CN105609870A - Preparation method of amorphous sulfide solid electrolyte - Google Patents
Preparation method of amorphous sulfide solid electrolyte Download PDFInfo
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- CN105609870A CN105609870A CN201510979014.7A CN201510979014A CN105609870A CN 105609870 A CN105609870 A CN 105609870A CN 201510979014 A CN201510979014 A CN 201510979014A CN 105609870 A CN105609870 A CN 105609870A
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- solid electrolyte
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- 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
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- 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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
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- 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 the field of lithium ion batteries, in particular to a preparation method of an amorphous sulfide solid electrolyte. The preparation method of the amorphous sulfide solid electrolyte is characterized by mainly comprising the following steps: (1) putting metallic lithium, elemental sulfur, germanium sulfide and phosphorus pentasulfide in a certain proportion into a water-free and oxygen-free sealed container for mixing; and (2) mechanically grinding the raw materials mixed in the step (1) so as to prepare the amorphous sulfide solid electrolyte. According to the preparation method, the proportion of lithium, sulfur to phosphorus can be accurately controlled, and the problem that raw material volatilization in a high-temperature solid-phase method causes relatively low product purity is solved; and meanwhile, the resources of the raw materials are abundant, the process is simple, and the high-purity amorphous sulfide solid electrolyte can be obtained through a ball-milling one-step method.
Description
Technical field
The present invention relates to lithium ion battery field, particularly a kind of preparation side of amorphous state sulfide solid electrolyteMethod.
Background technology
Low energy consumption, eco-friendly new-energy automobile are the directions of future automobile development, and electrokinetic cell is to affect new forms of energyThe key factor of automotive performance. The electrokinetic cell of existing new-energy automobile is selected liquid organic electrolyte conventionally, but is using, there is larger potential safety hazard in easily on fire or blast in situation improperly. All-solid-state battery uses solid electrolyte, does not exist easilyThe liquid electrolyte of burning, security significantly improves, and the charge capacity of all-solid-state battery is more simultaneously, power output is also larger. ButThe low ionic conductivity of solid electrolyte has hindered the practicality of all-solid-state battery at present.
In solid oxide electrolyte, in sulfide solid electrolyte, sulphion radius is larger, to the constraint of lithium ionLess, easily, electrical conductivity is higher in lithium ion migration. Document " Alithiumsuperionicconductor, Nat.Mater., 2011,10,682-686. " report the sulfuration of preparing taking lithium sulfide, germanium sulfide and phosphorus pentasulfide as raw materialThing solid electrolyte Li10GeP2S12Conductivity at room temperature is up to 1.2 × 10-2S/cm, reaches business level of electrolyte and outstandingFor attracting people's attention. But common synthetic method Raw generally adopts lithium sulfide at present, and lithium sulfide is expensive, easily moisture absorption waterSeparate, affected Industrialization Progress. Publication number is that the Chinese patent of CN1937301A discloses that " it is solid that one can be used as lithium ion batteryElectrolytical sulfide material of body and preparation method thereof ", adopt multiple lithium source high temperature method to prepare sulfide solid electrolyte, althoughCan prepare sulfide solid electrolyte, but high-temperature process causes material crystallization, ionic conductivity lower and increase energy consumption, materialVolatilization causes product proportioning to be difficult to accurate control.
Summary of the invention
The present invention, in order to make up the defect of prior art, provides a kind of raw material that adopts low price to be easy to get, by letterSingle mechanical milling method is prepared the method for amorphous state sulfide solid electrolyte material.
The present invention is achieved through the following technical solutions:
The preparation method of amorphous state sulfide solid electrolyte, is characterized in that: mainly comprise the following steps:
(1) will in the closed container of a certain proportion of lithium metal, elemental sulfur, germanium sulfide, phosphorus pentasulfide input anhydrous and oxygen-free, enterRow mixes;
(2) raw material mixing in step (1) is carried out to mechanical lapping, prepare amorphous state sulfide solid electrolyte.
