Composite solid-state electrolyte material, preparation method therefor and use thereof

Abstract

A composite solid-state electrolyte material, comprising a crystalline phase component and an amorphous phase component. The chemical general formula of the crystalline phase component is expressed as: B%AaREbX1 cDg <sb / >+C%AdMeX2 fDh, A being a carrier, RE being a rare earth element, M being a metal element, X1 and X2 being halide anions, D being an anion doping element or group, 0≤a≤3, 0<b≤1, 0.5<c≤12, 0<d≤5, 0<e≤2, 1<f≤20, 0≤g≤4, 0≤h≤5, AaREbX1 cDg and AdMeX2 fDh being crystalline phase substances, B% being the mass fraction of AaREbX1 cDg in the composite solid-state electrolyte material, C% being the mass fraction of AdMeX2 fDh in the composite solid-state electrolyte material, 85<B+C<98, 10%<B%≤85%, 10%<C%≤85% and 0.2≤C / B≤10.

Description

A composite solid electrolyte material, its preparation method and application Cross-references

[0001] This application is based on and claims priority to Chinese Patent Application No. 202411893783.0, filed on December 20, 2024, the entire contents of which are incorporated herein by reference.

[0002] Technical Field

[0003] This invention relates to the field of battery technology, and in particular to a composite solid electrolyte material, its preparation method, and its application. Background Technology

[0004] Lithium-ion batteries, as the most common energy storage method, are widely used in portable electronic devices, grid energy storage, and other fields. However, commercial lithium-ion batteries with organic liquid electrolytes suffer from safety issues such as short circuits and thermal runaway, which can lead to explosions. To meet the commercial demands of future electric vehicles and energy storage, solid-state lithium batteries, with their high specific capacity and safety, have attracted increasing attention. Solid-state electrolytes are key materials in all-solid-state batteries. To meet the requirements of all-solid-state batteries, solid-state electrolytes should possess several basic characteristics: high ionic conductivity exceeding 10⁻⁶. -4 S / cm, excellent lithium dendrite suppression capability, robust mechanical flexibility, wide electrochemical window stability, chemically stable properties and low interfacial resistance with lithium metal.

[0005] Currently, there are three main types of inorganic solid electrolytes: oxide solid electrolytes, halide electrolytes, and sulfide electrolytes. Sulfides have very high ionic conductivity, but they are chemically unstable with respect to metallic lithium and highly sensitive to air, making large-scale application difficult. Inorganic oxide solid electrolytes have poor mechanical properties and significant interfacial resistance, hindering lithium-ion transport across the interface. Halide electrolytes possess good mechanical properties, high ionic conductivity, and high oxidation potential. However, the room-temperature ionic conductivity of most halide electrolytes is still difficult to reach above 1 mS / cm, and their cost is generally much higher than that of oxide electrolytes due to the complex preparation and storage methods of anhydrous chlorides in the raw materials. More importantly, halide electrolytes readily absorb water and hydrolyze in air, which greatly limits their large-scale production and application. Summary of the Invention

[0006] (a) Purpose of the invention

[0007] The purpose of this invention is to provide a composite solid electrolyte material with high ionic conductivity and good moisture resistance, as well as its preparation method and application.

[0008] (II) Technical Solution

[0009] To address the above problems, this invention provides a composite solid electrolyte material, wherein the composite solid electrolyte material comprises a crystalline phase substance with the general chemical formula: B%A a RE b X 1 c D g +C%A d M e X 2 f D h ;

[0010] Where A represents charge carriers; RE represents rare earth elements; M represents metallic elements; X represents... 1 X 2 is a halide anion; D is an anion doping element or group.

[0011] A a RE b X 1 c D g and A d M e X 2 f D h It is a crystalline material;

[0012] B% is A a RE b X 1 c D g The mass fraction of the composite solid electrolyte material; C% is A d M e X 2 f D h The mass fraction of the composite solid electrolyte material;

[0013] Wherein, 0≤a≤3, 0<b≤1, 0.5<c≤12, 0<d≤5, 0<e≤2, 1<f≤20, 0≤g≤4, 0≤h≤5;

[0014] 85<B+C<98, 10%<B%≤85%; 10%<C%≤85%, 0.2≤C / B≤10.

[0015] In another aspect of the present invention, preferably,

[0016] The A is one or more of Li, Na, K, Ag, Zn, Mg, Ca, Al, and Cu;

[0017] RE can be one or more of Y, Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu;

[0018] M is one or more of In, Ta, Zr, Al, Ga, Hf, and Nb;

[0019] X 1 It is one or more of F, Cl, Br and I;

[0020] X 2 It is one or more of F, Cl, Br and I;

[0021] D represents P, O, S, N, and OH. - One or more of them.

[0022] In another aspect of the present invention, preferably, the...

[0023] 0≤a≤1.5, 0.5<b≤1, 1≤c≤6, 1<d≤3, 0<e≤1, 1<f≤10, 0≤g≤2, 0≤h≤2.5, 90<B+C<95;

[0024] 30%<B%≤65%; 30%<C%≤65%, 0.5≤C / B≤3.

[0025] In another aspect of the present invention, preferably,

[0026] The composite solid electrolyte material includes an amorphous phase substance Q, wherein the amorphous phase substance accounts for 5% < Q in the mass fraction of the composite electrolyte powder. wt <10%.

[0027] In another aspect of the present invention, preferably,

[0028] A is one or both of Li and Na;

[0029] RE can be one or more of La, Ce, Sm, Yb, Y, and Lu;

[0030] M can be one or more of Ta, Zr, Al, Ga, and Nb;

[0031] X 1 For Cl, F, Br;

[0032] X 2 For Cl, F, Br;

[0033] D represents O, S, and N.

[0034] In another aspect of the present invention, preferably,

[0035] A method for preparing a composite solid electrolyte material, the method comprising the following steps:

[0036] Step S1: According to A a RE b X 1 c D g Given the general chemical formula and mass fraction of the sample, weigh the raw material A, the raw material RE, and X. 1 The raw materials of D and D are mixed and post-processed, the post-processing including ball milling or a first heat treatment, to obtain a first precursor;

[0037] Step S2: According to A d M e X 2 f D h Given the general chemical formula and mass fraction, weigh out raw material A, raw material M, and X. 2 The raw materials of D and D are mixed and subjected to a second heat treatment to obtain a second precursor;

[0038] Step S3: Mix the first precursor and the second precursor to obtain the composite solid electrolyte material.

