CN116031475A - Halide solid electrolyte and preparation method and application thereof - Google Patents
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Abstract
The invention relates to a halide solid electrolyte, a preparation method and application thereof, wherein the chemical general formula of the halide solid electrolyte is Li a A 1‑x B1 x Cl 3+x‑a Or Li (lithium) a A 1‑x B2 x Cl 3+2x‑a Or Li (lithium) a A 1‑x B3 x Cl 3+3x‑a Or Li (lithium) a A 1‑x B1 y B2 z B3 x‑y‑z Cl 3+3x‑a Wherein a is more than or equal to 1 and less than or equal to 6; x is more than 0.4 and less than 1; y is more than 0.02 and less than 1; z is more than 0.02 and less than 1; a is selected from In 3+ 、Sc 3+ One or more of the following; b1 is selected from Zr 4+ 、Hf 4+ One or more of the following; b2 is selected from Nb 5+ 、Ta 5+ 、Mo 5+ 、W 5+ One or more of the following; b3 is W 6+ The method comprises the steps of carrying out a first treatment on the surface of the The preparation method comprises the following steps: general formula of chemical formula Li a ACl 3+a Is a B1 source compoundAnd doping one or more of the B2 source compound and the B3 source compound to obtain the halide solid electrolyte. The introduction of the high-valence ions can effectively improve lithium conduction vacancies and adjust lithium carrier concentration, so that the room-temperature ion conductivity of the halide matrix in the ccp configuration is improved, and the conductivity is higher than the humidity stability of the halide matrix treated by other modification methods.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a halide solid electrolyte, a preparation method and application thereof.
Background
Currently, the electrolyte of commercial lithium ion batteries is mainly liquid electrolyte, and the batteries are subject to larger safety problems when thermal runaway occurs. The safety of the power battery can be effectively improved by changing the liquid state into the solid state electrolyte. Solid electrolytes commonly used at present are largely classified into polymer electrolytes and inorganic electrolytes. The inorganic electrolyte is further classified into an oxide solid electrolyte, a sulfide solid electrolyte, and a halide solid electrolyte. Compared with other solid electrolytes, the halide solid electrolyte has the advantages that the ion conduction reaches mS/cm level, the matching property with a commercial lamellar positive electrode is good, the material is softer, the molding processing is easy, and the air stability is good, so that the halide solid electrolyte is hopeful to realize industrialized application.
Despite some advantages over other solid state electrolytes, halide solid state electrolytes are still limited in commercial applications by the drawbacks of insufficient ion conductivity at room temperature, poor humidity stability, and the like. The anion structure framework of the metal halide electrolyte is relatively closely related to ion conduction, and in the reported metal halide materials, three typical crystal structures are respectively an anion hexagonal close-packed orthorhombic system phase (hcp-O), an anion hexagonal close-packed trigonal system phase (hcp-T) and an anion cubic close-packed monoclinic system phase (ccp-M), wherein anions are halide crystals (Li 3 YCl 6 、Li 3 HoCl 6 、Li 3 ErCl 6 ) Is low (10) -4 S/cm), the anions are halide crystals (Li) with ccp structure 3 InCl 6 、Li 3 ScCl 6 ) Has high ionic conductivity of up to 10 -3 S/cm or more, this is mainly due to the low energy barrier ion conduction path that the ccp structure is octahedral-tetrahedral-octahedral in three dimensions. Researchers have found that hcp-configured halide electrolytes (Li) can be significantly enhanced by the incorporation of higher-valence ions such as Zr, hf 3 YCl 6 、Li 3 ErCl 6 、Li 3 YbCl 6 ) Is described (ACS Energy Lett.,2020,5,533-539,ACS Materials Lett.,2021,3,930-938, chem. Eng. J.,2021,425,130630). Studies have shown that Li can be enhanced by F doping (J.Power Sources,2022,545,231939) or ALD coating (adv. Funct. Mater.,2021,2108805) 3 InCl 6 Humidity stability of the electrolyte. Chinese patent publication No. CN112838264a discloses a method of improving air stability by introducing oxygen into a halide solid electrolyte to improve humidity stability. However, the single method has poor effect on the improved comprehensive performance, on one hand, after the hcp-configuration halide electrolyte is modified by introducing Zr or Hf, the ion conductivity of the material is generally near 1mS/cm, and the problem that the ion conductivity of the halide solid electrolyte at room temperature is not high can not be solved; on the other hand, oxygen is introduced during the synthesis of the halide electrolyte, which can improve the humidity stability of the material, but easily causes a decrease in ion conductivity. In addition, most of the modification processes are too complicated.