In step (1), the mol ratio of lithium metal and elemental sulfur is 1.8:1～3:1.
Preferably, according to the ratio-dependent of end product, in step (1), the mol ratio of lithium metal and elemental sulfur is 2:1.
In step (1), described lithium metal and the mol ratio of germanium sulfide are 8:1～12:1.
Preferably, according to Li10GeP2S12The ratio-dependent of compound, the mol ratio of step (1) lithium metal and germanium sulfide is10:1。
In step (1), described lithium metal and the mol ratio of phosphorus pentasulfide are 8:1～12:1.
Preferably, according to Li10GeP2S12The ratio-dependent of compound, in step (1), lithium metal and phosphorus pentasulfide rubsYou are than being 10:1.
Preferably, the closed container of the described anhydrous and oxygen-free of step (1) is the glove box that is full of inert gas, described glove boxThere is water scavenging system, because lithium metal is met water or oxygen and can be reacted, the also easy moisture absorption of phosphorus pentasulfide, thus must exclusion of water andOxygen therefore will operate in inert atmosphere, and the own water content of commercially available nitrogen or argon gas is extremely low, has except water system in glove box simultaneouslySystem, can ensure not change in sample preparation process.
The method of the mechanical lapping described in step (2) comprises ball-milling method and polishing.
Preferably, the method for the described mechanical lapping of step (2) is ball-milling method, ball-milling method can by control ratio of grinding media to material andTime is controlled the process of reaction, is applicable to extensive and automation mechanized operation simultaneously.
In step (2), described ratio of grinding media to material 10:1～20:1, ratio of grinding media to material is too large, can increase between abrasive media and be situated betweenThe idle work of impact friction loss between matter and ball grinder, not only makes power consumption increase, yield reducation, but also can aggravate ball grinderWearing and tearing; If ratio of grinding media to material is too little, the cushioning effect of material increases, and impact grinds effect and will weaken; Rotational speed of ball-mill is 150～250 revs/min, rotating speed too low reaction is difficult to completely, and material easily occurs adheres to the problem of ball grinder, and rotating speed is Gao Zeyi tooThe wearing and tearing of aggravation ball grinder, and temperature rise causes more greatly side reaction; Ball-milling Time is 10～48 hours, and the time is too short, and reaction is not filledPoint, size distribution is inhomogeneous; Time is oversize, affects efficiency, easily introduces impurity.
Preferably, ratio of grinding media to material 18:1 in described step (2), can give full play to the impact grinding effect of medium, improves ballThe ability to work of grinding machine; Rotational speed of ball-mill is 200 revs/min, and Ball-milling Time is 24 hours, can ensure that sufficient reacting is complete.
The invention has the beneficial effects as follows: the invention provides a kind of easy preparation amorphous state sulfide solid electrolyteMethod, can accurately control the ratio of lithium, sulphur, germanium, phosphorus, has solved the volatilization of high temperature solid-state method Raw and has caused product purity lowerProblem, simultaneously raw material sources are abundant, technique is simple, just can obtain highly purified amorphous state sulfide by ball-milling method one stepSolid electrolyte, can realize large-scale production.
Brief description of the drawings
Below in conjunction with accompanying drawing, the present invention is further illustrated.
The Li that accompanying drawing 1 is prepared for the embodiment of the present invention 110GeP2S12AC impedance figure.
Detailed description of the invention
Below by specific embodiments, the present invention is described in further detail, but these embodiments are only for exampleIllustrate, scope of the present invention is not limited.
