass of the sodium carbonate added to the glass composition is 62g of sodium oxide.
Further, considering that the purity of each oxide is less than 100%, it is exemplary ≧ 99%. The above 106g of sodium carbonate optionally corresponds to a pure amount, e.g., 99.5% pure sodium carbonate material, with 106g of sodium carbonate actually added to the glass composition accounting for 106.5g of total sodium carbonate material.
The inventors have found that ZrO is added to the glass composition of the present application2And NaF are effective in further improving the corrosion resistance of the glass.
In some optional embodiments, the glass composition further comprises, in mass percent: 1-2% of ZrO2And 1-2% of NaF. Due to ZrO2Is not easy to melt, ZrO2The above amount of (A) is required to ensure ZrO while effectively improving the glass properties2Can be sufficiently melted. It has been found that the addition of NaF lowers the softening point of the glass and that the above amount of NaF is required to maintain the glass at a higher transition temperature Tg while effectively improving the glass properties.
The inventors have found that the total amount of alkali metal in the glass composition of the present application is controlled within a certain range, which is advantageous for improving the fluidity and chemical stability of the glassQualitative and sealing property. Alternatively, Na2O、K2O and Li2The sum of the mass percentages of O in the glass composition is 11-14%, or 12-13%, such as but not limited to any one of 11%, 11.5%, 12%, 12.5%, 13%, and 13.5% and 14%, or a range between any two.
In some exemplary embodiments, the glass composition comprises the following components in percentage by mass:
SiO2is any one of 56%, 59%, 61%, 62% and 67% or a range between any two; BaO is any one of 12%, 15% and 18% or a range value between any two; b is2O3Is any one of 2%, 4%, 5% and 6% or a range between any two; na (Na)2O is any one of 6%, 7% and 8% or a range between any two; k2O is any one of a point value of 4%, 4.5% and 6% or a range value between any two; al (Al)2O3Is any one of 3%, 3.5% and 5% or a range between any two; li2O is any one of the values of 0.5%, 0.7%, 0.8% and 1% or a range value between any two; ZrO (ZrO)2Is any one of 1%, 1.5% and 2% or a range between any two; NaF is any one of 1%, 1.5%, and 2% or a range between any two.
In a second aspect, an embodiment of the present application provides a method for preparing glass raw powder, including: heating and melting the glass composition provided in the first aspect to obtain a molten liquid material; then, preparing the molten liquid material into tabletting glass; and then ball-milling and crushing the tabletting glass to obtain glass raw powder.
As for the heat-melting treatment step, it is exemplarily performed in a 95% high alumina crucible.
In some optional embodiments, the heating temperature in the heating and melting treatment step is 1350 to 1450 ℃, such as but not limited to, any one of 1350 ℃, 1380 ℃, 1400 ℃, 1420 ℃ and 1450 ℃, or a range between any two; the melting time is 90-120 min, for example, but not limited to, any one value of 90min, 100min, 110min and 120min or a range value between any two values, and the appropriate heating temperature and melting time are beneficial to ensuring that the components in the glass composition are well matched, and the quality of the prepared glass powder is more stable and controllable.
For the preparation of the sheet glass, the molten liquid material is rolled by a high-temperature resistant high-purity stainless steel rolling mill.
As for the ball-milling pulverization step, it is exemplarily performed in a corundum bottle or a zirconia bottle, and zirconia balls are added as an abrasive.
Considering that in the subsequent pressing process, the smaller the granularity of the sealing glass powder is, the higher the strength of the pressed glass component is under the same pressure; meanwhile, when the sealing glass powder is applied, components with specific shapes need to be pressed, the diameter is generally 4-10 mm, the particle size cannot be too large, and the components cannot be formed by too large pressing. Thus, a specific particle size distribution of the glass frit facilitates better compaction.
Optionally, in the step of ball milling, controlling the particle size of the pulverized powder obtained by pulverizing: d50 is 10-20 μm, such as but not limited to, any one or a range between 10 μm, 12 μm, 14 μm, 15 μm, 16 μm, 18 μm and 20 μm; and the particle size of the powder obtained by crushing is as follows: d99 is less than or equal to 160 mu m, so that the glass powder can better meet the subsequent pressing requirement.
