CN113675462A - NASICON type solid electrolyte material of fast sodium ion conductor and preparation method and application thereof - Google Patents

NASICON type solid electrolyte material of fast sodium ion conductor and preparation method and application thereof Download PDF

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CN113675462A
CN113675462A CN202110964000.3A CN202110964000A CN113675462A CN 113675462 A CN113675462 A CN 113675462A CN 202110964000 A CN202110964000 A CN 202110964000A CN 113675462 A CN113675462 A CN 113675462A
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electrolyte material
solid electrolyte
type solid
nasicon type
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刘立敏
周晓亮
刘雨剑
梁栋实
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Southwest Petroleum University
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
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    • 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 provides a fast sodium ion conductor NASICON type solid electrolyte material, a preparation method and application thereof, and provides an NASICON type solid electrolyte material with a general formula of Na3.4‑x+y‑ zZr2‑x‑yNbxLaySi2.4‑zP0.6+zO12Wherein 0 is<x≤0.5，0<y≤0.5，‑0.5≤z<0.2, relating to the technical field of electrolyte materials. The electrolyte material can be synthesized by a solution-assisted solid-phase reaction method and a solid-phase reaction method, the synthesis process is simple, the manufacturing cost is low, and two equivalent aliovalent metal cations Nb are doped into the Zr site of the NASICON type solid electrolyte material5+And La3+The bulk impedance and the grain boundary impedance of the material are reduced, the densification degree of the material is improved, and the material is obtained at room temperatureA NASICON type solid electrolyte material having a high ionic conductivity.

Description

NASICON type solid electrolyte material of fast sodium ion conductor and preparation method and application thereof
Technical Field
The invention relates to the technical field of solid electrolyte materials, in particular to a fast sodium ion conductor NASICON type solid electrolyte material and a preparation method and application thereof.
Background
With the rapid development of human society, fossil fuels as traditional non-renewable energy sources face the problem of energy exhaustion. On this basis, the research on some renewable clean energy sources such as solar energy, wind energy, tidal energy, geothermal energy and the like is in a vigorous development stage, but since the renewable clean energy sources are intermittently existed in the actual operation environment, the development of energy storage technology matched with the renewable clean energy sources is currently in wide interest of researchers. Among a plurality of energy storage technologies, electrochemical energy storage has the outstanding advantages of high energy storage efficiency, long service life, multiple application scenes and the like.
Among electrochemical secondary battery energy storage devices, lithium ion batteries occupy a wide market in the fields of digital products, smart homes, new energy automobiles and the like at present due to the advantages of high energy density, long cycle life, relatively mature technology and the like. When the lithium ion battery is arranged on a large scale, the problems of lithium resource shortage (the content of lithium element in the earth crust is about 0.067%) and the like are also inevitable, along with the continuous expansion of the new energy automobile market, the cost of lithium carbonate serving as a main raw material of the lithium ion battery is also high, and the lithium ion battery is difficult to meet the requirements of the two industries of the new energy automobile and the renewable clean energy storage. Compared with the shortage of lithium reserves, the high reserves of sodium resources have absolute advantages (the content of sodium element in earth crust is about 2.83 percent), and the sodium-ion battery is wide in distribution and low in cost.
Although the sodium ion battery has outstanding advantages, the currently used organic liquid electrolyte has safety problems of flammability, explosiveness, volatility and the like, is easy to cause safety accidents, and threatens the life and property safety of people. Therefore, the development of a solid electrolyte material with high safety, stable chemical properties and excellent conductivity is a prerequisite for large-scale application of solid sodium-ion batteries.