[0039] In another aspect of the present invention, preferably,

[0040] The raw materials of A include one or more of the following: halides, halide oxides, oxides, nitrides, hydroxides, and sulfides of A;

[0041] The raw materials for RE include one or more of the following: RE halides, halide oxides, oxides, nitrides, hydroxides, and sulfides;

[0042] The raw materials of M include one or more of the following: halides, halide oxides, oxides, nitrides, hydroxides, and sulfides of M;

[0043] The X 1 The raw materials include: metal ions A and X 1 Compounds, RE metal ions and X 1 Compounds and M metal ions with X 1 One or more of the compounds;

[0044] The X 2 The raw materials include: metal ions A and X 2 Compounds, RE metal ions and X 2 Compounds and M metal ions with X 2 One or more of the compounds;

[0045] The raw materials for D include: compounds of metal ions A and D, and RE metal ions DX. 2 One or more of the compounds of M metal ions and D.

[0046] In another aspect of the present invention, preferably,

[0047] In step S1, the mixing process temperature is room temperature, the first heat treatment includes quenching, the quenching temperature of the first heat treatment is 200-1200℃, the holding time is 1-10h, and the cold water temperature is room temperature.

[0048] In step S2, the mixing process temperature is room temperature, the second heat treatment temperature is 100-500℃, the reaction time is 1-24h, and the atmosphere is an inert atmosphere.

[0049] The mixing process in step S3 is a grinding method, and the grinding time is 5-48 hours.

[0050] In another aspect of the present invention, preferably,

[0051] The quenching temperature for the first heat treatment is 700-1000℃;

[0052] The holding time for the first heat treatment is 2-5 hours;

[0053] The second heat treatment temperature is 200-400℃;

[0054] The reaction time for the second heat treatment is 3-10 hours;

[0055] The mixing time for the mixed grinding method is 10-24 hours.

[0056] In another aspect of the present invention, preferably,

[0057] The composite solid electrolyte material as described above, and the composite solid electrolyte material prepared by the preparation method described above, are used in positive and negative electrode materials, solid electrolyte stabilizers, electrode-electrolyte interface modifiers, electrolyte membrane coatings, solid-state batteries, and semi-solid-state batteries.

[0058] (III) Beneficial Effects

[0059] The above-described technical solution of the present invention has the following beneficial technical effects:

[0060] The composite solid electrolyte material of this invention comprises a composite of crystalline and amorphous phase components. Because the mechanochemical reaction occurs on the particle surface, and according to the thermodynamic changes of the reaction, one crystalline phase component is generated in situ on the surface of another crystalline phase component, resulting in good contact between the grains of the two crystalline materials. Simultaneously, the intense compression and collision between the powder and the grinding beads and the grinding jar wall during high-speed ball milling introduces some amorphous phase components into the composite material, ensuring good contact between different grains, further reducing grain boundary resistance, and ultimately achieving rapid carrier conduction, giving the composite solid electrolyte material high ionic conductivity. Furthermore, the use of moisture-resistant non-metallic halide components instead of traditional halides and oxyhalides in the raw materials also introduces excellent air stability into this composite solid electrolyte.

[0061] The composite solid-state electrolyte material provided by this invention exhibits excellent compressibility; electrolyte sheets with a density exceeding 90% can be obtained through cold pressing in a mold. This is advantageous for its application in the assembly of all-solid-state batteries, the design of novel all-solid-state battery devices, or the reduction of the pressure required for assembling all-solid-state batteries at present. The composite solid-state electrolyte material of this invention demonstrates good stability to the cathode material and can serve as the electrolyte for the cathode side. Furthermore, due to its inheritance of the excellent deformability of halide electrolytes, it can achieve close contact with cathode particles, thereby realizing a rapid interfacial mass transfer process. Attached Figure Description

[0062] Figure 1 is an XRD analysis diagram of Embodiment 4 of the present invention;

[0063] Figure 2 is an EIS curve diagram of Embodiment 4 of the present invention. Detailed Implementation

[0064] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments and the accompanying drawings. It should be understood that these descriptions are merely exemplary and not intended to limit the scope of the invention. Furthermore, descriptions of well-known structures and techniques are omitted in the following description to avoid unnecessarily obscuring the concept of the invention.

[0065] Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0066] In the description of this invention, it should be noted that the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0067] Furthermore, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0068] Example

[0069] A composite solid electrolyte material, wherein the composite solid electrolyte material comprises a crystalline phase substance with the general chemical formula represented as: B%A a RE b X 1 c D g +C%A d M e X 2 f D h ;

[0070] Where A represents charge carriers; RE represents rare earth elements; M represents metallic elements; X represents... 1 X 2 is a halide anion; D is an anion doping element or group.

[0071] A a RE b X 1 c D g and A d M e X 2 f D h It is a crystalline material;

[0072] B% is A a RE b X 1 c D g The mass fraction of the composite solid electrolyte material; C% is A d M e X 2 f D h The mass fraction of the composite solid electrolyte material;

[0073] Wherein, 0≤a≤3, 0<b≤1, 0.5<c≤12, 0<d≤5, 0<e≤2, 1<f≤20, 0≤g≤4, 0≤h≤5;

[0074] 85<B+C<98, 10%<B%≤85%; 10%<C%≤85%, 0.2≤C / B≤10.

[0075] The room temperature ionic conductivity of most halide electrolytes is still difficult to reach above 1 mS / cm. Furthermore, due to the complex preparation and storage methods of anhydrous chlorides in the raw materials, the cost of halide electrolytes is usually much higher than that of oxide electrolytes. More importantly, halide electrolytes are extremely prone to absorbing water and hydrolyzing in the air, which greatly limits the large-scale production and application of halide electrolytes.

