CN109786815A - A kind of Nasicon type sodion solid electrolytes and its preparation method and application - Google Patents
A kind of Nasicon type sodion solid electrolytes and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to cell solid electrolyte technical field, a kind of Nasicon type sodion solid electrolytes and its preparation method and application are disclosed.The molecular formula of the Nasicon type sodion solid electrolytes is Na3+xAlxZr2‑xSi2PO12, wherein 0≤x≤0.5.Solid electrolyte prepared by the present invention has ionic conductivity height, the high feature of structural compactness.The ionic conductivity of Nasicon type solid electrolyte flake obtained at room temperature is up to 1.7 × 10‑3S·cm‑1, the relative volume density of electrolyte reaches 98%, is compared with the traditional method, and ionic conductivity significantly improves, and can effectively solve that solid electrolyte conductivity is lower, sintering temperature is higher, is prepared on a large scale the problems such as difficulty.
Description
Technical field
The invention belongs to cell solid electrolyte technical fields, more particularly, to a kind of Nasicon type sodion solid
Electrolyte and its preparation method and application.
Background technique
With the continuous aggravation of energy shortages and environmental pollution, finds clean reproducible energy and have become countries in the world
Common recognition.Extensive utilize of renewable energy requires production cost low, and performance efficiency is stablized, and can satisfy wanting for energy reserve
It asks.In existing various energy reserve technologies, lithium ion battery is due to having high-energy density, the spies such as excellent cyclical stability
Sign, becomes the most a kind of technologies studied in numerous power reserve technologies, therefore its technological development also becomes the most mature
It is a kind of.The lithium ion battery such as lithium-sulfur cell of a new generation, the power battery that the research and development of the battery technologies such as lithium-air battery are become
A kind of technology the most popular in automobile industry from now on, to cause the Industrial Revolution of an electric car.Currently, commercialized
Chargeable lithium ion battery has been widely applied to mobile electronic device, power grid energy storage, electric car etc..
With the extensive use of secondary lithium battery, disadvantage is also in showing slowly, and battery is in use process
In there is electrolyte leakage, the problems such as electrode corrosion is serious, or even generate excessively high temperature in use and battery is sent out
Raw explosion, is repeatedly reported in media, this also becomes the drawback of secondary lithium battery maximum.Meanwhile lithium ion battery is extensive
It uses so that the demand of lithium resource increases considerably, the price of lithium carbonate is from 2004 to 2018 year from 1500 beautiful yuan/ton hurricanes
Rise to 20000 beauty yuan/ton.A large amount of consumption of lithium resource and the reduction of the rapid increase of price and security performance, become limit
The major obstacle of large-scale application lithium electricity energy storage processed, therefore cost bottom is developed, the service life is long, the high novel energy-storing device of security performance
Part is extremely urgent.Due to the rich reserves on earth of sodium carbonate, and it is cheap, and sodium and lithium are all the first main group member
Element has similar electrochemical properties, and therefore, sodium-ion battery at room temperature becomes new selection as chemical energy storage battery.
It is inflammable since the electrolyte using liquid will cause the leakage of electrolyte, it is difficult to dendritic growth etc. is effectively prevented, because
This is likely to result in all solid state sode cell of battery explosion research efficiently, green, safe into effective way to solve this problem
Diameter.In numerous solid electrolytes, the Na with three-D space structure3Zr2Si2PO12Type solid electrolyte has safety easily system
Standby, high ion conductivity, wide electrochemical window, excellent chemistry and electrochemical stability easily assemble low with preparation cost etc. excellent
Point is widely paid close attention to.In its structure, tetrahedron PO4With octahedra ZrO6Network structure is collectively constituted, the sky in structure is produced
Cave and fillable coordination pass through sodium ion.
Summary of the invention
In order to solve above-mentioned the shortcomings of the prior art and disadvantage, the object of the present invention is to provide one kind
Nasicon type sodion solid electrolytes.The ionic conductivity of the solid electrolyte is higher, and sintering temperature is lower, has relatively strong
Practicability.