The NASICON type solid electrolyte is an inorganic solid electrolyte material which is widely researched at present and has a general formula of Na1+xZr2SixP3-xO12(x is more than or equal to 0 and less than or equal to 3) and is integrally composed of Si/PO4Tetrahedron and ZrO6Octahedron throughThe co-vertex oxygen atoms are connected to form a three-dimensional sodium ion transfer channel, which has the advantages of strong structural stability, high chemical stability, low electronic conductivity and wider electrochemical window, and is considered to be one of the most potential solid electrolyte materials applied to all-solid sodium ion batteries. However, it has an ionic conductivity of only 10 at room temperature-4Scm-1And the ionic conductivity of the electrolyte is far lower than that of the current liquid electrolyte at room temperature, so that the practical application of the solid-state sodium battery is limited. Therefore, the practical application of the sodium battery in various fields of the modern society can be effectively accelerated and expanded by improving the ionic conductivity of the NASICON type solid electrolyte material at room temperature.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an NASICON-type solid electrolyte material with high ionic conductivity, and therefore the present invention provides an NASICON-type solid electrolyte material with fast sodium ion conductor, and a preparation method and an application thereof.
A fast sodium ion conductor NASICON type solid electrolyte material is disclosed, the general structural formula of the solid electrolyte material is Na3.4-x+y-zZr2-x-yNbxLaySi2.4-zP0.6+zO12Wherein 0 is<x≤0.5，0<y≤0.5，-0.5≤z<0.2。
The invention also provides the NASICON type solid electrolyte material of the fast sodium ion conductor and a preparation method thereof, wherein the preparation method comprises a solution-assisted solid phase reaction method and a solid phase reaction method.
Preferably, the solution-assisted solid phase reaction method is carried out according to the following steps:
(1) firstly, adding a zirconium source into deionized water, adding a sodium source, a niobium source and a lanthanum source in sequence after the zirconium source is completely dissolved, stirring for 0.5-1 h, clarifying the solution, and then adding Si (OCH)2CH3)4And finally, adding a phosphorus source, and stirring for 1-2 hours to obtain a gel solution.
(2) Drying the gel solution at 70-90 ℃ to obtain dry gel, and carrying out heat treatment on the obtained dry gel in an air atmosphere to obtain precursor powder particles; the obtained precursor powderAnd ball-milling the powder particles in a planetary ball mill, drying and grinding the powder particles at the temperature of 80-90 ℃ into white solid powder, pressing the powder particles into tablets by using a tablet press, and calcining the tablets in air atmosphere to obtain the NASICON type fast sodium ion conductor solid electrolyte material. The zirconium source, the sodium source, the niobium source, the lanthanum source and the Si (OCH)2CH3)4The molar ratio of the phosphorus source is 1.5-1.98: 3.1-3.5: 0.01-0.25: 0.01-0.25: 2.3-2.9: 0.1 to 0.7.
(3) And grinding and polishing, ultrasonically cleaning and drying in an oven the calcined NASICON type solid electrolyte material of the flake fast sodium ion conductor, sputtering gold films on two surfaces of the solid electrolyte material to be used as blocking electrodes, then carrying out an alternating current impedance test at room temperature, wherein the frequency range is 1 Hz-1 MHz, and obtaining the ionic conductivity of the solid electrolyte material at room temperature by calculation.
Preferably, the solid phase reaction method is carried out according to the following steps:
(1) firstly, mixing a zirconium source, a sodium source, a silicon source, a phosphorus source, a niobium oxide and a lanthanum oxide, and then carrying out heat treatment on the mixture in an air atmosphere to obtain precursor powder particles; and (2) placing the obtained precursor powder particles in a planetary ball mill for ball milling, then drying and grinding the particles at the temperature of 80-90 ℃ into white solid powder, then pressing the powder into tablets by using a tablet press, and finally calcining the tablets in an air atmosphere to obtain the fast sodium ion conductor NASICON type solid electrolyte material. The molar ratio of the zirconium source to the sodium source to the niobium oxide to the lanthanum oxide to the silicon source to the phosphorus source is 1.5-1.98: 3.1-3.5: 0.01-0.25: 0.01-0.25: 2.3-2.9: 0.1 to 0.7.
