CN109687017B - Sodium ion solid electrolyte and preparation method thereof - Google Patents
Sodium ion solid electrolyte and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention relates to a sodium ion solid electrolyte and a preparation method thereof, belonging to the technical field of metal ion batteries. The chemical composition of the sodium ion solid electrolyte is NaaLibR(3‑a‑b)/ 2ApB1‑pXmY1‑m(ii) a Wherein R is selected from +2 metal ions, A, B is independently selected from SO4 2‑、SeO4 2‑X, Y is independently selected from one of chloride ion and fluorinion with the valence of-1, a is more than or equal to 2.45 and less than or equal to 3, b is more than or equal to 0 and less than or equal to 0.45, p is more than or equal to 0 and less than or equal to 1, and m is more than or equal to 0 and less than or equal to 1 in the ratio of (3-a-b)/2 and less than or equal to 0.05. The sodium ion solid electrolyte has excellent metal ion conductivity and thermodynamic stability, three-dimensional equivalent ultrafast ion transmission capacity, lower diffusion activation energy, higher sodium ion conductivity and good electrochemical compatibility with a sodium electrode.
Description
Technical Field
The invention relates to a sodium ion solid electrolyte and a preparation method thereof, belonging to the technical field of metal ion batteries.
Background
The research on the replacement of metal ion liquid organic electrolyte by metal ion all-solid electrolyte is expected to fundamentally solve the potential safety hazard of flammability of the existing liquid electrolyte battery. However, the ionic conductivity of the liquid electrolyte is used as a standard (the ionic conductivity of the metal is more than 1mS cm)-1) Achieving rapid transport of metal ions in solid electrolytes remains extremely challenging.
The type and important parameter indexes of the traditional oxide solid electrolyte for sodium ion solid state electrolysisQualitatively, metallosilicophosphate type Na1+xZr2SixP3-xO12(NZSP, x is not less than 0 and not more than 3) solid electrolyte, and the maximum sodium ion conductivity is 0.1 mS-cm at the temperature of 298K-1。Na3V2(PO4)3(NVP) sodium ion conductivity of 0.18mS cm at 25 deg.C-1. Therefore, it is known that the sodium ion conductivity of the oxygen-containing solid electrolyte is less than 1mS · cm-1Is the industry standard of (1).
In recent years, as research work related to sulfide solid electrolytes has progressed, some sulfur-based solid electrolytes exhibit higher sodium ion conductivity. Na (Na)10SnP2S12Is recognized as one of the best sodium ion solid electrolytes at the present stage. The metal ion conductivity can exceed 0.4 mS-cm under the room temperature condition-1The diffusion activation energy was 0.317 eV. However, the ionic conductance of the electrolyte is fully developed only when the c-axis direction of most of the crystal grains is close to the ion transport direction. In Na10SnP2S12On the basis of (1), Na having a tetragonal phase11Sn2PS12The solid electrolyte is synthesized, the conductivity of sodium ion is greatly improved, and the solid electrolyte can reach 1.4mS cm at room temperature-1Much greater than the conductivity of sodium ions in liquid electrolytes. However, this material is unstable in electrochemical properties when in contact with metallic Na, thus preventing its practical application in all-solid-state battery technology. Therefore, a novel isotropic and stable ultrafast sodium ion solid electrolyte is searched and constructed, and has very important scientific significance and application value for breaking through the technical barrier of the sodium ion battery.
Disclosure of Invention
The invention aims to provide a sodium ion solid electrolyte with ultra-fast ion transmission capability and stable electrochemical properties.
The invention also provides a preparation method of the sodium ion solid electrolyte with simple process.
In order to achieve the above purpose, the sodium ion solid electrolyte adopts the technical scheme that:
a sodium ion solid electrolyte contains Na as chemical componentaLibR(3-a-b)/2ApB1-pXmY1-m(ii) a Wherein R is selected from +2 metal ions, A, B is independently selected from SO4 2-、SeO4 2-X, Y is independently selected from one of chloride ion and fluorinion with the valence of-1, a is more than or equal to 2.45 and less than or equal to 3, b is more than or equal to 0 and less than or equal to 0.45, p is more than or equal to 0 and less than or equal to 1, and m is more than or equal to 0 and less than or equal to 1 in the ratio of (3-a-b)/2 and less than or equal to 0.05.
