CN108336400A - A kind of preparation method of sulfide solid electrolyte - Google Patents
A kind of preparation method of sulfide solid electrolyte Download PDFInfo
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- CN108336400A CN108336400A CN201810461344.0A CN201810461344A CN108336400A CN 108336400 A CN108336400 A CN 108336400A CN 201810461344 A CN201810461344 A CN 201810461344A CN 108336400 A CN108336400 A CN 108336400A
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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
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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
- 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
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Abstract
A kind of preparation method of sulfide solid electrolyte, belongs to solid electrolyte field.Include the following steps：(1) sulphur powder, lithium hydride, phosphorus pentasulfide, lithium phosphate raw material are dried in vacuum drying chamber；(2) under inert atmosphere protection; according to 15%~40% sulphur powder of mass percent, 5%~20% lithium hydride, 50%~70% phosphorus pentasulfide, 0%~10% lithium phosphate; the raw material after above-mentioned drying are weighed respectively; pre-grinding 5~20 minutes in mortar; it is added in the ball grinder of sealing, rotating speed is 24~60h of ball milling under the conditions of 200~600r/min at room temperature；(3) after ball-milling reaction, under an inert atmosphere, powder is taken out from ball grinder, is added in crucible, in high temperature process furnances, is sintered in a nitrogen atmosphere, sintering temperature is 200~400 DEG C, and sintering time is 2~6h.Powder is taken out from crucible to get to sulfide solid electrolyte.The preparation method of sulfide solid electrolyte of the present invention has the characteristics that simple for process, cost of material is low, is easy to industrialized production.
Description
Technical field
The invention belongs to solid electrolyte fields, and in particular to a kind of solid electrolytic can be used for all-solid lithium-ion battery
Material and preparation method thereof.
Background technology
The mobile electrochemical system of lithium ion battery with high energy density flourishes, and traditional system uses organic liquid electricity
It solves matter and requires to be improved in terms of safety and durability.This has just drawn the demand to suitable solid electrolyte.Solid
In state electrolyte, it is based on Li2S-P2S5System sulfide solid electrolyte is proved at 25 DEG C its ionic conductivity and makes at present
Liquid electrolyte is suitable.
This sulfide-based solid electrolyte mainly passes through high-energy ball milling method by lithium sulfide, phosphorus pentasulfide and additive
It being prepared with Post isothermal treatment, the solid electrolyte obtained from these conventional methods shows excellent lithium ion conductivity,
But the high cost of lithium sulfide raw material and existing lithium sulfide preparation method will solvent, by separation of solid and liquid process efficiency
Relatively low, cost is higher, and toxic solvent is harmful, expensive to be difficult to realize industrialized production, and the vulcanization that this method obtains
That there are purity is not high for lithium, consumes energy the shortcomings of high.It is comprehensive that lithium sulfide and mechanical ball mill are prepared by sulphur powder, lithium hydride mechanical attrition method
Method and rear heat treatment prepare sulfide solid electrolyte method, develop a kind of new and effective, environmental-friendly, inexpensive sulfide
Method for preparing solid electrolyte is of great significance.
Invention content
The invention aims to provide, one kind is efficient, inexpensive, environmental-friendly, is easy to industrialized production, suitable for complete
The novel processing step of the high ionic conductivity solid electrolyte of solid lithium ion battery.
Technical scheme of the present invention is illustrated below.
A kind of preparation method of sulfide solid electrolyte, which is characterized in that be as follows：
(1) sulphur powder, lithium hydride, phosphorus pentasulfide, lithium phosphate raw material are dried in vacuum drying chamber；
(2) under inert atmosphere protection, the raw material after drying, the beforehand research in mortar are weighed respectively according to mass percent
Mill 5~20 minutes, is added to ball milling in the ball grinder of sealing；
(3) after ball-milling reaction, under an inert atmosphere, powder is taken out from ball grinder, is added in crucible, in height
Powder taken out from crucible in warm tube furnace, after being sintered in a nitrogen atmosphere to get to sulfide solid electrolyte.
Further, sulphur powder in the step (1), lithium hydride, phosphorus pentasulfide powder raw material purity be not less than
90%.
Further, in the step (2), 15%~40% sulphur powder of raw material quality percentage, 5%~20% hydrogenation
Lithium, 50%~70% phosphorus pentasulfide, 0%~10% lithium phosphate.
Further, sulphur powder, lithium hydride, phosphorus pentasulfide, lithium phosphate raw material pass through vacuum drying in the step (2)
Case dry, drying temperature be 60~100 DEG C, drying time be 1~for 24 hours.
Further, sulphur powder, total matter of lithium hydride, the gross mass of phosphorus pentasulfide powder and abrading-ball in the step (2)
Amount is than being 1:(10~80).
