CN106505247A - All solid state sode cell electrolyte, its preparation method and all solid state sodium rechargeable battery - Google Patents
All solid state sode cell electrolyte, its preparation method and all solid state sodium rechargeable battery Download PDFInfo
- Publication number
- CN106505247A CN106505247A CN201611213714.6A CN201611213714A CN106505247A CN 106505247 A CN106505247 A CN 106505247A CN 201611213714 A CN201611213714 A CN 201611213714A CN 106505247 A CN106505247 A CN 106505247A
- Authority
- CN
- China
- Prior art keywords
- solid state
- rechargeable battery
- state sodium
- sodium rechargeable
- battery electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- H01M10/054—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a kind of all solid state sodium rechargeable battery electrolyte, its preparation method and all solid state sodium rechargeable battery, belong to sodium rechargeable battery technical field.This all solid state sodium rechargeable battery electrolyte includes Na3+xPS4+y(x=1～1, y=0.5～0.5).This all solid state sodium rechargeable battery electrolyte has preferably to stable sodium, higher ionic conductivity, and can make all solid state sodium rechargeable battery that there is good multiplying power and cycle characteristics.
Description
Technical field
The present invention relates to sodium rechargeable battery technical field, more particularly to all solid state sodium rechargeable battery electrolyte, its preparation side
Method and all solid state sodium rechargeable battery.
Background technology
Recently, lithium ion battery is widely used in the fields such as electronic mobile device, electric automobile.In lithium ion battery
In, although can improve the energy density of battery using metal lithium electrode, used in liquid lithium battery, lithium metal can cause lithium
The formation of dendrite, ultimately causes the danger such as battery short circuit, blast.Therefore in order that metal lithium electrode can be answered in lithium battery
With solid lithium battery has obtained extensive concern and research, although the use of all solid state electrolyte can suppress Li dendrite
Growth, significantly improves security performance, but lithium metal is expensive, make solid lithium battery industrial applications high cost.
In order to solve the problems, such as high cost, all solid state sodium rechargeable battery is suggested.Metallic sodium aboundresources, this are secondary for all solid state sodium
The commercial applications of battery it is critical that.
In all-solid-state battery, electrolyte functions simultaneously as the effect of barrier film, and its electrical conductivity, stability etc. all directly affect electricity
The performance in pond.The conventional method for preparing all solid state sodium rechargeable battery electrolyte is high-energy ball milling, but the method has cost mistake
Height, manufacturing cycle are long, and obtained electrolyte granular size is larger, skewness the shortcomings of.Therefore, offer one is provided badly
Plant the key technology for preparing all solid state sodium rechargeable battery electrolyte, it is ensured that the technology can shorten all solid state sodium rechargeable battery
The manufacturing cycle of electrolyte, can make electrolyte granular even size distribution again, and improve the electrical conductivity and electrification of electrolyte
Learn window.
Content of the invention
In view of this, present invention solves the technical problem that being to provide a kind of all solid state sodium rechargeable battery electrolyte and its system
Preparation Method, all solid state sodium rechargeable battery electrolyte that the application is provided have preferably to stable sodium, higher ion
Electrical conductivity, and can make all solid state sodium rechargeable battery that there is good multiplying power and cycle characteristics.
The present invention provides a kind of all solid state sodium rechargeable battery electrolyte, including：Na3+xPS4+y(x=-1.0～1.0, y
=-0.5～0.5).There is prepared all solid state sodium rechargeable battery electrolyte glass ceramics crystalline phase, electrolyte granular size to be
10nm～50um, electrical conductivity are 1.0 × 10-5～5.0 × 10-3S cm-1.Present invention also offers a kind of secondary electricity of all solid state sodium
The preparation method of pond electrolyte, including：(1) by Na2S, P2S5Mix with solvent, reaction obtains all solid state sodium rechargeable battery
Electrolyte Na3+xPS4+yPrecursor solution；(2) by step 1) the precursor solution sucking filtration that obtains, dry, obtain entirely solid
State sodium rechargeable battery electrolyte Na3+xPS4+yPrecursor powder；(3) by step 2) precursor powder that obtains is in protection
It is sintered under atmosphere, obtains the mutually all solid state sodium rechargeable battery electrolyte Na of glass ceramics3+xPS4+y.Further, this
Bright by adjusting reaction ratio, combination reaction temperature, the combination reaction time, it is secondary that annealing temperature etc. can effectively improve all solid state sodium
Cell electrolyte materials Na3+xPS4+yIonic conductivity, improve all solid state sodium rechargeable battery electrolyte Na3+xPS4+yRight
Stable sodium and widen electrochemical window.The present invention also provides a kind of all solid state sodium rechargeable battery, including：Positive pole, negative pole and sets
Put all solid state sodium rechargeable battery dielectric substrate between a positive electrode and a negative electrode.Institute's assembled battery have excellent cycle performance and times
Rate performance.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply for further illustrating the features and advantages of the present invention, rather than to the claims in the present invention
Limit.
