CN118833828A - Powder material with spherical particles and preparation method thereof - Google Patents

Abstract

The present application discloses a powder material with spherical particles and a preparation method thereof. The chemical formula of the powder material is Li _a M _b N _c R _d P _e T _f O _g ; wherein M is selected from at least one of In, Sc, B, Ga, Nb, Y, Zr, Al, Ni, Co, Mn, Mg, Ca, Sr, Cu, Zn, Fe, Na, and K; wherein N is selected from at least one of Ti, Zr, Hf, Si, Ge, and Sn; wherein R is at least one of Nb, Ti, Zr, Hf, As, Sb, Si, Ge, and Sn, but is different from N; wherein T is selected from at least one of S, Se, N, F, Cl, Br, and I. The primary particles and/or secondary particles of the powder material are spheroids; the spheroids have a first short axis, a second short axis and a long axis; the long axis is perpendicular to the plane where the first short axis and the second short axis are located; the dimensions of the spheroid at the first short axis, the second short axis and the long axis are x, y, and z, respectively, wherein 1≤z/x＜2, 1≤z/y＜2. The benefit of the present application is that it provides a powder material with spherical particles and a preparation method thereof that can improve the storage performance of the powder and thus improve the performance.

Description

Powder material with spherical particles and preparation method thereof

Technical Field

The present application relates to the technical field of new energy materials, and in particular to a powder material with spherical particles and a preparation method thereof.

Background Art

In the related technologies of new energy batteries, the use of lithium-containing powder materials to coat, blend, and coat the positive and negative active materials; or the use of powder materials to coat the separator and primer the current collector can greatly improve the compaction density of the positive and negative electrodes. The more commonly used lithium-containing powder materials include LATP, LLZO, LLZTO, etc.

However, when these lithium-containing powder materials are used in specific applications, they may be affected by the environment during storage, which may have unpredictable effects on the powder properties and the electrochemical properties after being finally applied to new energy batteries.

Summary of the invention

In view of this, the present application provides a powder material with spherical particles and a preparation method thereof, aiming to improve the existing problems.

The embodiment of the present application is implemented as follows: a powder material with spherical particles, the chemical formula of the powder material is Li _a M _b N _c R _d P _e T _f O _g ;

Wherein, M is selected from at least one of In, Sc, B, Ga, Nb, Y, Zr, Al, Ni, Co, Mn, Mg, Ca, Sr, Cu, Zn, Fe, Na, and K;

Wherein, N is selected from at least one of Ti, Zr, Hf, Si, Ge, and Sn;

Wherein, R is at least one of Nb, Ti, Zr, Hf, As, Sb, Si, Ge and Sn, but is different from N; wherein, T is S, Se, N, F, Cl, Br and I.

The primary particles and/or secondary particles of the powder material are spheroids; the spheroids have a first short axis, a second short axis and a long axis; the long axis is perpendicular to the plane where the first short axis and the second short axis are located; the dimensions of the spheroids at the first short axis, the second short axis and the long axis are x, y, z, respectively, wherein 1≤z/x＜2, 1≤z/y＜2.

Optionally, in some embodiments of the present application, the dimension z of the spheroid on the major axis is in the range of 0.01 μm ≤ z ≤ 100 μm.

Optionally, in some embodiments of the present application, the dimension x of the spheroid at the first short axis is in the range of 0.01 μm≤x≤100 μm.

Optionally, in some embodiments of the present application, the dimension y of the spheroid at the second short axis is in the range of 0.01 μm≤y≤100 μm.

Optionally, in some embodiments of the present application, the dimension z of the spheroid at the major axis is in the range of 0.014μm≤z≤32μm; the dimension x of the spheroid at the first minor axis is in the range of 0.014μm≤x≤32μm; the dimension y of the spheroid at the second minor axis is in the range of 0.014μm≤y≤32μm.

Optionally, in some embodiments of the present application, the dimension z of the spheroid at the major axis is in the range of 0.014μm≤x≤11μm; the dimension x of the spheroid at the first minor axis is in the range of 0.014μm≤x≤11μm; the dimension y of the spheroid at the second minor axis is in the range of 0.014μm≤x≤11μm.

Optionally, in some embodiments of the present application, the average particle size of the powder material ranges from 0.1 to 30 μm.

Optionally, in some embodiments of the present application, in Li _a M _b N _c R _d P _e T _f O _g , 1＜a≤6, 0＜b＜1, 0＜c＜2, 0＜d＜3, 0＜e＜3, 0＜f＜8, 0＜g＜12.

Optionally, in some embodiments of the present application, the ionic conductivity of the powder material is in the range of 10E ^-6 to 5E ^-2 S/cm.

Accordingly, the present invention also provides a preparation method, comprising the following steps:

Step 1: providing raw materials to be mixed corresponding to each element according to the chemical formula of the powder material: Li _a M b _{N c} R _d P _e T _f O _g ;

Step 2: Mixing the multiple raw materials to be mixed provided in step 1 to obtain a precursor material;

Step 3: heat-treating the precursor material obtained in step 2 to obtain a heat-treated product;

Step 4: crushing, ball milling, drying and sieving the heat-treated product obtained in step 3 to obtain the powder material;

Wherein, M is selected from at least one of In, Sc, B, Ga, Nb, Y, Zr, Al, Ni, Co, Mn, Mg, Ca, Sr, Cu, Zn, Fe, Na, and K;

Wherein, N is selected from at least one of Ti, Zr, Hf, Si, Ge, and Sn;

wherein R is at least one of Nb, Ti, Zr, Hf, As, Sb, Si, Ge and Sn, but is different from N; wherein T is S, Se, N, F, Cl, Br and I;

Among them, the primary particles and/or secondary particles of the powder material are spheroids; the spheroids have a first short axis, a second short axis and a long axis; the long axis is perpendicular to the plane where the first short axis and the second short axis are located; the dimensions of the spheroids at the first short axis, the second short axis and the long axis are x, y, z, respectively, wherein 1≤z/x＜2, 1≤z/y＜2.

