CN117682759A - Sealing glass blank for power lithium battery and preparation method thereof - Google Patents
Sealing glass blank for power lithium battery and preparation method thereof Download PDFInfo
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- CN117682759A CN117682759A CN202311579438.5A CN202311579438A CN117682759A CN 117682759 A CN117682759 A CN 117682759A CN 202311579438 A CN202311579438 A CN 202311579438A CN 117682759 A CN117682759 A CN 117682759A
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- Prior art keywords
- sealing glass
- glass
- lithium battery
- sealing
- power lithium
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- 239000005394 sealing glass Substances 0.000 title claims abstract description 55
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 64
- 239000000843 powder Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 12
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 9
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 9
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 9
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 9
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 9
- 238000001746 injection moulding Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 238000004017 vitrification Methods 0.000 claims description 6
- 229940105296 zinc peroxide Drugs 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001241 acetals Chemical class 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229940069328 povidone Drugs 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims 1
- 238000004898 kneading Methods 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 claims 1
- 238000005096 rolling process Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 11
- 238000007789 sealing Methods 0.000 abstract description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 239000005365 phosphate glass Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012536 packaging technology Methods 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910004856 P—O—P Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- XHGGEBRKUWZHEK-UHFFFAOYSA-L tellurate Chemical compound [O-][Te]([O-])(=O)=O XHGGEBRKUWZHEK-UHFFFAOYSA-L 0.000 description 2
- UTPYTEWRMXITIN-YDWXAUTNSA-N 1-methyl-3-[(e)-[(3e)-3-(methylcarbamothioylhydrazinylidene)butan-2-ylidene]amino]thiourea Chemical compound CNC(=S)N\N=C(/C)\C(\C)=N\NC(=S)NC UTPYTEWRMXITIN-YDWXAUTNSA-N 0.000 description 1
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
- C03B19/063—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction by hot-pressing powders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
- H01M50/19—Sealing members characterised by the material
- H01M50/191—Inorganic material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a sealing glass blank for a power lithium battery and a preparation method thereof, which belong to the technical field of glass powder preparation. The thermal expansion coefficient of the sealing glass blank prepared by the method is more than 170 multiplied by 10 at 300 DEG C ‑7 The softening point is less than 450 ℃, the sealing glass has the advantages of high thermal expansion coefficient, low sealing temperature, excellent chemical stability, low bubble content and the like, and can meet the performance requirement of the power lithium battery electrode cap on the sealing glass.
Description
Technical Field
The invention relates to the technical field of glass powder preparation, in particular to a sealing glass blank for a power lithium battery and a preparation method thereof.
Background
The new energy automobile industry is one of the emerging industries, and the power lithium battery is the heart of the new energy vehicle. The packaging material for the power lithium battery has the effects of isolating outside air, moisture and internal electrolyte on one hand, and has the effects of electric insulation on the other hand, separating a battery pole and a metal shell, and keeping the electric neutrality of the shell. Unlike a general lithium battery, a power lithium battery has a very severe operating environment, and thus has very high requirements on packaging technology. In addition to optimizing the structural design of the sealing member, the power lithium battery electrode packaging technology is characterized in that proper packaging materials are selected.
At present, packaging materials between a power lithium battery pole and a metal shell comprise a plastic sealing ring, a ceramic metallization material and a sealing glass powder material. The glass powder packaging technology has the greatest advantages that after packaging, the glass and the oxide film on the metal surface can form chemical bond combination, which is beneficial to realizing airtight sealing and excellent electrical insulation of the glass. The current sealing glass powder for the power lithium battery mainly comprises low-melting-point glass systems such as phosphate, vanadate, bismuthate and the like, the sealing glass powder is required to be manufactured into a glass blank for installation and sintering, the current common preparation method of the glass blank is a dry pressing method, namely, the glass powder and an organic binder are prepared into slurry, and spherical glass granulating powder with certain density is prepared by adopting spray granulation and then is subjected to die casting molding on a briquetting machine.