Another object of the present invention is the provision of the preparation method of above-mentioned Nasicon type sodion solid electrolytes.The party
Method is easy to operate, lower production costs, can produce solid electrolyte in enormous quantities, solves that electrolytic conductivity is lower, sintering temperature
It is higher, be prepared on a large scale the problems such as difficulty.
Still a further object of the present invention is the provision of the application of above-mentioned Nasicon type sodion solid electrolytes.
The purpose of the present invention is realized by following technical proposals:
The molecular formula of a kind of Nasicon type sodion solid electrolytes, the Nasicon type sodion solid electrolytes is
Na3+xAlxZr2-xSi2PO12, wherein 0≤x≤0.5；The solid electrolyte is the pH value that ethanol solution is adjusted with nitric acid, so
It adds citric acid again afterwards, mixed solution is sufficiently stirred to obtain；Silicon source, sodium source, silicon source and zirconium source are added in mixed solution, are heated to
It 70~90 DEG C and is sufficiently stirred to form mixed solution；Stirring in mixed solution is added in phosphorus source aqueous solution again and forms emulsion；It will
It is heat-treated at 500~600 DEG C after emulsion drying, grinding, after being then warming up to 900~1200 DEG C and keeping the temperature, is ground into
After powder is pressed into green body, it is made in 1000~1300 DEG C of sintering.
Preferably, deionized water and the volume ratio of dehydrated alcohol are (2~4) in the ethanol solution: 1.
Preferably, the silicon source is positive quanmethyl silicate, ethyl orthosilicate or silica；The sodium source be sodium carbonate,
Sodium bicarbonate, sodium nitrate, sodium phosphate, sodium acetate or sodium oxalate；Source of aluminium is aluminum nitrate, aluminium oxide, aluminum acetate or oxalic acid aluminium；
The zirconium source is zirconyl nitrate or zirconium nitrate；Phosphorus source is ammonium dihydrogen phosphate, diammonium hydrogen phosphate or phosphoric acid.
Preferably, the Volume fraction of the silicon source and mixed solution is (3~5): 20.
Preferably, the sodium source, silicon source and silicon source and the molar ratio in zirconium source are (6~7): (0~1): 4:(3~4).
Preferably, citric acid and Na in sodium source, silicon source and zirconium source in the mixed solution+、Al3+、Zr4+Cation it is total
The molar ratio of amount is 1:(1~4).
Preferably, the volume ratio of phosphorus source aqueous solution and mixed solution is 1:(5~12)；The matter of phosphorus source aqueous solution
Measuring concentration is 10~20%.
The preparation method of the Nasicon type sodion solid electrolytes, comprising the following specific steps
S1. then the pH value for adjusting ethanol solution with nitric acid is added citric acid again, is sufficiently stirred, must mix molten to 1~3
Liquid；
S2. silicon source is added drop-wise in the mixed solution of step S1, is sufficiently stirred to form siliceous original solution；By sodium source, aluminium
In the siliceous solution that source is added, stirring forms it into mixing salt solution；Zirconium source is added in above-mentioned mixing salt solution, is heated
It to 70~90 DEG C, is sufficiently stirred, forms transparent mixed solution；
S3. phosphorus source is dissolved in deionized water and obtains phosphorus source aqueous solution, be added into the mixed solution of step S2, sufficiently stir
It mixes, forms uniform emulsion；
S4. above-mentioned emulsion is dried at 100~120 DEG C, obtains white particle, be ground into fine powder, form presoma
Powder；Precursor powder is heat-treated at 500~600 DEG C, after being then warming up to 900~1200 DEG C and keeping the temperature, is pulverized
End；
S5. after the powder of step S4 being pressed into green body, it is solid that Nasicon type sodium ion is obtained in 1000~1300 DEG C of sintering
Body electrolyte sheet.