Thus, the prior art is still further improved.
Disclosure of Invention
In view of the limitations of the prior art, the invention aims to provide a halide solid electrolyte, a preparation method and application thereof, and aims to solve the problems of low ionic conductivity at room temperature and poor humidity stability of the conventional halide solid electrolyte.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a halide solid electrolyte, wherein the halide solid electrolyte has the chemical formula of Li a A 1- x B1 x Cl 3+x-a Or Li (lithium) a A 1-x B2 x Cl 3+2x-a Or Li (lithium) a A 1-x B3 x Cl 3+3x-a Or Li (lithium) a A 1-x B1 y B2 z B3 x-y-z Cl 3+3x-a Wherein a is more than or equal to 1 and less than or equal to 6; x is more than 0.4 and less than 1; y is more than 0.02 and less than 1; z is more than 0.02 and less than 1; a is selected from In 3+ 、Sc 3+ One or more of the following; b1 is selected from Zr 4+ 、Hf 4+ One or more of the following; b2 is selected from Nb 5+ 、Ta 5+ 、Mo 5+ 、W 5+ One or more of the following; b3 is W 6+ 。
A method of preparing the above halide solid electrolyte, comprising:
general formula of chemical formula Li a ACl 3+a And doping the matrix material with one or more of a B1 source compound, a B2 source compound or a B3 source compound to obtain the halide solid electrolyte.
Optionally, the preparation method, wherein the chemical formula is Li a ACl 3+a The substrate material of (a) is doped with one or more of a B1 source compound, a B2 source compound or a B3 source compound to obtain a halide solid electrolyte, which specifically comprises:
according to the chemical general formula of the halide solid electrolyte to be prepared, mixing a chloride raw material required for synthesizing the matrix material with the B1 source compound, the B2 source compound or the B3 source compound, and tabletting to obtain an electrolyte sheet;
placing the electrolyte sheet in a glass tube, vacuumizing to a certain vacuum degree, and sealing the tube;
and (3) placing the sealed glass tube in a heating furnace for heat treatment, cooling to room temperature, and grinding to obtain the B1, B2 or B3 doped or co-doped halide solid electrolyte.
Optionally, the preparation method, wherein the chloride is LiCl, scCl 3 Or InCl 3 The method comprises the steps of carrying out a first treatment on the surface of the The B1 source compound is TiCl 4 ，ZrCl 4 Or HfCl 4 The method comprises the steps of carrying out a first treatment on the surface of the The B2 source compound is NbCl 5 ，TaCl 5 ，MoCl 5 Or WCl 5 The method comprises the steps of carrying out a first treatment on the surface of the The B3 source compound is WCl 6 。
Optionally, the preparation method, wherein the mixing the chloride raw material required for synthesizing the base material with the B1 source compound, the B2 source compound or the B3 source compound includes: mixing by manpower, mixing by a ball milling tank, mixing by mechanical fusion or mixing by planetary high-speed ball milling; the manual mixing time is 5-60min; the rotating speed of the ball milling tank mixing material is 100-600 rpm; the linear speed of the mechanical fusion is 5-40m/s, and the fusion time is
2-10min; the speed of the planetary high-speed ball milling is 200-800 rpm, and the total mixing time is 5-50h.
Optionally, the preparation method, wherein the electrolyte sheet has a diameter of 5-20mm; the pressure during tabletting is 100-800Mpa.
Optionally, the preparation method, wherein the vacuum degree is-0.1 to-1 MPa.
Optionally, the preparation method comprises the step of placing the sealed glass tube in a heating furnace for heat treatment, wherein the heating temperature is 100-600 ℃, and the heating and heat preservation time is 5-50h.
Optionally, the preparation method, wherein the cooling is to room temperature, wherein the cooling rate is 2-10 ℃/min.
The application of the halide solid electrolyte or the halide solid electrolyte prepared by the preparation method in preparing all-solid battery electrodes or all-solid batteries.