It can be understood that in the ball milling and pulverizing step of the preparation method of the glass raw powder provided by the present application, the requirement of the ball-to-material ratio can be determined according to the product performance requirement, the ball milling efficiency or the standard known in the art.
Optionally, in the step of ball milling and crushing, the ball-to-material ratio is (3-4): 1, such as but not limited to 3: 1. 3.4: 1. 3.5: 1. 3.6: 1 and 4: 1, or a range between any two. The ball milling time is 120-240 min, such as but not limited to any one of 120min, 140min, 150min, 160min, 180min and 240min or a range value between any two.
Further, in the step of ball milling and crushing, the ball-to-material ratio is (3.4-3.6): 1, and the ball milling time is 140-160 min. As an example, in the ball milling pulverization step, the ball-to-material ratio is 3.5:1 and the ball milling time is 150 min.
In addition, after the step of ball milling and crushing is finished, screening can be carried out according to the known standard or specific product performance in the field, and the glass raw powder is obtained after screening is finished.
As an example, after the ball milling and pulverizing step, a 100-mesh standard sieve is used for sieving, and the sieved material is taken out to obtain the glass raw powder.
In a third aspect, embodiments of the present application provide a glass raw powder, which includes the glass composition provided in the first aspect, or is obtained by the method for preparing the glass raw powder provided in the second aspect.
The application provides a glass raw powder has following characteristics:
(1) the glass raw powder does not contain harmful metals such as lead, mercury, cadmium, chromium and the like, and meets the requirement of environmental protection.
(2) The expansion coefficient of the glass raw powder at 50-300 ℃ is 85 multiplied by 10-7～110×10-7at/deg.C, the expansion coefficient of the glass raw powder at 50-300 deg.C is 94 × 10-7～105-7The glass raw powder has moderate and adjustable expansion coefficient, and can be well matched and sealed with metal poles, such as mainstream alloy poles of 4J28, 4J52 and the like.
(3) The softening temperature of the glass raw powder is 540-590 ℃, and the transition temperature Tg of the glass raw powder is 740-790 ℃; furthermore, the softening temperature of the glass raw powder is 550-570 ℃, the transition temperature Tg of the glass raw powder is 770-790 ℃, and the softening temperature and the transition temperature Tg of the glass raw powder are moderate, so that sintering and binder removal are facilitated.
(4) The sealing temperature of the glass raw powder is 930-1000 ℃, further, the sealing temperature of the glass raw powder is 960-990 ℃, the sealing temperature of the glass raw powder is moderate, good matching sealing with the core column material can be well completed, and the air tightness of the core column material is guaranteed.
(5) The glass raw powder has good chemical stability,has good electrolyte resistance (LiPF)6And SOCl2Etc.) aggressive.
In a fourth aspect, an embodiment of the present application provides a method for preparing glass frit, including: preparing glass raw powder provided by the embodiment of the third aspect; preparing a viscous colloidal transparent solvent, wherein the viscous colloidal transparent solvent comprises an organic binder and a preparation solvent, and the preparation solvent is water or alcohol; mixing the glass raw powder with a viscous colloidal transparent solvent, and then stirring to form the granular powder glass powder.
In the embodiments of the present application, the manner of preparing the glass raw powder provided in the embodiment of the third aspect is not limited, and for example, the glass raw powder may be prepared by purchasing, or may be prepared by using the method for preparing the glass raw powder provided in the embodiment of the second aspect.
In the present application, the preparation method of the viscous gel-like transparent solvent is not limited, and the type of the organic binder is not limited, and each of them can be performed in a manner known in the art.
As an example of one aspect, a viscous, gelatinous, transparent solvent is prepared by: mixing an organic binder and a preparation solvent according to a certain proportion and placing the mixture into a glass beaker; and then heating in water bath at 30-40 ℃ while continuously stirring.
As an example of yet another aspect, the organic binder is selected from one or more of paraffin wax, polyvinyl alcohol, and polyethylene glycol.
It can be understood that, in the preparation method of the glass powder provided by the present application, after the stirring step is completed to form the granular powder, the granular powder can be further screened according to the standard known in the art or the specific product performance, and the glass powder is obtained after the screening is completed.