Preferably, the time of stirring described in step S2 is 10~30min；The time of stirring described in step S3 be 30~
60min。
Preferably, the time of heat treatment described in step S4 is 3~6h, and the time of the heat preservation is 3~6h；
Preferably, the time of calcining described in step S5 is 2~6h.
Application of the Nasicon type sodion solid electrolytes in all-solid-state battery or semisolid field of batteries.
Compared with prior art, the invention has the following advantages:
1. the present invention uses colloidal sol assisted Solid-state method, in conjunction with two-step sintering and isostatic cool pressing technique, be made compact structure and
The high solid electrolyte of ionic conductivity.The preparation method has the vacuum equipment that equipment requirement is simple, does not need complexity, preparation
The advantages that period is short.
2. solid electrolyte prepared by the present invention has, ionic conductivity is high, the high feature of structural compactness.It is obtained
The ionic conductivity of Nasicon type solid electrolyte sheet at room temperature is up to 1.7 × 10-3S·cm-1, the relative volume of electrolyte is close
Degree reach 98%, be compared with the traditional method, ionic conductivity significantly improves, can effectively solve solid electrolyte conductivity it is lower,
Sintering temperature is higher, is prepared on a large scale the problems such as difficulty.
Detailed description of the invention
Fig. 1 is the XRD diagram of Nasicon type sodion solid electrolytes piece prepared by embodiment 1；
Fig. 2 is the EIS figure of Nasicon type sodion solid electrolytes piece prepared by embodiment 1；
Fig. 3 is the SEM figure of Nasicon type sodion solid electrolytes piece prepared by embodiment 1；
Fig. 4 is the XRD diagram of Nasicon type sodion solid electrolytes piece prepared by embodiment 2；
Fig. 5 is the EIS figure of Nasicon type sodion solid electrolytes piece prepared by embodiment 2；
Fig. 6 is the SEM figure of Nasicon type sodion solid electrolytes piece prepared by embodiment 2.
Specific embodiment
The contents of the present invention are further illustrated combined with specific embodiments below, but should not be construed as limiting the invention.
Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.Except non-specifically
Illustrate, reagent that the present invention uses, method and apparatus is the art conventional reagents, method and apparatus.
Embodiment 1
1. taking 30ml deionized water and 10ml dehydrated alcohol, the dissolution of 6.28g citric acid is taken in the solution, adjusted with nitric acid molten
The pH value of liquid is sufficiently stirred to 1 or so；
2. 4.250g ethyl orthosilicate is taken to be added drop-wise in above-mentioned solution dropwise, 10min is sufficiently stirred, forms siliceous original
Solution；2.855g sodium nitrate is taken, is added in above-mentioned silicon original solution, stirring forms it into transparent uniform mixing salt solution；It takes
4.673 zirconyl nitrates are added to above-mentioned mixing salt solution, are heated to 70 DEG C, 10min is sufficiently stirred, and it is molten to form transparent mixing
Liquid；
3. 1.342g ammonium dihydrogen phosphate is taken to be dissolved in deionized water, obtain the saturated aqueous solution of ammonium dihydrogen phosphate, by its by
It is added dropwise to the transparent mixed solution of above-mentioned steps, stirs to get emulsion, 1h is sufficiently stirred, forms uniform emulsion；
4. above-mentioned emulsion is dried at 100~120 DEG C, white depositions are obtained, are ground into fine powder, form presoma
Powder；
5. above-mentioned precursor powder is heat-treated 6h at 600 DEG C, 5 DEG C/min is warming up to 900 DEG C, and at such a temperature
It pulverizes after heat preservation 6h, which is pressed into diameter 8mm, after the green body cylinders of 1mm, be heat-treated at 1000 DEG C
2h, sintering obtain Nasicon type sodion solid electrolytes piece, the molecular formula Na of the solid electrolyte3Zr2Si2PO12。
Performance test: being polished smooth obtained electrolyte sheet two sides with 1000 mesh to 3000 mesh sand paper, two-sided spray silver
