CN107482249A - A kind of solid-state sodium-ion battery electrolyte preparation method - Google Patents
A kind of solid-state sodium-ion battery electrolyte preparation method Download PDFInfo
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- CN107482249A CN107482249A CN201710673139.6A CN201710673139A CN107482249A CN 107482249 A CN107482249 A CN 107482249A CN 201710673139 A CN201710673139 A CN 201710673139A CN 107482249 A CN107482249 A CN 107482249A
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- Prior art keywords
- sodium
- ion battery
- solid
- battery electrolyte
- ion
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M2300/008—Halides
-
- 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 discloses a kind of solid-state sodium-ion battery electrolyte preparation method, comprise the following steps：Vulcanized sodium is dissolved in 1L ionized waters, is placed in afterwards in thermostat water bath and is heated to 80 90 DEG C, is put into sodium antimonate and NH4F, the mass ratio of vulcanized sodium, sodium antimonate and NH4F is 3.5 1.5：1：0.5 2.5, after being slowly stirred 34 hours, room temperature is naturally cooled to, is filtered.70 80 DEG C of dryings in drying baker, afterwards as in boiler tube, be heated to 300 400 DEG C reaction.The chemical formula of prepared solid-state sodium-ion battery electrolyte is Na3 xSbS4 xFx, containing F ion, and is nanostructured, the nanometer sheet of reason stacking forms, and contains substantial amounts of space between nanometer sheet.The F ion wherein adulterated, effective passage is provided for conductive ion.It is applied in sodium-ion battery, it will strengthen the high rate performance and cyclical stability of battery.
Description
Technical field
The present invention relates to a kind of sodium ion field, more particularly to a kind of solid-state sodium-ion battery electrolyte preparation method.
Background technology
In recent years, with the fast developments such as electronic equipment, electric tool, small power electric electrical automobile, research high energy efficiency, resource
Abundant and environment-friendly energy storage material turns into trend of the times.To meet the market demand in large scale, only rely on energy density,
The performance measure battery material such as charge-discharge magnification is far from being enough.Whether the manufacturing cost of battery causes dirt with energy consumption to environment
The recovery utilization rate of dye and resource is also by as the important indicator of evaluation battery material.
Sodium is one of more rich element of reserves on the earth, similar with the chemical property of lithium, but sodium-ion battery is compared
Lithium ion battery has many advantages, and as cost is low, security is good, and with going deep into for research, sodium-ion battery will increasingly have
Cost benefit, and be expected to be widely used in future substitution lithium ion battery.It is all the sodium ion of periodic table of elements I main group
There are many similarities with the property of lithium ion, and sodium-ion battery, compared with lithium ion battery, the cost of raw material compares lithium ion
Battery is low, and half-cell prtential is higher than lithium ion battery, is adapted to using the lower electrolyte of decomposition voltage, thus security performance is more
It is good；And raw material resources are enriched, cost is cheap, widely distributed；Sodium-ion battery has metastable chemical property, using more
Safety.
Solid-state sodium-ion battery utilizes the source of ubiquitous sodium, is a kind of up-and-coming low cost, high security
Substitute today lithium ion battery candidate's battery, especially in large-scale energy storage application aspect.However, solid-state sodium-ion battery
One key challenge of development is that sodion solid electrolytes do not have high ionic conductivity in room temperature.
The content of the invention
The problem of present invention exists in the prior art for solid-state sodium-ion battery, intend providing a kind of solid-state sodium ion electricity
Pond electrolyte preparation method.
The invention provides prepare the solid electrolyte Na as solid-state sodium-ion battery3-xSbS4-xFxMethod, prepare
Step is as follows：
Vulcanized sodium is dissolved in 1L ionized waters, is placed in thermostat water bath is heated to 80-90 DEG C afterwards, be put into antimony
Sour sodium and NH4F, the mass ratio of vulcanized sodium, sodium antimonate and NH4F is 3.5-1.5：1：0.5-2.5, after being slowly stirred 3-4 hours,
Room temperature is naturally cooled to, is filtered.70-80 DEG C of drying in drying baker, it is afterwards protective atmosphere as argon gas in boiler tube, is passed through, adds
Heat is incubated 1-2 hours, naturally cools to room temperature afterwards to 300-400 DEG C of reaction.Form Na3-xSbS4-xFxBlocks of solid, wherein
X=0.5-2.5.
The Na formed3-xSbS4-xFxBlocks of solid is made up of the nanometer sheet being laminated, and nanometer sheet is that 20-30nm is wide, 5-
10nm is thick, substantial amounts of space between nanometer sheet.The microstructure causes Na produced by the present invention3-xSbS4-xFxNano material is as solid
Body electrolyte, there is big specific surface area, be conducive to provide effective ion channel；And Na3-xSbS4-xFxIn be doped with it is a large amount of
F ion, provide effective passage for conductive ion.It is applied in sodium-ion battery, it will strengthen the multiplying power of battery
Performance and cyclical stability.And produced by the present invention is inorganic solid electrolyte, inorganic solid electrolyte is expected to avoid Organic Electricity
The potential safety hazard of matter is solved, is an important directions of electrolyte development.