The sodium ion solid electrolyte has excellent metal ion conductivity and thermodynamic stability, and is mixed with Na11Sn2PS12Compared with the solid electrolyte (one of the solid electrolytes with the highest ion conductivity is found), the solid electrolyte has three-dimensionally equivalent ultrafast sodium ion transport capacity, lower diffusion activation energy, higher sodium ion conductivity and good electrochemical compatibility with a sodium electrode.
The conductivity of the metal ions in the sodium ion solid electrolyte is determined by the diffusion coefficient of the metal ions, and the long-range diffusion coefficient of the metal ions in the sodium ion solid electrolyte is determined by the diffusion coefficient of the metal ions in Na6X、Na6Migration on octahedral building blocks such as Y is controlled. In the sodium ion solid electrolyte of the invention, the following metal ion transport modes mainly exist: a) under the condition of low sodium ion concentration, the + 1-valent sodium ions migrate along metal vacancies on the vertex angle of the octahedron, and the diffusion activation energy is usually larger at the moment; b) SO filled in crystal lattice4 2-Or SeO4 2-The group can rapidly vibrate and rotate at room temperature, and can further drive the adjacent sodium ions to diffuse for a long distance; c) under the condition of high sodium ion concentration, abundant + 1-valent sodium ions and + 1-valent sodium ions on the octahedral unit structure form dumbbell-type pairing of + 1-valent sodium ions and + 1-valent sodium ions, and the dumbbell-type pairing and the integral migration of the + 1-valent sodium ions at the other end of the octahedral unit structure are carried out, and at the moment, the diffusion activation energy is small and is often only one tenth of that of the transportation mode a).
Preferably, X is chloride, Y is fluoride and 0 < m < 1. X is chloride ion, Y is fluoride ion, and when m is more than 0,the sodium ion solid electrolyte has a double-type anti-perovskite structure, and m in the typical double-type anti-perovskite structure sodium ion solid electrolyte is 0.5. With Na having a double-type anti-perovskite structure3AX0.5Y0.5For example, Na6X、Na6Y octahedral structure unit is located on the corner of cubic inverse perovskite structure, A group is filled in the center of the cube, its thermodynamic stability and lattice size are mainly formed from Na6X、Na6The ionic bond length between M-X or M-Y in the Y octahedral structural unit is determined, and the contribution of elements on the A group is relatively weak; the bond length of the ion is determined by the electronegativity of the-1-valent halogen ion, and the stronger the electronegativity, the shorter the corresponding bond length. When X and Y are both selected from chloride ions or fluoride ions, the structure of the sodium ion solid electrolyte of the present invention is simplified to an anti-perovskite structure (space group number 221, symmetrical type P3 m). When the sublattice positions of X and Y are occupied by fluorine, the lattice size is minimum, the heat formation of the compound is maximum, and the metal ion conductivity is minimum.
Preferably, 0 < b.ltoreq.0.45. The introduction of + 1-valent lithium ions into the sodium ion solid electrolyte can effectively reduce the diffusion activation energy. For example, in Na3The AX is doped with lithium ions in a certain proportion, the lithium ions are easy to diffuse, sodium ions with larger ion radius can be driven to realize long-range diffusion, the diffusion barrier is obviously reduced, and the conductivity of the sodium ions is greatly improved. For example, Na2.55Li0.45SO4And a small amount of lithium ions are introduced into a sodium position, the lithium ions with small radius are easy to diffuse relative to the sodium ions, when the lithium ions diffuse, diffusion vacancies can be provided for adjacent sodium ions, and meanwhile, the introduction of the lithium ions can cause the distortion of an octahedral microstructure, so that the diffusion distance of the Li ions in adjacent units is shortened, and the diffusion of the Li ions is easier.