As blocking electrode, ionic conductivity is taken with the measurement of two electrode AC impedance methods, frequency test section is 1Hz~1MHz, is passed through
Electrochemical impedance measures electrochemical impedance spectroscopy, and the chemical property parameter of ceramic sheet body is obtained after impedance spectrum is fitted, by
The chemical property and formula arrived(in formula, L is the thickness of electrolyte sheet, and A is the sectional area of electrolyte, and R is electrolyte
Impedance), the ionic conductivity for the solid electrolyte flake being calculated.The Nasicon type solid electrolyte sheet of preparation exists
Ionic conductivity at room temperature is up to 8.4 × 10-4S·cm-1。
Fig. 1 is the XRD diagram of Nasicon type sodion solid electrolytes piece manufactured in the present embodiment；From fig. 1, it can be seen that
The not excessive impurity phase of 2h electrolyte obtained is sintered at 1000 DEG C, crystal structure degree is good, mentions for good electric conductivity
For stable crystal structure, illustrate the crystal that high-purity can be obtained at 1000 DEG C, which significantly reduces electricity
Solve the sintering temperature of matter piece；Fig. 2 is that the EIS of Nasicon type sodion solid electrolytes piece manufactured in the present embodiment schemes；From Fig. 2
It is found that such electrolyte sheet impedance reduces, illustrates that the preparation method can reduce the impedance of electrolyte sheet, be correspondingly improved electricity
The ionic conductivity for solving matter piece, provides good conductor for solid state battery；Fig. 3 be Nasicon type sodium manufactured in the present embodiment from
The SEM of sub- solid electrolyte sheet schemes；As can be seen from Figure 3, the crystal grain of crystal is relatively uniform, the not big cavity of electrolyte sheet, explanation
The preparation method can be improved the density of electrolyte sheet.
Embodiment 2
1. taking 30ml deionized water and 10ml dehydrated alcohol, the dissolution of 6.28g citric acid is taken in the solution, adjusted with nitric acid molten
The pH value of liquid is sufficiently stirred to 1 or so；
2. 4.29g ethyl orthosilicate is taken to be added drop-wise in above-mentioned solution dropwise, 10min is sufficiently stirred, forms siliceous original
Solution；1.84g sodium carbonate is taken, is added in above-mentioned silicon original solution, stirring forms it into transparent uniform mixing salt solution；It takes
4.673 zirconyl nitrates are added to above-mentioned mixing salt solution, are heated to 70 DEG C, 10min is sufficiently stirred, and it is molten to form transparent mixing
Liquid；
3. 1.7g ammonium phosphate is taken to be dissolved in deionized water, the aqueous solution of ammonium phosphate is obtained, above-mentioned steps are added dropwise
Transparent mixed solution, stir to get emulsion, 1h be sufficiently stirred, form uniform emulsion；
4. above-mentioned emulsion is dried at 100~120 DEG C, white depositions are obtained, are ground into fine powder, form presoma
The precursor powder is heat-treated 6h by powder at 600 DEG C, and 5 DEG C/min is warming up to 900 DEG C, and at such a temperature after heat preservation 6h
Grind into powder；
5. above-mentioned powder is pressed into diameter 8mm, after the green body cylinders of 1mm, 1000 DEG C of heat treatment 2h, sintering
Nasicon type sodion solid electrolytes piece is obtained, the molecular formula of the solid electrolyte is Na30.4Al0.04Zr1.96Si2PO12。
Fig. 4 is the XRD diagram of Nasicon type sodion solid electrolytes piece manufactured in the present embodiment；As can be seen from Figure 4, right
Na3Zr2Si2PO12The doping for carrying out the position Zr can reduce the amount of ZrO2, illustrate to Na3Zr2Si2PO12It is doped and improves
The purity of crystal also improves the crystallinity of electrolyte sheet accordingly.Fig. 5 is Nasicon type sodium ion manufactured in the present embodiment
The EIS of solid electrolyte sheet schemes；As can be seen from Figure 5, to Na3Zr2Si2PO12It is doped the impedance for reducing electrolyte sheet, explanation
