CN115425284A - Sodium ion halide solid electrolyte and preparation method and application thereof - Google Patents

Sodium ion halide solid electrolyte and preparation method and application thereof Download PDF

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CN115425284A
CN115425284A CN202211213350.7A CN202211213350A CN115425284A CN 115425284 A CN115425284 A CN 115425284A CN 202211213350 A CN202211213350 A CN 202211213350A CN 115425284 A CN115425284 A CN 115425284A
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sodium
halide solid
solid electrolyte
sodium ion
valence
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冯绪勇
傅成宇
项宏发
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Hefei University of Technology
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Abstract

The invention discloses a sodium ion halide solid electrolyte, a preparation method and application thereof, wherein the chemical composition of the sodium ion halide solid electrolyte is Na z La 4/3‑x‑y A x B y X 4 Wherein, A is a low-valence metal element with a valence less than 3 or a vacancy, and the low-valence metal element is selected from one of Na, K and Ca; b is a high valence transition metal element with valence more than or equal to 3One selected from Y, in, sc, zr, er, ti and Hf; x is at least one of Cl and Br; z is more than 0 and less than or equal to 1,0<x，y<4/3, x + y < 4/3 and charge balance is satisfied. It is a one-dimensional ion conductor, and the space group structure is P63/m, sodium ions can move along the c-axis direction. The sodium halide solid electrolyte has extremely high ionic conductivity (up to 10) ‑4 S·cm ‑1 ) Therefore, the application of the halide solid electrolyte in the all-solid-state sodium metal battery can be effectively improved, and the performance of the all-solid-state sodium metal battery is improved. In addition, the preparation method is simple and has lower preparation cost.

Description

Sodium ion halide solid electrolyte and preparation method and application thereof
Technical Field
The invention belongs to the technical field of solid sodium metal batteries, and particularly relates to a sodium ion halide solid electrolyte and a preparation method thereof, and application of the sodium ion halide solid electrolyte in a solid sodium metal battery.
Background
The all-solid-state battery is a secondary battery using a solid electrolyte (SSE), not a liquid electrolyte, and has advantages of high safety, compatibility with a higher voltage positive electrode material and a lower voltage metal negative electrode material, higher energy density, and the like, thereby gradually replacing a secondary battery using a conventional organic electrolyte. In all-solid-state batteries, because sodium resources are abundant and widely distributed, all-solid-state sodium metal batteries have lower cost than all-solid-state lithium metal batteries, and have more cost benefit in large-scale energy storage application.
Research has shown that some sodium ion oxide, sulfide and borohydride materials exhibit high ionic conductivity and are considered promising sodium ion solid state electrolyte materials. Among them, sulfide has the highest ion conductivity (e.g., na) 3 PS 4 、Na 3 SbS 4 Etc. having an ionic conductivity of 0.1 to 10mS · cm -1 ) The capacity of the battery is quickly attenuated when the battery is matched with a high-voltage anode or a sodium metal cathode; and oxide solid electrolyte such as Na 3 Zr 2 Si 2 PO 12 And the like, the lithium ion battery is hard in texture and not easy to deform, so that the physical contact between the lithium ion battery and an electrode material is poor, the transmission of sodium ions at an interface is seriously hindered, and the performance of the battery is deteriorated.
The halide solid electrolyte has a breakthrough progress in lithium ion batteries due to its high voltage stability and its interfacial compatibility advantage with electrode materials. Such as Asano research group, report two halide SSE's prepared by mechanochemical methods,li of hexagonal close-packed (hcp) structure respectively 3 YCl 6 And Li of cubic close-packed (ccp) structure 3 YBr 6 Can reach 0.51 mS cm and 1mS cm at room temperature -1 High ion conductivity. In addition, it has been reported that Zr is used 4+ Performing aliovalent substitution to synthesize halide Li 3-x M 1-x Zr x Cl 6 (M = Er, Y) which increases room temperature ionic conductivity to 10 by introducing vacancies -3 S·cm -1 . High voltage stability of sodium halide solid electrolyte is good (>3.7V vs.Na/Na + ) The material is soft, can be in good contact with the electrode material under certain pressure, and has low interface impedance; however, in the sodium ion battery, the room-temperature ionic conductivity in the halide is not high due to the large ion size of the sodium ions, which limits the application of the sodium ion battery in the all-solid-state sodium ion battery. At present, the highest reported ionic conductivity in the literature is 6.6 × 10 -5 S·cm -1 (Na 2.25 Y 0.25 Zr 0.75 Cl 6 ) This is still a large gap compared to lithium ion battery solid electrolytes and limits their use in all-solid-state sodium ion batteries.