As an example, after the stirring step forms granular powder, a 40-60 mesh standard sieve is used for sieving, and undersize products are taken to obtain glass powder.
Considering that the usage of the binder has certain influence on the powder making process and the performance of the obtained glass powder, the proper usage of the binder is beneficial to ensuring the reliability of the powder making process and the performance of the obtained glass powder.
Illustratively, the content of the organic binder in the granular powder is 3-6%, such as but not limited to any one of 3%, 4%, 5% and 6%, or a range between any two. If the content of the organic binder is too low, the organic binder cannot be bonded well, so that the pressed component is fragile; if the content of the organic binder is too high, the equipment is easy to adhere in the subsequent pressing process, and the subsequent glue discharging is not facilitated.
In a fifth aspect, embodiments of the present application provide a glass frit, which is exemplarily used as a sealing material for a primary lithium ion battery terminal. The glass powder raw material comprises an organic binder and the glass raw powder provided by the embodiment of the third aspect, or the glass powder is obtained by the preparation method of the glass powder provided by the embodiment of the fourth aspect.
The features and properties of the present application are described in further detail below with reference to examples.
Example (A) and comparative example
Examples 1 to 8 and comparative examples 1 to 3
A glass raw powder is prepared by the following steps:
s1, fully and uniformly mixing the glass composition, putting the mixture into a 95% high-alumina crucible, and heating and melting the mixture at 1450 ℃ for 90min to obtain a molten liquid material.
And S2, rolling and tabletting the molten liquid obtained in the step S1 by using a high-temperature-resistant stainless steel rolling mill to obtain the tabletting glass.
And S3, putting the pressed glass obtained in the step S2 into a corundum bottle, adding zirconia balls in a certain proportion according to the ball-to-material ratio of 3.5:1, and carrying out ball milling and crushing by using an omnibearing planetary ball mill.
The composition and mass percentage of the glass composition are shown in table 1.
Examples 9 to 16
A glass powder is prepared by the following steps:
s1, the glass composition corresponding to the embodiment 3 is fully and uniformly mixed and put into a 95 percent high-alumina crucible to be heated and melted to obtain a molten liquid material.
And S2, rolling and tabletting the molten liquid obtained in the step S1 by using a high-temperature-resistant stainless steel rolling mill to obtain the tabletting glass.
And S3, putting the pressed glass obtained in the step S2 into a corundum bottle, adding zirconia balls in a certain proportion, and carrying out ball milling and crushing by using an all-directional planetary ball mill.
And S4, screening the powder subjected to ball milling and crushing by a 100-mesh standard sieve, and taking undersize products to obtain the glass raw powder.
S5, mixing the organic binder and the preparation solvent according to a certain proportion, placing the mixture in a glass beaker, heating the mixture in a pure water bath at the temperature of 30-40 ℃, and continuously stirring the mixture during the heating; the viscous colloidal transparent solvent is prepared.
S6, mixing the glass raw powder obtained in the step S4 and the viscous colloidal transparent solvent obtained in the step S5 according to a certain proportion, placing the mixture into a ceramic mortar, and continuously stirring the mixture to prepare granular powder.
And S7, sieving the powder obtained in the step S6 by using a 40-60-mesh standard sieve, and taking undersize products to obtain glass powder.
Wherein, the technological parameter requirements in each step are shown in table 2.
TABLE 1 compositions and percentages by mass (%)
Figure BDA0003132544620000111
Figure BDA0003132544620000121
TABLE 2 Process parameter requirements
Figure BDA0003132544620000122
Note:
in Table 2, A is the heating temperature (. degree. C.) in the step S1, and B is the melting time (min) in the step S1; c is the ball material ratio in the step S3; d is the ball milling time (min) in the step S3; e is the type of the organic binder of the granular powder in the step S6; f is the organic binder content of the granular powder in step S6.
(II) test example
The performance of the glass powder provided in each example and comparative example was tested and evaluated as follows:
evaluation methods of expansion coefficient and softening temperature: accurately weighing 3g of glass powder, putting the glass powder into a stainless steel grinding tool, and compacting to prepare a cylindrical sample with the length of 25mm and the diameter of 8 mm; then placing the sample into a muffle furnace to be sintered into a glass state at 720 ℃, and grinding two ends of the sample after cooling; and then a DIL-402 thermal expansion instrument is used for testing, and the results of the expansion coefficient and the softening temperature value can be obtained. Wherein the expansion coefficient is read as an average expansion coefficient value of 50 to 300 ℃.