The benefit of the present application lies in that it provides a powder material with spherical particles and a preparation method thereof, which can improve the storage performance of the powder and thus improve the performance.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without paying any creative work.

FIG1 is a SEM image of a 30 μm-micron-grade powder material provided by the present application;

FIG2 is a SEM image of a 350 nm-nanoscale powder material provided in Example 1 of the present application;

FIG3 is a SEM image of a 30 nm-nanoscale powder material provided by the present application;

FIG4 is a schematic diagram of various defined axes of a powder material provided in an embodiment of the present application;

FIG. 5 is a schematic diagram of a preparation method provided in an embodiment of the present application.

DETAILED DESCRIPTION

The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without making creative work belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation methods described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and/or" used herein includes any and all combinations of one or more related listed items.

In this application, unless otherwise stated, directional words such as "upper" and "lower" generally refer to the upper and lower parts of the device in actual use or working state, specifically the drawing direction in the accompanying drawings; while "inner" and "outer" refer to the outline of the device. In addition, in the description of this application, the term "including" means "including but not limited to". The terms first, second, third, etc. are used only as labels and do not impose numerical requirements or establish an order.

In this application, "and/or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and/or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

In the present application, "at least one" means one or more, and "plurality" means two or more. "One or more", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, where a, b, c can be single or multiple, respectively.

In the present application, when a layer is formed "on" another layer, the so-called "on" is a broad concept, which may indicate that the formed another layer is adjacent to the certain layer, or may indicate that there are other spacing structural layers between the another layer and the certain layer. For example, when a second electrode is formed "on" the first carrier functional layer, the so-called "on" may indicate that the formed second electrode is adjacent to the first carrier functional layer, or may indicate that there are other spacing structural layers between the second electrode and the first carrier functional layer, such as a light-emitting layer.

Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present application; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values within the range. For example, the range description from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

The technical solution of this application is as follows:

In a first aspect, an embodiment of the present application provides a hydrophobic powder material, wherein the chemical formula of the hydrophobic powder material is Li _a M _b N _c R _d P _e T _f O _g ; wherein M is selected from at least one of In, Sc, B, Ga, Nb, Y, Zr, Al, Ni, Co, Mn, Mg, Ca, Sr, Cu, Zn, Fe, Na, and K; wherein N is selected from at least one of Ti, Zr, Hf, Si, Ge, and Sn; wherein d/(b+c+d+e) is defined as a first metrological characteristic value A; and f/(f+g) is defined as a second metrological characteristic value B; the value range of the first metrological characteristic value A is 0.005＜A≤0.6; and the value range of the second metrological characteristic value B is 0.001＜B≤0.4.

Based on the above scheme, the primary particles or secondary particles of the powder material of the present application have a spherical shape, so that the powder material of the present application has good hydrophobicity, which can improve the powder performance of the powder material of the present application and the electrochemical performance when specifically applied to secondary batteries. Among them, the content of T will affect the contact angle of the powder material of the present application to water and electrolyte; therefore, it is necessary to set the content of T in a more appropriate range to take into account the hydrophobicity and the performance of being wetted by the electrolyte (electrolyte affinity performance).

Optionally, the value range of the first metrological characteristic value A is 0.015≤A≤0.2; the value range of the second metrological characteristic value B is 0.005＜B≤0.35.

Optionally, the value range of the first metrological characteristic value A is 0.015＜A≤0.6; the value range of the second metrological characteristic value B is 0.005＜B≤0.4.

In some embodiments of the present application, in Li _a M _b N _c R _d P _e T _f O _g , 1＜a≤6, 0＜b＜1, 0＜c＜2, 0＜d＜3, 0＜e＜3, 0＜f＜8, and 0＜g＜12.

In some embodiments of the present application, the primary particles and/or secondary particles of the powder material are spheroids; the spheroids have a first short axis, a second short axis and a long axis; the long axis is perpendicular to the plane where the first short axis and the second short axis are located; the dimensions of the spheroids at the first short axis, the second short axis and the long axis are x, y, z, respectively, wherein 1≤z/x＜2, 1≤z/y＜2.

In some embodiments of the present application, the dimension z of the spheroid on the major axis ranges from 0.01 μm ≤ z ≤ 100 μm.

In some embodiments of the present application, the dimension x of the spheroid at the first minor axis ranges from 0.01 μm ≤ x ≤ 100 μm.

In some embodiments of the present application, the dimension y of the spheroid at the second minor axis ranges from 0.01 μm ≤ y ≤ 100 μm.

In some embodiments of the present application, the dimension z of the spheroid at the major axis is in the range of 0.014μm≤z≤32μm; the dimension x of the spheroid at the first minor axis is in the range of 0.014μm≤x≤32μm; the dimension y of the spheroid at the second minor axis is in the range of 0.014μm≤y≤32μm.

Optionally, in some embodiments of the present application, the dimension z of the spheroid at the major axis is in the range of 0.014μm≤z≤11μm; the dimension x of the spheroid at the first minor axis is in the range of 0.014μm≤x≤11μm; the dimension y of the spheroid at the second minor axis is in the range of 0.014μm≤y≤11μm.

Optionally, in some embodiments of the present application, the average particle size of the powder material ranges from 0.1 to 30 μm.

Optionally, in some embodiments of the present application, the ionic conductivity of the powder material is in the range of 10E ^-6 to 5E ^-2 S/cm.

Furthermore, the ionic conductivity of the powder material ranges from 10E ^-6 to 5E ^-3 S/cm.

In a second aspect, the present invention also provides a preparation method, which specifically comprises the following steps:

S101: _{providing raw} materials to be mixed corresponding _to each _element according to the chemical formula of the powder material _{: LiaMbNcRdPeTfOg .}

S102: Mix the multiple raw materials to be mixed provided in step S101 to obtain a precursor material.

S103: heat-treating the precursor material obtained in step S102 to obtain a heat-treated product.

S104: crushing, ball milling, drying and sieving the heat-treated product obtained in step S103 to obtain the powder material.