The present invention has been made in an effort to clarify a sodium halide solid electrolyte having high ionic conductivity and low production cost.
Disclosure of Invention
In view of the above, the present invention needs to provide a sodium halide solid electrolyte, which is a one-dimensional conductor structure, wherein sodium ions are continuously arranged along the c-axis, and the distance between different sodium ion sites is short, so that the sodium halide solid electrolyte is beneficial to the migration of sodium ions, has high ionic conductivity, and can improve the performance of an all-solid-state sodium metal battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a sodium ion halide solid electrolyte, the chemical composition of which is Na z La 4/3-x-y A x B y X 4 Wherein A is a low-valence metal element with valence less than 3 or a vacancy, and the low-valence metal element is selected from Na, K and CaOne kind of the material is selected; b is a high valence transition metal element with valence more than or equal to 3, and the high valence transition metal element is selected from one of Y, in, sc, zr, er, ti and Hf; x is at least one of Cl and Br; z is more than 0 and less than or equal to 1,0<x，y<4/3,x + y is less than 4/3 and satisfies charge balance;
the sodium ion halide solid electrolyte is a one-dimensional ion conductor, the space group structure is P63/m, and sodium ions can move along the c-axis direction.
In a further scheme, the chemical composition of the compound is Na 0.7 La 0.7 Zr 0.3 Cl 4 。
The invention further provides a method for preparing the sodium ion halide solid electrolyte, which comprises the following steps:
according to the stoichiometric ratio, halides of metals Na, la, A and B are respectively taken and synthesized into the sodium ion halide solid electrolyte by a mechanochemical method.
In a further scheme, the mechanochemical method comprises the step of high-energy ball milling, wherein the rotating speed of the high-energy ball milling is not lower than 500rpm, and the time is not lower than 8h;
preferably, the rotating speed of the high-energy ball mill is 500-600rpm, and the time is 8-12h;
preferably, the rotating speed of the high-energy ball mill is 550rpm, and the time is 10h.
Further, in an exemplary embodiment of the present invention, the preparation method includes the steps of:
in inert atmosphere, mixing the halides of Na, la, A and B according to stoichiometric ratio, and high-energy ball milling to obtain the sodium ion halide solid electrolyte.
Further, in another exemplary embodiment of the present invention, the preparation method includes the steps of:
mixing halides of Na, la, A and B according to a stoichiometric ratio in an inert atmosphere, and performing high-energy ball milling to obtain a precursor;
and sintering the precursor in an inert atmosphere to obtain the sodium ion halide solid electrolyte.
In a further scheme, the temperature rise rate of the sintering is 1-10 ℃/min, the temperature is 350-550 ℃, and the heat preservation time is 2-12 h.
Further, in another exemplary embodiment of the present invention, the preparation method includes the steps of:
mixing halides of Na, la, A and B according to a stoichiometric ratio in an inert atmosphere, and performing high-energy ball milling to obtain a precursor;
sintering the precursor in an inert atmosphere, and performing secondary high-energy ball milling to prepare a sodium ion halide solid electrolyte;
preferably, the temperature rise rate of the sintering is 1-5 ℃/min, the sintering temperature is 200-550 ℃, and the heat preservation time is 2-10h;
preferably, the rotation speed of the secondary high-energy ball mill is 500-600rpm, and the time is 1-12h.
The invention further provides the use of a sodium ion halide solid state electrolyte as hereinbefore described in the manufacture of a sodium ion battery.
The invention further provides an all-solid-state sodium ion battery which comprises a solid electrolyte, wherein the solid electrolyte is the sodium ion halide solid electrolyte or the sodium ion halide solid electrolyte prepared by the preparation method.
