CN109786815B - Nasicon type sodium ion solid electrolyte and preparation method and application thereof - Google Patents
Nasicon type sodium ion solid electrolyte and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of solid electrolytes of batteries, and discloses a Nasicon type sodium ion solid electrolyte, and a preparation method and application thereof. The molecular formula of the Nasicon type sodium ion solid electrolyte is Na3+xAlxZr2‑xSi2PO12Wherein x is more than or equal to 0 and less than or equal to 0.5. The solid electrolyte prepared by the method has the characteristics of high ionic conductivity and high structural density. The prepared Nasicon type solid electrolyte sheet has ion conductivity up to 1.7X 10 at room temperature‑3S·cm‑1The relative volume density of the electrolyte reaches 98%, compared with the traditional method, the ionic conductivity is obviously improved, and the problems of low conductivity, high sintering temperature, difficult mass preparation and the like of the solid electrolyte can be effectively solved.
Description
Technical Field
The invention belongs to the technical field of solid electrolytes of batteries, and particularly relates to a Nasicon type sodium ion solid electrolyte and a preparation method and application thereof.
Background
With the shortage of energy and the increasing environmental pollution, the search for clean and renewable energy has become a common consensus in all countries of the world. The large-scale utilization of renewable energy requires low production cost and efficient and stable performance, and can meet the requirement of energy storage. Among various energy storage technologies, lithium ion batteries have high energy density and excellent cycle stability, and thus have been the most studied among many power storage technologies, and therefore, the technical development thereof has become the most mature technology. The research and development of new generation lithium ion batteries such as lithium sulfur batteries, lithium air batteries and other battery technologies is that power batteries become the most popular technology in the automobile industry in the future, thereby initiating the industrial revolution of an electric automobile. Currently, commercial rechargeable lithium ion batteries are widely used in mobile electronic devices, power grid energy storage, electric vehicles, and the like.
With the wide application of the secondary lithium ion battery, the defects of the secondary lithium ion battery are gradually shown, the problems of electrolyte leakage, serious electrode corrosion and the like of the battery occur in the using process, even the battery is exploded due to the overhigh temperature generated in the using process, and the problems are frequently reported, so the defects of the secondary lithium ion battery are the biggest. Meanwhile, the large-scale use of lithium ion batteries greatly increases the demand of lithium resources, and the price of lithium carbonate rises from $ 1500/ton to $ 20000/ton from 2004 to 2018. The large consumption of lithium resources, the rapid increase of price and the reduction of safety performance become main obstacles for limiting the large-scale application of lithium battery energy storage, so that the development of novel energy storage devices with low cost, long service life and high safety performance is urgent. Sodium carbonate is abundant in earth, low in price, sodium and lithium are the same elements of the first main group and have similar electrochemical properties, so that a sodium ion battery at room temperature becomes a new choice as a chemical energy storage battery.
The adoption of the liquid electrolyte can cause the leakage of the electrolyte, the flammability and the difficulty in effectively preventing the growth of dendrite, so that the efficient, green and safe all-solid-state sodium battery for battery explosion research can be an effective way for solving the problem. Among the numerous solid electrolytes, Na having a three-dimensional structure3Zr2Si2PO12The solid electrolyte has the advantages of safety, easy preparation, high ionic conductivity, wide electrochemical window, excellent chemical and electrochemical stability, easy assembly, low preparation cost and the like, and is widely concerned. In the structure of tetrahedron PO4And octahedral ZrO6Together form a network structure, generate structural holes and fillable coordination so that sodium ions can pass through.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a Nasicon type sodium ion solid electrolyte. The solid electrolyte has high ionic conductivity, low sintering temperature and high practicability.
The invention also aims to provide a preparation method of the Nasicon type sodium ion solid electrolyte. The method has the advantages of simple operation and low production cost, can produce solid electrolytes in large batch, and solves the problems of low electrolyte conductivity, high sintering temperature, difficult large-batch preparation and the like.
The invention further aims to provide application of the Nasicon type sodium ion solid electrolyte.