Wherein, M is selected from at least one of In, Sc, B, Ga, Nb, Y, Zr, Al, Ni, Co, Mn, Mg, Ca, Sr, Cu, Zn, Fe, Na, and K;

Wherein, N is selected from at least one of Ti, Zr, Hf, Si, Ge, and Sn;

Wherein, d/(b+c+d+e) is defined as the first metrological characteristic value A; f/(f+g) is defined as the second metrological characteristic value B;

The value range of the first metrological characteristic value A is 0.005＜A≤0.6; the value range of the second metrological characteristic value B is 0.001＜B≤0.4.

Optionally, in some embodiments of the present application, the raw materials in step S101 may be: Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ , SiO ₂ , NH ₄ H ₂ PO ₄ , LiF, wherein LiOH (or Li ₂ CO ₃ ) needs to be configured in excess of 15 wt % according to the mass calculated by stoichiometry of the chemical formula.

Optionally, in some embodiments of the present application, the specific method of step S102 is:

The raw materials to be mixed are added to the dispersant in a certain order, and then fully mixed by wet grinding. After the wet grinding and mixing are completed, drying is carried out.

Wherein, as an optional solution, the dispersant used for wet grinding mixing is selected from one or more of ethanol, propanol, isopropanol, butanol, water, NMP, DMF and acetone.

Among them, as an optional solution, specific methods of wet grinding and mixing include but are not limited to ball milling, sand milling, high-speed dispersion, liquid phase spraying, ultrasonic vibration, and electrostatic spinning.

Among them, as an optional scheme, specific methods of drying treatment include but are not limited to oven drying, belt drying, microwave drying, rotary evaporator, freeze drying, centrifugal drying, and single cone drying.

Optionally, in some embodiments of the present application, the temperature range of the heat treatment in step S103 is 300-1000°C.

Optionally, in some embodiments of the present application, the time range of the heat treatment in step S103 is 4 to 12 hours.

Optionally, in some embodiments of the present application, the heating rate of the heat treatment in step S103 is in the range of 1 to 10° C./min.

Optionally, in some embodiments of the present application, the equipment used for the crushing process in step S104 includes but is not limited to a jaw crusher, a ball mill, a sand mill, and a gas crusher. As an optional solution, the crushing process can be performed twice or more.

In a third aspect, an embodiment of the present application further provides a battery, comprising: a positive electrode, a negative electrode, a separator and an electrolyte; wherein at least one of the positive electrode, the negative electrode and the separator contains the aforementioned hydrophobic powder material.

Through the above scheme, the hydrophobic powder material of the present application, when used in positive and negative electrode coating, blending, positive and negative electrode plate coating, diaphragm coating and current collector primer coating, in addition to being able to improve the compaction density of the positive and negative electrodes, has good hydrophobic properties and electrolyte affinity properties after element doping.

The spherical morphology and lithium-rich structure of the microscopic particles of the hydrophobic powder material of the present application can improve the electrochemical performance when applied to the electrode.

When the hydrophobic powder material of the present application is used to form a liquid, semi-solid or all-solid-state battery, it can reduce the electrolyte content and reduce side reactions to obtain better safety performance (increasing the temperature and time of the hot box, and improving the needle puncture pass rate) and better electrochemical performance (specific capacity, first efficiency, retention rate, energy density).

The present application is further described below in conjunction with specific embodiments of the present application.

Example 1

Chemical formula: Li _4.3 Al _0.4 Ti _1.6 Si _2.9 P _0.1 F _1.26 O _11.37 .

The first metrological characteristic value A=0.1; the second metrological characteristic value B=0.1.

Raw materials: Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ , SiO ₂ , NH ₄ H ₂ PO ₄ and LiF, wherein LiOH needs to be configured in excess of 15 wt % according to the mass calculated by the chemical formula.

Preparation method:

Step 1: Provide the above raw materials.

Step 2: Mix the raw materials using a VC mixer (20L, rotation speed 50HZ).

Step 3: Place the mixed raw materials in a sintering furnace and keep them at 900°C for 12 hours with a heating rate of 3°C/min; after the insulation is completed, allow the product to cool naturally.

Step 4: Use a jaw crusher (100kg material is continuously processed for 1h) to crush the product cooled in step 3. After the crushing is completed, alcohol is added to prepare a slurry with a certain solid content, and a slurry of 350nm is obtained by a ball mill (50L, main engine speed 50HZ) and a sand mill (5L, spindle speed 2000r/min). The slurry is then placed in an oven (100L blast oven, constant temperature 200°C) to dry the intermediate product, and finally a jaw crusher (100kg material is continuously processed for 1h) is used to crush the final product again, i.e., the hydrophobic powder material of the present application.

Example 2

The difference from Example 1 is:

Chemical formula: Li _3.9 Al _0.4 Ti _1.6 Si _2.5 P _0.5 F _1.26 O _11.37 .

The first metrological characteristic value A=0.5; the second metrological characteristic value B=0.1.

Example 3

The difference from Example 1 is:

Chemical formula: Li _3.4 Al _0.4 Ti _1.6 Si ₂ P ₁ F _1.26 O _11.37 .

The first metrological characteristic value A=0.4; the second metrological characteristic value B=0.1.

Example 4

The difference from Example 1 is:

Chemical formula: Li _2.9 Al _0.4 Ti _1.6 Si _1.5 P _1.5 F _1.26 O _11.37 .

The first metrological characteristic value A=0.3; the second metrological characteristic value B=0.1.

Example 5

The difference from Example 1 is:

Chemical formula: Li _2.4 Al _0.4 Ti _1.6 Si ₁ P ₂ F _1.26 O _11.37 .

The first metrological characteristic value A=0.2; the second metrological characteristic value B=0.1.

Example 6

The difference from Example 1 is:

Chemical formula: Li _1.9 Al _0.4 Ti _1.6 Si _0.5 P _2.5 F _1.26 O _11.37 .

The first metrological characteristic value A=0.1; the second metrological characteristic value B=0.1.

Example 7

The difference from Example 1 is:

Chemical formula: Li _1.46 Al _0.4 Ti _1.6 Si _0.06 P _2.94 F _1.26 O _11.37. The first stoichiometric characteristic value A=0.012; the second stoichiometric characteristic value B=0.1.