Brief description of the drawings
Fig. 1 is that Na is made in embodiment 13-xSbS4-xFxThe ESEM scanning figure of nano material.
Embodiment
The present invention is further illustrated below in conjunction with drawings and the specific embodiments.
Embodiment 1
Vulcanized sodium is dissolved in 1L ionized waters, is placed in afterwards in thermostat water bath and is heated to 80 DEG C, is put into metaantimmonic acid
Sodium and NH4F, the mass ratio of vulcanized sodium, sodium antimonate and NH4F is 3.5：1：0.5, after being slowly stirred 4 hours, naturally cool to room
Temperature, filtering.80 DEG C of dryings in drying baker, afterwards as 300 DEG C of reactions in boiler tube, are heated to, it is protective atmosphere to be passed through argon gas, is protected
Temperature 2 hours, naturally cools to room temperature afterwards.Form Na2.5SbS3.5F0.5Blocks of solid, wherein x=0.5.
Embodiment 2
Vulcanized sodium is dissolved in 1L ionized waters, is placed in afterwards in thermostat water bath and is heated to 90 DEG C, is put into metaantimmonic acid
Sodium and NH4F, the mass ratio of vulcanized sodium, sodium antimonate and NH4F is 1.5：1：2.5, after being slowly stirred 3 hours, naturally cool to room
Temperature, filtering.80 DEG C of dryings in drying baker, afterwards as 400 DEG C of reactions in boiler tube, are heated to, it is protective atmosphere to be passed through argon gas, is protected
Temperature 1 hour, naturally cools to room temperature afterwards.Form Na0.5SbS1.5F0.5Blocks of solid, wherein x=2.5.
Embodiment 3
Vulcanized sodium is dissolved in 1L ionized waters, is placed in afterwards in thermostat water bath and is heated to 90 DEG C, is put into metaantimmonic acid
Sodium and NH4F, the mass ratio of vulcanized sodium, sodium antimonate and NH4F is 3：1：1, after being slowly stirred 3 hours, room temperature is naturally cooled to,
Filtering.70 DEG C of dryings in drying baker, afterwards as 300 DEG C of reactions in boiler tube, are heated to, it is protective atmosphere to be passed through argon gas, insulation 1
Hour, room temperature is naturally cooled to afterwards.Form Na2SbS3F blocks of solid, wherein x=1.
Embodiment 4
Vulcanized sodium is dissolved in 1L ionized waters, is placed in afterwards in thermostat water bath and is heated to 90 DEG C, is put into metaantimmonic acid
Sodium and NH4F, the mass ratio of vulcanized sodium, sodium antimonate and NH4F is 2.5：1：0.5-1.5, after being slowly stirred 4 hours, natural cooling
To room temperature, filtering.80 DEG C of dryings in drying baker, afterwards as 350 DEG C of reactions in boiler tube, are heated to, argon gas is passed through as protection gas
Atmosphere, 2 hours are incubated, naturally cools to room temperature afterwards.Form Na1.5SbS2.5F1.5Blocks of solid, wherein x=1.5.
Embodiment 5
Vulcanized sodium is dissolved in 1L ionized waters, is placed in afterwards in thermostat water bath and is heated to 90 DEG C, is put into metaantimmonic acid
Sodium and NH4F, the mass ratio of vulcanized sodium, sodium antimonate and NH4F is 2：1：2, after being slowly stirred 3 hours, room temperature is naturally cooled to,
Filtering.80 DEG C of dryings in drying baker, afterwards as 400 DEG C of reactions in boiler tube, are heated to, it is protective atmosphere to be passed through argon gas, insulation 1
Hour, room temperature is naturally cooled to afterwards.Form NaSbS2F2Blocks of solid, wherein x=2.
By ESEM to the Na obtained by each embodiment3-xSbS4-xFxBlocks of solid nano material carries out microscopic appearance
Observation, the Na formed3-xSbS4-xFxBlocks of solid is made up of the nanometer sheet being laminated, and nanometer sheet is that 20-30nm is wide, 5-10nm
Thickness, substantial amounts of space between nanometer sheet；The Na as made from Fig. 1 is embodiment 12.5SbS3.5F0.5The scanning electron microscope (SEM) photograph of blocks of solid
(SEM).The microstructure causes Na produced by the present invention3-xSbS4-xFxNano material has big ratio as solid electrolyte
Surface area, it is conducive to provide effective ion channel；And Na3-xSbS4-xFxIn be doped with substantial amounts of F ion, carried for conductive ion
Effective passage is supplied.It is applied in sodium-ion battery, it will strengthen the high rate performance and cyclical stability of battery.
To the Na obtained by each embodiment3-xSbS4-xFxBlocks of solid nano material carries out ionic conductivity, sodium ion moves
The electrical performance testings such as number are moved, as shown in Table 1, wherein ionic conductivity electrolyte measures test result at room temperature.Compared to business
Barrier film Celgard2730 electrical conductivity 0.16mS/cm, Na produced by the present invention3-xSbS4-xFxThe ionic conductivity of display
It is very excellent.