The invention provides a kind of all solid state sodium rechargeable battery electrolyte Na3+xPS4+y, with regard to preparing all solid state sodium two
The raw material of primary cell electrolyte is above-mentioned to be had been carried out describing in detail, is no longer repeated herein.
In the present invention, raw material ratio (Na in described all solid state sodium rechargeable battery electrolyte2S/P2S5) be preferably
2.0～4.0.The all solid state sodium rechargeable battery electrolyte can pass through regulation raw material ratio, annealing temperature, annealing time etc. to be come
The electrical conductivity of all solid state sodium rechargeable battery electrolyte is adjusted, optimal conditionss are：Na2S/P2S5=3.0.
Present invention also offers a kind of all solid state sodium rechargeable battery electrolyte Na3+xPS4+yPreparation method, including：
(1) by Na2S, P2S5Mix with solvent, reaction obtains all solid state sodium rechargeable battery electrolyte Na3+xPS4+yPresoma molten
Liquid；(2) the precursor solution sucking filtration for obtaining step (1), dries, obtains all solid state sodium rechargeable battery electrolyte Na3+ xPS4+yPrecursor powder；(3) precursor powder that step (2) is obtained is sintered under protective atmosphere, obtains glass pottery
The mutually all solid state sodium rechargeable battery electrolyte of porcelain.Preparation method provided by the present invention compared with conventional solid-state method, with being prepared into
This is low, and reaction time is short, simple to operate, the advantages of prepared electrolyte granular size is little.
Preparing all solid state sodium rechargeable battery electrolyte Na3+xPS4+yDuring, the solvent be acetonitrile, tetrahydrochysene
Furan, N-METHYLFORMAMIDE, glycol dimethyl ether, dimethyl carbonate, ethyl acetate, chlorobenzene, normal hexane, ethanol, methanol, diformazan
Base Methanamide etc., has no particular limits to this present invention, example, and preferred solvent is selected from acetonitrile, glycol dimethyl ether, tetrahydrochysene
Furan.Described reaction temperature is preferably 25 DEG C～110 DEG C, and the response time is preferably 1h～120h.The all solid state sodium
Secondary cell is electrolysed material Na3+xPS4+yCan pass through to adjust reaction temperature, the response time adjusts all solid state sodium rechargeable battery electricity
Solution material Na3+xPS4+ySize；Can pass through to adjust annealing temperature, annealing time is regulating and controlling all solid state sodium rechargeable battery
Electrolyte Na3+xPS4+yCrystalline phase, crystallite dimension, and then regulate and control electrical conductivity.
Present invention also offers a kind of all solid state sodium rechargeable battery, including：Positive pole, negative pole and be arranged on positive pole and negative pole it
Between all solid state sodium rechargeable battery dielectric substrate.
The application is had no particular limits with the material of negative pole to the material of the positive pole.Example, the positive pole
Material is preferably selected from Co9S8、Bi2S3、NaCrO2One or more, and just extremely anode composite.The material of the negative pole is preferably golden
Category sodium.
The present invention can pass through to adjust reaction ratio (Na2S/P2S5=2.0～4.0), reaction temperature (25 DEG C～110 DEG C), instead
Between seasonable (1h～120h), annealing temperature (120 DEG C～600 DEG C), annealing time (0.5h～72h) effectively improve all solid state sodium
Secondary cell is electrolysed material Na3+xPS4+yElectrical conductivity, improve all solid state sodium rechargeable battery electrolyte Na3+xPS4+yRight
The stability of metallic sodium and widen electrochemical window.Test result indicate that：The all solid state sodium rechargeable battery electrolysis that the present invention is provided
Material Na3+xPS4+yElectrical conductivity be 1.0 × 10-5～5.0 × 10-3S cm-1；With good to stable sodium and wide electricity
Chemical window；And its battery for being assembled has excellent circulating ratio performance.