(2) And grinding and polishing, ultrasonically cleaning and drying in an oven the calcined NASICON type solid electrolyte material of the flake fast sodium ion conductor, sputtering gold films on two surfaces of the solid electrolyte material to be used as blocking electrodes, then carrying out an alternating current impedance test at room temperature, wherein the frequency range is 1 Hz-1 MHz, and obtaining the ionic conductivity of the solid electrolyte material at room temperature by calculation.
The application of the NASICON type solid electrolyte material of the fast sodium ion conductor is used for preparing all-solid-state sodium ion batteries.
The invention has the beneficial effects that:
1. the invention relates to a fast sodium ion conductor NASICON type solid electrolyte material and a preparation method thereof, which adopts a solution-assisted solid phase reaction method and a solid phase reaction method to carry out NASICON type solid electrolyte material Na3.4Zr2Si2.4P0.6O12The Zr site in the alloy is doped with Nb with the same amount5+And La3+To obtain Na3.4-x+y-zZr2-x-yNbxLaySi2.4-zP0.6+zO12A solid electrolyte material. By introducing La3+Can increase the concentration of mobile sodium ions in the crystal structure, and is also due to La3+Radius of ion
Figure BDA0003223291280000031
Greater than Zr4+Radius of ion
Figure BDA0003223291280000032
The bottleneck size of the sodium ion transfer channel is increased, so that the bulk impedance of the electrolyte material is obviously reduced, and the bulk conductivity is improved. Additional introduction of Nb5+The number of mobile sodium ions and the number of sodium vacancies in the electrolyte material can reach an optimal balance point, thereby effectively promoting the migration of the sodium ions in the crystal structure, and Nb is introduced5+The sintering of the electrolyte material is facilitated, and the density of the electrolyte material is improved, so that the grain boundary resistance of the electrolyte material is reduced, and the grain boundary ionic conductivity is improved. In conclusion, the co-introduction of the two aliovalent metal cations reduces the bulk impedance and the grain boundary impedance, and the NASICON type solid electrolyte material with higher ionic conductivity at room temperature is obtained.
2. The invention has simple synthesis process and low manufacturing cost, and can be used for large-scale production of solid electrolyte materials.
The invention can obtain a fast sodium ion conductor NASICON type solid electrolyte material and a preparation method and application thereof.
Drawings
FIG. 1 is an AC impedance spectrum of a NASICON type solid electrolyte material prepared in example 1 of the present invention;
FIG. 2 is an AC impedance spectrum of a NASICON type solid electrolyte material prepared in example 2 of the present invention;
Detailed Description
The first embodiment is as follows: in this embodiment, the general structural formula of the NASICON type solid electrolyte material is Na3.4-x+y-zZr2-x-yNbxLaySi2.4-zP0.6+zO12Wherein 0 is<x≤0.5，0<y≤0.5，-0.5≤z<0.2。
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the NASICON type solid electrolyte material Na3.4-x+y-zZr2-x-yNbxLaySi2.4-zP0.6+zO12Middle, 0<The atomic number of Nb is less than or equal to 0.5 and 0<The number of La atoms is less than or equal to 0.5 and 2.2<The atomic number of Si is less than or equal to 2.9, and the atomic number of P is less than or equal to 0.1<0.8, and the sum of the numbers of Si and P atoms is 3.
Other steps are the same as those in the first embodiment.
The third concrete implementation mode: the embodiment relates to a fast sodium ion conductor NASICON type solid electrolyte material and a preparation method thereof.
The fourth concrete implementation mode: preferably, the solution-assisted solid phase reaction method is carried out according to the following steps:
(1) firstly, adding a zirconium source into deionized water, adding a sodium source, a niobium source and a lanthanum source in sequence after the zirconium source is completely dissolved, stirring for 0.5-1 h, clarifying the solution, and then adding Si (OCH)2CH3)4And finally, adding a phosphorus source, and stirring for 1-2 hours to obtain a gel solution.