The invention has the following beneficial effects:
the sodium ion halide solid electrolyte has a one-dimensional conductor structure, has a space group of P63/m, and has extremely high ionic conductivity (up to 10) -4 S·cm -1 ) Therefore, the application of the halide solid electrolyte in the all-solid-state sodium metal battery can be effectively improved, and the performance of the all-solid-state sodium metal battery is improved.
The preparation method of the sodium ion halide solid electrolyte is simple, can be prepared by adopting a conventional mechanochemical method, and has lower preparation cost.
Drawings
FIG. 1 shows a solid NaLaCl electrolyte of sodium halide in an exemplary embodiment of the present invention 4 A schematic structural diagram of (a);
FIG. 2 is a schematic view of an exemplary embodiment of the present inventionSodium halide solid electrolyte NaLaCl in the examples 4 And Na 0.7 La 0.7 Zr 0.3 Cl 4 An XRD pattern of (a);
FIG. 3 shows a solid electrolyte Na of sodium halide in examples 5 and 6 of the present invention 0.7 La 0.7 Zr 0.3 Cl 4 And Na 0.6 La 0.6 Zr 0.4 Cl 4 The alternating current impedance profile of (a);
FIG. 4 is a schematic illustration of an NLZC + NVP/NLZC + NPS/Na-Sn all-solid-state battery assembled from a sodium halide solid-state electrolyte in example 5;
FIG. 5 shows the results of cycle performance tests of NLZC + NVP/NLZC + NPS/Na-Sn all-solid-state battery assembled from the sodium halide solid-state electrolyte of example 5.
Detailed Description
The following detailed description of the embodiments of the present invention is provided for illustration only and should not be construed as limiting the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention discloses a sodium ion halide solid electrolyte with a chemical composition of Na in a first aspect z La 4/3-x- y A x B y X 4 Wherein A is a low-valence metal element with valence less than 3 or a vacancy, and the low-valence metal element is selected from one of Na, K and Ca; b is a high valence transition metal element with valence more than or equal to 3, and the high valence transition metal element is selected from one of Y, in, sc, zr, er, ti and Hf; x is at least one of Cl and Br; z is more than 0 and less than or equal to 1,0<x，y<4/3,x + y < 4/3 and satisfies charge balance. The sodium ion halide solid electrolyte has high ionic conductivity (up to 10) at room temperature - 4 S·cm -1 ) Thereby making it applicable to solid sodium ion electricityWhen the battery is in the battery, the performance of the solid sodium ion battery can be effectively improved.
Specifically, the sodium halide solid electrolyte described herein is a one-dimensional ion conductor with a space group structure of P63/m, and sodium ions can migrate along the c-axis direction.
In an exemplary embodiment of the invention, a is a vacancy, X is Cl, y =0, X =1/3, z =1, and in this case, the composition of the sodium ion halide solid electrolyte is nalalcl 4 The structure of which is shown in FIG. 1, it can be seen that NaLaCl 4 The structure of (2) is a one-dimensional conductor, sodium ions are continuously arranged along the c axis, and the distance between different sodium ion sites is shorter, which is beneficial to the migration of the sodium ions. The Na ions do not completely occupy the sites, and a large number of vacancies exist, so that the migration and the transmission of the sodium ions are facilitated, and the ionic conductivity is improved.
In another exemplary embodiment of the invention, where A is a vacancy, B is Zr, X is Cl, X =1/3, 0.3. Ltoreq. Y.ltoreq.1, z = -1-y, then the composition of the sodium ion halide solid state electrolyte is Na z La 1-y Zr y Cl 4 The X-ray diffraction pattern (XRD) of one specific sodium halide solid electrolyte is shown in FIG. 2, and NLZC0.3 is Na in FIG. 2 0.7 La 0.7 Zr 0.3 Cl 4 NLC is NaLaCl 4 . As can be seen from fig. 2, NLZC0.3 is substantially identical to NLC in crystal structure, and the introduction of Zr ions does not change the structure of the solid electrolyte, and it is still a one-dimensional conductor and has high ionic conductivity.
Preferably, the chemical composition of the sodium ion halide solid electrolyte described herein is Na 0.7 La 0.7 Zr 0.3 Cl 4 。
In a second aspect of the present invention, there is disclosed a method for preparing a sodium halide solid electrolyte according to the first aspect of the present invention, comprising the steps of:
according to the stoichiometric ratio, halides of metals Na, la, A and B are respectively taken and synthesized into the sodium ion halide solid electrolyte by a mechanochemical method.