Embodiment 1:
Lithium metal and elemental sulfur, germanium sulfide, phosphorus pentasulfide, according to the ratio of mol ratio 10:5:1:1, are being full of the gloves of nitrogenIn case, take 0.2377g lithium metal, 0.5433g elemental sulfur, 0.4652g germanium sulfide and 0.7538g phosphorus pentasulfide, by above-mentionedRaw material and 36g zirconia ball drop in 100ml zirconia ball grinding jar, after sealing, from glove box, take out completely. Then use rowStar formula ball mill ball milling 24 hours under 200 revs/min of conditions, obtains amorphous state sulfide solid electrolyte Li10GeP2S12。
Sample is pressed into diameter 15mm, and the disk of thickness 0.5mm left and right, is clipped in disk between stainless steel disk, will encircleEpoxy resins glue spreads upon on exposed solid electrolyte, leave standstill within 10 minutes, wait solidify complete. Two ends stainless steel substrates is connected respectivelyPositive pole and negative pole are tested AC impedance figure on electrochemical workstation, can calculate sulfide solid electrolysis according to the impedance of testThe electrical conductivity of matter.
Testing impedance result shown in 1 with reference to the accompanying drawings, the computing formula by electrical conductivity:
Wherein, σ is electrolytical electrical conductivity (S/cm);
L is the thickness (cm) of electrolyte compressing tablet;
S is the area (cm of electrolyte compressing tablet2）；
R is the resistance value (Ω) that AC impedance figure obtains.
Calculate conductivityσ ≈ 0.6 × 10-2S/cm
Embodiment 2:
The ratio that lithium metal and elemental sulfur, germanium sulfide, phosphorus pentasulfide are 10:5:1:1 according to mol ratio, is being full of the hand of argon gasIn casing, take 0.2377g lithium metal, 0.5433g elemental sulfur, 0.4652g germanium sulfide and 0.7538g phosphorus pentasulfide, by upperState raw material and 30g zirconia ball and drop in 100ml zirconia ball grinding jar, after sealing, from glove box, take out completely. Then usePlanetary ball mill ball milling 48 hours under 200 revs/min of conditions, obtains amorphous state sulfide solid electrolyte Li10GeP2S12。
Sample is pressed into diameter 15mm, and the disk of thickness 0.5mm left and right, is clipped in disk between stainless steel disk, will encircleEpoxy resins glue spreads upon on exposed solid electrolyte, leave standstill within 10 minutes, wait solidify complete. Two ends stainless steel substrates is connected respectivelyPositive pole and negative pole are tested AC impedance figure on electrochemical workstation, can calculate sulfide solid electrolysis according to the impedance of testThe electrical conductivity of matter.
Experiment obtains testing impedance result, is calculated conductivityσ ≈ 0.6 × 10 by the computing formula of electrical conductivity-2S/cm。
Embodiment 3:
The ratio that lithium metal and elemental sulfur, germanium sulfide, phosphorus pentasulfide are 10:5:1:1 according to mol ratio, is being full of the hand of nitrogenIn casing, take 0.2377g lithium metal, 0.5433g elemental sulfur, 0.4652g germanium sulfide and 0.7538g phosphorus pentasulfide, by upperState raw material and 36g zirconia ball and drop in 100ml zirconia ball grinding jar, after sealing, from glove box, take out completely. Then usePlanetary ball mill ball milling 24 hours under 250 revs/min of conditions, obtains amorphous state sulfide solid electrolyte Li10GeP2S12。
Sample is pressed into diameter 15mm, and the disk of thickness 0.5mm left and right, is clipped in disk between stainless steel disk, will encircleEpoxy resins glue spreads upon on exposed solid electrolyte, leave standstill within 10 minutes, wait solidify complete. Two ends stainless steel substrates is connected respectivelyPositive pole and negative pole are tested AC impedance figure on electrochemical workstation, can calculate sulfide solid electrolysis according to the impedance of testThe electrical conductivity of matter.