Example 8

The difference from Example 1 is:

Chemical formula: Li _1.46 Al _0.4 Ti _1.6 Si _0.06 P ₂₉₄ F _0.06 O _11.97

The first metrological characteristic value A=0.012; the second metrological characteristic value B=0.005.

Example 9

The difference from Example 1 is:

Chemical formula: Li _1.9 Al _0.4 Ti _1.6 Si _0.5 P _2.5 F _0.06 O _11.97 .

The first metrological characteristic value A=0.1; the second metrological characteristic value B=0.005.

Example 10

The difference from Example 1 is:

Chemical formula: Li _1.9 Al _0.4 Ti _1.6 Si _0.5 P _2.5 F _2.67 O _10.67 .

The first metrological characteristic value A=0.1; the second metrological characteristic value B=0.2.

Embodiment 11

The difference of Example 1 is:

Chemical formula: Li _1.9 Al _0.4 Ti _1.6 Si _0.5 P _2.5 F _4.24 O _9.88 .

The first metrological characteristic value A=0.1; the second metrological characteristic value B=0.3.

Example 12

The difference of Example 1 is:

Chemical formula: Li _1.9 Al _0.4 Ti _1.6 Si _0.5 P _2.5 F ₆ O ₉ .

The first metrological characteristic value A=0.1; the second metrological characteristic value B=0.4.

Example 13

The difference of Example 1 is:

Chemical formula: Li _2.4 Al _0.4 Ti _1.6 Si ₁ P ₂ F _0.06 O _11.97 .

The first metrological characteristic value A=0.2; the second metrological characteristic value B=0.005.

Embodiment 14

The difference of Example 1 is:

Chemical formula: Li _2.4 Al _0.4 Ti _1.6 Si ₁ P ₂ F _2.67 O _10.67 .

The first metrological characteristic value A=0.2; the second metrological characteristic value B=0.2.

Embodiment 15

The difference of Example 1 is:

Chemical formula: Li _2.4 Al _0.4 Ti _1.6 Si ₁ P ₂ F _4.24 O _9.88 .

The first metrological characteristic value A=0.2; the second metrological characteristic value B=0.3.

Example 16

The difference of Example 1 is:

Chemical formula: Li _2.4 Al _0.4 Ti _1.6 Si ₁ P ₂ F ₆ O ₉ .

The first metrological characteristic value A=0.2; the second metrological characteristic value B=0.4.

Embodiment 17

The difference of Example 1 is:

Chemical formula: Li _2.9 Al _0.4 Ti _1.6 Si _1.5 P _1.5 F _0.06 O _11.97 .

The first metrological characteristic value A=0.3; the second metrological characteristic value B=0.005.

Embodiment 18

The difference of Example 1 is:

Chemical formula: Li _2.9 Al _0.4 Ti _1.6 Si _1.5 P _1.5 F _2.67 O _10.67 .

The first metrological characteristic value A=0.3; the second metrological characteristic value B=0.2.

Embodiment 19

The difference of Example 1 is:

Chemical formula: Li _2.9 Al _0.4 Ti _1.6 Si _1.5 P _1.5 F _4.24 O _9.88 .

The first metrological characteristic value A=0.3; the second metrological characteristic value B=0.3.

Embodiment 20

The difference of Example 1 is:

Chemical formula: Li _2.9 Al _0.4 Ti _1.6 Si _1.5 P _1.5 F ₆ O ₉ .

The first metrological characteristic value A=0.3; the second metrological characteristic value B=0.4.

Embodiment 21

The difference of Example 1 is:

Chemical formula: Li _2.4 Al _0.4 Ti _1.6 Si ₁ P ₂ F _0.06 O _11.97 .

The first metrological characteristic value A=0.4; the second metrological characteristic value B=0.005.

Embodiment 22

The difference of Example 1 is:

Chemical formula: Li _3.4 Al _0.4 Ti _1.6 Si ₂ P ₁ F _2.67 O _10.67 .

The first metrological characteristic value A=0.4; the second metrological characteristic value B=0.2.

Embodiment 23

The difference of Example 1 is:

Chemical formula: Li _3.4 Al _0.4 Ti _1.6 Si ₂ P ₁ F _4.24 O _9.88 .

The first metrological characteristic value A=0.4; the second metrological characteristic value B=0.3.

Embodiment 24

The difference of Example 1 is:

Chemical formula: Li _3.4 Al _0.4 Ti _1.6 Si ₂ P ₁ F ₆ O ₉ .

The first metrological characteristic value A=0.4; the second metrological characteristic value B=0.4.

Embodiment 25

The difference of Example 1 is:

Chemical formula: Li _3.9 Al _0.4 Ti _1.6 Si _2.5 P _0.5 F _0.06 O _11.97 .

The first metrological characteristic value A=0.5; the second metrological characteristic value B=0.005.

Embodiment 26

The difference of Example 1 is:

Chemical formula: Li _3.9 Al _0.4 Ti _1.6 Si _2.5 P _0.5 F _2.67 O _10.67 .

The first metrological characteristic value A=0.5; the second metrological characteristic value B=0.2.

Embodiment 27

The difference of Example 1 is:

Chemical formula: Li _3.9 Al _0.4 Ti _1.6 Si _2.5 P _0.5 F _4.24 O _9.88 .

The first metrological characteristic value A=0.5; the second metrological characteristic value B=0.3.

Embodiment 28

The difference of Example 1 is:

Chemical formula: Li _3.9 Al _0.4 Ti _1.6 Si _2.5 P _0.5 F ₆ O ₉ .

The first metrological characteristic value A=0.5; the second metrological characteristic value B=0.4.

Embodiment 29

The difference of Example 1 is:

Chemical formula: Li _1.9 Al _0.4 Ti _1.6 Si _0.5 P _2.5 Cl _1.26 O _11.37 .

The first metrological characteristic value A=0.1; the second metrological characteristic value B=0.1.