The purpose of the invention is realized by the following technical scheme:
a Nasicon type sodium ion solid electrolyte, the molecular formula of which is Na3+xAlxZr2-xSi2PO12Wherein x is more than or equal to 0 and less than or equal to 0.5; the solid electrolyte is prepared by adjusting the pH value of an ethanol solution by using nitric acid, then adding citric acid, and fully stirring to obtain a mixed solution; adding a silicon source, a sodium source, an aluminum source and a zirconium source into the mixed solution, heating to 70-90 ℃, and fully stirring to form a mixed solution; adding the phosphorus source water solution into the mixed solution and stirring to form emulsion; drying and grinding the emulsion, then carrying out heat treatment at 500-600 ℃, then heating to 900-1200 ℃, preserving heat, grinding into powder, pressing into a blank, and sintering at 1000-1300 ℃ to obtain the product.
Preferably, the volume ratio of the deionized water to the absolute ethyl alcohol in the ethyl alcohol solution is (2-4): 1.
preferably, the silicon source is tetramethyl orthosilicate, ethyl orthosilicate or silicon dioxide; the sodium source is sodium carbonate, sodium bicarbonate, sodium nitrate, sodium phosphate, sodium acetate or sodium oxalate; the aluminum source is aluminum nitrate, aluminum oxide, aluminum acetate or aluminum oxalate; the zirconium source is zirconyl nitrate or zirconium nitrate; the phosphorus source is ammonium dihydrogen phosphate, diammonium hydrogen phosphate or phosphoric acid.
Preferably, the volume fraction ratio of the silicon source to the mixed solution is (3-5): 20.
preferably, the molar ratio of the sodium source to the aluminum source to the silicon source to the zirconium source is (6-7): (0-1): 4: (3-4).
Preferably, the citric acid in the mixed solution is mixed with Na in a sodium source, an aluminum source and a zirconium source+、Al3+、Zr4+The molar ratio of the total amount of cations of (a) to (b) is 1: (1-4).
Preferably, the volume ratio of the phosphorus source water solution to the mixed solution is 1: (5-12); the mass concentration of the phosphorus source water solution is 10-20%.
The preparation method of the Nasicon type sodium ion solid electrolyte comprises the following specific steps:
s1, adjusting the pH value of an ethanol solution to 1-3 by using nitric acid, then adding citric acid, and fully stirring to obtain a mixed solution;
s2, dropwise adding a silicon source into the mixed solution obtained in the step S1, and fully stirring to form a silicon-containing original solution; adding a sodium source and an aluminum source into the silicon-containing solution, and stirring to form a mixed salt solution; adding a zirconium source into the mixed salt solution, heating to 70-90 ℃, and fully stirring to form a transparent mixed solution;
s3, dissolving a phosphorus source in deionized water to obtain a phosphorus source water solution, adding the phosphorus source water solution into the mixed solution obtained in the step S2, and fully stirring to form uniform emulsion;
s4, drying the emulsion at 100-120 ℃ to obtain white particles, and grinding the white particles into fine powder to form precursor powder; carrying out heat treatment on the precursor powder at 500-600 ℃, then heating to 900-1200 ℃, preserving heat, and grinding into powder;
and S5, pressing the powder obtained in the step S4 into a blank, and sintering at 1000-1300 ℃ to obtain the Nasicon type sodium ion solid electrolyte sheet.
Preferably, the stirring time in the step S2 is 10-30 min; and the stirring time in the step S3 is 30-60 min.
Preferably, the heat treatment time in the step S4 is 3-6 hours, and the heat preservation time is 3-6 hours;
preferably, the calcining time in the step S5 is 2-6 h.
The Nasicon type sodium ion solid electrolyte is applied to the field of all-solid batteries or semi-solid batteries.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts a sol-assisted solid phase method and combines two-step sintering and cold isostatic pressing processes to prepare the solid electrolyte with compact structure and high ionic conductivity. The preparation method has the advantages of simple equipment requirement, no need of complex vacuum equipment, short preparation period and the like.
2. The solid electrolyte prepared by the method has the characteristics of high ionic conductivity and high structural density. The prepared Nasicon type solid electrolyte sheet has ion conductivity up to 1.7X 10 at room temperature-3S·cm-1The relative volume density of the electrolyte reaches 98%, compared with the traditional method, the ionic conductivity is obviously improved, and the problems of low conductivity, high sintering temperature, difficult mass preparation and the like of the solid electrolyte can be effectively solved.