[0076] The composite solid electrolyte material of this embodiment is composed of crystalline and amorphous phase components. Due to the mechanochemical reaction occurring on the particle surface, and based on the thermodynamic changes of the reaction, one crystalline phase component will be generated in situ on the surface of another crystalline phase component, resulting in good contact between the grains of the two crystalline phase materials. At the same time, the strong extrusion and collision between the powder and the grinding beads and the grinding jar wall during high-speed ball milling introduces some amorphous phase components into the composite material, resulting in good contact between different grains, further reducing grain boundary resistance, and ultimately achieving rapid carrier conduction, giving the composite solid electrolyte material high ionic conductivity. The use of moisture-resistant non-metallic halide components instead of traditional halides and oxyhalides in the raw materials also introduces the characteristic of good air stability into this composite solid electrolyte.

[0077] Furthermore, in this embodiment,

[0078] The A is one or more of Li, Na, K, Ag, Zn, Mg, Ca, Al, and Cu;

[0079] RE can be one or more of Y, Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu;

[0080] M is one or more of In, Ta, Zr, Al, Ga, Hf, and Nb;

[0081] X 1 It is one or more of F, Cl, Br and I;

[0082] X 2 It is one or more of F, Cl, Br and I;

[0083] D represents P, O, S, N, and OH. - One or more of them.

[0084] Furthermore, in this embodiment,

[0085] 0≤a≤1.5, 0.5<b≤1, 1≤c≤6, 1<d≤3, 0<e≤1, 1<f≤10, 0≤g≤2, 0≤h≤2.5, 90<B+C<95; 30%<B%≤65%; 30%<C%≤65%, 0.5≤C / B≤3. Composite solid electrolyte materials within this range can improve the ionic conductivity of composite solid electrolyte materials.

[0086] Furthermore, in this embodiment,

[0087] The composite solid electrolyte material includes an amorphous phase substance Q, wherein the amorphous phase substance accounts for 5% < Q in the mass fraction of the composite electrolyte powder. wt <10%.

[0088] Furthermore, in this embodiment,

[0089] A is one or both of Li and Na; RE is one or more of La, Ce, Sm, Yb, Y, and Lu; M is one or more of Ta, Zr, Al, Ga, and Nb; X 1 For Cl, F, Br; X 2 For Cl, F, Br; for D, O, S, N. X 1 X 2 When Cl and O are present, the moisture resistance of the composite solid electrolyte material can be improved. When RE is one or more of La, Ce, Sm, Yb, and Lu, and M is one or more of Ta, Zr, Ga, and Nb, the ionic conductivity of the composite solid electrolyte material can be improved. When A is K and Cu, the α-ray diffraction pattern shows obvious diffraction peaks at positions of 2θ = 32 ± 0.5°, 35 ± 0.5°, and 41 ± 0.5°.

[0090] A method for preparing a composite solid electrolyte material, the method comprising the following steps:

[0091] Step S1: According to A a RE b X 1 c D g Given the general chemical formula and mass fraction of the sample, weigh the raw material A, the raw material RE, and X. 1 The raw materials of D and D are mixed and post-processed, the post-processing including ball milling or a first heat treatment, to partially transform them into a crystalline state to obtain a first precursor;

[0092] Step S2: According to A d M e X 2 f D hGiven the general chemical formula and mass fraction, weigh out raw material A, raw material M, and X. 2 The raw materials of D and D are mixed and subjected to a second heat treatment to obtain a second precursor;

[0093] Step S3: Mix the first precursor and the second precursor to obtain the composite solid electrolyte material.

[0094] Furthermore, in this embodiment,

[0095] The raw materials of A include one or more of the following: halides, halide oxides, oxides, nitrides, hydroxides, and sulfides of A;

[0096] The raw materials for RE include one or more of the following: RE halides, halide oxides, oxides, nitrides, hydroxides, and sulfides;

[0097] The raw materials of M include one or more of the following: halides, halide oxides, oxides, nitrides, hydroxides, and sulfides of M;

[0098] The X 1 The raw materials include: metal ions A and X 1 Compounds, RE metal ions and X 1 Compounds and M metal ions with X 1 One or more of the compounds;

[0099] The X 2 The raw materials include: metal ions A and X 2 Compounds, RE metal ions and X 2 Compounds and M metal ions with X 2 One or more of the compounds;

[0100] The raw materials for D include: compounds of metal ions A and D, and RE metal ions DX. 2 One or more of the compounds of M metal ions and D.

[0101] Furthermore, in this embodiment, the mixing process temperature in step S1 is room temperature, the first heat treatment includes quenching, the quenching temperature of the first heat treatment is 200-1200℃, the holding time is 1-10h, and the cold water temperature is room temperature; the quenching method, the raw material powder of the quenching method can be sealed in a quartz tube under low vacuum, and the heat treatment process can be carried out by heating and holding in an electric resistance furnace.

[0102] In step S2, the mixing process is carried out at room temperature using a solid-state method; the second heat treatment is performed at a temperature of 100-500℃ for 1-24 hours in an inert atmosphere.

[0103] The mixing process in step S3 is a grinding method, and the grinding time is 5-48 hours.

[0104] Furthermore, in this embodiment,

[0105] The quenching temperature for the first heat treatment is 700-1000℃;

[0106] The holding time for the first heat treatment is 2-5 hours;

[0107] The second heat treatment temperature is 200-400℃;

[0108] The reaction time for the second heat treatment is 3-10 hours;

[0109] The mixing time for the mixed grinding method is 10-24 hours.

[0110] The composite solid electrolyte material as described above, and the composite solid electrolyte material prepared by the preparation method described above, are used in positive and negative electrode materials, solid electrolyte stabilizers, electrode-electrolyte interface modifiers, electrolyte membrane coatings, solid-state batteries, and semi-solid-state batteries.

[0111] The composite solid-state electrolyte material provided in this embodiment has excellent compressibility; electrolyte sheets with a density of over 90% can be obtained by cold pressing in a mold. This is beneficial for its application in the assembly of all-solid-state batteries, the design of novel all-solid-state battery devices, or the reduction of the pressure required for assembling all-solid-state batteries at present. The composite solid-state electrolyte material of this invention exhibits good stability to the cathode material and can be used as the electrolyte on the cathode side. Simultaneously, due to its continued excellent deformability of halide electrolytes, it can achieve close contact with cathode particles, thereby realizing a rapid interfacial mass transfer process.

