CN114421003A - Preparation method of sulfide solid electrolyte - Google Patents
Preparation method of sulfide solid electrolyte Download PDFInfo
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- CN114421003A CN114421003A CN202210013433.5A CN202210013433A CN114421003A CN 114421003 A CN114421003 A CN 114421003A CN 202210013433 A CN202210013433 A CN 202210013433A CN 114421003 A CN114421003 A CN 114421003A
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- solid electrolyte
- sintering
- sulfide solid
- powder
- sheet
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002203 sulfidic glass Substances 0.000 title claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000003792 electrolyte Substances 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 23
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 16
- 239000010453 quartz Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 229910001216 Li2S Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910010848 Li6PS5Cl Inorganic materials 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 210000001161 mammalian embryo Anatomy 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000007784 solid electrolyte Substances 0.000 abstract description 20
- 230000007547 defect Effects 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 238000012512 characterization method Methods 0.000 abstract description 2
- 238000000840 electrochemical analysis Methods 0.000 abstract description 2
- 229910052945 inorganic sulfide Inorganic materials 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 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
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- 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
Abstract
The invention relates to a preparation method of an inorganic sulfide solid electrolyte, belonging to the field of lithium ion batteries. The invention aims at the solid electrolyte Li of the digermite6PS5The Cl primary solid phase sintering method is easy to generate defects of deformation, air holes, curling and the like in the preparation process, and the novel secondary sintering preparation method is obtained by improving on the basis of the primary sintering preparation method. The method is characterized in that the solid electrolyte sheet obtained by one-time sintering is crushed and then pressed again, and sintering is carried out again at a slightly higher temperature. Meanwhile, residual gas which cannot be volatilized in one-time sintering can be removed, the generation of electrolyte sheet deformation and defects is avoided, the obtained solid electrolyte has more uniform surface and more compact structure, the subsequent characterization and electrochemical test are convenient to carry out, and the ionic conductivity of the sulfide solid electrolyte can be improved。
Description
The technical field is as follows:
the invention relates to preparation of an all-solid-state battery in the field of lithium ion batteries, in particular to preparation of an inorganic sulfide solid electrolyte.
Background art:
lithium ion batteries have now occupied the consumer market in the new energy automobile and electronics fields. The lithium ion battery using the organic liquid electrolyte has the problem of lithium dendrite, so that the safety accidents such as electrolyte leakage, battery burning explosion and the like are easily caused. These safety problems can be alleviated by the use of inorganic solid-state electrolytes. The solid electrolyte can prevent the formation of lithium dendrites and withstand high voltage of 5V or more, compared to conventional organic electrolytes. In addition, the reduced packaging requirements also potentially improve weight and volumetric energy density.
The sulfide solid electrolyte has advantages of easy molding and high lithium ion conductivity. Wherein the Geranite solid electrolyte (Li)6PS5X, X ═ Cl, Br, I) have received extensive attention due to their higher ionic conductivity and lower raw material cost. However, since the sulfide solid electrolyte is sensitive to air and is easily contacted with air to cause performance deterioration, it is required to avoid contact with air as much as possible during the production process.
At present, a preparation method for a solid electrolyte of a silver germanite is mainly a one-step sintering forming method, but in the preparation process, the sulfide solid electrolyte sheet prepared by adopting a one-step sintering process is relatively fragile in texture, and in the sintering process in a sealed quartz tube, the sulfide solid electrolyte sheet is easy to deform and generate defects, such as curling deformation, bulging, air holes and the like, so that the problems are caused by a plurality of factors, such as uneven pressure distribution and stress generation in the pressing process; the ceramic plates are not placed flatly in the sintering process, so that the ceramic plates are heated unevenly in the sintering process; the temperature rising and falling speed in the sintering process is too fast, and easily decomposed components in the raw materials easily generate gas, and finally bulge and even crack are formed. The electrolyte sheet formed by one-time sintering is seriously deformed, so that subsequent tests are difficult to perform, and a battery sample cannot be prepared by using the electrolyte sheet, so that the important research field of the digermite solid electrolyte is the improvement of a preparation method. The key point of the invention is the secondary sintering process of the chalcogenide-germanite solid electrolyte, and the sulfide electrolyte sheet with more uniform surface and more compact structure can be obtained by the secondary sintering process, which is also beneficial to further improving the ionic conductivity of the sulfide solid electrolyte.
