Metal and non-metal element co-doped oxyhalide solid electrolyte and all-solid-state battery

Abstract

The application relates to a metal and non-metal element co-doped halide oxide solid electrolyte and a full solid-state battery, and belongs to the technical field of energy storage batteries. The general formula of the solid electrolyte is X 2a Ta b M c+2d N md Y 5b+mc O ax ; X is selected from one of Li, Na, K, Ca, Mg, Zn, Al, Fe; M is selected from one or more of Cs, Nb, Hf, La, Y, Fe, Ga, In, Pb, Bi, Ge, Sb; N is selected from one or more of S, Se, Te; Y is selected from one or more of F, Cl, Br, I; the value range of a, b, c, d is 0

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of energy storage batteries, and more particularly to a halide-oxy solid electrolyte co-doped with metal and non-metal elements and a full solid-state battery. BACKGROUND

[0002] In recent years, with the vigorous development of electronic devices such as electric vehicles and unmanned aerial vehicles, people's requirements for batteries have become increasingly strict. Traditional liquid electrolyte lithium ion batteries have many limitations. At the same time, full solid-state lithium ion batteries show the potential to break through the bottleneck of electrochemical energy storage and meet the needs of future development due to their high safety and high energy density, and have attracted people's attention.

[0003] Among them, halide solid electrolytes have high oxidation stability and do not produce harmful gases after contact with air, which can further improve safety. These advantages have attracted widespread attention. However, the low ionic conductivity of halide solid electrolytes has limited the application of halide solid electrolytes. For example, in the patent with publication number CN118173866A, a halide solid electrolyte with the chemical formula Li 2.3 Zr 0.6 Ce 1.7 Cl 8.2 O 0.8 has an ionic conductivity of 0.71x10 -3 S cm -1 .

[0004] Therefore, the prior art still needs further improvement and development. SUMMARY

[0005] In view of the above reasons, the purpose of the present application is to provide a halide-oxy solid electrolyte co-doped with metal and non-metal elements, a preparation method and application thereof. The halide-oxy solid electrolyte co-doped with metal and non-metal elements provided by the present application can significantly improve the ionic conductivity. Thus, the technical problem of low ionic conductivity of halide solid electrolytes in the prior art is solved.

[0006] According to the first aspect of the present application, a halide-oxy solid electrolyte co-doped with metal and non-metal elements is provided, and the chemical general formula of the halide-oxy solid electrolyte co-doped with metal and non-metal elements is X 2a Ta b M c+2d N md Y 5b+ mc O ax; wherein X is selected from one of Li, Na, K, Ca, Mg, Zn, Al, Fe; M is selected from one or more of Cs, Nb, Hf, La, Y, Fe, Ga, In, Pb, Bi, Ge, Sb; N is selected from one or more of S, Se, Te; Y is selected from one or more of F, Cl, Br, I; a, b, c, d are in the range of 0 < a < 4, 0 < b < 2, 0 < c < 2, 0 < d < 2; x, m are the valence of X and M respectively.

[0007] Preferably, the metal and non-metal co-doped halide solid electrolyte is in powder form.

[0008] Preferably, the metal and non-metal co-doped halide solid electrolyte has a particle size of 1 nm-100 μm.

[0009] According to another aspect of the present application, there is provided a method for preparing the metal and non-metal co-doped halide solid electrolyte, wherein a precursor X2O x , TaY5, MY m , M2N m are mixed and ground in the ratio of a:b:c:d, and then ball-milled to obtain the metal and non-metal co-doped halide solid electrolyte; wherein X is selected from one of Li, Na, K, Ca, Mg, Zn, Al, Fe; M is selected from one or more of Cs, Nb, Hf, La, Y, Fe, Ga, In, Pb, Bi, Ge, Sb; N is selected from one or more of S, Se, Te; Y is selected from one or more of F, Cl, Br, I; x, m are the valence of X and M respectively.