Drawings
Fig. 1 is an XRD pattern of the Nasicon-type sodium ion solid electrolyte sheet prepared in example 1;
fig. 2 is an EIS diagram of a Nasicon-type sodium ion solid electrolyte sheet prepared in example 1;
fig. 3 is an SEM image of the Nasicon-type sodium ion solid electrolyte sheet prepared in example 1;
fig. 4 is an XRD pattern of the Nasicon-type sodium ion solid electrolyte sheet prepared in example 2;
fig. 5 is an EIS diagram of the Nasicon-type sodium ion solid electrolyte sheet prepared in example 2;
fig. 6 is an SEM image of the Nasicon-type sodium ion solid electrolyte sheet prepared in example 2.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. Taking 30ml of deionized water and 10ml of absolute ethyl alcohol, dissolving 6.28g of citric acid in the solution, adjusting the pH value of the solution to about 1 by using nitric acid, and fully stirring;
2. dropwise adding 4.250g of tetraethoxysilane into the solution, and fully stirring for 10min to form a silicon-containing original solution; 2.855g of sodium nitrate is taken and added into the silicon raw solution, and the mixture is stirred to form a transparent and uniform mixed salt solution; adding 4.673 zirconyl nitrate into the mixed salt solution, heating to 70 deg.C, stirring for 10min to obtain transparent mixed solution;
3. dissolving 1.342g of ammonium dihydrogen phosphate in deionized water to obtain a saturated aqueous solution of ammonium dihydrogen phosphate, dropwise adding the saturated aqueous solution into the transparent mixed solution obtained in the previous step, stirring to obtain an emulsion, and fully stirring for 1 hour to form a uniform emulsion;
4. drying the emulsion at 100-120 ℃ to obtain white precipitate, and grinding the white precipitate into fine powder to form precursor powder;
5. heat-treating the precursor powder at 600 ℃ for 6h, heating to 900 ℃ at 5 ℃/min, preserving heat at the temperature for 6h, grinding into powder, pressing the powder into a cylindrical blank with the diameter of 8mm and the thickness of 1mm, heat-treating at 1000 ℃ for 2h, and sintering to obtain a Nasicon type sodium ion solid electrolyte sheet with the molecular formula of Na3Zr2Si2PO12。
And (3) performance testing: polishing two sides of the obtained electrolyte sheet with 1000-3000 mesh sand paper, spraying silver on the two sides to serve as blocking electrodes, measuring the ionic conductivity by a two-electrode alternating current impedance method, measuring the electrochemical impedance spectrum through the electrochemical impedance, fitting the impedance spectrum to obtain the electrochemical performance parameters of the ceramic sheet, and obtaining the electrochemical performance and formula
(wherein L is the thickness of the electrolyte sheet, A is the cross-sectional area of the electrolyte, and R isImpedance of electrolyte), the resulting ionic conductivity of the solid electrolyte sheet was calculated. The prepared Nasicon type solid electrolyte sheet has ion conductivity up to 8.4X 10 at room temperature-4S·cm-1。
Fig. 1 is an XRD pattern of the Nasicon-type sodium ion solid electrolyte sheet prepared in this example; as can be seen from fig. 1, the electrolyte obtained by sintering at 1000 ℃ for 2h has no excessive impurity phases, has good crystal crystallinity, provides a stable crystal structure for good conductivity, and illustrates that high-purity crystals can be obtained at 1000 ℃, and the preparation method significantly reduces the sintering temperature of the electrolyte sheet; fig. 2 is an EIS diagram of the Nasicon-type sodium ion solid electrolyte sheet prepared in this example; as can be seen from fig. 2, the impedance of the electrolyte sheet is reduced, which indicates that the preparation method can reduce the impedance of the electrolyte sheet, correspondingly improve the ionic conductivity of the electrolyte sheet, and provide a good conductor for the solid battery; fig. 3 is an SEM image of the Nasicon-type sodium ion solid electrolyte sheet prepared in this example; as can be seen from fig. 3, the crystal grains are relatively uniform and the electrolyte sheet has no large voids, indicating that the preparation method can increase the density of the electrolyte sheet.