At present, the granulated powder pressed compact prepared by spray granulation has several problems, namely, the density of the glass blank is lower (less than 85 percent) and the porosity is higher, so that more bubbles can be generated in the glass during sintering of the glass blank, and the insulating sealing performance of a product is affected; secondly, if a phosphate glass system is adopted as a sealing glass blank for the power lithium battery, glass hydrolysis is easy to generate in the process of preparing slurry for spray granulation, and the structure and the performance of the sealing glass are damaged; thirdly, the thermal expansion coefficient of the sealing glass existing at present is not high enough, the packaging technology is not mature, and the practical application of the sealing glass is limited.
Disclosure of Invention
Aiming at the problems actually existing in the current sealing glass powder for the power lithium battery, the invention discloses a sealing glass blank for the power lithium battery and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a sealing glass blank for a power lithium battery is prepared from the following oxides in mole percentage, P 2 O 5 ：30-50％，TeO 2 ：20-50％，ZnO 2 ：8-15％，Li 2 O：1-10％，Na 2 O：0-10％，K 2 O：1-15％，Al 2 O 3 ：1-10％，Bi 2 O 3 ：0.1-14％，CuO：0-20％。
Further, it is made of the following oxides in mole percent, P 2 O 5 ：35-45％，TeO 2 ：25-40％，ZnO 2 ：8-12％，Li 2 O：2-8％，Na 2 O：1-7％，K 2 O：2-12％，Al 2 O 3 ：2-7％，Bi 2 O 3 ：2-10％，CuO：5-15％。
Further, P 2 O 5 With TeO 2 The sum of the mole percentages is 55% -75%.
Further, li 2 O+Na 2 O+K 2 The sum of the mole percentages of O is 10% -20%.
Further, the preparation method of the sealing glass blank for the power lithium battery comprises the following steps:
a. and (3) batching: the glass oxide components are converted into the raw materials of the introduced compound according to the above formula, and the corresponding raw materials are weighed, wherein P 2 O 5 Introduced by sodium dihydrogen phosphate and ammonium dihydrogen phosphate;
b. precalcining: firstly, uniformly mixing weighed sodium dihydrogen phosphate, ammonium dihydrogen phosphate and zinc peroxide, placing the mixture in an electric furnace to react for 0.5 to 1.5 hours at 400 to 500 ℃, and then cooling the mixture to room temperature along with the furnace;
c. mixing: mixing the weighed residual raw materials with a mixture of pre-calcined sodium dihydrogen phosphate, ammonium dihydrogen phosphate and zinc peroxide, and fully and uniformly mixing the raw materials in a mixer added with zirconium balls for 1-3 hours to prepare a mixture;
d. melting: placing a crucible in a high-temperature electric furnace, adding a mixture, heating to 850-1100 ℃ according to a stepped temperature system, and preserving heat for 30-120min to obtain clarified glass liquid;
e. crushing and grinding: roll-pressing and cooling the molten glass in an open mill to room temperature, grinding and sieving;
f. injection molding: mixing the prepared sealing glass powder and the binder uniformly in an internal mixer according to the mass ratio (4-5), granulating or crushing to form a feed, heating, and injecting on an injection molding machine to prepare a sealing glass green body;
g. degumming: soaking the polished sealing glass green body in a solvent for 3-6 hours to perform degumming treatment, and removing the organic binder;
h. vitrification sintering: and (3) vitrification sintering is carried out on the degummed sealing glass green body in a sintering furnace in an inert gas atmosphere at 350-450 ℃, the temperature is kept for 0.5-1.5 hours, then the sealing glass green body is cooled along with the furnace, and the sealing glass green body is shrunk and shaped after sintering, so that the high-density sealing glass cooked body is finally prepared.
Further, the sealing glass powder used in step f has a particle size distribution of D50:60-80 μm, D99:150-180 μm.
Further, the binder used in the step f is an oil-soluble organic binder, and is one or more of ethylcellulose, povidone, polyvinyl acetate and polyvinyl acetal.