(2) Drying the gel solution at 70-90 ℃ to obtain dry gel, and carrying out heat treatment on the obtained dry gel in an air atmosphere to obtain precursor powder particles; placing the obtained precursor powder particles in a planetary ball mill for ball milling, then drying and grinding at 80-90 ℃ to obtain white solid powder, then pressing into tablets by using a tablet press, and finally calcining in air atmosphere to obtain the fast sodium ion conductor NASICON type solid stateAn electrolyte material. The zirconium source, the sodium source, the niobium source, the lanthanum source and the Si (OCH)2CH3)4The molar ratio of the phosphorus source is 1.5-1.98: 3.1-3.5: 0.01-0.25: 0.01-0.25: 2.3-2.9: 0.1 to 0.7.
(3) And grinding and polishing, ultrasonically cleaning and drying in an oven the calcined NASICON type solid electrolyte material of the flake fast sodium ion conductor, sputtering gold films on two surfaces of the solid electrolyte material to be used as blocking electrodes, then carrying out an alternating current impedance test at room temperature, wherein the frequency range is 1 Hz-1 MHz, and obtaining the ionic conductivity of the solid electrolyte material at room temperature by calculation.
The fifth concrete implementation mode: preferably, the solid phase reaction method is carried out according to the following steps:
(1) firstly, mixing a zirconium source, a sodium source, a silicon source, a phosphorus source, a niobium oxide and a lanthanum oxide, and then carrying out heat treatment on the mixture in an air atmosphere to obtain precursor powder particles; and (2) placing the obtained precursor powder particles in a planetary ball mill for ball milling, then drying and grinding the particles at the temperature of 80-90 ℃ into white solid powder, then pressing the powder into tablets by using a tablet press, and finally calcining the tablets in an air atmosphere to obtain the fast sodium ion conductor NASICON type solid electrolyte material. The molar ratio of the zirconium source to the sodium source to the niobium oxide to the lanthanum oxide to the silicon source to the phosphorus source is 1.5-1.98: 3.1-3.5: 0.01-0.25: 0.01-0.25: 2.3-2.9: 0.1 to 0.7.
(2) And grinding and polishing, ultrasonically cleaning and drying in an oven the calcined NASICON type solid electrolyte material of the flake fast sodium ion conductor, sputtering gold films on two surfaces of the solid electrolyte material to be used as blocking electrodes, then carrying out an alternating current impedance test at room temperature, wherein the frequency range is 1 Hz-1 MHz, and obtaining the ionic conductivity of the solid electrolyte material at room temperature by calculation.
The beneficial results of the embodiment are as follows:
1. the invention relates to a fast sodium ion conductor NASICON type solid electrolyte material and a preparation method thereof, which adopts a solution-assisted solid phase reaction method and a solid phase reaction method to carry out NASICON type solid electrolyte material Na3.4Zr2Si2.4P0.6O12The Zr site in the alloy is doped with Nb with the same amount5+And La3+To obtainNa3.4-x+y-zZr2-x-yNbxLaySi2.4-zP0.6+zO12A solid electrolyte material. By introducing La3+Can increase the concentration of mobile sodium ions in the crystal structure, and is also due to La3+Radius of ion
Figure BDA0003223291280000041
Greater than Zr4+Radius of ion
Figure BDA0003223291280000042
The bottleneck size of the sodium ion transfer channel is increased, so that the bulk impedance of the electrolyte material is obviously reduced, and the bulk conductivity is improved. Additional introduction of Nb5+The number of mobile sodium ions and the number of sodium vacancies in the electrolyte material can reach an optimal balance point, thereby effectively promoting the migration of the sodium ions in the crystal structure, and Nb is introduced5+The sintering of the electrolyte material is facilitated, and the density of the electrolyte material is improved, so that the grain boundary resistance of the electrolyte material is reduced, and the grain boundary ionic conductivity is improved. In conclusion, the co-introduction of the two aliovalent metal cations reduces the bulk impedance and the grain boundary impedance, and the NASICON type solid electrolyte material with higher ionic conductivity at room temperature is obtained.
2. The method has the advantages of simple synthesis process and low manufacturing cost, and can be used for large-scale production of the solid electrolyte material.