[0112] Example 1:

[0113] The general chemical formula is: 17%Li3LaCl6-77%Li2ZrCl4O;

[0114] Weigh 1.28g LiCl and 1.31g LaCl3 in a glove box, mix the two materials evenly and seal them in a quartz tube, heat to 1000℃ and keep warm for 1 hour, then quench the quartz tube in water to obtain the first precursor.

[0115] 0.91g Li2O and 7.09g ZrCl4 were weighed in a glove box. The two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5h under Ar atmosphere to obtain the second precursor.

[0116] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder 17%Li3LaCl6-77%Li2ZrCl4O.

[0117] Conduct electrical conductivity and moisture resistance tests on the powder:

[0118] The resulting powder has a room temperature ionic conductivity of 1.01 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0119] Example 2:

[0120] The general chemical formula is: 27%Li3LaCl6-67%Li2ZrCl4O;

[0121] Weigh 1.62g LiCl and 1.97g LaCl3 in a glove box, mix the two materials evenly and seal them in a quartz tube, heat to 200℃ and keep warm for 10h, then quench the quartz tube in water to obtain the first precursor.

[0122] 0.80 g Li2O and 6.20 g ZrCl4 were weighed in a glove box. The two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0123] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at 600 r / min for 20 h to obtain the final powder 27%Li3LaCl6-67%Li2ZrCl4O.

[0124] Conduct electrical conductivity and moisture resistance tests on the powder:

[0125] The resulting powder has a room temperature ionic conductivity of 1.21 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0126] Example 3:

[0127] The general chemical formula is: 37%Li3LaCl6-57%Li2ZrCl4O;

[0128] Weigh 1.97 g LiCl and 2.63 g LaCl3 in a glove box, mix the two materials evenly and seal them in a quartz tube, heat to 1000℃ and keep warm for 5 hours, then quench the quartz tube in water to obtain the first precursor.

[0129] 0.68 g Li₂O and 5.32 g ZrCl₄ were weighed in a glove box, and the two materials were mixed evenly by ball milling. The mixture was then heat-treated at 200℃ for 5 hours under an Ar atmosphere to obtain the second precursor.

[0130] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder 37%Li3LaCl6-57%Li2ZrCl4O.

[0131] Conduct electrical conductivity and moisture resistance tests on the powder:

[0132] The resulting powder has a room temperature ionic conductivity of 1.51 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0133] Example 4:

[0134] The general chemical formula is: 47%Li3LaCl6-47%Li2ZrCl4O;

[0135] Weigh 2.31 g LiCl and 3.29 g LaCl3 in a glove box, mix the two materials evenly and seal them in a quartz tube, heat to 1000℃ and keep warm for 5 hours, then quench the quartz tube in water to obtain the first precursor.

[0136] 0.57 g Li2O and 4.43 g ZrCl4 were weighed in a glove box. The two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0137] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder 47%Li3LaCl6-47%Li2ZrCl4O.

[0138] Figure 1 shows the XRD analysis diagram of Embodiment 4 of the present invention; Figure 2 shows the EIS curve of Embodiment 4 of the present invention. As shown in Figure 1, the horizontal axis is twice the diffraction angle of X-rays, and the vertical axis is the diffraction intensity.

[0139] Conduct electrical conductivity and moisture resistance tests on the powder:

[0140] As shown in Figure 2, the obtained powder has a room temperature ionic conductivity of 3 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0141] Example 5:

[0142] The general chemical formula is: 57%Li3LaCl6-37%Li5Zr2Cl3O5;

[0143] Weigh 2.55 g LiCl and 3.75 g LaCl3 in a glove box, mix the two materials evenly and seal them in a quartz tube, heat to 1000℃ and keep warm for 5 hours, then quench the quartz tube in water to obtain the first precursor.

[0144] 0.27g Li₂O, 1.16g LiCl, and 2.26g ZrO₂ were weighed in a glove box, and the mixture was ball-milled until homogeneous. The mixture was then heat-treated at 200℃ for 5 hours under an Ar atmosphere to obtain the second precursor.

[0145] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at 600 r / min for 20 h to obtain the final powder 57%Li3LaCl6-37%Li5Zr2Cl3O5.

[0146] Conduct electrical conductivity and moisture resistance tests on the powder:

[0147] The resulting powder has a room temperature ionic conductivity of 2.961 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0148] Example 6:

[0149] The general chemical formula is: 65%Li 1.5 LaCl 4.5 -27%Li5Zr2Cl8O 2.5 ;

[0150] Weigh 1.93g LiCl and 5.16g LaCl3 in a glove box, mix the two materials evenly and seal them in a quartz tube, heat to 1000℃ and keep warm for 5 hours, then quench the quartz tube in water to obtain the first precursor.

[0151] 0.37g Li2O and 2.32g ZrCl4 were weighed in a glove box. The two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5h under Ar atmosphere to obtain the second precursor.

[0152] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously milled at 600 r / min for 20 h to obtain the final powder containing 65% Li. 1.5 LaCl 4.5 -27%Li5Zr2Cl8O 2.5 .

[0153] Conduct electrical conductivity and moisture resistance tests on the powder:

[0154] The resulting powder has a room temperature ionic conductivity of 1.91 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0155] Example 7:

[0156] The general chemical formula is: 17%LaClO-77%Li2ZrCl4O;

[0157] 2.3 g of LaClO was weighed in a glove box, sealed in a quartz tube, heated to 1000℃ and held for 5 hours. The quartz tube was then quenched in water to obtain the first precursor.

[0158] 0.9 g Li2O and 6.8 g ZrCl4 were weighed in a glove box. The two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0159] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder 17%LaClO-77%Li2ZrCl4O.

[0160] Conduct electrical conductivity and moisture resistance tests on the powder:

[0161] The resulting powder has a room temperature ionic conductivity of 1.21 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0162] Example 8:

[0163] The general chemical formula is: 28%LaClO-67%Li2ZrCl4O;

[0164] 3.3 g of LaClO was weighed in a glove box, sealed in a quartz tube, heated to 1000℃ and held for 5 hours. The quartz tube was then quenched in water to obtain the first precursor.