Embodiment 30

The difference of Example 1 is:

Chemical formula: Li _1.9 Al _0.4 Ge _1.6 Si _0.5 P _2.5 F _1.26 O _11.37 .

The first metrological characteristic value A=0.1; the second metrological characteristic value B=0.1.

Embodiment 31

The difference from Example 1 is:

Chemical formula: Li _1.9 Al _0.4 Ti _1.6 Si _0.5 P _2.5 F _1.26 O _11.37 .

The first metrological characteristic value A=0.1; the second metrological characteristic value B=0.1.

Embodiment 32

The difference from Example 1 is:

Chemical formula: Li _1.9 Al _0.4 Ti _1.6 Si _0.5 P _2.5 F _1.26 O _11.37 .

The first metrological characteristic value A=0.1; the second metrological characteristic value B=0.1.

Embodiment 33

The difference from Example 1 is:

Chemical formula: Li _1.9 Al _0.4 Ti _1.6 Si _0.5 P _2.5 F _1.26 O _11.37 .

The first metrological characteristic value A=0.1; the second metrological characteristic value B=0.1.

Embodiment 34

The difference from Example 1 is:

Chemical formula: Li _1.9 Al _0.4 Ti _1.6 Si _0.5 P _2.5 F _1.26 O _11.37 .

The first metrological characteristic value A=0.1; the second metrological characteristic value B=0.1.

Embodiment 35

The difference from Example 1 is:

Chemical formula: Li _1.9 Al _0.4 Ti _1.6 Si _0.5 P _2.5 F _1.26 O _11.37 .

The first metrological characteristic value A=0.1; the second metrological characteristic value B=0.1.

Embodiment 36

The difference from Example 1 is:

Chemical formula: Li _1.9 Al _0.4 Ti _1.6 Si _0.5 P _2.5 F _1.26 O _11.37 .

The first metrological characteristic value A=0.1; the second metrological characteristic value B=0.1.

Comparative Example 1

The difference from Example 1 is:

Chemical formula: Li _4.3 Al _0.4 Ti _1.6 Si _2.9 P _0.1 O ₁₂ .

The first metrological characteristic value A=0.59; the second metrological characteristic value B=0.

Comparative Example 2

The difference from Example 1 is:

Chemical formula: Li _1.9 Al _0.4 Ti _1.6 Si _0.5 P _2.5 O ₁₂ .

The first metrological characteristic value A=0.1; the second metrological characteristic value B=0.

Comparative Example 3

The difference from Example 1 is:

Chemical formula: Li _1.4 Al _0.4 Ti _1.6 P ₃ F ₆ O ₉ .

The first metrological characteristic value A=0; the second metrological characteristic value B=0.4.

Comparative Example 4

The difference from Example 1 is:

Chemical formula: Li _1.4 Al _0.4 Ti _1.6 P ₃ F _1.26 O _11.37 .

The first metrological characteristic value A=0; the second metrological characteristic value B=0.1.

Comparative Example 5

The difference from Example 1 is:

Chemical formula: Li _1.4 Al _0.4 Ti _1.6 P ₃ O ₁₂ .

The first metrological characteristic value A=0; the second metrological characteristic value B=0.

Comparative Example 6

The powder material with the chemical formula of Li _1.4 Al _0.4 Ti _1.6 P ₃ O ₁₂ is directly used, that is, A=0, B=0.

Comparative Example 7

The powder material with the chemical formula of Li _1.4 Al _0.4 Ti _1.6 P ₃ O ₁₂ is directly used, that is, A=0, B=0.

Comparative Example 8

The powder material with the chemical formula of Li _1.4 Al _0.4 Ti _1.6 P ₃ O ₁₂ is directly used, that is, A=0, B=0.

Comparative Example 9

The powder material with the chemical formula of Li _1.4 Al _0.4 Ti _1.6 P ₃ O ₁₂ is directly used, that is, A=0, B=0.

Comparative Example 10

The powder material with the chemical formula of Li _1.4 Al _0.4 Ti _1.6 P ₃ O ₁₂ is directly used, that is, A=0, B=0.

Comparative Example 11

The powder material with the chemical formula of Li _1.4 Al _0.4 Ti _1.6 P ₃ O ₁₂ is directly used, that is, A=0, B=0.

Comparative Example 12

No LATP was added, that is, the LATP addition amount was 0%, while the nano-alumina addition amount was 1%, and the positive electrode was M94.

The physicochemical properties of the powders of Examples 1 to 36 and Comparative Examples 1 to 12 were tested:

The above powder materials were placed in a 300°C box furnace (100L, high temperature oven, the maximum temperature can reach 1200°C) for 12 hours to remove water, and then the morphology (statistics of z/x, z/y), XRD, ionic conductivity, water absorption, and specific surface area were detected.

Among them, the powder materials with a median particle size (D50) of 350nm of the above-mentioned embodiments 1 to 30 and comparative examples 1 to 5 are mixed in the positive electrode at a ratio of 1% (wherein the ratio of the ternary materials M94, LMNSPTO, Super P and PVDF is 96%:1%:1%:2%), fully stirred in NMP solvent, coated on a 16μm aluminum foil, and a positive electrode sheet is prepared to detect the contact angle. Together with Li metal, it is assembled into a Li||M94 button battery, and the battery's first cycle efficiency, cycle capacity and retention rate at a current rate of 1C, and battery capacity and retention rate at high temperature are detected. Graphite, acetylene black, CMC and SBR are weighed in a ratio of 95%:2.5%:1.5%:1%, dispersed into an aqueous slurry, coated on a copper foil, and a negative electrode sheet is prepared. The positive electrode was mixed with LMNSPTO at a ratio of 1%, and the graphite negative electrode was assembled into a 2Ah AG||M94 soft-pack battery. The 55℃-7-day storage, 150℃-0.5h hot box, and needle puncture safety performance were tested.