Experiment obtains testing impedance result, is calculated conductivityσ ≈ 0.6 × 10 by the computing formula of electrical conductivity-2S/cm。
Embodiment 4:
The ratio that lithium metal and elemental sulfur, germanium sulfide, phosphorus pentasulfide are 12:5:1:1 according to mol ratio, is being full of the hand of nitrogenIn casing, take 0.2791g lithium metal, 0.5316g elemental sulfur, 0.4518g germanium sulfide and 0.7375g phosphorus pentasulfide, by upperState raw material and 25g zirconia ball and drop in 100ml zirconia ball grinding jar, after sealing, from glove box, take out completely. Then usePlanetary ball mill ball milling 24 hours under 200 revs/min of conditions, obtains amorphous state sulfide solid electrolyte Li12GeP2S12。
Sample is pressed into diameter 15mm, and the disk of thickness 0.5mm left and right, is clipped in disk between stainless steel disk, will encircleEpoxy resins glue spreads upon on exposed solid electrolyte, leave standstill within 10 minutes, wait solidify complete. Two ends stainless steel substrates is connected respectivelyPositive pole and negative pole are tested AC impedance figure on electrochemical workstation, can calculate sulfide solid electrolysis according to the impedance of testThe electrical conductivity of matter.
Experiment obtains testing impedance result, is calculated conductivityσ ≈ 0.5 × 10 by the computing formula of electrical conductivity-2S/cm。
Embodiment 5:
The ratio that lithium metal and elemental sulfur, germanium sulfide, phosphorus pentasulfide are 12:6:1:1 according to mol ratio, is being full of the hand of nitrogenIn casing, take 0.2646g lithium metal, 0.6047g elemental sulfur, 0.4315g germanium sulfide and 0.6992g phosphorus pentasulfide, by upperState raw material and 36g zirconia ball and drop in 100ml zirconia ball grinding jar, after sealing, from glove box, take out completely. Then usePlanetary ball mill ball milling 24 hours under 150 revs/min of conditions, obtains amorphous state sulfide solid electrolyte Li12GeP2S13。
Sample is pressed into diameter 15mm, and the disk of thickness 0.5mm left and right, is clipped in disk between stainless steel disk, will encircleEpoxy resins glue spreads upon on exposed solid electrolyte, leave standstill within 10 minutes, wait solidify complete. Two ends stainless steel substrates is connected respectivelyPositive pole and negative pole are tested AC impedance figure on electrochemical workstation, can calculate sulfide solid electrolysis according to the impedance of testThe electrical conductivity of matter.
Experiment obtains testing impedance result, is calculated conductivityσ ≈ 0.6 × 10 by the computing formula of electrical conductivity-2S/cm。
Claims (10)
1. a preparation method for amorphous state sulfide solid electrolyte, is characterized in that: mainly comprise the following steps:
(1) will in the closed container of a certain proportion of lithium metal, elemental sulfur, germanium sulfide, phosphorus pentasulfide input anhydrous and oxygen-free, enterRow mixes;
(2) raw material mixing in step (1) is carried out to mechanical lapping, prepare amorphous state sulfide solid electrolyte.
2. the preparation method of amorphous state sulfide solid electrolyte according to claim 1, is characterized in that: step (1)The mol ratio of middle lithium metal and elemental sulfur is 1.8:1～3:1.
3. the preparation method of amorphous state sulfide solid electrolyte according to claim 2, is characterized in that: step (1)The mol ratio of middle lithium metal and elemental sulfur is 2:1.
4. the preparation method of amorphous state sulfide solid electrolyte according to claim 1, is characterized in that: step (1)In, described lithium metal and the mol ratio of germanium sulfide are 8:1～12:1, the mol ratio of lithium metal and phosphorus pentasulfide be 8:1～12:1。
5. the preparation method of amorphous state sulfide solid electrolyte according to claim 4, is characterized in that: step (1)The mol ratio of middle lithium metal and germanium sulfide is 10:1, and the mol ratio of lithium metal and phosphorus pentasulfide is 10:1.
6. the preparation method of amorphous state sulfide solid electrolyte according to claim 1, is characterized in that: step (1)The closed container of described anhydrous and oxygen-free is the glove box that is full of inert gas, and described glove box has water scavenging system, described inertiaAtmosphere is nitrogen or argon gas.
7. the preparation method of amorphous state sulfide solid electrolyte according to claim 1, is characterized in that: step (2)The method of described mechanical lapping comprises ball-milling method and polishing.