The sixth specific implementation mode: the present embodiment differs from the first to fifth embodiments in that: the zirconium source in the fourth step (1) is selected from Zr (NO)3)2And Zr (NO)3)4·5H2One or two of O; the sodium source is selected from NaNO3、Na2CO3、Na2C2O4One or more of the above; the niobium source is selected from C10H5NbO20、C4H4NNbO9One or two of them; the lanthanum source is selected from Lan3O9·6H2O、C6H9LaO6One or two of them; the phosphorus source is selected fromNH4H2PO4、(NH4)3PO4、Na3PO4One or more of them.
The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the present embodiment differs from the first to sixth embodiments in that: the heat treatment temperature in the step four (2) is 500-1000 ℃, and the time is 3-7 h; in the ball milling, absolute ethyl alcohol with the content of 99.1-99.9% is adopted for wet milling for 24-48 h, and the ball milling rotating speed is 200-800 rpm; the calcination temperature is 1000-1500 ℃, and the calcination time is 5-7 h.
The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from the first to seventh embodiments in that: and 4, the current of the sputtered gold film in the step four (3) is 5-10 mA, and the sputtering time is 60-300 s.
The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: the zirconium source in the step five (1) is ZrO2(ii) a The silicon source is SiO2(ii) a The lanthanum oxide is La2O3(ii) a The niobium oxide is selected from NbO and Nb2O2、NbO2、Nb2O3、Nb2O5One or more of the above; the phosphorus source is selected from P2O5、H3PO4、NH4H2PO4、(NH4)3PO4、(NH4)2HPO4、Na3PO4One or more of the above; the sodium source is selected from NaNO3、Na2CO3、NaHCO3、Na2C2O4One or more of them.
The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from the first to ninth embodiments in that: the heat treatment temperature in the step five (1) is 500-1000 ℃, and the time is 3-7 h; in the ball milling, absolute ethyl alcohol with the content of 99.1-99.9% is adopted for wet milling for 24-48 h, and the ball milling rotating speed is 200-800 rpm; the calcination temperature is 1000-1500 ℃, and the calcination time is 5-7 h.
The other steps are the same as those in the first to ninth embodiments.
The concrete implementation mode eleven: the present embodiment differs from the first to tenth embodiments in that: and (3) sputtering the gold film in the step (2) at a current of 5-10 mA for 60-300 s.
The other steps are the same as those in the first to tenth embodiments.
The specific implementation mode twelve: the embodiment provides application of a fast sodium ion conductor NASICON type solid electrolyte material, and the solid electrolyte material can be used for preparing all-solid-state sodium ion batteries.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: a preparation method of a fast sodium ion conductor NASICON type solid electrolyte material comprises the following steps:
(1) zr (NO)3)2Adding into deionized water, dissolving completely, and sequentially adding Na2C2O4、C10H5NbO20、C6H9LaO6Stirring for 1h for clarifying, adding Si (OCH)2CH3)4Finally adding Na3PO4Stirring for 2h to obtain a gel-like solution.