[0010] Preferably, the ball-to-material mass ratio of the ball-milling is 5:1-200:1.

[0011] Preferably, the rotation speed of the ball-milling is 100-2000 rpm, and the ball-milling time is 1h-48h.

[0012] According to another aspect of the present application, there is provided the use of the metal and non-metal co-doped halide solid electrolyte in a full solid-state battery.

[0013] According to another aspect of the present application, there is provided a full solid-state battery comprising a solid electrolyte layer, wherein the solid electrolyte layer comprises the metal and non-metal co-doped halide solid electrolyte.

[0014] In general, the above technical solutions conceived by the present application have the following technical advantages compared with the prior art:

[0015] (1) The application provides a metal and non-metal element co-doped halide oxide solid electrolyte and a preparation method and application thereof. The ion conductivity of a traditional halide solid electrolyte is about 1*10 -3 S cm -1 The application dopes Cs, Nb, Hf, La, Y, Fe, Ga, In, Pb, Bi, Ge, Sb and other metals with S, Se, Te, O and other non-metal elements, and the halide oxide solid electrolyte provided has high ion conductivity, and the room temperature ion conductivity thereof can reach 10*10 -3 S cm -1 Theoretically, the above can be applied to manufacture secondary batteries with high safety performance and high specific energy.

[0016] (2) Preferably, the X element is Li, and lithium ions have smaller ion radius and stronger electric field effect in the solid electrolyte, which makes the lithium ions more effectively pass through the crystal lattice structure, thereby having higher mobility.

[0017] (3) The application provides a method for preparing a metal and non-metal element co-doped halide oxide solid electrolyte, which only needs to be simply ball milled, and the obtained powder-shaped metal and non-metal element co-doped halide oxide solid electrolyte can be directly applied without further heat treatment, and the process is simple, efficient and low in energy consumption, which is conducive to practical production and application. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 is an XRD pattern of Li8Ta2Hf3Te4Cl 14 O4 prepared based on Example 1 of the application.

[0019] Figure 2 is an electrochemical impedance spectrogram of Li8Ta2Hf3Te4Cl 14 O4 prepared based on Example 1 of the application.

[0020] Figure 3 is an electrochemical impedance spectrogram of Li8Ta2Bi4S3Cl 16 O4 prepared based on Example 3 of the application.

[0021] Figure 4 is a first cycle charge-discharge cycle voltage curve of a full solid-state battery prepared from the Li8Ta2Hf3Te4Cl 14 O4 solid electrolyte based on Example 1 of the application.

[0022] Figure 5 is an electronic impedance spectrogram of Li8Ta2Bi4S3Cl 16 O4 prepared based on Example 3 of the application. DETAILED DESCRIPTION

[0023] In order to make the objectives, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and not used to limit the present application. In addition, the technical features involved in the various embodiments of the present application described below can be combined with each other as long as they do not conflict with each other.

[0024] Embodiment 1

[0025] This embodiment provides a halide oxide solid electrolyte Li8Ta2Hf3Te4Cl 14 O4 co-doped with metal and non-metal elements, and the specific preparation method is as shown below:

[0026] In an Ar atmosphere glove box, Li2O, TaCl5, HfCl 4、 HfTe2 precursor powders were weighed according to the molar ratio of 4:2:1:2, and were placed in an agate mortar; the agate pestle was used to grind for 20 min, and the ground precursor powders were added to a zirconia ball mill jar, and the mass ratio of balls to materials in the ball mill jar was 80:1; the ball mill jar was transferred to a ball mill, and ball milling was performed at a speed of 800 rpm for 48 h, and then it was naturally cooled to room temperature to obtain a powder of Li8Ta2Hf5Te4Cl 14 O4 halide oxide solid electrolyte. The ionic conductivity of the electrolyte is 11 x 10 -3 S cm -1 .