Preferably, 0 < (3-a-b)/2. ltoreq.0.05. In the general formula NaaLibR(3-a-b)/2ApB1-pXmY1-mWhen (3-a-b)/2 is 0, the sodium ion solid electrolyte Na of the present inventionaLibApB1-pXmY1-mHaving a standard anti-perovskite structureThe standard anti-perovskite structure has no defects, so that effective diffusion vacancies can not be provided for the diffusion of sodium ions, and the standard anti-perovskite structure is not beneficial to the generation of effective long-range diffusion of the sodium ions; (3-a-b)/2 > 0, corresponding to Na as a basic componentaLi3-aApB1-pXmY1-mThe high-valence metal ions R are added in (a is more than or equal to 2.55 and less than or equal to 3), and the doping of the + 2-valence large-radius metal ions R can further widen the diffusion channel of the sodium ions, and a small amount of vacancies are introduced at the vertex angle of the octahedron microstructure, so that an effective jumping position can be provided for the diffusion of the sodium ions, and the long-range diffusion is generated, and the transportation of the sodium ions is facilitated. However, the R ions are in a high valence state, strong in electronegativity, large in ion radius and large in mass, and if the R metal ions are excessively introduced, the concentration of the sodium ions can be reduced, and a diffusion channel of the sodium ions is blocked. Combining the factors of diffusion channel expansion and sodium concentration, the sodium ion conductivity of the sodium ion solid electrolyte is found to be the highest when 0 < (3-a-b)/2 is less than or equal to 0.05.
R is preferably Ba2+。Ba2+The radius of the ions is larger, the lattice constant of the sodium ion solid electrolyte can be enlarged, the diffusion path of the sodium ions is further widened, and the higher sodium ion concentration is kept to the greatest extent possible.
The sodium ion solid electrolyte has a crystal structure. The sodium ion solid electrolyte having a crystal structure has an advantage of high sodium ion conductivity.
The sodium ion solid electrolyte can be prepared by the prior art, such as a melting method, a mechanical alloying method, a powder metallurgy method, a vacuum coating method or a chemical vapor deposition method. The preparation process needs to be carried out in a protective atmosphere or anhydrous aprotic solvent which can provide inert protection for metal ions; the protective atmosphere can adopt inert gas, nitrogen or vacuum environment; the anhydrous aprotic solvent can adopt at least one of N, N-dimethylformamide, absolute ethyl alcohol, acetone, heptane and ethyl acetate.
The sodium ion solid electrolyte can be used as an additive of an active material layer in a pole piece of a sodium ion battery, and accounts for 10-90% of the mass of the active material layer.
The preparation method of the sodium ion solid electrolyte adopts the technical scheme that:
a preparation method of a sodium ion solid electrolyte comprises the following steps: according to the chemical composition of the sodium ion solid electrolyte, one or two of metal sulfate and metal selenate and metal halide are uniformly mixed in a protective atmosphere and then are pressed and formed, then the heat preservation treatment is carried out at the temperature of 750-855 ℃ for 8-12 h, and the sodium ion solid electrolyte is obtained after cooling.
The preparation method of the sodium ion solid electrolyte has simple process, and the prepared sodium ion solid electrolyte is a crystal. In the method for preparing the sodium ion solid electrolyte, the metal halide may be at least one halide of sodium, lithium and R, the metal sulfate may be at least one sulfate of sodium, lithium and R, and the metal selenate may be at least one selenate of sodium, lithium and R. When the sodium ion solid electrolyte is prepared, the selection of which metal halide, which metal sulfuric acid, which metal selenate, and whether metal selenate or metal sulfate, or both, is selected according to the specific elemental composition in the chemical composition of the sodium ion solid electrolyte.
Drawings
FIGS. 1 to 6 are schematic structural views of sodium ion solid electrolytes in examples 1 to 6 of the sodium ion solid electrolyte of the present invention, respectively;
FIG. 7 is an XRD pattern of the sodium ion solid electrolyte in examples 1 to 6 of the sodium ion solid electrolyte of the present invention;
FIG. 8 is a graph showing the relationship between the sodium ion conductivity of the sodium ion solid electrolyte in examples 1 to 6 and 21 of the sodium ion solid electrolyte of the present invention and the temperature.