(2) Drying the gel solution at 70 ℃ to obtain dried gel, and carrying out heat treatment on the dried gel in air atmosphere to obtain precursor powder particles; and (3) placing the obtained precursor powder particles into a planetary ball mill for ball milling, and adding absolute ethyl alcohol for wet milling. Then dried at 80 ℃ and ground to a white solid powder, then compressed into tablets with a tablet press and finally calcined in an air atmosphere to obtain Na3.4Zr1.8Nb0.1La0.1Si2.4P0.6O12Solid state electrolyte material, said Zr (NO)3)2、Na2C2O4、C10H5NbO20、C6H9LaO6、Si(OCH2CH3)4With Na3PO4In a molar ratio of 1.8: 3.4: 0.1: 0.1: 2.4: 0.6. polishing, ultrasonically cleaning and drying the calcined NASICON type solid electrolyte material of the flake fast sodium ion conductor, sputtering gold films on two surfaces of the solid electrolyte material to be used as blocking electrodes, sputtering current of 5mA for 60s, performing alternating current impedance test at room temperature, wherein the frequency range is 1 Hz-1 MHz, and calculating to obtain the ionic conductivity of 5.90mS cm at room temperature-1。
Example 2: a preparation method of a fast sodium ion conductor NASICON type solid electrolyte material comprises the following steps:
(1) first ZrO is added2、Na2C2O4、SiO2、P2O5、Nb2O5And La2O3Mixing, and then carrying out heat treatment on the mixture in an air atmosphere to obtain precursor powder particles; and (3) placing the obtained precursor powder particles into a planetary ball mill for ball milling, and adding absolute ethyl alcohol for wet milling. Then dried at 80 ℃ and ground into white solid powder, then pressed into tablets by a tablet press, and finally calcined under air atmosphere to obtain the fast sodium ion conductor NASICON type solid electrolyte material. To obtain Na3.4Zr1.6Nb0.2La0.2Si2. 4P0.6O12Solid state electrolyte material of said ZrO2、Na2C2O4、Nb2O5、La2O3、SiO2And P2O5In a molar ratio of 1.6: 3.4: 0.2: 0.2: 2.4: 0.6.
(2) polishing, ultrasonic cleaning and drying the calcined NASICON type solid electrolyte material of the flake fast sodium ion conductor, sputtering gold films on two surfaces of the solid electrolyte material as blocking electrodes with sputtering current of 5mA for 130s, and then performing alternating current impedance test at room temperature with the frequency range of 1Hz to E1MHz, and the ionic conductivity at room temperature is 2.32mS cm-1。
The highest room-temperature ionic conductivity of the fast sodium ion conductor NASICON type solid electrolyte material can reach 5.90mS cm-1. Therefore, the fast sodium ion conductor NASICON type solid state electrolyte material provided by the invention has higher ion conductivity at room temperature.

Claims (7)

1. A fast sodium ion conductor NASICON type solid electrolyte material, a preparing method and an application thereof are characterized in that the general structural formula of the solid electrolyte material is Na3.4-x+y-zZr2-x-yNbxLaySi2.4-zP0.6+zO12Wherein 0 is<x≤0.5，0<y≤0.5，-0.5≤z<0.2。
2. The NASICON type solid electrolyte material of claim 1, wherein Na is used as the solid electrolyte material3.4-x+y-zZr2-x-yNbxLaySi2.4-zP0.6+zO12Middle, 0<The atomic number of Nb is less than or equal to 0.5 and 0<The number of La atoms is less than or equal to 0.5 and 2.2<The atomic number of Si is less than or equal to 2.9, and the atomic number of P is less than or equal to 0.1<0.8, and the sum of the numbers of Si and P atoms is 3.
3. The fast sodium ion conductor NASICON type solid state electrolyte material according to claim 1 or 2, characterized in that the preparation method is a solution assisted solid phase reaction method or a solid phase reaction method.
4. The method according to claim 3, wherein the solution-assisted solid phase reaction method comprises the steps of:
firstly, adding a zirconium source into deionized water, adding a sodium source, a niobium source and a lanthanum source in sequence after the zirconium source is completely dissolved, stirring for 0.5-1 h, clarifying the solution, and then adding Si (OCH)2CH3)4Finally, adding a phosphorus source, and stirring for 1-2 hours to obtain a gel solution; will be described inDrying the gel solution at 70-90 ℃ to obtain dry gel, and carrying out heat treatment on the obtained dry gel in an air atmosphere to obtain precursor powder particles; placing the obtained precursor powder particles into a planetary ball mill for ball milling, then drying and grinding the particles at the temperature of 80-90 ℃ into white solid powder, then pressing the white solid powder into tablets by using a tablet press, and finally calcining the tablets in air atmosphere to obtain the fast sodium ion conductor NASICON type solid electrolyte material; and grinding and polishing, ultrasonically cleaning and drying in an oven the calcined NASICON type solid electrolyte material of the flake fast sodium ion conductor, sputtering gold films on two surfaces of the solid electrolyte material to be used as blocking electrodes, then carrying out an alternating current impedance test at room temperature, wherein the frequency range is 1 Hz-1 MHz, and obtaining the ionic conductivity of the solid electrolyte material at room temperature by calculation.