To Na3Zr2Si2PO12It is doped the ionic conductivity that electrolyte sheet can be improved.Fig. 6 is Nasicon manufactured in the present embodiment
The SEM of type sodion solid electrolytes piece schemes.As can be seen from Figure 3, to Na3Zr2Si2PO12It is doped the ruler that can reduce crystal grain
It is very little, electrolyte sheet is more densified, illustrates Na3Zr2Si2PO12Electrolyte can be made more from crystallite dimension is reduced by being doped
Densification, so that the conductivity of electrolyte sheet is improved, the ionic conductance of the Nasicon type solid electrolyte flake of preparation at room temperature
Rate is up to 1.5 × 10-3S·cm-1。
Embodiment 3
1. taking 30ml deionized water and 10ml dehydrated alcohol, the dissolution of 6.28g citric acid is taken in the solution, adjusted with nitric acid molten
The pH value of liquid is sufficiently stirred to 1 or so；
2. 4.29g ethyl orthosilicate is taken to be added drop-wise in above-mentioned solution dropwise, 10min is sufficiently stirred, forms siliceous original
Solution；2.93g sodium nitrate is taken, is added in above-mentioned silicon original solution, stirring forms it into transparent uniform mixing salt solution, takes
8.7g Zr(NO3)4·5H2O is added to above-mentioned mixing salt solution, is heated to 70 DEG C, 10min is sufficiently stirred, and is formed transparent
Mixed solution；
3. 1.7g ammonium phosphate is taken to be dissolved in deionized water, the aqueous solution of ammonium phosphate is obtained, above-mentioned steps are added dropwise
Transparent mixed solution, stir to get emulsion, 1h be sufficiently stirred, form uniform emulsion；
4. above-mentioned emulsion is dried at 100~120 DEG C, white depositions are obtained, are ground into fine powder, form presoma
The precursor powder is heat-treated 6h by powder at 600 DEG C, and 5 DEG C/min is warming up to 900 DEG C, and at such a temperature after heat preservation 6h
It pulverizes；
5. the powder of above-mentioned steps is pressed into diameter 8mm, after the green body cylinders of 1mm, 1000 DEG C of heat treatments
2h, sintering obtain Nasicon type sodion solid electrolytes piece, and the molecular formula of the solid electrolyte is
Na3.08Al0.08Zr1.92Si2PO12.The ionic conductivity of the Nasicon type solid electrolyte flake of preparation at room temperature up to 1.7 ×
10-3S·cm-1。
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination and simplify,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of Nasicon type sodion solid electrolytes, which is characterized in that the Nasicon type sodion solid electrolytes
Molecular formula be Na3+xAlxZr2-xSi2PO12, wherein 0≤x≤0.5；The solid electrolyte is to adjust ethanol solution with nitric acid
PH value, then add citric acid again, mixed solution be sufficiently stirred to obtain；Silicon source, sodium source, silicon source and zirconium source are added to mixed solution
In, it is heated to 70~90 DEG C and is sufficiently stirred to form mixed solution；Again phosphorus source aqueous solution is added to stir in mixed solution and be formed
Emulsion；It will be heat-treated at 500~600 DEG C after emulsion drying, grinding, be then warming up to 900~1200 DEG C and keep the temperature
Afterwards, it after grind into powder is pressed into green body, is made in 1000~1300 DEG C of sintering.
2. Nasicon type sodion solid electrolytes according to claim 1, which is characterized in that in the ethanol solution
Deionized water and the volume ratio of dehydrated alcohol are (2~4): 1.
3. Nasicon type sodion solid electrolytes according to claim 1, which is characterized in that the silicon source is positive silicon
Sour four methyl esters, ethyl orthosilicate or silica；The sodium source is sodium carbonate, sodium bicarbonate, sodium nitrate, sodium phosphate, sodium acetate
Or sodium oxalate；Source of aluminium is aluminum nitrate, aluminium oxide, aluminum acetate or oxalic acid aluminium；The zirconium source is zirconyl nitrate or zirconium nitrate；Institute
Stating phosphorus source is ammonium dihydrogen phosphate, diammonium hydrogen phosphate or phosphoric acid.