Detailed Description
The preparation method of the sodium ion solid electrolyte provided by the invention comprises the following steps: according to the chemical composition of the sodium ion solid electrolyte, one or two of metal sulfate and metal selenate and metal halide are uniformly mixed in a protective atmosphere and then are pressed and formed, then the heat preservation treatment is carried out at the temperature of 750-855 ℃ for 8-12 h, and the sodium ion solid electrolyte is obtained after cooling.
Preferably, the temperature of the heat preservation treatment is 800-850 ℃. The time of the heat preservation treatment is 10 hours.
The technical solution of the present invention will be further described with reference to the following embodiments.
Example 1 of sodium ion solid electrolyte
The chemical composition of the sodium ion solid electrolyte of this example was Na3SO4F0.5Cl0.5The structure is schematically shown in figure 1.
The preparation method of the sodium ion solid electrolyte of the embodiment comprises the following steps:
1) mixing raw materials sodium sulfate (Na)2SO4) Drying the powder, sodium chloride (NaCl) powder and sodium fluoride (NaF) powder in a vacuum drying oven for 24 hours;
under the protection of argon atmosphere in a glove box, uniformly mixing sodium sulfate powder, sodium chloride powder and sodium fluoride powder according to the molar ratio of 2:1:1, then putting the mixture into a ball milling tank, putting 15 zirconia ball milling balls with the diameter of 10mm into the ball milling tank, then taking the sealed ball milling tank out of the glove box, putting the ball milling tank into an omnibearing planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 300rpm, ball milling each time for 20min by the ball mill, standing and cooling for 5min, wherein the total effective ball milling time is 5h, and obtaining mixed powder after ball milling;
2) taking out the obtained mixed powder, weighing a certain amount of the mixed powder, carrying out cold pressing to obtain a ceramic blank with the diameter of 16mm, carrying out heat preservation treatment in a vacuum tube furnace at the temperature of 850 ℃ for 10h, and slowly cooling to room temperature after the heat preservation treatment is finished to obtain the ceramic body.
Example 2 of sodium ion solid electrolyte
The chemical composition of the sodium ion solid electrolyte of this example was Na3SeO4F0.5Cl0.5The structure is schematically shown in figure 2.
The preparation method of the sodium ion solid electrolyte of the embodiment comprises the following steps:
1) mixing raw materials sodium selenate (Na)2SeO4) Drying the powder, sodium chloride (NaCl) powder and sodium fluoride (NaF) powder in a vacuum drying oven for 24 hours;
under the protection of argon atmosphere in a glove box, taking sodium selenate powder, sodium chloride powder and sodium fluoride powder according to the molar ratio of 2:1:1, uniformly mixing, then putting into a ball milling tank, putting 15 zirconia ball milling balls with the diameter of 10mm into the ball milling tank, then taking out the sealed ball milling tank from the glove box, putting into an omnibearing planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 320rpm, ball milling for 20min each time by the ball mill, standing and cooling for 5min, and obtaining mixed powder after ball milling, wherein the total effective ball milling time is 5 h;
2) and taking out the obtained mixed powder, weighing a certain amount of the mixed powder, carrying out cold pressing on the weighed mixed powder to obtain a ceramic blank with the diameter of 16mm, carrying out heat preservation treatment in a vacuum tube furnace at the temperature of 820 ℃ for 10h, and slowly cooling to room temperature after the heat preservation treatment is finished to obtain the ceramic body.
Example 3 of sodium ion solid electrolyte
The chemical composition of the sodium ion solid electrolyte of this example was Na3S0.5Se0.5O4F0.5Cl0.5The structure is schematically shown in figure 3.