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply for further illustrating the features and advantages of the present invention, rather than to the claims in the present invention
Limit.
Embodiment 1
Under argon gas atmosphere protection, (1) is by Na2S and P2S5(Na2S/P2S5=2), acetonitrile mixes, and 25 DEG C issue biochemical conjunction
Reaction 1h, obtains the precursor solution of all solid state sodium rechargeable battery electrolyte；(2) by step 1) obtained by presoma molten
Liquid sucking filtration, dries, obtains all solid state sodium rechargeable battery electrolyte precursor powder；By step 2) precursor powder that obtains
At 120 DEG C, annealing 0.5h obtains all solid state sodium rechargeable battery electrolyte of glass ceramics phase.Scanning electron microscope
(SEM) test structure shows, particle size is 20.3um-38.9um.At ambient temperature, secondary to prepared all solid state sodium
Cell electrolyte materials carry out electrochemical alternate impedance spectrum (EIS) and test (using carbon plate as blocking electrode), as a result show：Conductance
Rate is 7.8 × 10-5S cm-1.
Using the electrolyte obtained by under above-described embodiment as all solid state sodium rechargeable battery dielectric substrate, metallic sodium piece makees
For negative pole, Co9S8, used as positive pole, the assembled all solid state sodium rechargeable battery for forming sandwich structure is under 50mA/g for combination electrode
Charge-discharge test is carried out, is as a result shown：Its first discharge specific capacity is 521mAh/g, and efficiency is 67% first.And circulate 50 circles
Afterwards, its capacity is maintained at 300mAh/g.
Embodiment 2
Under argon gas atmosphere protection, (1) is by Na2S and P2S5(Na2S/P2S5=4), tetrahydrofuran mixes, and occurs at 50 DEG C
Combination reaction 48h, obtains the precursor solution of all solid state sodium rechargeable battery electrolyte；By step 1) obtained by presoma
Solution sucking filtration, dries, obtains all solid state sodium rechargeable battery electrolyte precursor powder；By step 2) precursor that obtains
End annealing 0.5h at 600 DEG C obtains all solid state sodium rechargeable battery electrolyte of glass ceramics phase.Scanning electron microscope
(SEM) test structure shows, particle size is 9.4um-15.6um.At ambient temperature, secondary to prepared all solid state sodium
Cell electrolyte materials carry out electrochemical alternate impedance spectrum (EIS) and test (using carbon plate as blocking electrode), as a result show：Conductance
Rate is 8.8 × 10-4S cm-1.
Obtained electrolyte presses 1 same steps of embodiment and condition assembled battery, by the battery for being assembled in 50mA/g
Under carry out charge-discharge test, as a result show：Its first discharge specific capacity is 617.2mAh/g, and efficiency is 71.6% first.And follow
After ring 50 is enclosed, its capacity is maintained at 416.9mAh/g.
Embodiment 3
Under argon gas atmosphere protection, (1) is by Na2S and P2S5(Na2S/P2S5=3), glycol dimethyl ether mixes, at 40 DEG C
Generation combination reaction 120h, obtains the precursor solution of all solid state sodium rechargeable battery electrolyte；By step 1) obtained by
Precursor solution sucking filtration, dries, obtains all solid state sodium rechargeable battery electrolyte precursor powder；By step 2) obtain before
Drive the body powder 1h that anneals at 330 DEG C and obtain all solid state sodium rechargeable battery electrolyte of glass ceramics phase.X ray electronics spreads out
Penetrate (XRD) test result to show：Prepared all solid state sodium rechargeable battery electrolyte has Na3PS4Crystal structure.Scanning
Ultramicroscope (SEM) test structure shows that particle size is 1.5um-9.8um.At ambient temperature, prepared is consolidated entirely
State sodium rechargeable battery electrolyte Na3PS4Carry out electrochemical alternate impedance spectrum (EIS) to test (using carbon plate as blocking electrode),
As a result show：Electrical conductivity is 1.0 × 10-3S cm-1.
Using the electrolyte obtained by under above-described embodiment as all solid state sodium rechargeable battery dielectric substrate, metallic sodium piece is
Negative pole, Bi2S3Used as positive pole, the assembled all-solid sodium ion battery for forming sandwich structure enters under 50mA/g combination electrode
Row charge-discharge test, as a result shows：Its first discharge specific capacity is 721.5mAh/g, and efficiency is 74.3% first.And circulate 50
After circle, its capacity is maintained at 502.5mAh/g.