Further, in the step (2), rotational speed of ball-mill is 200~600r/min, and Ball-milling Time is 24~60h.
Further, the inert atmosphere is the gas not reacted with sulphur powder, lithium hydride, phosphorus pentasulfide powder.
Further, in the step (3), sintering atmosphere is nitrogen, and the flow velocity of nitrogen is 0~100mL/min.
Further, in the step (3), sintering temperature is 200~400 DEG C, and sintering time is 2~6h.
Compared with prior art, the present invention advantage is mainly reflected in：
(1) lithium sulfide is generated under mechanical ball mill using elemental sulfur and lithium hydride in the present invention, and lithium sulfide and five vulcanizes
Two phosphorus generate amorphous Li under mechanical ball mill2S-P2S5The sulfide solid electrolyte of system
(2) ball milling of the preparation of mechanical attrition method lithium sulfide and sulfide solid electrolyte two ball-milling methods are prepared to integrate
It is raw materials used cheap at a step, and no liquid, separation of solid and liquid process is needed not move through, it is environmental-friendly, it is easy to industrialize
Implement.
Specific implementation mode
The present invention provides a kind of preparation method for the sulfide solid electrolyte can be used for all-solid lithium-ion battery, under
In face of specific implementation method, the present invention will be further described.
Embodiment 1
Sulphur powder, lithium hydride, phosphorus pentasulfide, lithium phosphate raw material are dried into 12h in 100 DEG C of vacuum drying chambers.In argon
By 2.24g sulphur powders, 1.12g lithium hydrides, 6.66g phosphorus pentasulfides, the beforehand research in mortar of 0.116g lithium phosphates under gas atmosphere protection
Mill 10 minutes, is added in the ball grinder of sealing, and wherein abrading-ball gross mass and material total mass ratio are 20:1, rotating speed at room temperature
For ball milling 60h under the conditions of 400r/min.After ball-milling reaction, under an inert atmosphere, powder is taken out from ball grinder, is added
It into crucible, in high temperature process furnances, is sintered under 80mL/min nitrogen atmospheres, sintering temperature is 300 DEG C, sintering time
For 4h.Powder is taken out from crucible to get to sulfide solid electrolyte.
Embodiment 2
Sulphur powder, lithium hydride, phosphorus pentasulfide, lithium phosphate raw material are dried into 18h in 80 DEG C of vacuum drying chambers.In argon gas
By 2.56g sulphur powders, 1.28g lithium hydrides, 4.44g phosphorus pentasulfides, 0.116g lithium phosphates pre-grinding in mortar under atmosphere protection
It 10 minutes, is added in the ball grinder of sealing, wherein abrading-ball gross mass and material total mass ratio are 30:1, at room temperature rotating speed be
Ball milling 48h under the conditions of 500r/min.After ball-milling reaction, under an inert atmosphere, powder is taken out from ball grinder, is added to
It in crucible, in high temperature process furnances, is sintered under 40mL/min nitrogen atmospheres, sintering temperature is 260 DEG C, and sintering time is
3h.Powder is taken out from crucible to get to sulfide solid electrolyte.
Embodiment 3
Sulphur powder, lithium hydride, phosphorus pentasulfide, lithium phosphate raw material are dried for 24 hours in 60 DEG C of vacuum drying chambers.In argon gas
By 2.4g sulphur powders, 1.2g lithium hydrides, 5.55g phosphorus pentasulfides, 0.116g lithium phosphates pre-grinding 10 in mortar under atmosphere protection
Minute, it is added in the ball grinder of sealing, wherein abrading-ball gross mass and material total mass ratio are 40:1, at room temperature rotating speed be
Ball milling 36h under the conditions of 300r/min.After ball-milling reaction, under an inert atmosphere, powder is taken out from ball grinder, is added to
It in crucible, in high temperature process furnances, is sintered under 60mL/min nitrogen atmospheres, sintering temperature is 280 DEG C, and sintering time is
5h.Powder is taken out from crucible to get to sulfide solid electrolyte.
Claims (9)
1. a kind of preparation method of sulfide solid electrolyte, which is characterized in that be as follows：
(1) sulphur powder, lithium hydride, phosphorus pentasulfide, lithium phosphate raw material are dried in vacuum drying chamber；
(2) under inert atmosphere protection, the raw material after drying, pre-grinding 5 in mortar are weighed respectively according to mass percent
~20 minutes, it is added to ball milling in the ball grinder of sealing；
(3) after ball-milling reaction, under an inert atmosphere, powder is taken out from ball grinder, is added in crucible, in high temperature pipe
Powder taken out from crucible in formula stove, after being sintered in a nitrogen atmosphere to get to sulfide solid electrolyte.
2. the preparation method of sulfide solid electrolyte as described in claim 1, it is characterised in that：Sulphur in the step (1)
Powder, lithium hydride, phosphorus pentasulfide powder raw material purity be not less than 90%.