Among them, the powder material with a median particle size of 350nm of the above-mentioned Example 31 and Comparative Example 6 is coated on the surface of the M94 positive electrode (oxygen atmosphere, 700°C) with 0.5%wt.LATSPF, and the composite positive electrode, mixed conductive agent, and PVDF (96%:2%:2%, wt.) are evenly mixed in the NMP system to prepare the positive electrode sheet and detect the contact angle. Together with Li metal, it is assembled into a Li||M94 button battery to detect the first cycle efficiency of the battery, the cycle capacity and retention rate at a current rate of 1C, and the capacity and retention rate of the battery at high temperature. Graphite, acetylene black, CMC and SBR are weighed in a ratio of 95%:2.5%:1.5%:1%, dispersed into an aqueous slurry, coated on copper foil, and prepared as a negative electrode sheet. The above-mentioned coated positive electrode and graphite negative electrode were assembled into a 2Ah AG||M94 soft-pack battery and tested for 55°C-7 days storage, 150°C-0.5h hot box, and needle puncture safety performance.

Among them, the powder material with a median particle size of 350nm of the above-mentioned embodiment 32 and comparative example 7 is coated on the surface of the silicon-carbon negative electrode (silicon-carbon particle size D50 is 12.5μm, nitrogen atmosphere, 900°C) with 0.5%wt.LATSPF, and mixed with artificial graphite in a ratio of 20:80 to prepare a composite material. The composite graphite, acetylene black, CMC and SBR are weighed in a ratio of 95%:2.5%:1.5%:1%, dispersed into an aqueous slurry, coated on copper foil to prepare a negative electrode sheet, and the contact angle is detected. Together with Li metal, it is assembled into a Li||AG button battery, and the battery's first cycle efficiency, cycle capacity and retention rate at a current rate of 1C, and the battery's capacity and retention rate at high temperature are detected. M94 positive active material, conductive agent, PVDF (96%:2%:2%, wt.) are mixed evenly in the NMP system to prepare a positive electrode sheet M94. The above-mentioned coated graphite and M94 positive electrode were assembled into a 2Ah AG||M94 soft-pack battery, and the 55℃-7-day storage, 150℃-0.5h hot box, and needle puncture safety performance were tested.

Among them, the median particle size 350nm powder material of the above-mentioned embodiment 33 and comparative example 8 was taken to prepare a 30% solid content aqueous slurry, which was coated on two sides of a 10μm thick PE diaphragm with a coating thickness of 2μm to obtain a LATP diaphragm and detect the contact angle. M94 positive electrode active material, conductive agent, PVDF (96%: 2%: 2%, wt.), were mixed evenly in an NMP system and coated on an aluminum foil to prepare a positive electrode sheet M94. Together with Li metal, LATP diaphragm, assembled into a Li||M94 button battery, the battery's first cycle efficiency, cycle capacity and retention rate at a current rate of 1C, and the battery's capacity and retention rate at high temperature were detected. Graphite, acetylene black, CMC and SBR were weighed in a ratio of 95%: 2.5%: 1.5%: 1%, dispersed into an aqueous slurry, coated on a copper foil, and a negative electrode sheet was prepared. The above-mentioned LATP separator was used to assemble a 2Ah AG||M94 soft-pack battery with an M94 positive electrode and a graphite negative electrode, and the 55°C-7-day storage, 150°C-0.5h hot box, and needle puncture safety performance were tested.

Among them, the powder material with a median particle size of 350nm of the above-mentioned Example 34 and Comparative Example 9 was used to prepare a 30% solid content aqueous slurry (LATP:CMC:SBR=96%:2%:2%), which was coated on the surface of the graphite negative electrode (graphite, acetylene black, CMC and SBR were weighed in a ratio of 95%:2.5%:1.5%:1%, dispersed into an aqueous slurry, and coated on copper foil to prepare the negative electrode first.) The coating thickness was 2μm, and the LATP coated electrode was obtained to detect the contact angle. Together with Li metal, it was assembled into a Li||AG button battery to detect the battery's first cycle efficiency, cycle capacity and retention rate at a current rate of 1C, and the capacity and retention rate of the battery at high temperature. M94 positive electrode active material, conductive agent, PVDF (96%:2%:2%, wt.), mixed evenly in the NMP system, coated on aluminum foil, and prepared positive electrode sheet M94. The above-mentioned LATP-coated negative electrode and M94 positive electrode were assembled into a 2Ah AG||M94 soft-pack battery, and the 55℃-7-day storage, 150℃-0.5h hot box, and needle puncture safety performance were tested.

Among them, the powder material with a median particle size of 350nm of the above-mentioned embodiment 35 and comparative example 10 was used to prepare a 30% solid content NMP slurry (LATP:PVDF=96%:4%), which was coated on the surface of the M94 positive electrode sheet (wherein, the M94 positive electrode active material, conductive agent, PVDF (96%:2%:2%, wt.) were mixed evenly in the NMP system and coated on aluminum foil to prepare the positive electrode sheet M94.) The coating thickness was 4μm, and the LATP coated electrode sheet was obtained, and the contact angle was detected. Together with Li metal, it was assembled into a Li||M94 button battery, and the battery's first cycle efficiency, cycle capacity and retention rate at a current rate of 1C, and the battery's capacity and retention rate at high temperature were detected. Graphite, acetylene black, CMC and SBR were weighed in a ratio of 95%:2.5%:1.5%:1%, dispersed into an aqueous slurry, coated on a copper foil, and a negative electrode sheet was prepared. The above-mentioned LATP-coated positive electrode and graphite negative electrode were assembled into a 2Ah AG||M94 soft-pack battery, and the 55℃-7-day storage, 150℃-0.5h hot box, and needle puncture safety performance were tested.