The beneficial effects are that: compared with the prior art, in the halide solid electrolyte provided by the invention, on one hand, the introduction of high-valence ions can effectively improve lithium conduction vacancies and adjust lithium carrier concentration, so that the room-temperature ion conductivity of a halide matrix with a ccp configuration is improved, and the conductivity is higher than that of halides treated by other modification methods;
on the other hand, due to the introduction of high valence metal ions, the surface of the material readily forms B1OCl when exposed to moisture 2 /B2OCl 3 /B3OCl 4 /B3O 2 Cl 4 Or the hydrate thereof, the formed compound acts as a protective layer to inhibit further erosion of moisture, improve the humidity stability of the halide matrix of ccp configuration, and unexpectedly improve the room temperature ion conduction and the chemical stability in moisture, thus being used as a commercial solid electrolyte material with excellent performance.
Drawings
FIG. 1 is a XRD before and after exposure to 5% relative humidity, which is in fact 1 according to the invention;
FIG. 2 is a XRD before and after exposure to 5% relative humidity, which is actually 2 according to the present invention;
FIG. 3 is a XRD before and after exposure to 5% relative humidity, which is in fact 3 according to the invention;
FIG. 4 is a XRD before and after exposure to 5% relative humidity, which is in fact 4 according to the invention;
FIG. 5 is XRD before and after exposure to 5% relative humidity, which is compared to 1;
fig. 6 is XRD before and after exposure to 5% relative humidity, which is comparative to 2.
The concrete practice is that
For the purpose of the present invention, the technical solution and the advantages of the present invention, the following drawings are further drawings for illustrating the present invention. It should be understood that the embodiments described herein are practical to practice the invention and are not intended to limit the invention.
The reality is 1: li (Li) 2.5 Sc 0.5 Zr 0.5 Cl 6 Solid electrolyte material
The invention is to provide a Li doped with Zr of high valence metal ion 1 3 ScCl 6 The preparation method of the solid electrolyte comprises the following specific steps:
2g of LiCl, scCl of the target stoichiometric ratio were weighed out 3 、ZrCl 4 In agate, mixing materials manually for 30min, placing the mixture into a tabletting mold, tabletting at 400Mpa, placing the pressed tablets into a glass tube, vacuumizing to-0.2 Mpa, sealing the tube, placing the tube into a muffle furnace, performing heat treatment at 500 ℃ for 12h, cooling to room temperature at a speed of 2 ℃/min, and grinding the burnt tablets. As shown in the XRD chart of FIG. 1, the fact that the halide solid electrolyte prepared by 1 has main characteristic peaks of (001), (200)/(131) and (131) shows that the halide solid electrolyte prepared by the method has monoclinic phase with ccp configuration and space group C2/m. The inorganic halide solid electrolyte Li is prepared 2.5 Sc 0.5 Zr 0.5 Cl 6 The following tests were performed.
(1) The ionic conductivity was tested as follows: 100mg of electrolyte powder is weighed and placed in a special solid-state battery mould, the electrolyte powder is pressed and molded under the pressure of 300MPa, an alternating current impedance spectrum test is carried out, the ion conductivity of the halide solid-state electrolyte is calculated according to an impedance value and an Arrhenius formula, and the test result is shown in table 1.
(2) Humidity stability test was as follows: 500mg of electrolyte powder was weighed, placed in a special bin, the humidity in the bin was adjusted by adjusting the ratio of inert gas to water vapor, the electrolyte powder was exposed to 5% and 20% relative humidity for 12 hours, and then taken out and subjected to XRD test as shown in FIG. 1. The electrolyte material was also tested for ion conductivity after exposure to 5% relative humidity and the test results are shown in table 1.
It was found that the ionic conductivity of the electrolyte before exposure was 2.23mS/cm, and that the ionic conductivity of the electrolyte after exposure at 5% relative humidity was still as high as 1.12mS/cm. From the structure of the electrolyte after exposure to 5% relative humidity, the material remained in the original monoclinic phase structure without impurity phase generation, indicating that the electrolyte can be applied in a 5% relative humidity environment. The structure of the electrolyte after exposure to 20% relative humidity showed new peaks around 12.6 °, 30.7 ° and 32 °, the new phase being ZrOCl 2 (H2O) 8 Indicating that the electrolyte material can react with water to generate ZrOCl under the high humidity environment 2 (H2O) 8。 The formation of this new phase helps to inhibit further hydrolysis of the electrolyte, thereby improving the humidity stability of the electrolyte.