Specifically, according to the chemical composition of the sodium ion halide solid electrolyte to be prepared, the halides of metals Na, la, A and B are taken according to the stoichiometric ratio of the chemical composition, and then the synthesis of the sodium ion halide solid electrolyte is carried out by a mechanochemical method.
The mechanochemical method at least comprises the step of high-energy ball milling, wherein the rotating speed of the high-energy ball milling is not lower than 500rpm, and the time is not lower than 8h; preferably, the rotating speed of the high-energy ball mill is 500-600rpm, and the time is 8-12h; more preferably, the rotation speed of the high-energy ball mill is 550rpm, and the time is 10h.
There are three synthesis methods of the sodium halide solid electrolyte, and each synthesis method will be described below.
In an exemplary embodiment of the present invention, a method for preparing a sodium halide solid electrolyte (herein, referred to as method one) is disclosed, which comprises the following specific steps:
in an inert atmosphere, mixing halides of metals Na, la, A and B according to a stoichiometric ratio, and performing high-energy ball milling to obtain the sodium ion halide solid electrolyte.
In another exemplary embodiment of the present invention, a method for preparing a sodium halide solid electrolyte (herein, referred to as method two) is disclosed, which comprises the following specific steps:
mixing halides of Na, la, A and B according to a stoichiometric ratio in an inert atmosphere, and performing high-energy ball milling to obtain a precursor; sintering the precursor in inert atmosphere to obtain the sodium ion halide solid electrolyte.
Wherein, the sintering parameters can be adjusted according to the actual situation, preferably, the heating rate is 1-10 ℃/min, the sintering temperature is 350-550 ℃, and the heat preservation time is 2-12 h; more preferably, the temperature is raised to 400 ℃ at a rate of 5 ℃/min and annealed for 2 hours.
In another exemplary embodiment of the present invention, a method for preparing a sodium halide solid electrolyte (herein, referred to as method three) is disclosed, which comprises the following specific steps:
mixing halides of Na, la, A and B according to a stoichiometric ratio in an inert atmosphere, and performing high-energy ball milling to obtain a precursor;
and sintering the precursor in an inert atmosphere, and then carrying out secondary high-energy ball milling to adjust the structure to obtain the sodium ion halide solid electrolyte.
Wherein, the sintering parameters can be adjusted according to the actual situation, preferably, the heating rate is 1-5 ℃/min, the sintering temperature is 200-550 ℃, and the heat preservation time is 2-10h; more preferably, the temperature is raised to 400 ℃ at a rate of 5 ℃/min and annealed for 5 hours. Preferably, the rotation speed of the secondary high-energy ball milling is 500rpm-600rpm, the time is 1h-12h, and more preferably, the rotation speed of the secondary high-energy ball milling is 550rpm for 10h.
It is to be understood that, in the above preparation method, the inert atmosphere has the same meaning, which refers to at least one of rare gases (i.e., group 0 element gases such as helium, argon, etc.) or nitrogen, and is selected according to the needs of those skilled in the art and thus will not be described in detail.
In a third aspect of the invention, there is disclosed the use of a sodium ion halide solid state electrolyte as described in the first aspect of the invention in the manufacture of a sodium ion battery.
The invention discloses an all-solid-state sodium ion battery, which comprises a solid electrolyte and is characterized in that the solid electrolyte is the sodium ion halide solid electrolyte of the first aspect of the invention or the sodium ion halide solid electrolyte prepared by the preparation method of the second aspect of the invention. It is understood that the all-solid-state sodium ion battery further includes a positive electrode, a negative electrode, etc., which may all employ sodium ion battery materials conventional in the art, and thus will not be described in detail herein. Since the sodium ion halide solid electrolyte herein has excellent ionic conductivity, the assembled all-solid-state sodium ion battery has excellent cycle performance and rate performance.
The present invention is illustrated below by way of specific examples, which are intended to be illustrative only and not to limit the scope of the present invention in any way, and reagents and materials used therein are commercially available, unless otherwise specified, and conditions or steps thereof are not specifically described.