Example 2
1. Taking 30ml of deionized water and 10ml of absolute ethyl alcohol, dissolving 6.28g of citric acid in the solution, adjusting the pH value of the solution to about 1 by using nitric acid, and fully stirring;
2. dropwise adding 4.29g of tetraethoxysilane into the solution, and fully stirring for 10min to form a silicon-containing original solution; adding 1.84g of sodium carbonate into the silicon raw solution, and stirring to form a transparent and uniform mixed salt solution; adding 4.673 zirconyl nitrate into the mixed salt solution, heating to 70 deg.C, stirring for 10min to obtain transparent mixed solution;
3. dissolving 1.7g of ammonium phosphate in deionized water to obtain an aqueous solution of ammonium phosphate, dropwise adding the aqueous solution of ammonium phosphate into the transparent mixed solution obtained in the step, stirring to obtain an emulsion, and fully stirring for 1 hour to form a uniform emulsion;
4. drying the emulsion at 100-120 ℃ to obtain white precipitate, grinding the white precipitate into fine powder to form precursor powder, carrying out heat treatment on the precursor powder at 600 ℃ for 6h, heating the precursor powder to 900 ℃ at 5 ℃/min, keeping the temperature for 6h, and grinding the precursor powder into powder;
5. pressing the powder into a cylindrical blank with the diameter of 8mm and the thickness of 1mm, then carrying out heat treatment at 1000 ℃ for 2h, and sintering to obtain a Nasicon type sodium ion solid electrolyte sheet, wherein the molecular formula of the solid electrolyte is Na30.4Al0.04Zr1.96Si2PO12。
Fig. 4 is an XRD pattern of the Nasicon-type sodium ion solid electrolyte sheet prepared in this example; as can be seen from FIG. 4, for Na3Zr2Si2PO12Doping at the Zr site reduced the amount of ZrO2, indicating that Na3Zr2Si2PO12Doping increases the purity of the crystal and correspondingly increases the crystallinity of the electrolyte sheet. Fig. 5 is an EIS diagram of the Nasicon-type sodium ion solid electrolyte sheet prepared in this example; as can be seen from FIG. 5, for Na3Zr2Si2PO12Doping reduces the resistance of the electrolyte sheet, indicating that Na is present3Zr2Si2PO12Doping can improve the ionic conductivity of the electrolyte sheet. Fig. 6 is an SEM image of the Nasicon-type sodium ion solid electrolyte sheet prepared in this example. As can be seen from FIG. 3, for Na3Zr2Si2PO12Doping can be performed to reduce the grain size and to more densify the electrolyte sheet, indicating that Na3Zr2Si2PO12The doping can reduce the grain size and make the electrolyte more compact, thereby improving the conductivity of the electrolyte sheet, and the ion conductivity of the prepared Nasicon type solid electrolyte sheet can reach 1.5 multiplied by 10 at room temperature-3S·cm-1。
Example 3
1. Taking 30ml of deionized water and 10ml of absolute ethyl alcohol, dissolving 6.28g of citric acid in the solution, adjusting the pH value of the solution to about 1 by using nitric acid, and fully stirring;
2. dropwise adding 4.29g of tetraethoxysilane into the solution, and fully stirring for 10min to form a silicon-containing original solution; 2.93g of sodium nitrate was added to the above silicon stock solutionStirring the solution to form a transparent and uniform mixed salt solution, and taking 8.7g of Zr (NO)3)4·5H2Adding O into the mixed salt solution, heating to 70 ℃, and fully stirring for 10min to form a transparent mixed solution;
3. dissolving 1.7g of ammonium phosphate in deionized water to obtain an aqueous solution of ammonium phosphate, dropwise adding the aqueous solution of ammonium phosphate into the transparent mixed solution obtained in the step, stirring to obtain an emulsion, and fully stirring for 1 hour to form a uniform emulsion;
4. drying the emulsion at 100-120 ℃ to obtain white precipitate, grinding the white precipitate into fine powder to form precursor powder, carrying out heat treatment on the precursor powder at 600 ℃ for 6h, heating the precursor powder to 900 ℃ at 5 ℃/min, keeping the temperature for 6h, and grinding the precursor powder into powder;