The reality is 2:Li 2.4 In 0.7 Nb 0.3 Cl 6 Solid electrolyte material
The invention is that 2 provides Li doped with Nb which is a high valence metal ion 3 InCl 6 The preparation method of the solid electrolyte comprises the following specific steps:
weighing 2g of LiCl and InCl with target stoichiometric ratio 3 、NbCl 5 Setting planetary high-speed ball milling at 600 rpm in ball milling tank for 20 hr, tabletting the mixture in tabletting mold at 400MPa, vacuum pumping to-0.2 MPa, sealing, heat treating at 200 deg.c for 10 hr at 10 deg.c/minThe pellets were cooled to room temperature and the fired pellets were then ground. As shown in the XRD diagram in fig. 2, the main characteristic peaks (001) and (131) are present in the halide solid electrolyte prepared by 2, which shows that the prepared halide solid electrolyte has monoclinic phase with ccp configuration, space group C2/m and no generation of impurity phase. The inorganic halide solid electrolyte Li is prepared 2.4 In 0.7 Nb 0.3 Cl 6 The following tests were performed. The ion guide test and the humidity stability test are 1 in the same entity. The results of the ion guide test are shown in Table 1.
It was found that the ionic conductivity of the electrolyte before exposure was 1.5mS/cm, and that the ionic conductivity of the electrolyte after exposure at 5% relative humidity was still as high as 1.03mS/cm. After exposure to 5% relative humidity, the electrolyte material remained in the original monoclinic phase structure, no impurity phase was generated, indicating that the electrolyte can be applied in a 5% relative humidity environment.
The reality is 3:Li 2.4 In 0.7 Ta 0.3 Cl 6 Solid electrolyte material
The invention is that 3 provides Li doped with high valence metal ion Ta 3 InCl 6 The preparation method of the solid electrolyte comprises the following specific steps:
weighing 2g of LiCl and InCl with target stoichiometric ratio 3 、TaCl 5 Setting planetary high-speed ball milling at 600 rpm in a ball milling tank for 20h, putting the ball milled mixture in a tabletting mold, tabletting at 400Mpa, putting the pressed tablets in a glass tube, vacuumizing to-0.2 Mpa, sealing the tube, putting the tube in a tube furnace, heat-treating at 220 ℃ for 10h, cooling to room temperature at a rate of 10 ℃/min, and grinding the burned tablets. As shown in the XRD diagram in fig. 3, the solid state electrolyte of the halide prepared by 2 has main characteristic peaks (001) and (131), which shows that the solid state electrolyte of the halide prepared has monoclinic phase with ccp configuration, space group C2/m and no generation of impurity phase. The inorganic halide solid electrolyte Li is prepared 2.4 In 0.7 Ta 0.3 Cl 6 The following tests were performed. The ion guide test and the humidity stability test are the same as each other1. The results of the ion guide test are shown in Table 1.
It was found that the ionic conductivity of the electrolyte before exposure was 1.8mS/cm, and that the ionic conductivity of the electrolyte after exposure at 5% relative humidity was still as high as 1.2mS/cm. After 12h exposure at 5% relative humidity, the electrolyte material structure produced TaOCl 3 The impurity phase, although generated, still maintains higher ion conductivity, indicating that the electrolyte can be applied in a 5% relative humidity environment.
The reality is 4:Li 2.7 In 0.9 W 0.1 Cl 6 Solid electrolyte material
The invention is that 4 provides a Li doped with high valence metal ion W 3 InCl 6 The preparation method of the solid electrolyte comprises the following specific steps:
weighing 2g of LiCl and InCl with target stoichiometric ratio 3 、WCl 5 Setting planetary high-speed ball milling rotation speed of 550 r/min in a ball milling tank for 20h, putting the ball milled mixture in a tabletting mold, tabletting at 400Mpa pressure, putting the pressed tablets in a glass tube, vacuumizing to-0.2 Mpa, sealing the tube, putting the tube in a tube furnace, heat-treating at 170 ℃ for 10h, cooling to room temperature at a rate of 10 ℃/min, and grinding the burned tablets. As shown in the XRD diagram in fig. 4, the solid state electrolyte of the halide prepared by 2 has main characteristic peaks (001) and (131), which shows that the solid state electrolyte of the halide prepared has monoclinic phase with ccp configuration, space group C2/m and no generation of impurity phase. The inorganic halide solid electrolyte Li is prepared 2.7 In 0.9 W 0.1 Cl 6 The following tests were performed. The ion guide test and the humidity stability test are 1 in the same entity. The results of the ion guide test are shown in Table 1.