[0165] 0.8g Li2O and 5.9g ZrCl4 were weighed in a glove box. The two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5h under Ar atmosphere to obtain the second precursor.

[0166] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder 28%LaClO-67%Li2ZrCl4O.

[0167] Conduct electrical conductivity and moisture resistance tests on the powder:

[0168] The resulting powder has a room temperature ionic conductivity of 1.68 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0169] Example 9:

[0170] The general chemical formula is: 35%LaClO-56%Li2ZrCl4O;

[0171] 4.4g of LaClO was weighed in a glove box, sealed in a quartz tube, heated to 1000℃ and held for 5 hours. The quartz tube was then quenched in water to obtain the first precursor.

[0172] 0.6g Li2O and 5g ZrCl4 were weighed in a glove box. The two materials were mixed evenly by ball milling and then heat-treated at 100℃ for 24h under Ar atmosphere to obtain the second precursor.

[0173] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder 35%LaClO-56%Li2ZrCl4O.

[0174] Conduct electrical conductivity and moisture resistance tests on the powder:

[0175] The resulting powder has a room temperature ionic conductivity of 1.79 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0176] Example 10:

[0177] The general chemical formula is: 46%LaClO-46%Li2ZrCl4O;

[0178] 5.4 g of LaClO was weighed in a glove box, sealed in a quartz tube, heated to 1000℃ and held for 5 hours. The quartz tube was then quenched in water to obtain the first precursor.

[0179] 0.5 g Li2O and 4.1 g ZrCl4 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0180] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder 46%LaClO-46%Li2ZrCl4O.

[0181] Conduct electrical conductivity and moisture resistance tests on the powder:

[0182] The resulting powder has a room temperature ionic conductivity of 1.86 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0183] Example 11:

[0184] The general chemical formula is: 55%LaClO-34%Li2ZrCl4O;

[0185] 6.6 g of LaClO was weighed in a glove box, sealed in a quartz tube, heated to 1000℃ and held for 5 hours. The quartz tube was then quenched in water to obtain the first precursor.

[0186] 0.4 g Li2O and 3 g ZrCl4 were weighed in a glove box. The two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 2 hours under Ar atmosphere to obtain the second precursor.

[0187] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder 55%LaClO-34%Li2ZrCl4O.

[0188] Conduct electrical conductivity and moisture resistance tests on the powder:

[0189] The resulting powder has a room temperature ionic conductivity of 1.51 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0190] Example 12:

[0191] The general chemical formula is: 64%Al3LaCl4O4-27%Li2ZrCl4O;

[0192] Weigh 2.9g AlCl3, 1.5g Al2O3, 1.2g LaCl3, and 1.6g La2O3 in a glove box, seal them in a quartz tube, heat them to 700℃, keep them at that temperature for 2 hours, and then quench the quartz tube in water to obtain the first precursor.

[0193] 0.3 g Li2O and 2.4 g ZrCl4 were weighed in a glove box. The two materials were mixed evenly by ball milling and then heat-treated at 500℃ for 1 h under Ar atmosphere to obtain the second precursor.

[0194] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The mill was then continuously run at 600 r / min for 20 h to obtain the final powder of 64%Mg3LaCl3O3-27%Li2ZrCl4O.

[0195] Conduct electrical conductivity and moisture resistance tests on the powder:

[0196] The resulting powder has a room temperature ionic conductivity of 1.43 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0197] Example 13:

[0198] The general chemical formula is: 72%Li₂LaClO₂-15%Mg₅Ta₂Cl 20 ;

[0199] Weigh 1.8g Li2O, 1.4g LiCl, and 5.3g La2O3 in a glove box, seal them in a quartz tube, heat them to 1000℃, keep them at that temperature for 5 hours, and then quench the quartz tube in water to obtain the first precursor.

[0200] 0.6g of MgCl2 and 0.9g of TaCl5 were weighed in a glove box. The two materials were mixed evenly by ball milling and then heat-treated at 400℃ for 5h under Ar atmosphere to obtain the second precursor.

[0201] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously milled at 600 r / min for 24 h to obtain the final powder of 72% Li₂LaClO₂-15% Mg₅Ta₂Cl. 20 .

[0202] Conduct electrical conductivity and moisture resistance tests on the powder:

[0203] The resulting powder has a room temperature ionic conductivity of 1.1 mS / cm and retains 95% of its room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0204] Example 14:

[0205] The general chemical formula is: 17%CeCl3-77%Li2ZrCl4O;

[0206] 2.3g of CeCl3 was weighed in a glove box and subjected to high-energy ball milling to obtain the first precursor;

[0207] 0.9 g Li2O and 6.8 g ZrCl4 were weighed in a glove box. The two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0208] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 10 h to obtain the final powder 17%CeCl3-77%Li2ZrCl4O.

[0209] Conduct electrical conductivity and moisture resistance tests on the powder:

[0210] The resulting powder has a room temperature ionic conductivity of 0.9 mS / cm and retains 95% of its room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0211] Example 15:

[0212] The general chemical formula is: 24%CeCl3-65%Li2ZrCl4O;

[0213] 2.4g of CeCl3 was weighed in a glove box and subjected to high-energy ball milling to obtain the first precursor;

[0214] 1.8g Li2O and 5.8g ZrCl4 were weighed in a glove box. The two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5h under Ar atmosphere to obtain the second precursor.

[0215] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 12 h to obtain the final powder 24%CeCl3-65%Li2ZrCl4O.

[0216] Conduct electrical conductivity and moisture resistance tests on the powder:

[0217] The resulting powder has a room temperature ionic conductivity of 1.13 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0218] Example 16:

[0219] The general chemical formula is: 38%CeCl3-54%Li2ZrCl4O;

[0220] 4.6 g of CeCl3 was weighed in a glove box and subjected to high-energy ball milling to obtain the first precursor;

[0221] 0.6 g Li2O and 4.8 g ZrCl4 were weighed in a glove box. The two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0222] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at 600 r / min for 1 hour to obtain the final powder 38%CeCl3-54%Li2ZrCl4O.