Embodiment 4
Under argon gas atmosphere protection, (1) is by Na2S and P2S5(Na2S/P2S5=3), acetonitrile mixes, and 50 DEG C issue biochemical conjunction
Reaction 36h, obtains the precursor solution of all solid state sodium rechargeable battery electrolyte；By step 1) obtained by precursor solution
Sucking filtration, dries, obtains all solid state sodium rechargeable battery electrolyte precursor powder；By step 2) precursor powder that obtains exists
At 270 DEG C, annealing 2h obtains all solid state sodium rechargeable battery electrolyte of glass ceramics phase.X ray electronic diffraction (XRD) is surveyed
Test result shows：Prepared electrolyte has Na3PS4Crystal structure.Scanning electron microscope (SEM) test structure table
Bright, particle size is 10nm-1.8um.At ambient temperature, to prepared all solid state sodium rechargeable battery electrolyte
Na3PS4Carry out electrochemical alternate impedance spectrum (EIS) to test (using carbon plate as blocking electrode), as a result show：Electrical conductivity be 1.4 ×
10-3S cm-1.
Obtained electrolyte presses 3 same steps of embodiment and condition assembled battery, by the battery for being assembled in 50mA/g
Under carry out charge-discharge test, as a result show：Its first discharge specific capacity is 780.3mAh/g, and efficiency is 78.9% first.And follow
After ring 50 is enclosed, its capacity is maintained at 584.2mAh/g.
Embodiment 5
Under argon gas atmosphere protection, (1) is by Na2S and P2S5(Na2S/P2S5=4), N-METHYLFORMAMIDE mixes, at 110 DEG C
Generation combination reaction 120h, obtains the precursor solution of all solid state sodium rechargeable battery electrolyte；By step 1) obtained by
Precursor solution sucking filtration, dries, obtains all solid state sodium rechargeable battery electrolyte precursor powder；By step 2) obtain before
Drive the body powder 36h that anneals at 420 DEG C and obtain all solid state sodium rechargeable battery electrolyte of glass ceramics phase.Scanning electron shows
Micro mirror (SEM) test structure shows that particle size is 12.8um-21.6um.At ambient temperature, to prepared all solid state sodium
Secondary cell electrolysis material carries out electrochemical alternate impedance spectrum (EIS) and tests (using carbon plate as blocking electrode), as a result shows：
Electrical conductivity is 1.0 × 10-4S cm-1.
Using the electrolyte obtained by under above-described embodiment as all solid state sodium rechargeable battery dielectric substrate, metallic sodium piece is
Negative pole, NaCrO2, used as positive pole, the assembled all-solid sodium ion battery for forming sandwich structure is under 50mA/g for combination electrode
Charge-discharge test is carried out, is as a result shown：Its first discharge specific capacity is 130mAh/g, and efficiency is 87.1% first.And circulate 50
After circle, its capacity is maintained at 108.5mAh/g.
Embodiment 6
Under nitrogen atmosphere protection, (1) is by Na2S and P2S5(Na2S/P2S5=2.33), acetonitrile mixes, and 50 DEG C issue biochemistry
Reaction 72h is closed, the precursor solution of all solid state sodium rechargeable battery electrolyte is obtained；By step 1) obtained by presoma molten
Liquid sucking filtration, dries, obtains all solid state sodium rechargeable battery electrolyte precursor powder；By step 2) precursor powder that obtains
At 250 DEG C, annealing 4h obtains all solid state sodium rechargeable battery electrolyte of glass ceramics phase.Scanning electron microscope (SEM)
Test structure shows that particle size is 37.5um-50um.At ambient temperature, to prepared all solid state sodium rechargeable battery electricity
Solution material carries out electrochemical alternate impedance spectrum (EIS) and tests (using carbon plate as blocking electrode), as a result shows：Electrical conductivity is
1.0×10-5S cm-1.
Obtained electrolyte presses 5 same steps of embodiment and condition assembled battery, by the battery for being assembled in 50mA/g
Under carry out charge-discharge test, as a result show：Its first discharge specific capacity is 125mAh/g, and efficiency is 67.5% first.And circulate
After 50 circles, its capacity is maintained at 71.4mAh/g.