Example 1 NaLaCl 4 Preparation of (1)
Sodium chloride (NaCl) and lanthanum chloride (LaCl) were added under argon atmosphere 3 ) Mixing the raw materials according to the molar ratio of 1 2 ) Ball-milling in a ball-milling tank for 8h in a planetary ball mill at the rotating speed of 550rpm to obtain NaLaCl 4 And (4) sampling.
Example 2 Na 0.4 La 0.6 In 0.6 Cl 4 Preparation of (2) (method two)
Sodium chloride (NaCl), lanthanum chloride (LaCl) in argon atmosphere 3 ) And indium chloride (InCl) 3 ) Mixing the raw materials according to the molar ratio of 2 2 ) In a ball milling tank, milling for 10 hours in a planetary ball mill at the rotating speed of 550rpm to obtain Na 0.4 La 0.6 In 0.6 Cl 4 A precursor;
in an argon atmosphere, adding Na 0.4 La 0.6 In 0.6 Cl 4 The precursor is put into a tube furnace, the temperature is raised to 400 ℃ at the speed of 5 ℃/min, and Na is obtained after annealing for 2h 0.4 La 0.6 In 0.6 Cl 4 And (4) sampling.
Example 3 Na 0.7 La 0.7 Zr 0.3 Cl 4 Preparation of (1)
Sodium chloride (NaCl), lanthanum chloride (LaCl) in argon atmosphere 3 ) And zirconium chloride (ZrCl) 4 ) Mixing the raw materials according to the molar ratio of 7 2 ) Ball milling is carried out in a ball milling tank for 8 hours in a planetary ball mill at the rotating speed of 500rpm to obtain Na 0.7 La 0.7 Zr 0.3 Cl 4 And (4) sampling.
Example 4 Na 0.7 La 0.7 Zr 0.3 Cl 4 Preparation of (2) (method two)
Sodium chloride (NaCl), lanthanum chloride (LaCl) in argon atmosphere 3 ) And zirconium chloride (ZrCl) 4 ) The components were mixed in a molar ratio of 7 2 ) In a ball milling tank, at 550rBall milling for 9 hours in a planetary ball mill at the rotating speed of pm to obtain Na 0.7 La 0.7 Zr 0.3 Cl 4 A precursor;
in an argon atmosphere, adding Na 0.7 La 0.7 Zr 0.3 Cl 4 The precursor is put into a tube furnace, the temperature is raised to 400 ℃ at the speed of 5 ℃/min, and Na is obtained after annealing for 2h 0.7 La 0.7 Zr 0.3 Cl 4 And (3) sampling.
Example 5 Na 0.7 La 0.7 Zr 0.3 Cl 4 Preparation of (2) (method three)
Sodium chloride (NaCl), lanthanum chloride (LaCl) in argon atmosphere 3 ) And zirconium chloride (ZrCl) 4 ) Mixing according to the molar ratio of 7 0.7 La 0.7 Zr 0.3 Cl 4 A precursor;
in an argon atmosphere, adding Na 0.7 La 0.7 Zr 0.3 Cl 4 Putting the precursor into a tube furnace, heating to 500 ℃ at the speed of 5 ℃/min, and annealing for 2h; the sintered sample was sealed in zirconia (ZrO) 2 ) Ball milling is carried out in a ball milling tank for 10 hours in a planetary ball mill at the rotating speed of 550rpm to obtain Na 0.7 La 0.7 Zr 0.3 Cl 4 And (3) sampling.
Example 6 Na 0.6 La 0.6 Zr 0.4 Cl 4 Preparation of (method three)
Sodium chloride (NaCl), lanthanum chloride (LaCl) in argon atmosphere 3 ) And zirconium chloride (ZrCl) 4 ) Mixing the raw materials according to the molar ratio of 6 2 ) In a ball milling tank, ball milling is carried out for 12 hours in a planetary ball mill at the rotating speed of 550rpm to obtain Na 0.6 La 0.6 Zr 0.4 Cl 4 A precursor;
in an argon atmosphere, adding Na 0.6 La 0.6 Zr 0.4 Cl 4 Putting the precursor into a tube furnace, heating to 400 ℃ at the speed of 5 ℃/min, and annealing for 2 hours; sealing the sintered sample in a zirconia ball milling tank, and carrying out ball milling at 550rpm for 5h to obtain Na 0.6 La 0.6 Zr 0.4 Cl 4 And (3) sampling.