Among them, the powder with a median particle size of 350nm in the above-mentioned embodiment 36 was used to prepare a 30% solid content NMP slurry (LATP:PVDF=96%:4%), which was coated on the surface of the M94 positive electrode sheet (wherein, the M94 positive electrode active material, conductive agent, PVDF (96%:2%:2%, wt.) were mixed evenly in the NMP system and coated on aluminum foil to prepare the positive electrode sheet M94.) The coating thickness was 4μm, and the LATP coated electrode sheet was obtained. A layer of 2μm PVDF-HFP was sprayed and the contact angle was detected. Together with Li metal, it was assembled into a Li||M94 button battery, and the battery's first cycle efficiency, cycle capacity and retention rate at a current rate of 1C, and the battery's capacity and retention rate at high temperature were detected. Graphite, acetylene black, CMC and SBR were weighed in a ratio of 95%:2.5%:1.5%:1%, dispersed into an aqueous slurry, and coated on a copper foil to prepare a negative electrode sheet. The above-mentioned LATP-coated positive electrode and graphite negative electrode were assembled into a 2Ah AG||M94 all-solid-state soft-pack battery after hot pressing treatment, and the 55℃-7-day storage, 150℃-0.5h hot box, and needle puncture safety performance were tested.

The specific detection methods are as follows:

Physical and chemical properties testing

Moisture detection: GB/T 24533-2019 Karl Fischer modified method. Dry the powder at 200℃ for 24h, then place it in an environment of 25℃ and 60% humidity to detect moisture at different times. Moisture detection is completed in a dry room, and the dew point of the dry room is required to be lower than -35℃.

Lithium ion conductivity detection: The electrochemical workstation is used to detect the AC impedance of the solid electrolyte sheet, and the lithium ion conductivity is calculated by the formula. The detection frequency is 1000000-0.01Hz, the amplitude is 5mA, and each sample is tested in parallel 3 times. Sample preparation: Take 0.5g of dry LATP powder, press it at 300MPa for 1min under a 15mm diameter mold, keep the sheet thickness 1-2mm, heat treat it at 850℃ for 10h, cool it to room temperature and vacuum seal it for storage, and the density is >90%. The LATP sheet is evenly gold-plated on both sides, and then the AC impedance spectrum is detected on EC-Lab. Select a swagelok mold (the inner wall is made of Teflon insulation material), connect the two ends of the LATP sheet with stainless steel sheets, and set the torque wrench to 5mN. According to the formula δ=l/(RS), l and S are the sheet thickness and surface area, respectively, R is the detected AC impedance value, and δ is the lithium ion conductivity.

Powder conductivity test: GBT30835-2014 "Carbon composite lithium iron phosphate cathode material for lithium-ion batteries". Four-probe test principle, applied pressure range 10-200MPa, pressurization interval 10MPa, pressure maintenance 10s, pressure relief to 3MPa, pressure maintenance 10s;

Phase detection: JY/T 0587-2020 General rules for polycrystal X-ray diffraction methods.

Morphology detection: JY/T 0584-2020 General rules for scanning electron microscopy analysis methods.

Laser particle size detection: Prepare a 10% solid content aqueous solution, ultrasonicate for 5 minutes, and detect the particle size on Malvern 3000. Select a refractive index of 2.42 and an absorbance of 1. The dispersant is water, and the refractive index of water is 1.33.

Specific surface area test: GB/T 19587-2017.

Contact angle detection: The contact angle detector detects the wettability of electrolyte electrode slurry diaphragm and electrode sheet. The contact angle detection uses a contact angle meter to drop electrolyte on the surface of solid electrolyte sheet/diaphragm/positive electrode/negative electrode sheet, measure the distance and height between the two ends of the droplet, and calculate the contact angle. The smaller the contact angle value, the better the lyophilic ability of the diaphragm.

Compaction density test: GB/T 24533-2019 and GBT30835-2014 "Carbon composite lithium iron phosphate cathode material for lithium-ion batteries"

Electrochemical performance testing

Preparation and testing of button batteries: GB/T 24533-2019. The ternary materials M94, LMNSPTO, Super P and PVDF are weighed in a ratio of 96:1:1:2, dispersed in NMP slurry, and then coated on 16μm thick Al foil, and vacuum dried at 100℃ for 12h as the positive electrode. The above-mentioned positive electrode, conventional PP diaphragm and Li metal negative electrode are used to assemble CR232 button batteries, where the positive and negative electrode diameters are 15mm, the diaphragm diameter is 20mm, and the electrolyte is 1.2mol/L LiPF6-EC/DEC/EMC+1.5%VC+1.5%FEC+2.5%PS battery, and 1C constant current charge and discharge test is performed. The constant current charge and discharge voltage range is 2.5V-4.3V, and the current is 1C. If the positive electrode is AG and the negative electrode is Li, the corresponding constant current charge and discharge voltage range is 0.01V-1.5V.

Preparation and testing of soft-pack batteries: The ternary materials M94, LMNSPTO, Super P and PVDF were weighed in a ratio of 96:1:1:2 (coating system, M94, Super P and PVDF ratio is 96%:2%:2%), dispersed in NMP slurry, and then coated on 16μm thick Al foil, and vacuum dried at 80℃ for 12h as the positive electrode. Graphite, acetylene black, CMC and SBR were weighed in a ratio of 95:2.5:1.5:1, dispersed into an aqueous slurry, and then coated on a 10μm copper foil, and vacuum dried at 100℃ for 12h as the negative electrode. The above-mentioned positive electrode, conventional PP separator and negative electrode were used to assemble a 2Ah soft-pack battery, the electrolyte was 1.2mol/LLiPF6-EC/DEC/EMC+1.5%VC+1.5%FEC+2.5%PS battery, and 1C constant current charge and discharge test was performed. The constant current charge and discharge voltage range is 2.5V-4.3V, and the current is 1C. For all-solid-state batteries, the positive electrode and the negative electrode are directly hot-pressed at a temperature of 300°C and a pressure of 300MPa-20S, and then encapsulated in an aluminum-plastic film to prepare a 2Ah all-solid-state soft-pack battery. The constant current charge and discharge voltage range is 2.5V-4.3V, and the current is 0.2C.

Battery safety performance testing:

High temperature thermal storage retention rate and recovery rate: GB/T 31484-2015. The battery in the fully charged state is fully charged at 1C, stored at 55℃ for 7 days, cooled to 25℃, and left to stand for 4 hours. The capacity retention rate and recovery rate are tested respectively.