[0223] Conduct electrical conductivity and moisture resistance tests on the powder:

[0224] The resulting powder has a room temperature ionic conductivity of 1.45 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0225] Example 17:

[0226] The general chemical formula is: 48%CeCl3-46%Li2ZrCl4O;

[0227] 5.4 g of CeCl3 was weighed in a glove box and subjected to high-energy ball milling to obtain the first precursor;

[0228] 0.5 g Li2O and 4.1 g ZrCl4 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0229] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at 600 r / min for 24 h to obtain the final powder 24%CeCl3-67%Li2ZrCl4O.

[0230] Conduct electrical conductivity and moisture resistance tests on the powder:

[0231] The resulting powder has a room temperature ionic conductivity of 2.62 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0232] Example 18:

[0233] The general chemical formula is: 57%CeCl3-35%Li2ZrCl4O;

[0234] 6.5 g of CeCl3 was weighed in a glove box and subjected to high-energy ball milling to obtain the first precursor;

[0235] 0.4 g Li2O and 3.1 g ZrCl4 were weighed in a glove box. The two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0236] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 10 h to obtain the final powder 24%CeCl3-67%Li2ZrCl4O.

[0237] Conduct electrical conductivity and moisture resistance tests on the powder:

[0238] The resulting powder has a room temperature ionic conductivity of 2.34 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0239] Example 19:

[0240] The general chemical formula is: 69%CeCl3-21%Li2ZrCl4O;

[0241] 7.9 g of CeCl3 was weighed in a glove box and subjected to high-energy ball milling to obtain the first precursor;

[0242] 0.2 g Li2O and 1.9 g ZrCl4 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0243] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder of 69% CeCl3-21% Li2ZrCl4O.

[0244] Conduct electrical conductivity and moisture resistance tests on the powder:

[0245] The resulting powder has a room temperature ionic conductivity of 2.20 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0246] Example 20:

[0247] The general chemical formula is: 75%CeCl3-12%Li2ZrCl4O;

[0248] 8.8 g of CeCl3 was weighed in a glove box and subjected to high-energy ball milling to obtain the first precursor;

[0249] 0.1 g Li2O and 1.1 g ZrCl4 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0250] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at 600 r / min for 20 h to obtain the final powder 24%CeCl3-67%Li2ZrCl4O.

[0251] Conduct electrical conductivity and moisture resistance tests on the powder:

[0252] The resulting powder has a room temperature ionic conductivity of 0.8 mS / cm, and retains 95% of its room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0253] Example 21:

[0254] The general chemical formula is: 15%CeCl3-80%Li2ZrCl6;

[0255] 2 g of CeCl3 was weighed in a glove box and subjected to high-energy ball milling to obtain the first precursor.

[0256] 2.1 g LiCl and 5.9 g ZrCl4 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0257] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder 15%CeCl3-80%Li2ZrCl6.

[0258] Conduct electrical conductivity and moisture resistance tests on the powder:

[0259] The resulting powder has a room temperature ionic conductivity of 1.14 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0260] Example 22:

[0261] The general chemical formula is: 23%CeCl3-68%Li2ZrCl6;

[0262] 3.2 g of CeCl3 was weighed in a glove box and subjected to high-energy ball milling to obtain the first precursor;

[0263] 1.8 g LiCl and 5 g ZrCl4 were weighed in a glove box. The two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0264] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder 23%CeCl3-68%Li2ZrCl6.

[0265] Conduct electrical conductivity and moisture resistance tests on the powder:

[0266] The resulting powder has a room temperature ionic conductivity of 1.65 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0267] Example 23:

[0268] The general chemical formula is: 35%CeCl3-56%Li2ZrCl6;

[0269] 4.4 g of CeCl3 was weighed in a glove box and subjected to high-energy ball milling to obtain the first precursor;

[0270] 1.5 g LiCl and 4.1 g ZrCl4 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0271] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder of 35% CeCl3-56% Li2ZrCl6.

[0272] Conduct electrical conductivity and moisture resistance tests on the powder:

[0273] The resulting powder has a room temperature ionic conductivity of 1.76 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0274] Example 24:

[0275] The general chemical formula is: 46%CeCl3-47%Li2ZrCl6;

[0276] 5.3 g of CeCl3 was weighed in a glove box and subjected to high-energy ball milling to obtain the first precursor;

[0277] 1.3 g LiCl and 3.4 g ZrCl4 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0278] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder of 46% CeCl3-47% Li2ZrCl6.

[0279] Conduct electrical conductivity and moisture resistance tests on the powder:

[0280] The resulting powder has a room temperature ionic conductivity of 3.35 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0281] Example 25:

[0282] The general chemical formula is: 55%CeCl3-32%Li2ZrCl6;

[0283] 6.8 g of CeCl3 was weighed in a glove box and subjected to high-energy ball milling to obtain the first precursor;

[0284] 0.9 g LiCl and 2.3 g ZrCl4 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0285] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder of 55% CeCl3-32% Li2ZrCl6.

[0286] Conduct electrical conductivity and moisture resistance tests on the powder:

[0287] The resulting powder has a room temperature ionic conductivity of 2.54 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0288] Example 26:

[0289] The general chemical formula is: 67%CeCl3-25%Li2ZrCl6;

[0290] 7.5 g of CeCl3 was weighed in a glove box and subjected to high-energy ball milling to obtain the first precursor;

[0291] 0.7 g LiCl and 1.8 g ZrCl4 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0292] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder 15%CeCl3-80%Li2ZrCl6.

[0293] Conduct electrical conductivity and moisture resistance tests on the powder:

[0294] The resulting powder has a room temperature ionic conductivity of 1.54 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0295] Example 27:

[0296] The general chemical formula is: 74%CeCl3-12%Li2ZrCl6;

[0297] 8.8 g of CeCl3 was weighed in a glove box and subjected to high-energy ball milling to obtain the first precursor;

[0298] 0.3 g LiCl and 0.9 g ZrCl4 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0299] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder of 74% CeCl3-12% Li2ZrCl6.