8. according to the preparation method of the amorphous state sulfide solid electrolyte described in claim 1 or 7, it is characterized in that: step(2) method of described mechanical lapping is ball-milling method.
9. the preparation method of amorphous state sulfide solid electrolyte according to claim 1, is characterized in that: step (2)In, described ratio of grinding media to material 10:1～20:1, rotational speed of ball-mill is 150～250 revs/min, Ball-milling Time is 10～48 hours.
10. according to the preparation method of the amorphous state sulfide solid electrolyte described in claim 1 or 9, it is characterized in that: described inRatio of grinding media to material 18:1 in step (2); Rotational speed of ball-mill is 200 revs/min, and Ball-milling Time is 24 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107069080A (en) * | 2017-02-13 | 2017-08-18 | 桂林电器科学研究院有限公司 | A kind of lithium sulfide system solid electrolyte material for adding lithium-tin alloy and silver chlorate and preparation method thereof |
| CN108878962A (en) * | 2018-07-11 | 2018-11-23 | 桑德集团有限公司 | A kind of sulfide solid electrolyte and preparation method thereof |
| CN109301336A (en) * | 2018-09-18 | 2019-02-01 | 郑州新世纪材料基因组工程研究院有限公司 | Amorphous state sulfide solid electrolyte and preparation method thereof, lithium ion battery |
| CN110526278A (en) * | 2019-08-26 | 2019-12-03 | 浙江工业大学 | A method of red mercuric sulfide is synthesized using mechanical attrition method low temperature |
| CN111066189A (en) * | 2017-09-14 | 2020-04-24 | 富士胶片株式会社 | Solid electrolyte composition, method for producing same, method for storing same, kit, solid electrolyte-containing sheet, method for storing same, kit, and all-solid-state secondary battery |
| CN113839086A (en) * | 2021-08-05 | 2021-12-24 | 恒大新能源技术(深圳)有限公司 | Sulfide solid electrolyte, preparation method thereof, solid electrolyte sheet and solid battery |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107069080A (en) * | 2017-02-13 | 2017-08-18 | 桂林电器科学研究院有限公司 | A kind of lithium sulfide system solid electrolyte material for adding lithium-tin alloy and silver chlorate and preparation method thereof |
| CN111066189A (en) * | 2017-09-14 | 2020-04-24 | 富士胶片株式会社 | Solid electrolyte composition, method for producing same, method for storing same, kit, solid electrolyte-containing sheet, method for storing same, kit, and all-solid-state secondary battery |
| US11621436B2 (en) | 2017-09-14 | 2023-04-04 | Fujifilm Corporation | Solid electrolyte composition, manufacturing method thereof, storage method thereof, kit thereof, solid electrolyte-containing sheet, storage method thereof, kit thereof, and all-solid state secondary battery |
| CN111066189B (en) * | 2017-09-14 | 2024-03-01 | 富士胶片株式会社 | Solid electrolyte composition, solid electrolyte-containing sheet, method for producing and storing solid electrolyte-containing sheet, method for producing solid electrolyte-containing sheet, method for storing solid electrolyte-containing sheet, and kit for producing solid electrolyte-containing sheet |
| CN108878962A (en) * | 2018-07-11 | 2018-11-23 | 桑德集团有限公司 | A kind of sulfide solid electrolyte and preparation method thereof |
| CN109301336A (en) * | 2018-09-18 | 2019-02-01 | 郑州新世纪材料基因组工程研究院有限公司 | Amorphous state sulfide solid electrolyte and preparation method thereof, lithium ion battery |
| CN110526278A (en) * | 2019-08-26 | 2019-12-03 | 浙江工业大学 | A method of red mercuric sulfide is synthesized using mechanical attrition method low temperature |
| CN113839086A (en) * | 2021-08-05 | 2021-12-24 | 恒大新能源技术(深圳)有限公司 | Sulfide solid electrolyte, preparation method thereof, solid electrolyte sheet and solid battery |
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Application publication date: 20160525 |