5. The fast sodium ion conductor NASICON type solid state electrolyte material of claim 1, wherein said zirconium source of claim 4 is selected from Zr (NO)3)2And Zr (NO)3)4·5H2One or two of O; the sodium source is selected from NaNO3、Na2CO3、Na2C2O4One or more of the above; the niobium source is selected from C10H5NbO20、C4H4NNbO9One or two of them; the lanthanum source is selected from Lan3O9·6H2O、C6H9LaO6One or two of them; the phosphorus source is selected from NH4H2PO4、(NH4)3PO4、Na3PO4One or more of the above; the zirconium source, the sodium source, the niobium source, the lanthanum source and the Si (OCH)2CH3)4The molar ratio of the phosphorus source is 1.5-1.98: 3.1-3.5: 0.01-0.25: 0.01-0.25: 2.3-2.9: 0.1 to 0.7; the heat treatment temperature is 500-1000 ℃, and the time is 3-7 h; in the ball milling, absolute ethyl alcohol with the content of 99.1-99.9% is adopted for wet milling for 24-48 h, and the ball milling rotating speed is 200-800 rpm; the calcining temperature is 1000-1500 ℃, and the calcining time is 5-7 h; the current of the sputtered gold film is 5-10 mA, and the gold film is sputteredThe shooting time is 60-300 s.
6. The method according to claim 3, wherein the solid phase reaction method comprises the steps of:
firstly, mixing a zirconium source, a sodium source, a silicon source, a phosphorus source, a niobium oxide and a lanthanum oxide, and then carrying out heat treatment on the mixture in an air atmosphere to obtain precursor powder particles; placing the obtained precursor powder particles in a planetary ball mill for ball milling, then drying and grinding the particles at 80-90 ℃ into white solid powder, then pressing the powder into tablets by using a tablet press, and finally calcining the tablets in air atmosphere to obtain the fast sodium ion conductor NASICON type solid electrolyte material; and grinding and polishing, ultrasonically cleaning and drying in an oven the calcined NASICON type solid electrolyte material of the flake fast sodium ion conductor, sputtering gold films on two surfaces of the solid electrolyte material to be used as blocking electrodes, then carrying out an alternating current impedance test at room temperature, wherein the frequency range is 1 Hz-1 MHz, and obtaining the ionic conductivity of the solid electrolyte material at room temperature by calculation.
7. The NASICON-type solid electrolyte material as claimed in claim 1, wherein the zirconium source is ZrO 22(ii) a The silicon source is SiO2(ii) a The lanthanum oxide is La2O3(ii) a The niobium oxide is selected from NbO and Nb2O2、NbO2、Nb2O3、Nb2O5One or more of the above; the phosphorus source is selected from P2O5、H3PO4、NH4H2PO4、(NH4)3PO4、(NH4)2HPO4、Na3PO4One or more of the above; the sodium source is selected from NaNO3、Na2CO3、NaHCO3、Na2C2O4One or more of the above; the molar ratio of the zirconium source to the sodium source to the niobium oxide to the lanthanum oxide to the silicon source to the phosphorus source is 1.5-1.98: 3.1-3.5: 0.01-0.25: 0.01-0.25: 2.3-2.9: 0.1 to 0.7; said heatThe treatment temperature is 500-1000 ℃, and the time is 3-7 h; in the ball milling, absolute ethyl alcohol with the content of 99.1-99.9% is adopted for wet milling for 24-48 h, and the ball milling rotating speed is 200-800 rpm; the calcining temperature is 1000-1500 ℃, and the calcining time is 5-7 h; the current of the sputtered gold film is 5-10 mA, and the sputtering time is 60-300 s.
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