5. pressing the powder obtained in the step into a cylindrical blank with the diameter of 8mm and the thickness of 1mm, then carrying out heat treatment at 1000 ℃ for 2h, and sintering to obtain a Nasicon type sodium ion solid electrolyte sheet, wherein the molecular formula of the solid electrolyte is Na3.08Al0.08Zr1.92Si2PO12. The prepared Nasicon type solid electrolyte sheet has ion conductivity up to 1.7X 10 at room temperature-3S·cm-1。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. The Nasicon type sodium ion solid electrolyte is characterized in that the molecular formula of the Nasicon type sodium ion solid electrolyte is Na3+xAlxZr2-xSi2PO12Wherein 0 is<x is less than or equal to 0.5; the solid electrolyte is prepared by adjusting the pH value of an ethanol solution by using nitric acid, then adding citric acid, and fully stirring to obtain a mixed solution; adding a silicon source, a sodium source, an aluminum source and a zirconium source into the mixed solution, heating to 70-90 ℃, and fully stirring to form a mixed solution; adding the phosphorus source aqueous solution into the mixtureMixing the solution and stirring to form emulsion; drying and grinding the emulsion, then carrying out heat treatment at 500-600 ℃, then heating to 900-1200 ℃, preserving heat, grinding into powder, pressing into a blank body, and sintering at 1000-1300 ℃ to obtain the product; the volume fraction ratio of the silicon source to the mixed solution is (3-5): 20; the molar ratio of the sodium source to the aluminum source to the silicon source to the zirconium source is (6-7): (0-1): 4: (3-4); citric acid in the mixed solution is mixed with Na in a sodium source, an aluminum source and a zirconium source+、Al3+、Zr4+The molar ratio of the total amount of cations of (a) is 1: (1-4); the volume ratio of the phosphorus source water solution to the mixed solution is 1: (5-12); the mass concentration of the phosphorus source water solution is 10-20%.
2. The Nasicon type sodium ion solid electrolyte as claimed in claim 1, wherein the volume ratio of the deionized water to the absolute ethanol in the ethanol solution is (2-4): 1.
3. the Nasicon-type sodium ion solid electrolyte as claimed in claim 1, wherein the silicon source is tetramethyl orthosilicate, ethyl orthosilicate, or silicon dioxide; the sodium source is sodium carbonate, sodium bicarbonate, sodium nitrate, sodium phosphate, sodium acetate or sodium oxalate; the aluminum source is aluminum nitrate, aluminum oxide, aluminum acetate or aluminum oxalate; the zirconium source is zirconyl nitrate or zirconium nitrate; the phosphorus source is ammonium dihydrogen phosphate, diammonium hydrogen phosphate or phosphoric acid.
4. A method for preparing Nasicon-type sodium ion solid electrolyte as claimed in any one of claims 1 to 3, characterized by comprising the following specific steps:
s1, adjusting the pH value of the ethanol solution to 1-3 by using nitric acid, then adding citric acid, and fully stirring to obtain a mixed solution;
s2, adding a silicon source into the mixed solution obtained in the step S1 dropwise, and fully stirring to form a silicon-containing original solution; adding a sodium source and an aluminum source into the silicon-containing solution, and stirring to form a mixed salt solution; adding a zirconium source into the mixed salt solution, heating to 70-90 ℃, and fully stirring to form a transparent mixed solution;
s3, dissolving a phosphorus source in deionized water to obtain a phosphorus source water solution, adding the phosphorus source water solution into the mixed solution obtained in the step S2, and fully stirring to form uniform emulsion;
s4, drying the emulsion at 100-120 ℃ to obtain white particles, and grinding the white particles into fine powder to form precursor powder; carrying out heat treatment on the precursor powder at 500-600 ℃, then heating to 900-1200 ℃, preserving heat, and grinding into powder;
and S5, pressing the powder obtained in the step S4 into a blank, and sintering at 1000-1300 ℃ to obtain the Nasicon type sodium ion solid electrolyte sheet.