Further, the solvent used in the step g is one or more of ethanol, ethyl acetate, acetone, chloroform and xylene.
Further, the mixing temperature is 170-240 ℃, the injection temperature is 170-250 ℃, and the injection pressure is 12-30MPa.
The reasons for selecting the functions and the contents of the glass components in the formula and the technical principle on which the invention is based are as follows:
P 2 O 5 is a glass-forming oxide which is formed by phosphorus-oxygen tetrahedra [ PO ] 4 ]Forming a structural network of phosphate glass, but reducing the chemical stability of the glass, too much P 2 O 5 The content of P in the invention can lead to easy hydrolysis of phosphate glass 2 O 5 Is suitably in the range of 30-50%. TeO (TeO) 2 Is a glass-forming oxide, the structural units in the glass are mainly tetradentate [ TeO ] 4 ]Three coordinated [ TeO ] 3 ]The Te-O-Te chain structure or more complex fabric network structure exists, the glass with tellurate glass as main structure has larger thermal expansion coefficient, but the introduction of excessive tellurate glass can reduce the chemical stability of the glass, and the TeO in the invention 2 Is suitably in the range of 20-50%. Alkali metal oxide Li 2 O、Na 2 O、K 2 O does not participate in the network structure, belongs to the oxide of the network external body, plays roles of improving the thermal expansion coefficient of the glass and reducing the softening temperature, but the chemical stability of the glass is damaged, and the Li is regulated and controlled 2 O、Na 2 O、K 2 O mole percent, using alkali metal ion Li + 、Na + 、K + The radius difference enables the glass to form a mixed alkali effect, is favorable for melting glass and forming glass state, and remarkably improves the chemical stability of the glass. Li in the invention 2 O is suitably in the range of 1-10%, na 2 O is suitably in the range of 0-10%, K 2 The suitable range of O is 1-15%. ZnO (zinc oxide) 2 The ZnO is decomposed into zinc oxide to become a glass network intermediate oxide at high temperature, the softening point of the glass can be reduced within a certain range, the stability of the glass is improved, the glass is not easy to form due to the fact that the content is too small, the glass is easy to crystallize due to the fact that the content is too high, and the softening point is increased 2 Is suitably in the range of 8-15%.
Al 2 O 3 Is a glass network intermediate oxide, has special effect in phosphate glass, and aluminum can form an aluminum oxide tetrahedron with oxygen with double bonds in phosphorus-oxygen glass. Due to the formation of [ AlPO in the glass 4 ]The group converts the original lamellar (or chain) structure of the phosphate into a frame-shaped structure, plays a role in effectively improving and strengthening the structure of the phosphate glass, and improves the thermal stability and the chemical stability. However, if too much is introduced, the viscosity of the glass liquid is increased rapidly, the melting is difficult, the thermal expansion coefficient is reduced rapidly, and the Al in the invention 2 O 3 Is suitably in the range of 1 to 10%. Bi (Bi) 2 O 3 The glass network generates oxide with low softening point, and Bi is introduced along with the oxide 2 O 3 The doping amount is increased, bi 3+ Enters a glass network structure to play a role of connecting P-O-P, enhances the compactness of the glass network structure, improves the chemical stability of glass, but the content of Bi in the invention is too large to cause glass crystallization easily 2 O 3 Is suitably in the range of 0.1 to 14%. CuO is an external oxide of a glass network, can effectively reduce the diffusion rate of water molecules in glass after being introduced, and can also realize the effect of Na + The barrier effect is generated, and the chemical stability of the glass is greatly improved. Furthermore, copper ions can be present between 2 linear phosphates or 2 adjacent phosphorus-oxygen tetrahedra of linear phosphates [ PO ] according to the chelation mechanism of the polyphosphate 4 ]The phosphate glass is connected by non-bridging oxygen, so that the strength of P-O-P chain in the phosphate glass can be increased, and the structure of the glass tends toThe glass is stable, and the chemical stability of the glass is obviously improved; meanwhile, the copper ions can be introduced to improve the wettability and the sealing strength between the glass and the metal, but excessive introduction can increase the high-temperature viscosity and the crystallization tendency of the glass, and the suitable range of CuO in the invention is 0-20%.