[0027] Embodiment 2

[0028] This embodiment provides a halide oxide solid electrolyte Zn4TaLa6S6Cl 11 O4 co-doped with metal and non-metal elements, and the specific preparation method is as shown below:

[0029] In an Ar atmosphere glove box, ZnO, TaCl5, LaCl3, and La2S3 precursor powders were weighed according to the molar ratio of 4:1:2:2, and were placed in an agate mortar; the agate pestle was used to grind for 20 min, and the ground precursor powders were added to a zirconia ball mill jar, and the mass ratio of balls to materials in the ball mill jar was 200:1; the ball mill jar was transferred to a ball mill, and ball milling was performed at a speed of 800 rpm for 48 h, and then it was naturally cooled to room temperature to obtain a powder of Zn4TaLa6S6Cl 11 O4 halide oxide solid electrolyte. The ionic conductivity of the electrolyte is 1.6 x 10 -3 S cm -1 .

[0030] Embodiment 3

[0031] The embodiment provides a halide oxide solid electrolyte Li8Ta2Bi4S3Cl co-doped with metal and nonmetal elements 16 O4, and a specific preparation method is as shown in the following:

[0032] In an Ar atmosphere glove box, Li2O, TaCl5, BiCl3 and Ga2Te3 precursor powders are weighed according to a molar ratio of 4:2:2:1, and are placed in a marigold mortar; the marigold pestle is used to grind for 20 min, the ground precursor powders are added into a zirconia ball mill jar, and a ball-to-material mass ratio in the ball mill jar is 80:1; the ball mill jar is transferred into a ball mill, and after ball milling at a speed of 800 rpm for 48 h, the ball mill jar is naturally cooled to room temperature, and a powder-shaped Li8Ta2Bi4S3Cl halide oxide solid electrolyte is prepared. 3、 Bi2S3 precursor powders are weighed according to a molar ratio of 4:2:2:1, and are placed in a marigold mortar; the marigold pestle is used to grind for 20 min, the ground precursor powders are added into a zirconia ball mill jar, and a ball-to-material mass ratio in the ball mill jar is 80:1; the ball mill jar is transferred into a ball mill, and after ball milling at a speed of 800 rpm for 48 h, the ball mill jar is naturally cooled to room temperature, and a powder-shaped Li8Ta2Bi4S3Cl halide oxide solid electrolyte is prepared. 16 The ionic conductivity of the electrolyte is 7.42 x 10-4 S cm-1. -3 S cm-1. -1 .

[0033] Embodiment 4

[0034] The embodiment provides a halide oxide solid electrolyte Na4TaGa3Te3Cl8O2 co-doped with metal and nonmetal elements, and a specific preparation method is as shown in the following:

[0035] In an Ar atmosphere glove box, Na2O, TaCl5, GaCl3 and Ga2Te3 precursor powders are weighed according to a molar ratio of 2:1:1:1, and are placed in a marigold mortar; the marigold pestle is used to grind for 20 min, the ground precursor powders are added into a zirconia ball mill jar, and a ball-to-material mass ratio in the ball mill jar is 100:1; the ball mill jar is transferred into a ball mill, and after ball milling at a speed of 900 rpm for 48 h, the ball mill jar is naturally cooled to room temperature, and a powder-shaped Na4TaGa3Te3Cl8O2 halide oxide solid electrolyte is prepared. The ionic conductivity of the electrolyte is 2.56 x 10-4 S cm-1. -3 S cm-1. -1 .

[0036] Embodiment 5

[0037] The embodiment provides a halide oxide solid electrolyte Al6TaNb2S2Br4Cl5O9 co-doped with metal and nonmetal elements, and a specific preparation method is as shown in the following:

[0038] In an Ar atmosphere glove box, Al2O3, TaCl5, NbBr4, NbSe2 precursor powders were weighed according to the molar ratio of 3:1:1:1, and placed in an agate mortar; the agate pestle was used to grind for 20 min, and the ground precursor powders were added to a zirconia ball mill jar, and the mass ratio of balls to materials in the ball mill jar was 100:1; the ball mill jar was transferred to a ball mill, and ball milled at a speed of 900 rpm for 48 h, and then naturally cooled to room temperature to obtain a powder of Al6TaNb2S2Br4Cl5O9 oxyhalide solid electrolyte. The ionic conductivity of the electrolyte was 1.26×10 -3 S cm -1 .