5. The method for preparing Nasicon-type sodium ion solid electrolyte according to claim 4, wherein the stirring time in step S2 is 10-30 min; the stirring time in the step S3 is 30-60 min; in the step S4, the heat treatment time is 3-6 hours, and the heat preservation time is 3-6 hours; and the sintering time in the step S5 is 2-6 h.
6. Use of the Nasicon-type sodium ion solid electrolyte as claimed in any one of claims 1 to 3 in the field of all-solid batteries or semi-solid batteries.
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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 |
| CN113073357B (en) * | 2021-03-19 | 2022-05-17 | 西南石油大学 | Electrolytic device based on solid electrolyte diaphragm material and method for preparing sodium by using electrolytic device |
| 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 |
| 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 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4526844A (en) * | 1983-04-14 | 1985-07-02 | Westinghouse Electric Corp. | Rhombohedral nasicon compound and battery |
| EP1345280A1 (en) * | 2002-03-07 | 2003-09-17 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Solid electrolyte with nanometre size pores |
| JP2010015782A (en) * | 2008-07-02 | 2010-01-21 | Kyushu Univ | All-solid battery |
| CN103449815A (en) * | 2013-07-30 | 2013-12-18 | 广东工业大学 | Codoped apatite structure ceramic material and preparation method thereof |
| CN105355966A (en) * | 2015-11-16 | 2016-02-24 | 天津工业大学 | Preparation method of NASICON-type sodion solid electrolyte |
| CN105609871A (en) * | 2016-01-22 | 2016-05-25 | 昆明理工大学 | Preparation method of sodium-ion solid electrolyte with NASICON structure |
| CN105742698A (en) * | 2014-12-12 | 2016-07-06 | 中国科学院物理研究所 | NASICON-type sodion solid electrolyte material and preparation method thereof |
| CN108493478A (en) * | 2018-04-11 | 2018-09-04 | 桑德集团有限公司 | A kind of all-solid-state battery and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0680462A (en) * | 1992-08-31 | 1994-03-22 | Shinagawa Refract Co Ltd | Solid electrolyte |
| JP6861942B2 (en) * | 2015-08-10 | 2021-04-21 | 日本電気硝子株式会社 | Solid electrolyte sheet and its manufacturing method, and sodium ion all-solid-state secondary battery |
-
2018
- 2018-12-20 CN CN201811563020.4A patent/CN109786815B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4526844A (en) * | 1983-04-14 | 1985-07-02 | Westinghouse Electric Corp. | Rhombohedral nasicon compound and battery |
| EP1345280A1 (en) * | 2002-03-07 | 2003-09-17 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Solid electrolyte with nanometre size pores |
| JP2010015782A (en) * | 2008-07-02 | 2010-01-21 | Kyushu Univ | All-solid battery |
| CN103449815A (en) * | 2013-07-30 | 2013-12-18 | 广东工业大学 | Codoped apatite structure ceramic material and preparation method thereof |
| CN105742698A (en) * | 2014-12-12 | 2016-07-06 | 中国科学院物理研究所 | NASICON-type sodion solid electrolyte material and preparation method thereof |
| CN105355966A (en) * | 2015-11-16 | 2016-02-24 | 天津工业大学 | Preparation method of NASICON-type sodion solid electrolyte |
| CN105609871A (en) * | 2016-01-22 | 2016-05-25 | 昆明理工大学 | Preparation method of sodium-ion solid electrolyte with NASICON structure |
| CN108493478A (en) * | 2018-04-11 | 2018-09-04 | 桑德集团有限公司 | A kind of all-solid-state battery and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Durable Sodium Battery with a Flexible Na3Zr2Si2PO12-PVDF-HFP Composite Electrolyte and Sodium/Carbon Cloth Anode;Yi, Qiang; Zhang, Wenqiang等;《ACS APPLIED MATERIALS & INTERFACES》;20181017;第10卷(第41期);第35039-35046页 * |
| Improving the ionic conductivity of NASICON through aliovalent cation substitution of Na3Zr2Si2PO12;Adam G.Jolley等;《IONICS》;20151130;第21卷(第11期);第3031-3038页 * |
| Sol-Gel法制备NASICON材料即表征;张爽，全宝富等;《高等学校化学学报》;20030831;第24卷(第8期);第1356-1359页 * |
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