Comparative example 1
Under argon gas atmosphere protection, (1) is by Na2S and P2S5(Na2S/P2S5=1), dimethyl carbonate mixes, and 25 DEG C issue
Raw combination reaction 36h, obtains the precursor solution of all solid state sodium rechargeable battery electrolyte；By step 1) obtained by forerunner
Liquid solution sucking filtration, dries, obtains all solid state sodium rechargeable battery electrolyte precursor powder；By step 2) presoma that obtains
The powder 2h that anneals at 720 DEG C obtains all solid state sodium rechargeable battery electrolyte of glass ceramics phase.Scanning electron microscope
(SEM) test structure shows, particle size is 65.7um-91.6um.At ambient temperature, to prepared all-solid sodium ion
Electrolyte carries out electrochemical alternate impedance spectrum (EIS) and tests (using carbon plate as blocking electrode), as a result shows：Electrical conductivity is 1.0
×10-6S cm-1.
Obtained electrolyte presses 1 same steps of embodiment and condition assembled battery, by the battery for being assembled in 50mA/g
Under carry out charge-discharge test, as a result show：Its first discharge specific capacity is 250.3mAh/g, and efficiency is 51% first.And circulate
After 50 circles, its capacity is maintained at 65.2mAh/g.
Comparative example 2
Under argon gas atmosphere protection, (1) is by Na2S and P2S5(Na2S/P2S5=5.5), solvent mixes, and 60 DEG C issue biochemistry
Reaction 48h is closed, the precursor solution of all solid state sodium rechargeable battery electrolyte is obtained；By step 1) obtained by presoma molten
Liquid sucking filtration, dries, obtains all solid state sodium rechargeable battery electrolyte precursor powder；By step 2) precursor powder that obtains
At 800 DEG C, annealing 2h obtains all solid state sodium rechargeable battery electrolyte of glass ceramics phase.Scanning electron microscope (SEM)
Test structure shows that particle size is 52.3um-79.5um.At ambient temperature, to prepared all solid state sodium rechargeable battery
Electrolyte carries out electrochemical alternate impedance spectrum (EIS) and tests (using carbon plate as blocking electrode), as a result shows：Electrical conductivity is
5.4×10-6S cm-1.
Obtained electrolyte presses 1 same steps of embodiment and condition assembled battery, by the battery for being assembled in 50mA/g
Under carry out charge-discharge test, as a result show：Its first discharge specific capacity is 265.2mAh/g, and efficiency is 56.2% first.And follow
After ring 50 is enclosed, its capacity is maintained at 83.7mAh/g.
Embodiment and comparative example relevant parameter and result are as shown in Table 1：
Table one：Embodiment and comparative example relevant parameter and result
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these improvement and modification are also fallen in the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
Multiple modifications of these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized without departing from the spirit or scope of the present invention in other embodiments.Therefore, the present invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope for causing.
Claims (10)
1. a kind of all solid state sodium rechargeable battery electrolyte, it is characterised in that including Na3+xPS4+y(x=-1～1, y=-0.5～
0.5).
2. all solid state sodium rechargeable battery electrolyte according to claim 1, it is characterised in that the Na3+xPS4+yThere is glass
Glass pottery crystalline phase.
3. all solid state sodium rechargeable battery electrolyte according to claim 1, it is characterised in that the Na3+xPS4+yGranule chi
Very little for 10nm-50 μm.
4. all solid state sodium rechargeable battery electrolyte according to claim 1, it is characterised in that the Na3+xPS4+yElectrical conductivity
For 1.0 × 10-5～5.0 × 10-3S cm-1.
5. a kind of all solid state sodium rechargeable battery electrolyte preparation method, it is characterised in that include：
(1) by Na2S, P2S5Mix with solvent, combination reaction obtains all solid state sodium rechargeable battery electrolyte Na3+xPS4+y's
Precursor solution；
(2) the precursor solution sucking filtration for obtaining step (1), dries, obtains all solid state sodium rechargeable battery electrolyte Na3+ xPS4+yPrecursor powder；
(3) precursor powder that step (2) is obtained is sintered under protective atmosphere, obtains the mutually all solid state sodium two of glass ceramics
Primary cell electrolyte Na3+xPS4+y.
6. preparation method according to claim 5, it is characterised in that the solvent is selected from acetonitrile, tetrahydrofuran, N- methyl
Methanamide, glycol dimethyl ether, dimethyl carbonate, ethyl acetate, chlorobenzene, normal hexane, ethanol, methanol, dimethylformamide
One or more.