[0300] Conduct electrical conductivity and moisture resistance tests on the powder:

[0301] The resulting powder has a room temperature ionic conductivity of 1.21 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0302] Example 28:

[0303] The general chemical formula is: 15%CeCl3-80%LiTaCl6;

[0304] 2 g of CeCl3 was weighed in a glove box and subjected to high-energy ball milling to obtain the first precursor.

[0305] 0.8 g LiCl and 7.2 g TaCl5 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0306] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder of 15% CeCl3-80% LiTaCl6.

[0307] Conduct electrical conductivity and moisture resistance tests on the powder:

[0308] The resulting powder has a room temperature ionic conductivity of 1.54 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0309] Example 29:

[0310] The general chemical formula is: 24%CeCl3-63%LiTaCl6;

[0311] Weigh 3.7 g of CeCl3 in a glove box, seal the material in a quartz tube, heat it to 1000℃ and hold it for 5 hours. Then quench the quartz tube in water to obtain the first precursor.

[0312] 0.6 g LiCl and 5 g TaCl5 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0313] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder of 24% CeCl3-63% LiTaCl6.

[0314] Conduct electrical conductivity and moisture resistance tests on the powder:

[0315] The resulting powder has a room temperature ionic conductivity of 1.79 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0316] Example 30:

[0317] The general chemical formula is: 37%CeCl3-56%LiTaCl6;

[0318] 4.4 g of CeCl3 was weighed in a glove box, the material was sealed in a quartz tube, heated to 1000℃ and held for 5 hours, and then the quartz tube was quenched in water to obtain the first precursor.

[0319] 0.6 g LiCl and 5 g TaCl5 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200 °C for 5 h under Ar atmosphere to obtain the second precursor.

[0320] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder of 37% CeCl3-56% LiTaCl6.

[0321] Conduct electrical conductivity and moisture resistance tests on the powder:

[0322] The resulting powder has a room temperature ionic conductivity of 2.21 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0323] Example 31:

[0324] The general chemical formula is: 47%CeCl3-47%LiTaCl6;

[0325] 5.3 g of CeCl3 was weighed in a glove box, the material was sealed in a quartz tube, heated to 1000℃ and held for 5 hours, and then the quartz tube was quenched in water to obtain the first precursor.

[0326] 0.5 g LiCl and 4.2 g TaCl5 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0327] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder of 47% CeCl3-47% LiTaCl6.

[0328] Conduct electrical conductivity and moisture resistance tests on the powder:

[0329] The resulting powder has a room temperature ionic conductivity of 4.35 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0330] Example 32:

[0331] The general chemical formula is: 59%CeCl3-32%LiTaCl6;

[0332] 6.8 g of CeCl3 was weighed in a glove box, the material was sealed in a quartz tube, heated to 1000℃ and held for 5 hours, and then the quartz tube was quenched in water to obtain the first precursor.

[0333] 0.3 g LiCl and 2.9 g TaCl5 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0334] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder of 59% CeCl3-32% LiTaCl6.

[0335] Conduct electrical conductivity and moisture resistance tests on the powder:

[0336] The resulting powder has a room temperature ionic conductivity of 3.21 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0337] Example 33:

[0338] The general chemical formula is: 66%CeCl3-22%LiTaCl6;

[0339] 7.8 g of CeCl3 was weighed in a glove box, the material was sealed in a quartz tube, heated to 1000℃ and held for 5 hours, and then the quartz tube was quenched in water to obtain the first precursor.

[0340] 0.2 g LiCl and 2 g TaCl5 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5 h under Ar atmosphere to obtain the second precursor.

[0341] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder of 66% CeCl3-22% LiTaCl6.

[0342] Conduct electrical conductivity and moisture resistance tests on the powder:

[0343] The resulting powder has a room temperature ionic conductivity of 1.34 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0344] Example 34:

[0345] The general chemical formula is: 85%Al3CeCl 12 -12%LiTaCl6;

[0346] Weigh 5.6g of AlCl3 and 3.2g of CeCl3 in a glove box, seal the materials in a quartz tube, heat them to 1000℃ and hold for 5 hours, then quench the quartz tube in water to obtain the first precursor.

[0347] 0.1g LiCl and 1.1g TaCl5 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5h under Ar atmosphere to obtain the second precursor.

[0348] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously milled at 600 r / min for 20 h to obtain the final powder (85% Al3CeCl). 12 -12%LiTaCl6.

[0349] Conduct electrical conductivity and moisture resistance tests on the powder:

[0350] The resulting powder has a room temperature ionic conductivity of 0.78 mS / cm, and retains 95% of its room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0351] Example 35:

[0352] The general chemical formula is: 12%Li3SmCl6-85%Li3GaCl6;

[0353] Weigh 0.7g LiCl and 0.8g SmCl3 in a glove box, mix the two materials evenly and seal them in a quartz tube, heat to 1000℃ and keep warm for 5 hours, then quench the quartz tube in water to obtain the first precursor.

[0354] 3.6g LiCl and 4.9g GaCl3 were weighed in a glove box, and the two materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5h under Ar atmosphere to obtain the second precursor.

[0355] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder 12%Li3SmCl6-85%Li3GaCl6.

[0356] Conduct electrical conductivity and moisture resistance tests on the powder:

[0357] The resulting powder has a room temperature ionic conductivity of 2.57 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0358] Example 36:

[0359] The general chemical formula is: 15%Li3SmCl6-80%Li3GaCl4S;

[0360] Weigh 1 g LiCl and 1 g SmCl3 in a glove box, mix the two materials evenly and seal them in a quartz tube, heat to 1000℃ and keep warm for 5 hours, then quench the quartz tube in water to obtain the first precursor.

[0361] 1.3g LiCl, 5.3g GaCl3 and 1.3g Li2S were weighed in a glove box. The three materials were mixed evenly by ball milling and then heat-treated at 200℃ for 5h under Ar atmosphere to obtain the second precursor.

[0362] The first and second precursors were added to a zirconia ball mill jar with zirconia beads of different sizes at a ball-to-material ratio of 60:1 under an Ar atmosphere. The jar was then continuously run at a speed of 600 r / min for 20 h to obtain the final powder 15%Li3SmCl6-80%Li3GaCl4S.