The invention content is as follows:
the invention mainly aims at the problems of deformation, cracking and the like of the solid electrolyte of the digermorite in the sintering process, and can further improve the compactness of the solid electrolyte of the digermorite so as to improve the ionic conductivity.
The basic idea of the invention is essentially Li2S、LiCl、P2S5As raw material, Li is obtained by high-energy ball milling6PS5Cl powder, taken after being pressed into tabletsBy using a secondary sintering method, the deformation of an electrolyte sheet in the sintering process is improved, and meanwhile, the Li is increased6PS5Ionic conductivity of Cl solid electrolyte.
A preparation method of a sulfide solid electrolyte is characterized by comprising the following preparation steps:
(1)Li6PS5preparing a Cl element embryo: raw material Li2S、LiCl、P2S5Mixing according to a certain mole ratio, loading into a stainless steel ball-milling tank with an air valve, then loading into zirconia balls, fixing, and ball-milling in a planetary ball mill for a period of time to obtain Li6PS5Cl powder, placing the powder in a mould, and pressing the powder into electrolyte sheet element blanks by using a cold press;
(2) a primary sintering process: heating a quartz tube containing an electrolyte sheet in a box-type furnace to a set temperature at a certain heating rate, preserving the temperature for a period of time, and cooling the quartz tube to room temperature along with the furnace;
(3) and (3) secondary sintering process: crushing and grinding the electrolyte sheet obtained by primary sintering to powder, tabletting and sealing the tube, and using the graphite sheet as a burning bearing plate during secondary sintering to ensure that the ceramic sheet is heated as uniformly as possible; heating to a set temperature in a box-type furnace at a certain heating rate, preserving heat for a period of time, and cooling to room temperature along with the furnace; the steps are all operated in a glove box except for sealing the tube.
Further, in the step (1), Li is used as a raw material2S、LiCl、P2S5Mixing according to a molar fraction of 5:2: 1; the ball-to-material ratio of the ball mill is set to be 20: 1.
Further, the ball milling speed in the step (1) is 500-600 rpm/h; the ball milling time is 18-24 h.
Further, Li in the mold in the step (1)6PS5The mass of Cl powder is 120-150 mg; the size of the mould is 10 mm; the thickness of the pressed electrolyte sheet blank is 1-1.2 mm; compacted Li6PS5The pressure of the Cl electrolyte sheet needs to be greater than 300 Mpa.
Further, the heat preservation temperature of the primary sintered quartz tube in the step (2) is 480-520 ℃; the temperature rise rate of the primary sintering is 1-5 ℃/min; the heat preservation time of the primary sintering is 5-7 h.
Further, the grinding time of the secondary sintering quartz tube in the step (3) is 18-22 min; the pressure of the tabletting and tube sealing is 360 MPa.
Further, the temperature rise rate of the secondary sintering in the step (3) is 1 ℃/min; the temperature of the heat preservation is 550 ℃. The heat preservation time of the secondary sintering is 6-12h respectively. The solid electrolyte prepared by the method is crystalline Li6PS5A Cl type solid electrolyte.
The flaky Li prepared by the above method6PS5The Cl solid electrolyte has uniform surface, no curling deformation phenomenon and no obvious defects of air holes, bulges and the like on a macroscopic view.
Li prepared by the above method6PS5The thickness of the Cl solid electrolyte sheet is 1-1.2mm, and the diameter is 10 mm.
The key points of the technology of the invention are as follows:
1. the method removes the non-volatile residual gas in the primary sintering material, improves the crystallinity and the density of the material, and prepares the obtained Li6PS5The Cl solid electrolyte sheet has no defects of curling deformation and air holes, and the prepared solid electrolyte has higher ionic conductivity.
2. The diameter of the electrolyte sheet conforms to the size of the inner diameter and the outer diameter of the quartz tube, the thickness is not too thin to reduce the strength of the biscuit, and the thickness is not too thick to influence the ionic conductivity of the material.
Li prepared according to the above-mentioned secondary sintering method6PS5Compared with the solid electrolyte prepared by the one-time sintering method, the Cl solid electrolyte has the following advantages:
electrolyte sheets do not deform, macroscopic defects do not exist on the surfaces, subsequent characterization and testing are convenient to directly carry out, secondary sintering can homogenize the sizes of crystal grains, the total sizes of the crystal grains are enlarged, the crystallinity and the density are improved, and electrochemical tests show that Li prepared by a secondary sintering method6PS5The Cl solid electrolyte has higher ionic conductivity.