Evaluation methods of the transition temperature Tg and the sealing temperature: accurately weighing 1.5g of glass powder, putting the glass powder into a stainless steel grinding tool, and compacting to prepare a cylindrical sample; then placing the columnar sample on a stainless steel plate and placing the columnar sample in a muffle furnace, heating at the speed of 2 ℃/min, and if the columnar sample is softened and deformed at a certain temperature point, setting the corresponding temperature as a transition temperature Tg; when the sealing temperature is completely spread and soaked, the sealing temperature is obtained.
Evaluation method of erosion resistance: simulating the working environment of the electrolyte of the primary lithium battery, and putting a sintered glass column filled with 5 percent LiPF6And (3) storing the electrolyte in a sealed glass container at 80 ℃ for 100h, taking out the glass, cleaning the glass, drying the glass, weighing the glass, and calculating the weight erosion ratio expressed by surface weight loss w%.
Evaluation method of particle size: a certain amount of glass powder is taken, and the median diameter D50 and the maximum particle diameter D99 are detected by a laser particle sizer.
Evaluation method of sintered density: accurately weighing 1.5g of glass powder, putting the glass powder into a stainless steel grinding tool, and compacting to prepare a cylindrical sample; then the column sample is put on a ceramic plate paved with talcum powder and put into a muffle furnace, the temperature is raised at the speed of 2 ℃/min for glue discharge, the temperature is raised to 970 ℃ (sealing temperature), the sample is cooled to room temperature along with the furnace, and the sample is wiped clean and the density of the sample is measured by a specific gravity balance.
The results of the performance test of each example and comparative example are shown in tables 3 and 4.
TABLE 3 test results of glass raw powder properties
Figure BDA0003132544620000131
Figure BDA0003132544620000141
TABLE 4 glass powder Performance test results
Figure BDA0003132544620000142
As can be seen from table 3, the glass raw powder provided in the examples of the present application has a suitable expansion coefficient, softening temperature, transition temperature Tg and sealing temperature; and the glass raw powder has good electrolyte corrosion resistance, so that the glass has good air tightness and insulativity and good electrolyte corrosion resistance effect.
According to examples 1 to 8 and comparative examples 1 to 3:
the expansion coefficient of the glass can be obviously improved by increasing the content of BaO; the electrolyte corrosion resistance of the glass can be effectively improved by increasing the content of BaO.
When B is present2O3At lower contents of (A), B is reduced2O3In such an amount that the softening temperature of the glass is lowered and the transition temperature Tg is raised; when B is present2O3When the content of (B) is higher, B is decreased2O3The amount of (c) is such that the softening temperature of the glass is increased and the transition temperature Tg is increased. When B is present2O3When the mass percentage of (b) is increased to 10% or even 15%, the transition temperature Tg is significantly reduced.
As can be seen from examples 1 to 4, the mass percent of BaO was controlled to 12 to 18%, and B was adjusted to2O3The mass percent of the Na is controlled to be 2-6%, and meanwhile, the Na is added2O、K2O and Li2The total amount of O is controlled to be more than 11 percent and less than 14 percent, and the expansion coefficient can be even regulated to 94 multiplied by 10-7～105-7Within the range of/° c, can be made softThe transformation temperature is controlled within the range of 550-570 ℃, and the transformation temperature Tg can be regulated within the range of 770-790 ℃.
Comparative example 1 and example 3 have a lower BaO content and B2O3Has a high content of (A), and the expansion coefficient, the electrolyte corrosion resistance and the transition temperature Tg are remarkably reduced.
Comparative example 2 compares with example 4, B2O3Is higher and the transition temperature Tg is significantly reduced.
Comparative example 3 to example 3, Li2The content of O is higher, and the electrolyte corrosion resistance is obviously reduced.