[0363] Conduct electrical conductivity and moisture resistance tests on the powder:

[0364] The resulting powder has a room temperature ionic conductivity of 3.54 mS / cm, and retains 95% of the room temperature ionic conductivity after being exposed to 5% humidity for 24 hours.

[0365] It should be understood that the specific embodiments described above are merely illustrative or explanatory of the principles of the invention and do not constitute a limitation thereof. Therefore, any modifications, equivalent substitutions, improvements, etc., made without departing from the spirit and scope of the invention should be included within the protection scope of the invention. Furthermore, the appended claims are intended to cover all variations and modifications falling within the scope and boundaries of the appended claims, or equivalent forms of such scope and boundaries.

[0366] The present invention has been described above with reference to embodiments thereof. However, these embodiments are merely illustrative and not intended to limit the scope of the invention. The scope of the invention is defined by the appended claims and their equivalents. Various substitutions and modifications can be made by those skilled in the art without departing from the scope of the invention, and all such substitutions and modifications should fall within the scope of the invention.

[0367] Although embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and modifications can be made to the embodiments of the present invention without departing from the spirit and scope of the invention.

[0368] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A composite solid electrolyte material, characterized in that, The composite solid electrolyte material contains a crystalline substance whose general chemical formula is represented by: B%A a RE b X 1 c D g +C%A d M e X 2 f D h ; Where A represents charge carriers; RE represents rare earth elements; M represents metallic elements; X represents... 1 X 2 is a halide anion; D is an anion doping element or group. A a RE b X 1 c D g and A d M e X 2 f D h It is a crystalline material; B% is A a RE b X 1 c D g The mass fraction of the composite solid electrolyte material; C% is A d M e X 2 f D h The mass fraction of the composite solid electrolyte material; Wherein, 0≤a≤3, 0<b≤1, 0.5<c≤12, 0<d≤5, 0<e≤2, 1<f≤20, 0≤g≤4, 0≤h≤5; 85<B+C<98, 10%<B%≤85%; 10%<C%≤85%, 0.2≤C / B≤10.

2. The composite solid electrolyte material according to claim 1, characterized in that, The A is one or more of Li, Na, K, Ag, Zn, Mg, Ca, Al, and Cu; RE can be one or more of Y, Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; M is one or more of In, Ta, Zr, Al, Ga, Hf, and Nb; X 1 It is one or more of F, Cl, Br and I; X 2 It is one or more of F, Cl, Br and I; D represents P, O, S, N, and OH. - One or more of them.

3. The composite solid electrolyte material according to claim 1, characterized in that, The 0≤a≤1.5, 0.5<b≤1, 1≤c≤6, 1<d≤3, 0<e≤1, 1<f≤10, 0≤g≤2, 0≤h≤2.5, 90<B+C<95; 30%<B%≤65%; 30%<C%≤65%, 0.5≤C / B≤3.

4. The composite solid electrolyte material according to claim 1, characterized in that, The composite solid electrolyte material includes an amorphous phase substance Q, wherein the amorphous phase substance accounts for 5% < Q in the mass fraction of the composite electrolyte powder. wt <10%.

5. The composite solid electrolyte material according to claim 2, characterized in that, A is one or both of Li and Na; RE can be one or more of La, Ce, Sm, Yb, Y, and Lu; M can be one or more of Ta, Zr, Al, Ga, and Nb; X 1 For Cl, F, Br; X 2 For Cl, F, Br; D represents O, S, and N.

6. A method for preparing a composite solid electrolyte material, characterized in that, The preparation method is used to prepare the composite solid electrolyte material as described in any one of claims 1-5, and the preparation method includes the following steps: Step S1: According to A a RE b X 1 c D g Given the general chemical formula and mass fraction of the sample, weigh the raw material A, the raw material RE, and X. 1 The raw materials of D and D are mixed and post-processed, the post-processing including ball milling or a first heat treatment, to obtain a first precursor; Step S2: According to A d M e X 2 f D h Given the general chemical formula and mass fraction, weigh out raw material A, raw material M, and X. 2 The raw materials of D and D are mixed and subjected to a second heat treatment to obtain a second precursor; Step S3: Mix the first precursor and the second precursor to obtain the composite solid electrolyte material.

7. The preparation method according to claim 6, characterized in that: The raw materials of A include one or more of the following: halides, halide oxides, oxides, nitrides, hydroxides, and sulfides of A; The raw materials for RE include one or more of the following: RE halides, halide oxides, oxides, nitrides, hydroxides, and sulfides; The raw materials of M include one or more of the following: halides, halide oxides, oxides, nitrides, hydroxides, and sulfides of M; The X 1 The raw materials include: metal ions A and X 1 Compounds and RE metal ions with X 1 One or more of the compounds; The X 2 The raw materials include: metal ions A and X 2 Compounds and M metal ions with X 2 One or more of the compounds; The raw materials for D include: compounds of metal ions A and D, and RE metal ions DX. 2 One or more of the compounds of M metal ions and D.

8. The preparation method according to claim 6, characterized in that: In step S1, the mixing process temperature is room temperature, the first heat treatment includes quenching, the quenching temperature of the first heat treatment is 200-1200℃, the holding time is 1-10h, and the cold water temperature is room temperature. In step S2, the mixing process temperature is room temperature, the second heat treatment temperature is 100-500℃, the reaction time is 1-24h, and the atmosphere is an inert atmosphere. The mixing process in step S3 is a grinding method, and the grinding time is 5-48 hours.

9. The preparation method according to claim 8, characterized in that: The quenching temperature for the first heat treatment is 700-1000℃; The holding time for the first heat treatment is 2-5 hours; The second heat treatment temperature is 200-400℃; The reaction time for the second heat treatment is 3-10 hours; The mixing time for the mixed grinding method is 10-24 hours.

10. The application of a composite solid electrolyte material as described in claims 1-5, and the composite solid electrolyte material prepared by the preparation method according to any one of claims 6-9, in positive and negative electrode materials, solid electrolyte stabilizers, electrode-electrolyte interface modifiers, electrolyte membrane coatings, solid-state batteries, and semi-solid-state batteries.

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