Detailed Description
Example one
1) First step Li6PS5Preparation of Cl embryo, raw material Li2S、LiCl、P2S5Mixing according to the molar fraction of 5:2:1, putting into a stainless steel ball-milling tank with an air valve, then putting into zirconia balls with the ball-material ratio of 20:1, fixing in a planetary ball mill, and ball-milling at 550rpm/min for 24h to obtain Li6PS5Cl powder, 150mg Li was weighed6PS5And (3) pressing Cl powder into electrolyte sheet blank with the diameter of 10mm and the thickness of 1.2mm by using a cold press under the pressure of more than 360 MPa.
2) The second step is a sintering process, heating the quartz tube containing the electrolyte sheet in a box-type furnace to 500 ℃, heating up at a rate of 1 ℃/min, keeping the temperature for 6h, and cooling to room temperature along with the furnace.
3) And the third step is a secondary sintering process, wherein the electrolyte sheet obtained by primary sintering is crushed and ground into powder, the tube is sealed after the electrolyte sheet is pressed into a sheet under 360Mpa, and the graphite sheet is used as a burning bearing plate during secondary sintering, so that the ceramic sheet is uniformly heated. Heating to 550 ℃ in a box type furnace, heating at the rate of 1 ℃/min, keeping the temperature for 6h, and cooling to room temperature along with the furnace to obtain the compact ceramic body. The steps for removing the sealed tube are all operated in a glove box.
Example two
1) First step Li6PS5Preparation of Cl embryo, raw material Li2S、LiCl、P2S5Mixing according to the molar fraction of 5:2:1, putting into a stainless steel ball-milling tank with an air valve, then putting into zirconia balls with the ball-material ratio of 20:1, fixing in a planetary ball mill, and ball-milling at 550rpm/min for 24h to obtain Li6PS5Cl powder, 150mg Li was weighed6PS5And (3) pressing Cl powder into electrolyte sheet blank with the diameter of 10mm and the thickness of 1.2mm by using a cold press under the pressure of more than 360 MPa.
2) The second step is a sintering process, heating the quartz tube containing the electrolyte sheet in a box-type furnace to 500 ℃, heating up at a rate of 1 ℃/min, keeping the temperature for 6h, and cooling to room temperature along with the furnace.
3) And the third step is a secondary sintering process, wherein the electrolyte sheet obtained by primary sintering is crushed and ground into powder, the tube is sealed after the electrolyte sheet is pressed into a sheet under 360Mpa, and the graphite sheet is used as a burning bearing plate during secondary sintering, so that the ceramic sheet is uniformly heated. Heating to 550 ℃ in a box type furnace, heating at the rate of 1 ℃/min, keeping the temperature for 8h, and cooling to room temperature along with the furnace to obtain the compact ceramic body. The steps for removing the sealed tube are all operated in a glove box.
EXAMPLE III
1) First step Li6PS5Preparation of Cl embryo, raw material Li2S、LiCl、P2S5Mixing according to the molar fraction of 5:2:1, putting into a stainless steel ball-milling tank with an air valve, then putting into zirconia balls with the ball-material ratio of 20:1, fixing in a planetary ball mill, and ball-milling at 550rpm/min for 24h to obtain Li6PS5Cl powder, 150mg Li was weighed6PS5And (3) pressing Cl powder into electrolyte sheet blank with the diameter of 10mm and the thickness of 1.2mm by using a cold press under the pressure of more than 360 MPa.
2) The second step is a sintering process, heating the quartz tube containing the electrolyte sheet in a box furnace to 500 ℃, heating up at a rate of 1 ℃/min, keeping the temperature for 10h, and cooling to room temperature along with the furnace.
3) And the third step is a secondary sintering process, wherein the electrolyte sheet obtained by primary sintering is crushed and ground into powder, the tube is sealed after the electrolyte sheet is pressed into a sheet under 360Mpa, and the graphite sheet is used as a burning bearing plate during secondary sintering, so that the ceramic sheet is uniformly heated. Heating to 550 ℃ in a box type furnace, heating at the rate of 1 ℃/min, keeping the temperature for 10h, and cooling to room temperature along with the furnace to obtain the compact ceramic body. The steps for removing the sealed tube are all operated in a glove box.