[0039] Example 6

[0040] This example provides a metal and non-metal element co-doped oxyhalide solid electrolyte Na 3.2 Ta 0.8 Ge 0.2 S 0.2 Cl 4.4 O 1.6 , and the specific preparation method is as follows:

[0041] In an Ar atmosphere glove box, Na2O, TaCl5, GeCl4, GeS2 precursor powders were weighed according to the molar ratio of 1.6:0.8:0.1:0.1, and placed in an agate mortar; the agate pestle was used to grind for 20 min, and the ground precursor powders were added to a zirconia ball mill jar, and the mass ratio of balls to materials in the ball mill jar was 100:1; the ball mill jar was transferred to a ball mill, and ball milled at a speed of 900 rpm for 48 h, and then naturally cooled to room temperature to obtain a powder of Na 3.2 Ta 0.8 Ge 0.2 S 0.2 Cl 4.4 O 1.6 oxyhalide solid electrolyte. The ionic conductivity of the electrolyte was 2.54×10 -3 S cm -1 .

[0042] Example 7

[0043] This example provides a metal and non-metal element co-doped oxyhalide solid electrolyte Fe 1.6 Ta 0.8 Y 0.3 S 0.3 I 0.3 Cl4O 1.6 , and the specific preparation method is as follows:

[0044] In an Ar atmosphere glove box, FeO, TaCl5, YI3, Y2S3 precursor powders were weighed according to the molar ratio of 1.6:0.8:0.1:0.1, and placed in a agate mortar; the agate pestle was used to grind for 20 min, and the ground precursor powders were added to a zirconia ball mill jar, and the mass ratio of ball to material in the ball mill jar was 120:1; the ball mill jar was transferred to a ball mill, and ball milled at a speed of 1000 rpm for 48 h, and then naturally cooled to room temperature, to obtain a powder of Fe 1.6 Ta 0.8 Y 0.3 S 0.3 I 0.3 Cl4O 1.6 halide oxyhalide solid electrolyte. The ionic conductivity of the electrolyte is 1.08 x 10 -3 S cm -1 .

[0045] Example 8

[0046] This example provides a metal and non-metal element co-doped halide oxyhalide solid electrolyte Mg 3.2 Ta 0.8 In 0.3 Te 0.3 F 0.3 Cl4O 3.2 , and the specific preparation method is as shown below:

[0047] In an Ar atmosphere glove box, MgO, TaCl5, InF3, In2Te3 precursor powders were weighed according to the molar ratio of 3.2:0.8:0.1:0.1, and placed in a agate mortar; the agate pestle was used to grind for 20 min, and the ground precursor powders were added to a zirconia ball mill jar, and the mass ratio of ball to material in the ball mill jar was 120:1; the ball mill jar was transferred to a ball mill, and ball milled at a speed of 1000 rpm for 36 h, and then naturally cooled to room temperature, to obtain a powder of Mg 3.2 Ta 0.8 In 0.3 Te 0.3 F 0.3 Cl4O 3.2 halide oxyhalide solid electrolyte. The ionic conductivity of the electrolyte is 1.49 x 10 -3 S cm -1 .