It was found that the ionic conductivity of the electrolyte before exposure was 2.1mS/cm, and that the ionic conductivity of the electrolyte after exposure at 5% relative humidity was still as high as 1.24mS/cm. XRD results showed that the electrolyte material produced hetero-phase WOCL after 12h exposure at 5% relative humidity 2 . After 12h exposure at 20% relative humidity, the electrolyte material produced a hetero-phase WO 2 Cl 2 Indicating that the electrolyte can pass WOCl 2 、WO 2 Cl 2 The intermediate phase is used for relieving the electrolyte from hydrolysis, and the electrolyte can be applied to a 5% relative humidity environment.
The actual comparison is 1-2
Li (lithium ion battery) 3 ScCl 6 And Li (lithium) 3 InCl 6 The preparation method of the halide solid electrolyte comprises the steps of 1 and 2-4 in the same synthesis method except for different synthesis raw materials. The comparative ion guides before and after exposure to 5% relative humidity are shown in Table 1, XRD is shown in FIGS. 5 and 6. It can be seen that the ion guide of comparative 1 after 12h exposure at 5% relative humidity drops from 0.68 to 0.21mS/cm, a new hetero-phase appears after exposure as ScOCl, the formation of which phase significantly impairs ion transport. The comparison shows that after 12h exposure at 25% relative humidity, the ion guide is reduced from 0.82 to 0.12mS/cm, and XRD results show that the new impurity phase Li exists after exposure 3 InCl 6 ·H 2 O is generated, which is also believed to be the cause of greater attenuation of the electrolyte ion guide.
Table 1. The results of the ion conductivity tests for the resulting electrolyte materials are shown in the examples and comparative examples.
In summary, the present invention provides a halide solid electrolyte, a preparation method and applications thereof, wherein the chemical formula of the halide solid electrolyte is Li a A 1-x B1 x Cl 3+x- a or Li a A 1-x B2 x Cl 3+2x- a or Li a A 1-x B3 x Cl 3+3x- a or Li a A 1-x B1 y B2 z B3 x-y-z Cl 3+3x-a Wherein a is more than or equal to 1 and less than or equal to 6; x is more than 0.4 and less than 1; y is more than 0.02 and less than 1; z is more than 0.02 and less than 1; a is selected from In 3+ 、Sc 3+ One or more of the following; b1 is selected from Zr 4+ 、Hf 4+ One or more of the following; b2 is selected from Nb 5+ 、Ta 5+ 、Mo 5+ 、W 5+ One or more of the following; b3 is W 6+ The method comprises the steps of carrying out a first treatment on the surface of the The preparation method comprises the following steps: according to the chemical general formula of the halide solid electrolyte to be prepared, mixing a chloride raw material required for synthesizing the matrix material with the B1 source compound, the B2 source compound or the B3 source compound, and tabletting to obtain an electrolyte sheet; placing the electrolyte sheet in a glass tube, vacuumizing to a certain vacuum degree, and sealing the tube; and (3) placing the sealed glass tube in a heating furnace for heat treatment, cooling to room temperature, and grinding to obtain the B1, B2 or B3 doped or co-doped halide solid electrolyte. In the halide solid electrolyte material provided by the invention, on one hand, the introduction of high-valence ions can effectively improve lithium conduction vacancies and adjust lithium carrier concentration, so that the room-temperature ion conductivity of a ccp-structured halide matrix is improved, and the conductivity is higher than that of halides treated by other modification methods, on the other hand, the introduction of high-valence metal ions can easily form B1OCl on the surface of the material when the material is exposed to moisture 2 /B2OCl 3 /B3OCl 4 /B3O 2 Cl 4 Or the hydrate thereof, the formed compound acts as a protective layer to inhibit further erosion of moisture, improve the humidity stability of the halide matrix of ccp configuration, and unexpectedly improve the room temperature ion conduction and the chemical stability in moisture, thus being used as a commercial solid electrolyte material with excellent performance. Compared with the method of adopting wet chemical method synthesis and vacuum heat treatment in the prior art, the preparation method of the halide solid electrolyte material provided by the invention adopts a dry mixing method, effectively improves the utilization rate of the material, and is safe and environment-friendly. The cost of the element (Zr, hf, nb, ta, mo, W) of the doping agent is far lower than that of the halide matrix element (In and Sc), and the doping agent has the advantage of cost. The invention adopts a rapid cooling mode, thereby effectively avoiding the generation of impurity phases. The method has the advantages of simple operation steps, easily obtained raw materials, low cost, easy industrialization, high production efficiency, suitability for large-scale industrial production, wide commercial application prospect and great theoretical and practical significance.