Comparative example Na 3 PS 4 Preparation of (2)
Sodium sulfide (Na) was added in a molar ratio of 3 2 S) and phosphorus pentasulfide (P) 2 S 5 ) Sealed in zirconia (ZrO) 2 ) Ball milling is carried out in a ball milling tank for 10 hours in a planetary ball mill at the rotating speed of 500rpm, and then annealing is carried out for 1 hour at the temperature of 270 ℃ to obtain the sulfide electrolyte Na 3 PS 4 。
Test example
1. Alternating current impedance spectroscopy (EIS) and activation energy testing
The sodium ion halide solid state electrolytes of examples 1-6 were subjected to EIS and activation energy tests, respectively, as follows:
200mg of sodium halide solid electrolyte was tableted with a 12mm diameter teflon mold, and after stainless steel current collectors were attached to both ends, alternating current impedance spectroscopy (EIS) tests were performed at different temperatures using a toyowa DH70001 electrochemical workstation, and the test results are shown in table 1 and fig. 3.
TABLE 1EIS and activation energy test results
Sample(s) Preparation method Ionic conductivity Activation energy
Example 1 NaLaCl 4 Method one 3.47×10 -5 S·cm -1 0.42eV
Example 2 Na 0.4 La 0.6 In 0.6 Cl 4 Method two 1.37×10 -5 S·cm -1 0.43eV
Example 3 Na 0.7 La 0.7 Zr 0.3 Cl 4 Method one 4.48×10 -5 S·cm -1 0.34eV
Example 4 Na 0.7 La 0.7 Zr 0.3 Cl 4 Method two 4.13×10 -5 S·cm -1 0.38eV
Example 5 Na 0.7 La 0.7 Zr 0.3 Cl 4 Method III 2.90×10 -4 S·cm -1 0.33eV
Example 6 Na 0.6 La 0.6 Zr 0.4 Cl 4 Method III 1.00×10 -4 S·cm -1 0.35eV
As can be seen from the test results in the AC impedance plots of Table 1 and FIG. 3, na prepared by method three (two high energy ball milling after sintering) in example 5 0.7 La 0.7 Zr 0.3 Cl 4 The sample can reach about 2.90X 10 -4 S cm -1 Has a minimum activation energy of 0.33eV; na prepared by method three in example 6 0.6 La 0.6 Zr 0.4 Cl 4 Its ionic conductivity can reach 1.00X 10 -4 S·cm -1 The activation energy was 0.35eV.
2. Full cell assembly and testing
Sodium ion halide solid electrolyte Na prepared in example 5 0.7 La 0.7 Zr 0.3 Cl 4 After the anode material is prepared, the full cell is assembled, and the specific steps are as follows:
preparation of the positive electrode: adding vanadium sodium phosphate (Na) as positive electrode active material 3 V 2 (PO4) 3 )、Na 0.7 La 0.7 Zr 0.3 Cl 4 (NLZC) and a conductive agent SP were mixed at a mass ratio of 11.
Preparing a negative electrode: mixing metal sodium and metal tin in a stainless steel ball milling tank according to a molar ratio of 2.
Assembling the full cell: with Na 3 V 2 (PO4) 3 Sodium vanadium phosphate (NVP), na 0.7 La 0.7 Zr 0.3 Cl 4 (NLZC) (example 5) with conductive agent SP as the positive electrode, na-Sn alloy as the negative electrode, NLZC and Na 3 PS 4 Is used as an electrolyte and is characterized in that,the sheets were pressed into 12 mm-diameter teflon molds to form full cells, and the full cells are schematically shown in fig. 4. The full cell was subjected to cycle test at a rate of 0.1C, and the test results are shown in fig. 5.
As can be seen from the test results in FIG. 5, the novel halide electrolyte Na 1-x La 1-x Zr x Cl 4 The lithium ion battery can be assembled with a common cathode material into a full battery, and the battery also has excellent cycle performance and rate capability.