[0048] Example 9

[0049] This example provides a metal and non-metal element co-doped halide oxyhalide solid electrolyte K 1.6 Ta 0.8 Pb 0.2 Se 0.1 Cl 4.2O 1.6 The specific preparation method is as shown below:

[0050] In an Ar atmosphere glove box, KOH, TaCl5, PbCl2, and PbSe precursor powders were weighed according to a molar ratio of 1.6:0.8:0.1:0.1, and were placed in a agate mortar. A pestle was used to grind for 20 min. The ground precursor powders were added to a zirconia ball mill jar, and the mass ratio of balls to materials in the ball mill jar was 100:1. The ball mill jar was transferred to a ball mill, and was ball milled at a speed of 900 rpm for 48 h. After natural cooling to room temperature, a powder of KTa2Pb2Pb2Se2O12 was prepared. 1.6 Ta 0.8 Pb 0.2 Se 0.1 Cl 4.2 O 1.6 The ionic conductivity of the electrolyte was 1.69 x 10 -3 S cm -1 .

[0051] Example 10

[0052] This example provides a halide oxyride solid electrolyte Ca4Ta2Sb 0.75 Te 0.75 Cl 10 O4 that is co-doped with metal and non-metal elements. The specific preparation method is as shown below:

[0053] In an Ar atmosphere glove box, CaO, TaCl5, SbCl3, and Sb2Te3 precursor powders were weighed according to a molar ratio of 4:2:0.25:0.25, and were placed in a agate mortar. A pestle was used to grind for 20 min. The ground precursor powders were added to a zirconia ball mill jar, and the mass ratio of balls to materials in the ball mill jar was 160:1. The ball mill jar was transferred to a ball mill, and was ball milled at a speed of 900 rpm for 48 h. After natural cooling to room temperature, a powder of Ca4Ta2Sb 0.75 Te 0.75 Cl 10 O4 halide oxyride solid electrolyte was prepared. The ionic conductivity of the electrolyte was 1.04 x 10 -3 S cm -1 .

[0054] Example 11

[0055] This example provides a halide oxyride solid electrolyte Li 6.4 Ta 0.8 Cs 0.3 S 0.1 Cl 4.1 O 3.2, the specific preparation method is as follows:

[0056] Li2O, TaCl5, CsCl, and Cs2S precursor powders were weighed in a molar ratio of 3.2:0.8:0.1:0.1 in an Ar atmosphere glove box and placed in an agate mortar. The ground precursor powders were hand-milled with an agate pestle for 20 min and added to a zirconia ball mill with a ball-to-material mass ratio of 120:1. The ball mill was transferred to a ball mill and milled at 1000 rpm for 36 h. The powder was then cooled to room temperature to obtain powdered Li 6.4 Ta 0.8 Cs 0.3 S 0.1 Cl 4.1 O 3.2 Oxyhalide solid electrolyte. The ionic conductivity of this electrolyte is 6.49×10 -3 S cm -1 .

[0057] Example 12

[0058] This embodiment provides a metal and non-metal element co-doped oxyhalide solid electrolyte Li 3.2 Ta 0.8 Fe 0.3 S 0.3 Cl 4.3 O 1.6 , the specific preparation method is as follows:

[0059] Li2O, TaCl5, FeCl3, and Fe2S3 precursor powders were weighed in a molar ratio of 1.6:0.8:0.1:0.1 in an Ar atmosphere glove box and placed in an agate mortar. The ground precursor powders were hand-milled with an agate pestle for 20 min and added to a zirconia ball mill with a ball-to-material mass ratio of 100:1. The ball mill was transferred to a ball mill and milled at 900 rpm for 48 h. The powder was then cooled to room temperature to obtain powdered Li 3.2 Ta 0.8 Fe 0.3 S 0.3 Cl 4.3 O 1.6 Oxyhalide solid electrolyte. The ionic conductivity of this electrolyte is 6.54×10 -3 S cm -1 .

[0060] Performance Testing

[0061] like Figure 1 As shown, the sample Li8Ta2Hf3Te4Cl obtained in Example 1 14XRD data of O4 shows that the material bulk is amorphous.

[0062] As shown in Figure 2 Figure 1, the sample Li8Ta2Hf3Te4Cl 14 O4 has an ionic conductivity of up to 11 x 10 -3 S cm -1 .