4. Nasicon type sodion solid electrolytes according to claim 1, which is characterized in that the silicon source with mix
The Volume fraction of solution is (3~5): 20.
5. Nasicon type sodion solid electrolytes according to claim 1, which is characterized in that the sodium source, silicon source and
Silicon source and the molar ratio in zirconium source are (6~7): (0~1): 4:(3~4).
6. Nasicon type sodion solid electrolytes according to claim 1, which is characterized in that in the mixed solution
Na in citric acid and sodium source, silicon source and zirconium source+、Al3+、Zr4+Cation total amount molar ratio be 1:(1~4).
7. Nasicon type sodion solid electrolytes according to claim 1, which is characterized in that phosphorus source aqueous solution
Volume ratio with mixed solution is 1:(5~12)；The mass concentration of phosphorus source aqueous solution is 10~20%.
8. the preparation method of Nasicon type sodion solid electrolytes according to claim 1-7, feature exist
In, comprising the following specific steps
S1. then the pH value for adjusting ethanol solution with nitric acid is added citric acid again, is sufficiently stirred, obtain mixed solution to 1~3；
S2. silicon source is added drop-wise in the mixed solution of step S1, is sufficiently stirred to form siliceous original solution；Sodium source, silicon source are added
In the siliceous solution entered, stirring forms it into mixing salt solution；Zirconium source is added in above-mentioned mixing salt solution, is heated to 70
It~90 DEG C, is sufficiently stirred, forms transparent mixed solution；
S3. phosphorus source is dissolved in deionized water and obtains phosphorus source aqueous solution, be added into the mixed solution of step S2, be sufficiently stirred,
Form uniform emulsion；
S4. above-mentioned emulsion is dried at 100~120 DEG C, obtains white particle, be ground into fine powder, form precursor powder；
Precursor powder is heat-treated at 500~600 DEG C, after being then warming up to 900~1200 DEG C and keeping the temperature, grind into powder；
S5. after the powder of step S4 being pressed into green body, Nasicon type sodion solid electricity is obtained in 1000~1300 DEG C of sintering
Solve matter piece.
9. the preparation method of Nasicon type sodion solid electrolytes according to claim 8, which is characterized in that step
The time of stirring described in S2 is 10~30min；The time of stirring described in step S3 is 30~60min；Described in step S4
The time of heat treatment is 3~6h, and the time of the heat preservation is 3~6h；The time of calcining described in step S5 is 2~6h.
10. the described in any item Nasicon type sodion solid electrolytes of claim 1-7 are in all-solid-state battery or semisolid electricity
Application in the field of pond.
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| CN113073357A (en) * | 2021-03-19 | 2021-07-06 | 西南石油大学 | Electrolytic device based on solid electrolyte diaphragm material and method for preparing sodium by using electrolytic device |
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| CN114267871A (en) * | 2021-12-13 | 2022-04-01 | 溧阳天目先导电池材料科技有限公司 | Mixed ion conductor material and preparation method and application thereof |
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| CN113683119A (en) * | 2020-05-18 | 2021-11-23 | 天津理工大学 | Preparation method and application of sodium ion solid electrolyte with NASICON structure |
| CN113073357A (en) * | 2021-03-19 | 2021-07-06 | 西南石油大学 | Electrolytic device based on solid electrolyte diaphragm material and method for preparing sodium by using electrolytic device |
| CN114267872A (en) * | 2021-12-13 | 2022-04-01 | 溧阳天目先导电池材料科技有限公司 | Modified NASICON structure sodium ion solid electrolyte material and preparation method and application thereof |
| CN114267871A (en) * | 2021-12-13 | 2022-04-01 | 溧阳天目先导电池材料科技有限公司 | Mixed ion conductor material and preparation method and application thereof |
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