7. preparation method according to claim 5, it is characterised in that the combination reaction temperature is 25 DEG C～110 DEG C；Institute
The combination reaction time is stated for 1h～120h.
8. preparation method according to claim 5, it is characterised in that the Na2S and P2S5Proportioning be 2.0～4.0.
9. preparation method according to claim 5, it is characterised in that the annealing temperature is 120 DEG C～600 DEG C；Described
Annealing time is 0.5h～72h；The Annealing Protection atmosphere is argon or nitrogen.
10. a kind of all solid state sode cell, including positive pole, negative pole and arranges the secondary electricity of all solid state sodium between a positive electrode and a negative electrode
Pond dielectric substrate, it is characterised in that all solid state sodium rechargeable battery dielectric substrate is Na3+xPS4+y.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611213714.6A CN106505247A (en) | 2016-12-26 | 2016-12-26 | All solid state sode cell electrolyte, its preparation method and all solid state sodium rechargeable battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611213714.6A CN106505247A (en) | 2016-12-26 | 2016-12-26 | All solid state sode cell electrolyte, its preparation method and all solid state sodium rechargeable battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106505247A true CN106505247A (en) | 2017-03-15 |
Family
ID=58334158
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611213714.6A Pending CN106505247A (en) | 2016-12-26 | 2016-12-26 | All solid state sode cell electrolyte, its preparation method and all solid state sodium rechargeable battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106505247A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107180992A (en) * | 2017-06-09 | 2017-09-19 | 中国科学院宁波材料技术与工程研究所 | A kind of solid lithium battery combination electrode material and preparation method thereof and a kind of solid lithium battery |
| CN107331848A (en) * | 2017-07-12 | 2017-11-07 | 中国科学院宁波材料技术与工程研究所 | A kind of composite positive pole of all solid state sodium rechargeable battery and a kind of all solid state sodium rechargeable battery |
| CN108695553A (en) * | 2018-07-11 | 2018-10-23 | 中国科学院宁波材料技术与工程研究所 | A kind of all solid state sodium rechargeable battery electrolyte, preparation method and its application |
| CN108933282A (en) * | 2018-07-11 | 2018-12-04 | 中国科学院宁波材料技术与工程研究所 | NASICON structure sodion solid electrolytes, preparation method and solid-state sodium-ion battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102334225A (en) * | 2009-02-27 | 2012-01-25 | 丰田自动车株式会社 | Solid sulfide electrolyte material |
| CN103500853A (en) * | 2013-10-08 | 2014-01-08 | 中国科学院宁波材料技术与工程研究所 | Sulfide electrolyte material and preparation method thereof |
| CN103620855A (en) * | 2011-07-26 | 2014-03-05 | 公立大学法人大阪府立大学 | All-solid-state secondary cell |
| US20150030938A1 (en) * | 2012-03-06 | 2015-01-29 | Osaka Prefecture University Public Corporation | Ion conducting glass-ceramics, method for manufacturing same and all-solid-state secondary battery including same |
| CN105098228A (en) * | 2014-05-05 | 2015-11-25 | 中国科学院宁波材料技术与工程研究所 | Sulfide solid electrolyte material and preparation method thereof |
-
2016
- 2016-12-26 CN CN201611213714.6A patent/CN106505247A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102334225A (en) * | 2009-02-27 | 2012-01-25 | 丰田自动车株式会社 | Solid sulfide electrolyte material |
| CN103620855A (en) * | 2011-07-26 | 2014-03-05 | 公立大学法人大阪府立大学 | All-solid-state secondary cell |
| US20150030938A1 (en) * | 2012-03-06 | 2015-01-29 | Osaka Prefecture University Public Corporation | Ion conducting glass-ceramics, method for manufacturing same and all-solid-state secondary battery including same |
| CN103500853A (en) * | 2013-10-08 | 2014-01-08 | 中国科学院宁波材料技术与工程研究所 | Sulfide electrolyte material and preparation method thereof |
| CN105098228A (en) * | 2014-05-05 | 2015-11-25 | 中国科学院宁波材料技术与工程研究所 | Sulfide solid electrolyte material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| AKITOSHI HAYASHI ET AL: "High sodium ion conductivity of glass-ceramic electrolytes with cubic Na3PS4", 《JOURNAL OF POWER SOURCES》 * |
| SO YUBUCHI ET AL: "Sodium-ion Conducting Na3PS4 Electrolyte Synthesize via a Liquid-phase Process Using N-Methylformamide", 《CHEMISTRY LETTERS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107180992A (en) * | 2017-06-09 | 2017-09-19 | 中国科学院宁波材料技术与工程研究所 | A kind of solid lithium battery combination electrode material and preparation method thereof and a kind of solid lithium battery |