[0063] As shown in Figure 3 Figure 3, the sample Li8Ta2Bi4S3Cl 16 O4 has an ionic conductivity of up to 7.42 x 10 -3 S cm -1 .

[0064] As shown in Figure 4 Figure 4, a full cell was assembled using the Li8Ta2Hf3Te4Cl 14 O4 electrolyte obtained from Example 1. A LiNi 0.8 Co 0.1 Mn 0.1 O2 cathode; Li8TaHfCl9O4 and Li6PS5Cl as electrolyte; Li-In alloy as anode was used for charge-discharge test at 0.2C rate. The full cell exhibits high specific capacity due to the fact that the Li8TaHfCl9O4 electrolyte synthesized by the synthesis method mentioned in the present application exhibits an amorphous phase. The long-range structure with disorder has a large amount of free volume, which provides a transport channel for Li+diffusion; and the ion transport is not hindered by the grain boundary. Thus, the ion transport inside the battery is ensured, and high specific capacity is exhibited.

[0065] As shown in Figure 5 Figure 3, the sample Li8Ta2Bi4S3Cl 16 O4 has very low electronic conductivity, indicating that it is a good ionic conductor.

[0066] Table 1: Summary of test results

[0067]

[0068]

[0069] Those skilled in the art will readily understand that the above description is only preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A metal and non-metallic element co-doped oxyhalide solid electrolyte, characterized in that: The chemical general formula of the metal and non-metal co-doped oxyhalide solid electrolyte is X 2a Ta b M c+2d N md Y 5b+mc O ax ; where X is selected from one of Li, Na, K, Ca, Mg, Zn, Al, Fe; M is selected from one or more of Cs, Nb, Hf, La, Y, Fe, Ga, In, Pb, Bi, Ge, Sb; N is selected from one or more of S, Se, Te; Y is selected from one of F, Cl, Br, I; the value ranges of a, b, c, d are: 0 < a ≤ 4, 0 < b ≤ 2, 0 < c ≤ 2, 0 < d ≤ 2; x and m are the numerical values of the valence of element X and element M respectively.

2. The metal and non-metal element co-doped oxyhalide solid electrolyte according to claim 1, characterized in that: The metal and non-metal element co-doped oxyhalide solid electrolyte is in powder form.

3. The metal and non-metal element co-doped oxyhalide solid electrolyte according to claim 1, characterized in that: The particle size of the oxyhalide solid electrolyte co-doped with metal and non-metal elements is 1 nm-100 μm.

4. A method for preparing a metal and non-metallic element co-doped oxyhalide solid electrolyte according to any one of claims 1 to 3, characterized in that: In a protective gas atmosphere, the precursor X2O x 、TaY5、MY m 、M2N m After mixing and grinding according to the molar ratio of a:b:c:d, ball milling is performed to obtain the halide oxide solid electrolyte co-doped with the metal and non-metal elements; wherein X is selected from one of Li, Na, K, Ca, Mg, Zn, Al, and Fe; M is selected from one or more of Cs, Nb, Hf, La, Y, Fe, Ga, In, Pb, Bi, Ge, and Sb; N is selected from one or more of S, Se, and Te; Y is selected from one or more of F, Cl, Br, and I; and x and m are the valence values ​​of the X element and the M element, respectively.

5. The preparation method according to claim 4, characterized in that The ball-to-material mass ratio of the ball mill is 5:1-200:

1.

6. The preparation method according to claim 4, characterized in that The ball milling speed is 100-2000 rpm, and the ball milling time is 1 h-48 h.

7. Use of the metal and non-metallic element co-doped oxyhalide solid electrolyte according to any one of claims 1 to 3 in an all-solid-state battery.

8. An all-solid-state battery comprising a solid electrolyte layer, characterized in that: The solid electrolyte layer comprises the oxyhalide solid electrolyte co-doped with a metal and a non-metallic element according to any one of claims 1 to 3.

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