The invention has the beneficial effects that:
1. the sealing glass blank prepared by the invention has high thermal expansion coefficient and low softening temperature, and the thermal expansion coefficient is more than 170 multiplied by 10 at 300 DEG C -7 The softening temperature is less than 450 ℃, and the sealing of aluminum/aluminum or aluminum/copper in the electrode cover plate of the power lithium battery is satisfied.
2. The injection molding technology is adopted to prepare the sealing glass blank, the glass powder slurry is not required to be prepared for spray granulation, the hydrolysis of phosphate glass is avoided, and compared with the traditional method for manufacturing the glass blank, the method has the advantages of high density, less bubble content, excellent chemical stability and the like, and is beneficial to improving the performance indexes such as the sealing property, the insulation property and the like of the electrode cover plate. The inside of the glass blank is more uniform, and the qualified rate of the vitrified and sintered product is high.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation method of the sealing glass blank for the power lithium battery comprises the following operation steps:
a. and (3) batching: the glass oxide components are converted into the raw materials of the introduced compound according to the above formula, and the corresponding raw materials are weighed, wherein P 2 O 5 Introduced by sodium dihydrogen phosphate and ammonium dihydrogen phosphate;
b. precalcining: firstly, uniformly mixing weighed sodium dihydrogen phosphate, ammonium dihydrogen phosphate and zinc peroxide, placing the mixture in an electric furnace to react for 1.2 hours at 460 ℃, and cooling the mixture to room temperature along with the furnace;
c. mixing: mixing the weighed residual raw materials with a mixture of pre-calcined sodium dihydrogen phosphate, ammonium dihydrogen phosphate and zinc peroxide, fully and uniformly mixing the raw materials in a mixer added with zirconium balls, and mixing for 2 hours to prepare a mixture;
d. melting: a crucible is arranged in a high-temperature electric furnace, the mixture is added, the temperature is increased to 900 ℃ according to a stepped temperature system, and the temperature is kept for 90 minutes, so that clarified glass liquid is obtained;
e. crushing and grinding: roll-pressing and cooling the molten glass in an open mill to room temperature, grinding and sieving;
f. injection molding: uniformly mixing the prepared sealing glass powder (the particle size distribution of the sealing glass powder is D50:70 mu m, D99:170 mu m) and ethyl cellulose in an internal mixer according to the mass ratio of 4.5:1, then cutting into particles to form a feed, heating, and injecting the feed on an injection molding machine (the injection temperature is 210 ℃ and the injection pressure is 15 MPa) to prepare a sealing glass green body;
g. degumming: placing the polished sealing glass green body into dimethylbenzene for soaking for 5 hours for degumming treatment, and removing the organic binder;
h. vitrification sintering: and (3) vitrification sintering is carried out on the degummed sealing glass green body in a sintering furnace in an inert gas atmosphere at 360 ℃, the sealing glass green body is cooled along with the furnace after heat preservation for 1 hour, and the sealing glass green body is shrunk and shaped after sintering, so that the high-density sealing glass cooked body is finally prepared.
i. And (3) detection: the thermal expansion coefficient, softening temperature, water resistance stability and sealing tightness of the glass powder are respectively tested, wherein the thermal expansion coefficient of the glass is tested by adopting GB 16920-2015 ' determination of average linear thermal expansion coefficient of the glass ', the softening temperature is tested by adopting ATSM 1350 ' standard test method for measuring viscosity of the glass between a softening point and an annealing range ', the water resistance stability is tested by adopting GB/T6582-1997 ' particle test method and classification of water resistance of the glass at 98 ℃, and the air tightness test method of the sealing piece is tested according to the test condition C program I of the method 112 in GJB360B-2009 ' test method for electronic and electric elements '.