Other parallel embodiments
Example 7 NaLaBr 4 Preparation of (2)
Sodium bromide (NaBr), and lan Br (LaBr) in an argon atmosphere 3 ) Mixing the raw materials according to the molar ratio of 1 2 ) In a ball milling tank, ball milling is carried out for 8 hours in a planetary ball mill at the rotating speed of 550rpm to obtain NaLaBr 4 A precursor;
under argon atmosphere, naLaBr 4 Putting the precursor into a tube furnace, heating to 450 ℃ at the speed of 5 ℃/min, and annealing for 2h; sealing the sintered sample in a zirconia ball milling tank, and ball milling for 5h at 550rpm to obtain NaLaBr 4 And (4) sampling.
Example 8 Na 0.3 La 0.3 Hf 0.7 Cl 4 Preparation of (2)
In an argon atmosphere, naCl and LaCl are added 3 、HfCl 4 According to the following steps of 3:3:7, then sealing in zirconium oxide (ZrO) 2 ) In the ball milling tank, the mixture is ball milled for 12 hours in a planetary ball mill at the rotating speed of 500rpm to obtain Na 0.3 La 0.3 Hf 0.7 Cl 4 A precursor;
in an argon atmosphere, adding Na 0.3 La 0.3 Hf 0.7 Cl 4 The precursor is put into a tube furnace, the temperature is raised to 350 ℃ at the speed of 1 ℃/min, and the annealing is carried out for 12h to obtain Na 0.3 La 0.3 Hf 0.7 Cl 4 And (4) sampling.
Example 9 Na 0.5 La 1.1 Na 0.2 Cl 4 Preparation of (2)
In an argon atmosphere, the mixture isNaCl and LaCl 3 Mixing the raw materials according to the molar ratio of 7 2 ) In a ball milling tank, ball milling is carried out for 8 hours in a planetary ball mill at the rotating speed of 600rpm to obtain Na 0.5 La 1.1 Na 0.2 Cl 4 A precursor;
in an argon atmosphere, adding Na 0.5 La 1.1 Na 0.2 Putting the Cl precursor into a tube furnace, heating to 550 ℃ at the speed of 5 ℃/min, and annealing for 2h; sealing the sintered sample in a zirconia ball milling tank, and ball milling at 600rpm for 1h to obtain Na 0.5 La 1.1 Na 0.2 And (4) Cl samples.
Example 10 NaLa 0.7 Sc 0.3 Cl 4 Preparation of
In an argon atmosphere, naCl and LaCl are added 3 And ScCl 3 Respectively pressing 10:7:3, and then sealing the mixture in zirconia (ZrO) 2 ) In a ball milling tank, ball milling is carried out in a planetary ball mill for 10 hours at the rotating speed of 550rpm to obtain NaLa 0.7 Sc 0.3 Cl 4 A precursor;
under argon atmosphere, naLa 0.7 Sc 0.3 Cl 4 The precursor is put into a tube furnace, the temperature is raised to 550 ℃ at the speed of 10 ℃/min, and the NaLa is obtained after annealing for 2h 0.7 Sc 0.3 Cl 4 And (4) sampling.
Example 11 NaLa 0.7 Er 0.3 Cl 4 Preparation of
In an argon atmosphere, naCl and LaCl are added 3 And ErCl 3 Respectively pressing 10:7:3, and then sealing the mixture in zirconia (ZrO) 2 ) In a ball milling tank, ball milling is carried out in a planetary ball mill for 10 hours at the rotating speed of 550rpm to obtain NaLa 0.7 Er 0.3 Cl 4 A precursor;
NaLa is added under argon atmosphere 0.7 Er 0.3 Cl 4 Putting the precursor into a tube furnace, heating to 200 ℃ at the speed of 1 ℃/min, and annealing for 5 min; sealing the sintered sample in a zirconia ball milling tank, and carrying out ball milling at 550rpm for 10h to obtain NaLa 0.7 Er 0.3 Cl 4 And (3) sampling.
Example 12 Na 0.5 La 0.7 Zr 0.3 K 0.2 Cl 4 Preparation of
In an argon atmosphere, naCl and LaCl are added 3 ，ZrCl 4 And KCl as 5:7:3:2, then sealing in zirconium oxide (ZrO) 2 ) In a ball milling tank, milling for 10 hours in a planetary ball mill at the rotating speed of 550rpm to obtain Na 0.5 La 0.7 Zr 0.3 K 0.2 Cl 4 A precursor;
in an argon atmosphere, adding Na 0.5 La 0.7 Zr 0.3 K 0.2 Cl 4 Putting the precursor into a tube furnace, heating to 300 ℃ at the speed of 5 ℃/min, and annealing for 30 min; sealing the sintered sample in a zirconia ball milling tank, and carrying out ball milling at 550rpm for 10h to obtain Na 0.5 La 0.7 Zr 0.3 K 0.2 Cl 4 And (4) sampling.