Table one
| Embodiment | Chemical formula | Ionic conductivity (mS/cm) | Sodium ion transport number |
| Embodiment 1 | Na2.5SbS3.5F0.5 | 4.96 | 0.23 |
| Embodiment 2 | Na0.5SbS1.5F0.5 | 5.23 | 0.26 |
| Embodiment 3 | Na2SbS3F | 5.65 | 0.27 |
| Embodiment 4 | Na1.5SbS2.5F1.5 | 5.78 | 0.30 |
| Embodiment 5 | NaSbS2F2 | 6.54 | 0.32 |
It is described above, it will only be presently preferred embodiments of the present invention, any formal limitation not is made to the present invention.
Any those skilled in the art, without departing from the scope of the technical proposal of the invention, all using the disclosure above
Methods and technical content makes many possible changes and modifications to technical solution of the present invention, or is revised as the equivalent of equivalent variations
Embodiment.Therefore, every content without departing from technical scheme, the technical spirit according to the present invention is to above example
Any simple modifications, equivalents, and modifications done, still fall within technical solution of the present invention protection in the range of.
Claims (4)
1. a kind of solid-state sodium-ion battery electrolyte preparation method, it is characterised in that comprise the following steps：
Vulcanized sodium is dissolved in 1L ionized waters, is placed in thermostat water bath is heated to 80-90 DEG C afterwards, be put into sodium antimonate
And NH4F, the mass ratio of vulcanized sodium, sodium antimonate and NH4F is 3.5-1.5：1：0.5-2.5 is natural after being slowly stirred 3-4 hours
Room temperature is cooled to, is filtered.70-80 DEG C of drying in drying baker, it is afterwards protective atmosphere as argon gas in boiler tube, is passed through, is heated to
300-400 DEG C of reaction, is incubated 1-2 hours, naturally cools to room temperature afterwards.
A kind of 2. solid-state sodium-ion battery electrolyte preparation method according to claim 1, it is characterised in that：It is described solid
The chemical formula of state sodium-ion battery electrolyte is Na3xSbS4xFx, wherein x=0.5-2.5.
A kind of 3. solid-state sodium-ion battery electrolyte preparation method according to claim 2, it is characterised in that：It is described solid
State sodium-ion battery electrolyte contains F ion.
A kind of 4. solid-state sodium-ion battery electrolyte preparation method according to claim 2, it is characterised in that：It is described
Na3xSbS4xFxIt is made up of the nanometer sheet being laminated, nanometer sheet is that 20-30nm is wide, 5-10nm is thick, containing substantial amounts of empty between nanometer sheet
Gap.
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Cited By (3)
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|---|---|---|---|---|
| WO2019093273A1 (en) * | 2017-11-10 | 2019-05-16 | 公立大学法人大阪府立大学 | Solid electrolyte for all-solid sodium batteries, and all-solid sodium battery |
| WO2020022342A1 (en) * | 2018-07-24 | 2020-01-30 | 公立大学法人大阪 | Solid electrolyte for all-solid-state sodium battery, manufacturing method therefor, and all-solid-state sodium battery |
| CN114388773A (en) * | 2021-12-31 | 2022-04-22 | 华南师大(清远)科技创新研究院有限公司 | High-performance Sb-based sodium ion battery negative electrode material and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019093273A1 (en) * | 2017-11-10 | 2019-05-16 | 公立大学法人大阪府立大学 | Solid electrolyte for all-solid sodium batteries, and all-solid sodium battery |
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| US11342580B2 (en) | 2017-11-10 | 2022-05-24 | University Public Corporation Osaka | Solid electrolyte for all-solid sodium battery, and all-solid sodium battery |
| JP7281195B2 (en) | 2017-11-10 | 2023-05-25 | 公立大学法人大阪 | Solid electrolyte for all-solid-state sodium battery and all-solid-state sodium battery |
| WO2020022342A1 (en) * | 2018-07-24 | 2020-01-30 | 公立大学法人大阪 | Solid electrolyte for all-solid-state sodium battery, manufacturing method therefor, and all-solid-state sodium battery |
| JPWO2020022342A1 (en) * | 2018-07-24 | 2021-08-02 | 公立大学法人大阪 | Solid electrolytes for all-solid-state sodium batteries, their manufacturing methods, and all-solid-state sodium batteries |
| JP7270991B2 (en) | 2018-07-24 | 2023-05-11 | 公立大学法人大阪 | SOLID ELECTROLYTE FOR ALL-SOLID SODIUM BATTERY, MANUFACTURING METHOD THEREOF, AND ALL-SOLID SODIUM BATTERY |
| CN114388773A (en) * | 2021-12-31 | 2022-04-22 | 华南师大(清远)科技创新研究院有限公司 | High-performance Sb-based sodium ion battery negative electrode material and preparation method and application thereof |
| CN114388773B (en) * | 2021-12-31 | 2023-07-21 | 华南师大(清远)科技创新研究院有限公司 | High-performance Sb-based sodium ion battery anode material and preparation method and application thereof |
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