Example four
1) First step Li6PS5Preparation of Cl embryo, raw material Li2S、LiCl、P2S5Mixing according to the molar fraction of 5:2:1, putting into a stainless steel ball-milling tank with an air valve, then putting into zirconia balls with the ball-material ratio of 20:1, fixing in a planetary ball mill, and ball-milling at 550rpm/min for 24h to obtain Li6PS5Cl powder, 150mg Li was weighed6PS5And (3) pressing Cl powder into electrolyte sheet blank with the diameter of 10mm and the thickness of 1.2mm by using a cold press under the pressure of more than 360 MPa.
2) The second step is a sintering process, heating the quartz tube containing the electrolyte sheet in a box-type furnace to 500 ℃, heating up at a rate of 1 ℃/min, keeping the temperature for 6h, and cooling to room temperature along with the furnace.
3) And the third step is a secondary sintering process, wherein the electrolyte sheet obtained by primary sintering is crushed and ground into powder, the tube is sealed after the electrolyte sheet is pressed into a sheet under 360Mpa, and the graphite sheet is used as a burning bearing plate during secondary sintering, so that the ceramic sheet is uniformly heated. Heating to 550 ℃ in a box type furnace, heating at the rate of 1 ℃/min, keeping the temperature for 12h, and cooling to room temperature along with the furnace to obtain the compact ceramic body. The steps for removing the sealed tube are all operated in a glove box.
The present embodiment is only for explaining the present invention, and not for limiting the present invention, and those skilled in the art can make modifications without inventive contribution to the present embodiment as needed after reading the present specification, but all of which are protected by patent law within the scope of the claims of the present invention.
Claims (7)
1. A preparation method of a sulfide solid electrolyte is characterized by comprising the following preparation steps:
(1)Li6PS5preparing a Cl element embryo: raw material Li2S、LiCl、P2S5Mixing according to a certain mole ratio, loading into a stainless steel ball-milling tank with an air valve, then loading into zirconia balls, fixing, and ball-milling in a planetary ball mill for a period of time to obtain Li6PS5Cl powder, placing the powder in a mould, and pressing the powder into electrolyte sheet element blanks by using a cold press;
(2) a primary sintering process: heating a quartz tube containing an electrolyte sheet in a box-type furnace to a set temperature at a certain heating rate, preserving the temperature for a period of time, and cooling the quartz tube to room temperature along with the furnace;
(3) and (3) secondary sintering process: crushing and grinding the electrolyte sheet obtained by primary sintering to powder, tabletting and sealing the tube, and using the graphite sheet as a burning bearing plate during secondary sintering to ensure that the ceramic sheet is heated as uniformly as possible; heating to a set temperature in a box-type furnace at a certain heating rate, preserving heat for a period of time, and cooling to room temperature along with the furnace; the steps are all operated in a glove box except for sealing the tube.
2. The method according to claim 1, wherein the sulfide solid electrolyte is prepared by a method comprising
In the step (1), raw material Li2S、LiCl、P2S5Mixing according to a molar fraction of 5:2: 1;
the ball-to-material ratio of the ball mill is set to be 20: 1.
3. The method for preparing a sulfide solid electrolyte according to claim 1, wherein the ball milling speed in step (1) is 500-600 rpm/h; the ball milling time is 18-24 h.
4. The production method of a sulfide solid electrolyte according to claim 1, characterized in that Li in the mold in step (1)6PS5The mass of Cl powder is 120-150 mg; the size of the mould is 10 mm; the thickness of the pressed electrolyte sheet blank is 1-1.2 mm; compacted Li6PS5The pressure of the Cl electrolyte sheet needs to be greater than 300 Mpa.
5. The method according to claim 1, wherein the temperature of the primary sintered quartz tube in step (2) is 480-520 ℃; the temperature rise rate of the primary sintering is 1-5 ℃/min; the heat preservation time of the primary sintering is 5-7 h.
6. The production method of a sulfide solid electrolyte according to claim 1, characterized in that the grinding time of the twice-sintered quartz tube in the step (3) is 18 to 22 min; the pressure of the tabletting and tube sealing is 360 MPa.
7. The production method of a sulfide solid electrolyte according to claim 1, characterized in that the temperature rise rate of the secondary sintering in step (3) is 1 ℃/min; the temperature of the heat preservation is 550 ℃. The heat preservation time of the secondary sintering is 6-12h respectively.
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| CN114421003B (en) | 2024-03-22 |
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