It is to be understood that the invention is not limited in its application to the details shown and described and that modifications and alterations will occur to those skilled in the art based on the foregoing description, all such modifications and alterations being intended to fall under the protection of the appended claims.
Claims (10)
1. A halide solid electrolyte, characterized in that the halide solid electrolyte has the chemical formula of Li a A 1- x B1 x Cl 3+x-a Or Li (lithium) a A 1-x B2 x Cl 3+2x-a Or Li (lithium) a A 1-x B3 x Cl 3+3x-a Or Li (lithium) a A 1-x B1 y B2 z B3 x-y-z Cl 3+3x-a Wherein a is more than or equal to 1 and less than or equal to 6; x is more than 0.4 and less than 1; y is more than 0.02 and less than 1; z is more than 0.02 and less than 1; a is selected from In 3+ 、Sc 3+ One or more of the following; b1 is selected from Zr 4+ 、Hf 4+ One or more of the following; b2 is selected from Nb 5+ 、Ta 5+ 、Mo 5+ 、W 5+ One or more of the following; b3 is W 6+ 。
2. A method of preparing the halide solid state electrolyte of claim 1, comprising:
general formula of chemical formula Li a ACl 3+a And doping the matrix material with one or more of a B1 source compound, a B2 source compound or a B3 source compound to obtain the halide solid electrolyte.
3. The method of claim 2, wherein the compound has the chemical formula of Li a ACl 3+a The substrate material of (a) is doped with one or more of a B1 source compound, a B2 source compound or a B3 source compound to obtain a halide solid electrolyte, which specifically comprises:
according to the chemical general formula of the halide solid electrolyte to be prepared, mixing a chloride raw material required for synthesizing the matrix material with the B1 source compound, the B2 source compound or the B3 source compound, and tabletting to obtain an electrolyte sheet;
placing the electrolyte sheet in a glass tube, vacuumizing to a certain vacuum degree, and sealing the tube;
and (3) placing the sealed glass tube in a heating furnace for heat treatment, cooling to room temperature, and grinding to obtain the B1, B2 or B3 doped or co-doped halide solid electrolyte.
4. The process according to claim 3, wherein the chloride is LiCl, scCl 3 Or InCl 3 The method comprises the steps of carrying out a first treatment on the surface of the The B1 source compound is TiCl 4 ，ZrCl 4 Or HfCl 4 The method comprises the steps of carrying out a first treatment on the surface of the The B2 source compound is NbCl 5 ，TaCl 5 ，MoCl 5 Or WCl 5 The method comprises the steps of carrying out a first treatment on the surface of the The B3 source compound is WCl 6 。
5. The method according to claim 3, wherein the chloride raw material required for synthesizing the base material is mixed with the B1 source compound, the B2 source compound or the B3 source compound, wherein the mixing means includes: mixing by manpower, mixing by a ball milling tank, mixing by mechanical fusion or mixing by planetary high-speed ball milling; the manual mixing time is 5-60min; the rotating speed of the ball milling tank mixing material is 100-600 rpm; the linear speed of the mechanical fusion is 5-40m/s, and the fusion time is 2-10min; the speed of the planetary high-speed ball milling is 200-800 rpm, and the total mixing time is 5-50h.
6. The method according to claim 3, wherein the electrolyte sheet has a diameter of 5 to 20mm; the pressure during tabletting is 100-800Mpa.
7. The method according to claim 3, wherein the vacuum degree is from-0.1 to-1 MPa.
8. The method according to claim 3, wherein the sealed glass tube is placed in a heating furnace for heat treatment, wherein the heating temperature is 100-600 ℃ and the heating and heat preservation time is 5-50h.
9. A method of manufacture according to claim 3, wherein the cooling is to room temperature at a cooling rate of 2-10 ℃/min.
10. Use of a halide solid electrolyte according to claim 1 or a halide solid electrolyte prepared by a method according to any one of claims 2 to 9 for the preparation of an all-solid battery electrode or an all-solid battery.
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| CN117468090A (en) * | 2023-12-27 | 2024-01-30 | 上海交通大学 | Tantalum (IV) oxyhalide compound crystal material and preparation method and application thereof |
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| CN117468090A (en) * | 2023-12-27 | 2024-01-30 | 上海交通大学 | Tantalum (IV) oxyhalide compound crystal material and preparation method and application thereof |
| CN117468090B (en) * | 2023-12-27 | 2024-03-22 | 上海交通大学 | Tantalum (IV) oxyhalide compound crystal material and preparation method and application thereof |
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