TABLE 1
The foregoing describes one embodiment of the present invention in detail, but the description is only a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (9)
1. A sealing glass blank for a power lithium battery is characterized in that the sealing glass blank comprises the following oxide components in mole percentage 2 O 5 ：30-50％，TeO 2 ：20-50％，ZnO 2 ：8-15％，Li 2 O：1-10％，Na 2 O：0-10％，K 2 O：1-15％，Al 2 O 3 ：1-10％，Bi 2 O 3 ：0.1-14％，CuO：0-20％。
2. The sealing glass blank for a power lithium battery according to claim 1, wherein the mol percentage of the oxide component of the sealing glass blank comprises P 2 O 5 ：35-45％，TeO 2 ：25-40％，ZnO 2 ：8-12％，Li 2 O：2-8％，Na 2 O：1-7％，K 2 O：2-12％，Al 2 O 3 ：2-7％，Bi 2 O 3 ：2-10％，CuO：5-15％。
3. The sealing glass blank for a power lithium battery according to claim 1, wherein P 2 O 5 With TeO 2 The sum of the mole percentages is 55% -75%.
4. The sealing glass blank for a power lithium battery according to claim 1, wherein Li 2 O+Na 2 O+K 2 The sum of the mole percentages of O is 10% -20%.
5. A method for preparing a sealing glass blank for a power lithium battery according to claim 1, which is characterized by comprising the following steps:
(1) And (3) batching: the glass oxide components are converted into the raw materials of the introduced compound according to the above formula, and the corresponding raw materials are weighed, wherein P 2 O 5 Introduced by sodium dihydrogen phosphate and ammonium dihydrogen phosphate;
(2) Precalcining: firstly, uniformly mixing weighed sodium dihydrogen phosphate, ammonium dihydrogen phosphate and zinc peroxide, placing the mixture in an electric furnace to react for 0.5 to 1.5 hours at 400 to 500 ℃, and then cooling the mixture to room temperature along with the furnace;
(3) Mixing: mixing the weighed residual raw materials with a mixture of pre-calcined sodium dihydrogen phosphate, ammonium dihydrogen phosphate and zinc peroxide, and fully and uniformly mixing the raw materials in a mixer added with zirconium balls for 1-3 hours to prepare a mixture;
(4) Melting: placing a crucible in a high-temperature electric furnace, adding a mixture, heating to 850-1100 ℃ according to a stepped temperature system, and preserving heat for 30-120min to obtain clarified glass liquid;
(5) Crushing and grinding: rolling and cooling the melted glass liquid to room temperature in an open mill, grinding and sieving to obtain sealing glass powder;
(6) Injection molding: uniformly mixing the prepared sealing glass powder and a binder in a mass ratio of 4-5:1 in an internal mixer, granulating or crushing to form a feed, heating, and injecting on an injection molding machine to prepare a sealing glass green body;
(7) Degumming: soaking the polished sealing glass green body in a solvent for 3-6 hours to perform degumming treatment, and removing the organic binder;
(8) Vitrification sintering: and (3) vitrification sintering is carried out on the degummed sealing glass green body in a sintering furnace in an inert gas atmosphere at 350-450 ℃, the temperature is kept for 0.5-1.5 hours, then the sealing glass green body is cooled along with the furnace, and the sealing glass green body is shrunk and shaped after sintering, so that the high-density sealing glass cooked body is finally prepared.
6. The method for producing a sealing glass preform for a lithium power battery according to claim 5, wherein the sealing glass powder used in the step (6) has a particle size distribution of D50:60-80 μm, D99:150-180 μm.
7. The method of claim 5, wherein the binder used in the step (6) is an oil-soluble organic binder, and is one or more of ethylcellulose, povidone, polyvinyl acetate, and polyvinyl acetal.
8. The method of claim 5, wherein the solvent used in the step (7) is one or more of ethanol, ethyl acetate, acetone, chloroform and xylene.
9. The method for producing a sealing glass preform for a lithium-ion power battery according to claim 5, wherein the kneading temperature is 170 to 240 ℃, the injection temperature is 170 to 250 ℃, and the injection pressure is 12 to 30MPa.
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