The preparation method of the sodium ion solid electrolyte of the embodiment comprises the following steps:
1) mixing raw materials sodium sulfate (Na)2SO4) Powder, sodium selenate (Na)2SeO4) Drying the powder, sodium chloride (NaCl) powder and sodium fluoride (NaF) powder in a vacuum drying oven for 24 hours;
under the protection of argon atmosphere in a glove box, uniformly mixing sodium sulfate powder, sodium selenate powder, sodium chloride powder and sodium fluoride powder according to the molar ratio of 1:1:1:1, then putting the mixture into a ball milling tank, putting 15 zirconia ball milling balls with the diameter of 10mm into the ball milling tank, then taking the sealed ball milling tank out of the glove box, putting the ball milling tank into an all-directional planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 300rpm, ball milling each time for 20min by the ball mill, standing and cooling for 5min, setting the total effective ball milling time to be 5h, and obtaining mixed powder after ball milling;
2) and taking out the obtained mixed powder, weighing a certain amount of the mixed powder, carrying out cold pressing on the weighed mixed powder to obtain a ceramic blank with the diameter of 16mm, carrying out heat preservation treatment in a vacuum tube furnace at the temperature of 800 ℃ for 10h, and slowly cooling to room temperature after the heat preservation treatment is finished to obtain the ceramic body.
Example 4 of sodium ion solid electrolyte
The chemical composition of the sodium ion solid electrolyte of this example was Na3SO4Cl, schematic structural diagram is shown in figure 4.
The preparation method of the sodium ion solid electrolyte of the embodiment comprises the following steps:
1) mixing raw materials sodium sulfate (Na)2SO4) Drying the powder and sodium chloride (NaCl) powder in a vacuum drying oven for 24 h;
under the protection of argon atmosphere in a glove box, uniformly mixing sodium sulfate powder and sodium chloride powder according to the molar ratio of 1:1, then loading the mixture into a ball milling tank, loading 15 zirconia ball milling balls with the diameter of 10mm into the ball milling tank, then taking the sealed ball milling tank out of the glove box, loading the ball milling tank into an omnibearing planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 360rpm, ball milling each time for 20min in the ball mill, standing and cooling for 5min, setting the total effective ball milling time to be 5h, and obtaining mixed powder after ball milling;
2) and taking out the obtained mixed powder, weighing a certain amount of the mixed powder, carrying out cold pressing on the weighed mixed powder to obtain a ceramic blank with the diameter of 16mm, carrying out heat preservation treatment in a vacuum tube furnace, wherein the heat preservation treatment temperature is 855 ℃, the heat preservation time of the heat preservation treatment is 10 hours, and slowly cooling the obtained ceramic blank to room temperature after the heat preservation treatment is finished to obtain the ceramic body.
Example 5 of sodium ion solid electrolyte
The chemical composition of the sodium ion solid electrolyte of this example was Na3SeO4Cl, structural schematic as shown in FIG. 5.
The preparation method of the sodium ion solid electrolyte of the embodiment comprises the following steps:
1) mixing raw materials sodium selenate (Na)2SeO4) Drying the powder and sodium chloride (NaCl) powder in a vacuum drying oven for 24 h;
under the protection of argon atmosphere in a glove box, uniformly mixing sodium selenate powder and sodium chloride powder according to the molar ratio of 1:1, then loading the mixture into a ball milling tank, loading 15 zirconia ball milling balls with the diameter of 10mm into the ball milling tank, then taking the sealed ball milling tank out of the glove box, loading the ball milling tank into an omnibearing planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 340rpm, ball milling each time for 20min in the ball mill, standing and cooling for 5min, setting the total effective ball milling time to be 5h, and obtaining mixed powder after ball milling;
2) and taking out the obtained mixed powder, weighing a certain amount of the mixed powder, carrying out cold pressing on the weighed mixed powder to obtain a ceramic blank with the diameter of 16mm, carrying out heat preservation treatment in a vacuum tube furnace at the temperature of 825 ℃ for 10h, and slowly cooling to room temperature after the heat preservation treatment is finished to obtain the ceramic body.
Example 6 of sodium ion solid electrolyte
The chemical composition of the sodium ion solid electrolyte of this example was Na3S0.5Se0.5O4Cl, structural schematic as shown in FIG. 6.