| CN107331848A (en) * | 2017-07-12 | 2017-11-07 | 中国科学院宁波材料技术与工程研究所 | A kind of composite positive pole of all solid state sodium rechargeable battery and a kind of all solid state sodium rechargeable battery |
| CN107331848B (en) * | 2017-07-12 | 2020-03-17 | 中国科学院宁波材料技术与工程研究所 | Composite positive electrode material of all-solid-state sodium secondary battery and all-solid-state sodium secondary battery |
| CN108695553A (en) * | 2018-07-11 | 2018-10-23 | 中国科学院宁波材料技术与工程研究所 | A kind of all solid state sodium rechargeable battery electrolyte, preparation method and its application |
| CN108933282A (en) * | 2018-07-11 | 2018-12-04 | 中国科学院宁波材料技术与工程研究所 | NASICON structure sodion solid electrolytes, preparation method and solid-state sodium-ion battery |
| CN108933282B (en) * | 2018-07-11 | 2021-01-22 | 中国科学院宁波材料技术与工程研究所 | NASICON structure sodium ion solid electrolyte, preparation method thereof and solid sodium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110931849B (en) | Gradient composite solid electrolyte, preparation method thereof and solid lithium battery | |
| CN104659412B (en) | Lithium-carbon-boron oxide solid electrolyte material containing plane triangle group and battery | |
| CN107180992A (en) | A kind of solid lithium battery combination electrode material and preparation method thereof and a kind of solid lithium battery | |
| CN101609883B (en) | Preparation method of nano-silver particle dispersed Li4Ti5O12 thin film lithium ion battery negative electrode | |
| CN106505247A (en) | All solid state sode cell electrolyte, its preparation method and all solid state sodium rechargeable battery | |
| CN110492097B (en) | NCM ternary composite positive electrode material and preparation and application thereof | |
| CN110233285A (en) | A method of improving solid state battery interface stability using polymer dielectric | |
| CN107732158A (en) | Lithium ion battery negative electrode preparation method, cathode pole piece and lithium ion battery | |
| CN102760876A (en) | Niobate and niobate composite material and application of niobate composite material to secondary lithium battery | |
| CN106505246A (en) | A kind of preparation method of multistage loose structure mangano-manganic oxide/carbon nanosheet lithium ion battery negative material | |
| CN109728342B (en) | Self-repairing composite solid electrolyte, quasi-solid electrolyte and lithium battery | |
| CN114789993B (en) | Modified sulfur silver germanium mineral solid electrolyte and preparation method and application thereof | |
| CN113072051B (en) | Post-treatment method of phosphate system anode material | |
| CN103094580A (en) | Composite anode material and synthesis method and application thereof | |
| CN107845791B (en) | Preparation method of double-layer asphalt carbon-coated lithium iron phosphate cathode material | |
| CN102299334A (en) | Carbon coated LiFePO4 porous anode and preparation method thereof | |
| CN102491410A (en) | Synthesis method of negative electrode material oxygen vacancy lithium titanate of lithium ion battery | |
| CN111017903A (en) | High-performance carbon anode PAN hard carbon material and preparation method thereof | |
| CN110931730A (en) | Titanium niobate negative electrode material and preparation method and application thereof | |
| CN112786860B (en) | Composite positive electrode material and preparation method thereof, positive electrode slurry, positive electrode plate and all-solid-state battery | |
| CN108695553A (en) | A kind of all solid state sodium rechargeable battery electrolyte, preparation method and its application | |
| CN105810901A (en) | Ti<3+>/Ti<4+> mixed-valence lithium titanate negative electrode material doped with iron element and preparation of negative electrode material | |
| CN112736242A (en) | High-performance carbon negative electrode PTCDA hard carbon material and preparation method thereof | |
| CN104485443A (en) | Preparation method for graphene polymer cladding niobium-doping cobalt and lithium aluminate composite anode material | |
| CN108899211B (en) | Sodium ion capacitor with high energy density and high power density and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170315 |