The obtained sodium halide solid electrolyte was subjected to the test of ion conductivity in the same manner as in examples 1 to 6, and the ion conductivity was measured to be 10 -6 -10 -4 S·cm -1 In the meantime. Meanwhile, the all-solid-state sodium ion battery is assembled by adopting the same method as the examples 1 to 6, and the all-solid-state sodium ion battery also has excellent cycle performance and rate capability through tests.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.

Claims (10)

1. A sodium halide solid electrolyte characterized in that the chemical composition thereof is Na z La 4/3-x-y A x B y X 4 Wherein A is a low-valence metal element with valence less than 3 or a vacancy, and the low-valence metal element is selected from one of Na, K and Ca; b is a high valence transition metal element with valence more than or equal to 3, and the high valence transition metal element is selected from one of Y, in, sc, zr, er, ti and Hf; x is selected from at least one of Cl and Br; z is more than 0 and less than or equal to 1,0<x，y<4/3,x + y is less than 4/3 and satisfies charge balance;
the sodium ion halide solid electrolyte is a one-dimensional ion conductor, the space group structure is P63/m, and sodium ions can move along the c-axis direction.
2. The sodium halide solid state electrolyte of claim 1 having a chemical composition Na 0.7 La 0.7 Zr 0.3 Cl 4 。
3. A method of producing a sodium ion halide solid state electrolyte as claimed in claim 1 or 2, comprising the steps of:
and (3) respectively taking halides of metals Na, la, A and B according to the stoichiometric ratio, and synthesizing the sodium ion halide solid electrolyte by a mechanochemical method.
4. The method of claim 3, wherein the mechanochemical method includes the steps of high energy ball milling at a speed of not less than 500rpm for a time of not less than 8 hours;
preferably, the rotating speed of the high-energy ball mill is 500-600rpm, and the time is 8-12h;
preferably, the rotation speed of the high-energy ball mill is 550rpm, and the time is 10h.
5. The method of claim 3 or 4, comprising the steps of:
in an inert atmosphere, mixing halides of metals Na, la, A and B according to a stoichiometric ratio, and performing high-energy ball milling to obtain the sodium ion halide solid electrolyte.
6. The method of claim 3 or 4, comprising the steps of:
in an inert atmosphere, mixing halides of Na, la, A and B according to a stoichiometric ratio, and performing high-energy ball milling to obtain a precursor;
and sintering the precursor in an inert atmosphere to obtain the sodium ion halide solid electrolyte.
7. The preparation method of claim 6, wherein the sintering is performed at a temperature rise rate of 1-10 ℃/min, at a temperature of 350-550 ℃, and for a holding time of 2-12 h.
8. The method of claim 3 or 4, comprising the steps of:
in an inert atmosphere, mixing halides of Na, la, A and B according to a stoichiometric ratio, and performing high-energy ball milling to obtain a precursor;
sintering the precursor in an inert atmosphere, and performing secondary high-energy ball milling to prepare a sodium ion halide solid electrolyte;
preferably, the temperature rise rate of the sintering is 1-5 ℃/min, the sintering temperature is 200-550 ℃, and the heat preservation time is 2-10h;
preferably, the rotation speed of the secondary high-energy ball mill is 500-600rpm, and the time is 1-12h.
9. Use of a sodium ion halide solid state electrolyte as claimed in any one of claims 1 or 2 in the manufacture of a sodium ion battery.
10. An all-solid-state sodium-ion battery comprising a solid-state electrolyte, wherein the solid-state electrolyte is the sodium-ion halide solid-state electrolyte according to claim 1 or 2 or the sodium-ion halide solid-state electrolyte prepared by the preparation method according to any one of claims 3 to 8.
CN202211213350.7A 2022-09-30 2022-09-30 Sodium ion halide solid electrolyte and preparation method and application thereof Pending CN115425284A (en)

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