Example 5 compares with example 3, Na2O、K2O and Li2The total amount of O is relatively low; example 6 compares with example 3, Na2O、K2O and Li2The total amount of O is relatively high. From the comparison between example 3 and examples 5 to 6, it can be seen that: when Na is present2O、K2O and Li2When the total amount of O is reduced compared with that of the embodiment 3, the expansion coefficient of the glass is obviously reduced, the softening temperature is increased, the transformation temperature is also reduced, and the matching of the sealing material and the later-stage rubber discharge are influenced to a certain extent. When Na is present2O、K2O and Li2When the total amount of O is increased compared with that of the glass in the embodiment 3, the expansion coefficient of the glass is obviously increased, and the transformation temperature is also obviously reduced, so that the later glue discharging of the glass powder is not facilitated. In addition, due to Na2O、K2O and Li2The total O content was changed from example 3, and the protective film of silicon oxide formed in the silicate system was also affected, resulting in the glass showing a decrease in the resistance to electrolyte attack.
The comparison between comparative examples 9 to 12 shows that the particle size of the glass powder crushed by ball milling has a significant influence on the density of the glass powder, the ball milling time cannot be too long, the particle size cannot be too fine, otherwise the density of the glass powder is reduced.
It is clear from comparative examples 11 and 13 to 16 that the content of the binder added to the glass frit is also important, and too high content of the binder causes difficulty in removing the glass frit, and the residual amount increases, resulting in a decrease in the density of the glass frit.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

Claims (10)

1. A glass composition, characterized in that it comprises, in mass percent: 56-68% SiO210-20% of BaO and 1-6% of B2O36-8% of Na2O, 4-6% of K2O, 3-5% of Al2O3And 0.5 to 1% of Li2O。
2. The glass composition according to claim 1, characterized in that it comprises, in mass percent: 56-67% of the SiO212-18% of BaO, 2-4% of B2O36 to 8% of the Na2O, 4-6% of the K2O, 3-5% of the Al2O3And 0.5 to 1% of the Li2O。
3. The glass composition of claim 1, wherein the Na is2O, said K2O and the Li2The sum of the mass percentages of O in the glass composition is 11-14%;
alternatively, the Na2O, said K2O and the Li2The sum of the mass percentages of O in the glass composition is 12.5%.
4. The glass composition according to any one of claims 1 to 3, further comprising, in mass percent: 1-2% of ZrO2And 1-2% of NaF.
5. A method for preparing glass raw powder is characterized by comprising the following steps:
heating and melting the glass composition according to any one of claims 1 to 4 to obtain a molten material;
then, preparing the molten liquid material into sheet glass;
and then ball-milling and crushing the tabletting glass to obtain glass raw powder.
6. The method for preparing glass raw powder according to claim 5, wherein in the heating and melting step, the heating temperature is 1350-1450 ℃, and the melting time is 90-120 min.
7. The method for preparing glass raw powder according to claim 5 or 6, wherein in the step of ball milling and grinding, the grain size of the powder obtained by grinding is as follows: d50 is 10-20 μm and D99 is less than or equal to 160 μm;
and/or in the step of ball milling and crushing, the ball-material ratio is (3-4): 1.
8. a glass raw powder characterized in that the raw material thereof comprises the glass composition according to any one of claims 1 to 4 or is obtained by the method for producing a glass raw powder according to any one of claims 5 to 7;
the expansion coefficient of the glass raw powder at 50-300 ℃ is 85 multiplied by 10-7～110×10-7/℃；
The softening temperature of the glass raw powder is 540-590 ℃;
the transition temperature Tg of the glass raw powder is 740-790 ℃;
and the sealing temperature of the glass raw powder is 930-1000 ℃.
9. A method for preparing glass powder is characterized by comprising the following steps:
preparing the glass raw powder according to claim 8;
preparing a viscous colloidal transparent solvent, wherein the viscous colloidal transparent solvent comprises an organic binder and a preparation solvent, and the preparation solvent is water or alcohol;
mixing the glass raw powder with the viscous colloidal transparent solvent, and then stirring to form granular powder-shaped glass powder;
optionally, in the granular powder, the content of the organic binder is 3-6%;
optionally, the organic binder is selected from one or more of paraffin wax, polyvinyl alcohol and polyethylene glycol.
10. A glass frit comprising a raw material comprising an organic binder and the glass raw powder according to claim 8, or obtained by the method for producing a glass frit according to claim 9.
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