The preparation method of the sodium ion solid electrolyte of the embodiment comprises the following steps:
1) mixing raw materials sodium sulfate (Na)2SO4) Powder, sodium selenate (Na)2SeO4) Drying the powder and sodium chloride (NaCl) powder in a vacuum drying oven for 24 h;
under the protection of argon atmosphere in a glove box, uniformly mixing sodium sulfate powder, sodium selenate powder and sodium chloride powder according to the molar ratio of 1:1:2, then putting the mixture into a ball milling tank, putting 15 zirconia ball milling balls with the diameter of 10mm into the ball milling tank, then taking the sealed ball milling tank out of the glove box, putting the ball milling tank into an omnibearing planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 350rpm, ball milling each time for 20min by the ball mill, standing and cooling for 5min, setting the total effective ball milling time to be 5h, and obtaining mixed powder after ball milling;
2) and taking out the obtained mixed powder, weighing a certain amount of the mixed powder, carrying out cold pressing on the weighed mixed powder to obtain a ceramic blank with the diameter of 16mm, carrying out heat preservation treatment in a vacuum tube furnace at the temperature of 830 ℃, carrying out heat preservation treatment for 10 hours, and slowly cooling to room temperature after the heat preservation treatment is finished to obtain the ceramic body.
Examples 7 to 40 of the sodium ion solid electrolyte are shown in table 1, and the preparation method of each sodium ion solid electrolyte in table 1 is not described except for the raw material composition and the molar ratio, as in example 1 of the sodium ion solid electrolyte.
TABLE 1 examples 7 to 40 of sodium ion solid electrolyte
Examples of the experiments
1) XRD tests are carried out on the sodium ion solid electrolytes in the embodiments 1-6 of the sodium ion solid electrolyte to obtain XRD characteristic spectrums of related materials, and as shown in figure 7, XRD main peaks of different electrolytes are consistent and have a small amount of shift. In the traditional anti-perovskite and double-type anti-perovskite structures, oxygen elements are used as octahedral centers, and halogen elements occupy interstitial positions, so that the structure of the sodium ion solid electrolyte is obviously different from the traditional anti-perovskite and double-type anti-perovskite structures (such as Na)3OCl and Na3O0.5S0.5Cl), therefore, the halogen-based sodium ion solid electrolyte of the present invention is a solid electrolyte under an entirely new system.
2) Calculation and analysis
Through a material genome engineering method, under the theoretical framework of a Density Functional (DFT) method and first principle molecular dynamics (AIMD), the influence of the elements of the same group or adjacent group on the thermodynamic stability and the ion transport performance of the solid electrolyte of the sodium ion battery can be systematically researched.
Na salt of example 1 of the above sodium ion solid electrolyte3SO4F0.5Cl0.5Na salt of example 23SeO4F0.5Cl0.5And Na of example 33S0.5Se0.5O4F0.5Cl0.5Both have a double-type anti-perovskite structure. Na in example 1 as sodium ion solid electrolyte3SO4F0.5Cl0.5For example, the structure is shown in FIG. 1, which has Na6F and Na6Cl octahedral structural units, two structural units are connected in a staggered manner to form a structural framework of the material, and meanwhile, the large-size SO4 2-The ions are filled in the crystal lattice gaps, and the effect of improving the structural stability is achieved.
For standard chemical composition of sodium ion solid electrolytes, e.g. Na3AX, according to the Goldschmidt calculation formula
Can be calculated to obtain the structure tolerance factor, wherein R isNa、RX、RAThe ionic radii of the respective ions; the tolerance factors of the sodium ion solid electrolytes of examples 1 to 8 of the sodium ion solid electrolyte were calculated, and the results are shown in table 2.