3. the preparation method of sulfide solid electrolyte as described in claim 1, it is characterised in that：It is former in the step (2)
15%~40% sulphur powder of quality of materials percentage, 5%~20% lithium hydride, 50%~70% phosphorus pentasulfide, 0%~10% phosphorus
Sour lithium.
4. the preparation method of sulfide solid electrolyte as claimed in claim 1 or 2, it is characterised in that：In the step (2)
Sulphur powder, lithium hydride, phosphorus pentasulfide, lithium phosphate raw material are dried by vacuum drying chamber, and drying temperature is 60~100 DEG C, is done
The dry time be 1~for 24 hours.
5. the preparation method of sulfide solid electrolyte as described in claim 1, it is characterised in that：Sulphur in the step (2)
Powder, lithium hydride, the gross mass of phosphorus pentasulfide powder and abrading-ball total mass ratio be 1:(10~80).
6. the preparation method of sulfide solid electrolyte as described in claim 1, it is characterised in that：In the step (2), ball
Mill rotating speed is 200~600r/min, and Ball-milling Time is 24~60h.
7. the preparation method of sulfide solid electrolyte as described in claim 1, it is characterised in that the inert atmosphere is
The gas not reacted with sulphur powder, lithium hydride, phosphorus pentasulfide powder.
8. the preparation method of sulfide solid electrolyte as described in claim 1, it is characterised in that：In the step (3), burn
Knot atmosphere is nitrogen, and the flow velocity of nitrogen is 0~100mL/min.
9. the preparation method of sulfide solid electrolyte as described in claim 1, it is characterised in that：In the step (3), burn
Junction temperature is 200~400 DEG C, and sintering time is 2~6h.
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| CN201810461344.0A CN108336400A (en) | 2018-05-15 | 2018-05-15 | A kind of preparation method of sulfide solid electrolyte |
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| CN201810461344.0A CN108336400A (en) | 2018-05-15 | 2018-05-15 | A kind of preparation method of sulfide solid electrolyte |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110323488A (en) * | 2019-06-25 | 2019-10-11 | 浙江锋锂新能源科技有限公司 | A kind of preparation method of the sulfide solid electrolyte ceramics of high conductivity |
Citations (5)
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|---|---|---|---|---|
| CN102544580A (en) * | 2012-02-29 | 2012-07-04 | 中国科学院宁波材料技术与工程研究所 | Fully solid-state lithium secondary battery electrolyte material, preparation method thereof and fully solid-state lithium secondary battery |
| CN103943880A (en) * | 2013-01-22 | 2014-07-23 | 华为技术有限公司 | Sulphur-based glass ceramic electrolyte, preparation method thereof, all-solid-state lithium battery and preparation method of the all-solid-state lithium battery |
| CN104609376A (en) * | 2015-01-30 | 2015-05-13 | 浙江工业大学 | Preparation method of lithium sulfide powder |
| CN105552433A (en) * | 2015-12-23 | 2016-05-04 | 山东玉皇新能源科技有限公司 | Preparation method for amorphous state sulfide solid electrolyte |
| CN106684441A (en) * | 2017-01-09 | 2017-05-17 | 郑州新世纪材料基因组工程研究院有限公司 | Sulfur phosphide solid electrolyte and preparation method thereof |
-
2018
- 2018-05-15 CN CN201810461344.0A patent/CN108336400A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102544580A (en) * | 2012-02-29 | 2012-07-04 | 中国科学院宁波材料技术与工程研究所 | Fully solid-state lithium secondary battery electrolyte material, preparation method thereof and fully solid-state lithium secondary battery |
| CN103943880A (en) * | 2013-01-22 | 2014-07-23 | 华为技术有限公司 | Sulphur-based glass ceramic electrolyte, preparation method thereof, all-solid-state lithium battery and preparation method of the all-solid-state lithium battery |
| CN104609376A (en) * | 2015-01-30 | 2015-05-13 | 浙江工业大学 | Preparation method of lithium sulfide powder |
| CN105552433A (en) * | 2015-12-23 | 2016-05-04 | 山东玉皇新能源科技有限公司 | Preparation method for amorphous state sulfide solid electrolyte |
| CN106684441A (en) * | 2017-01-09 | 2017-05-17 | 郑州新世纪材料基因组工程研究院有限公司 | Sulfur phosphide solid electrolyte and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110323488A (en) * | 2019-06-25 | 2019-10-11 | 浙江锋锂新能源科技有限公司 | A kind of preparation method of the sulfide solid electrolyte ceramics of high conductivity |
| CN110323488B (en) * | 2019-06-25 | 2023-07-04 | 浙江锋锂新能源科技有限公司 | Preparation method of sulfide solid electrolyte ceramic with high conductivity |
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Application publication date: 20180727 |