TABLE 2 Structure tolerance factor for sodium ion solid electrolytes in examples 1-8
M3The key of whether the AX type can form an anti-perovskite structure is whether a structure tolerance factor t is within a range of 0.75-1.05. As is clear from Table 2, Na was contained in example 5 as a sodium ion solid electrolyte3SeO4The tolerance factor for Cl is 0.995 so they can form a standard anti-perovskite structure as shown in fig. 5; na salt of sodium ion solid electrolyte example 13SO4F0.5Cl0.5(Na3SO4Cl+Na3SO4F) And Na of example 23SeO4F0.5Cl0.5(Na3SO4Cl+Na3SO4F) Are 0.937 and 0.903, respectively, so that they can form standard anti-perovskite structures as shown in fig. 1 and 2, respectively.
3) The sodium ion conductivity of the sodium ion battery solid electrolytes of examples 1 to 40 were respectively tested, and the test results were normalized and shown in table 3.
TABLE 3 sodium ion conductivity and diffusion activation energy Ea of sodium ion solid electrolytes of examples 1 to 40 of sodium ion solid electrolytes
As can be seen from Table 3, a sodium ion solid electrolyte such as Na obtained by incorporating a trace amount of a high-valent metal ion2.98Ba0.01SO4Cl and the like, further optimizes the Na ion diffusion channel, can simultaneously realize multi-metal ion conduction, and is favorable for further improving the performance of the solid-state battery. Similar chemical compositions deviate, and the modification idea of adding a trace amount of high-valence metal ions is also suitable for the sodium ion solid electrolyte with an anti-perovskite or double-type anti-perovskite structure in other embodiments mentioned in the invention, and the order of magnitude of the conductivity of the metal ions can be greatly improved.
4) Sodium ion conductivities of the sodium ion solid electrolytes of examples 1 to 6 and 21 were respectively tested at 800-1200K, and a change curve of the sodium ion conductivity with temperature was plotted, and the result is shown in fig. 8. As can be seen from FIG. 8, the conductivity of the sodium ions in the sodium ion solid electrolyte is determined by their diffusion coefficient, and the long-range diffusion coefficient of the sodium ions is determined by the presence of Na ions in Na6Cl、Na6F, etc. on octahedral structural units.
Claims (5)
1. A sodium ion solid electrolyte characterized by: chemical composition of NaaLibR(3-a-b)/2ApB1-pXmY1-m(ii) a Wherein R is selected from +2 metal ions, A, B is independently selected from SO4 2-、SeO4 2-Wherein X is chloride ion, Y is fluoride ion, a is more than or equal to 2.45 and less than or equal to 3, b is more than or equal to 0 and less than or equal to 0.45, 3-a-b is more than or equal to 0 and less than or equal to 2 and less than or equal to 0.05, p is more than or equal to 0 and less than or equal to 1, and m is more than 0 and less than 1; the sodium ion solid electrolyte has a crystal structure and a double-type anti-perovskite structure.
2. The sodium ion solid electrolyte of claim 1, wherein: b is more than 0 and less than or equal to 0.45.
3. The sodium ion solid electrolyte according to any one of claims 1 to 2, wherein: 0 < (3-a-b)/2 is less than or equal to 0.05.
4. The sodium ion solid electrolyte according to any one of claims 1 to 2, wherein: r is Ba2+。
5. A method for producing the sodium ion solid electrolyte according to claim 1, characterized in that: the method comprises the following steps: according to the chemical composition of the sodium ion solid electrolyte, one or two of metal sulfate and metal selenate and metal halide are uniformly mixed in a protective atmosphere and then are pressed and formed, then the heat preservation treatment is carried out at the temperature of 750-855 ℃ for 8-12 h, and the sodium ion solid electrolyte is obtained after cooling.
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| CN114300788A (en) * | 2020-08-18 | 2022-04-08 | 台湾中国制釉股份有限公司 | Solid sodium carbon dioxide battery |
| CN112563565B (en) * | 2020-11-13 | 2022-03-25 | 上海空间电源研究所 | Preparation method of lithium-sodium ion mixed solid electrolyte and solid-state mixed battery |
| CN116216747A (en) * | 2023-01-12 | 2023-06-06 | 天祥安氢(上海)科技有限公司 | Preparation method of sulfate inverse perovskite, product and application thereof |
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