Hot box test: GB/T 36276-2023 "Lithium-ion batteries for power energy storage" Place a 2Ah soft pack battery in a high temperature oven with a protective environment, and perform a 45℃-200℃ program heating process, heating at 5℃/min, keeping the temperature for 30 minutes every 5℃, and perform hot box safety testing to observe whether the battery catches fire, smokes or explodes. Six parallel samples are required for each group.

Acupuncture: GB 31241-2014 and GB/T 31485-2015, GB 38031-2020. Select a 2Ah small soft-pack battery, fully charge the battery, and use a high-temperature resistant steel needle with a diameter of 5 to 8 mm to vertically penetrate the battery plate at a speed of (25±5) mm/s. The steel needle stays in the battery for 1 hour without catching fire or exploding to be qualified. It is required that there are fire-fighting facilities and an open environment around, and the operator has professional ability and protective measures. 8 parallel samples per group.

The test results are shown in Tables 1 to 4.

Table 1 shows the moisture detection data of the powder materials of different embodiments and comparative examples when placed in the same air environment over time.

Table 2 shows the physicochemical performance data of the powder materials of different embodiments and comparative examples.

Table 3 shows the power cycle performance test data of button batteries formed from powder materials of different embodiments and comparative examples.

Table 4 shows the safety performance test data of soft-pack batteries formed from powder materials of different embodiments and comparative examples.

Table 1

Table 2

Table 3

Table 4

Based on the above data and mechanism, it can be seen that spherical materials have a lower specific surface area, so they have less water absorption and are not easy to agglomerate, so they are easy to store. At the same time, they can obtain more stable performance in the preparation of electrodes or solid electrolytes. The preparation of high-nickel positive electrode slurry is not easy to jelly, and the drying time of diaphragm materials and pole pieces can be greatly shortened.

The powder material of the present application has a spherical structure and can realize the hydrophobic function. In addition, it also has the following beneficial effects:

The positive electrode replenishes lithium, stabilizes the lattice structure, and improves the initial efficiency and cycle stability;

Pole sheet preparation improves the compaction density of the pole sheet to obtain a high energy density battery;

Prepare all-solid-state batteries, reduce the amount of electrolyte, and achieve battery thermal safety and acupuncture safety;

Reduce the expansion of silicon-carbon, silicon-oxygen materials and graphite negative electrodes, and form a stable SEI film with lithium metal, enhance contact stability, stabilize the negative electrode, and improve cycle capacity.

Referring to Examples 1 to 36, Examples 1 to 30 are 1% LMNSPTO doped positive electrodes, and Examples 29 and 30 correspond to different LMNSPTO materials. Examples 31 to 36 correspond to coated positive electrodes, coated silicon-carbon negative electrodes, coated LATP separators, coated positive electrode plates, coated negative electrode plates, and all-solid-state batteries. Comparative Examples 1 to 2 are spherical LMNSPTO materials, which do not contain the T element.

Comparative Examples 3 to 11 are non-spherical LMNSPTO materials, among which 1 to 5 are 1% LMNSPTO mixed positive electrodes, and 6 to 11 correspond to LMNSPTO coated positive electrodes, coated silicon carbon negative electrodes, coated LATP separators, coated positive electrode plates, coated negative electrode plates, and all-solid-state batteries.

Comparative Example 12 is a positive electrode material without LATP and 1% alumina blended and its battery.

A affects the spherical morphology. The larger the A value, the larger the z/x and z/y values, the poorer the spherical morphology, and the lower the physical and lithium ion conductivity. B affects the hydrophobicity and lyophilicity of LMNSPTO, which is manifested as differences in wettability and contact angles.

Referring to Table 1, the moisture content of 350nm LMNSPTO material and micron-sized M94 positive electrode material after being placed in the air for different periods of time is shown.

As time goes by, the moisture content of both M94 and LMNSTPO materials will increase. The increase rate of LMNSTPO material is more obvious, significantly higher than that of positive electrode powder, which may be attributed to the smaller LMNSTPO particles.

LATP materials have strong water absorption, which will cause the electrode slurry to agglomerate, the coating material to become hard, and difficult to sieve, which may be related to the strong water absorption capacity of its phosphate. However, spherical LMNSTPO materials can reduce water absorption to a certain extent, making it easier for LATP materials to be applied and promoted.

Refer to Table 2, which shows the physicochemical properties of the 350nm LMNSPTO material. It can be found that the specific surface area and contact angle have a great influence on the moisture content of the material. When A is large (A=0.59), z/x and z/y>1, the sphericity of the material is not good, it will appear flat, the phase purity is low, and the lithium ion conductivity is low; as A gradually decreases, the specific surface area of the material decreases, and the contact angle of the prepared positive electrode to water increases, the contact angle to the electrolyte is small, and the compaction of the electrode is greatly improved. When A=0.1, B=0.1, the sphericity of the LMNSPTO material is good, z/x and z/y are close to 1, and the phase purity and lithium ion conductivity are high. Referring to Figures 1 and 2, the particle size of the LATP spherical particles is controllable, close to 20nm~30um.

Referring to Table 3, the electrochemical properties of 350nm LMNSPTO materials as coating materials, admixtures and coating materials. When A is large (A = 0.59 ~ 0.3), z / x and z / y > 1.2, the sphericity of the material is poor, the physical phase and conductivity are low, resulting in low initial capacity and first efficiency of the material. As z / x and z / y approach 1.0, the first efficiency and initial capacity, 1C cycle retention rate are greatly improved. At the same time, LATP materials (Comparative Examples 1 to 11), especially spherical LATP materials (Examples 1 to 36), are added. Compared with Comparative Example 12, their low-temperature cycle performance is significantly improved. Comparison of Example 6 and Comparative Example 5 shows that its excellent cycle performance may come from the lower specific surface area and better hydrophobic and lyophilic properties of the spherical material, and its volume expansion after high-temperature storage is also greatly reduced.

As shown in Table 4, as z/x and z/y approach 1.0, the safety performance of the soft-pack battery gradually improves. Among them, when A=0.1, B=0.1, the soft-pack battery prepared with LMNSPTO material obtains a higher 55°C capacity retention rate and recovery rate and a smaller volume expansion, and its 150°C~30min hot box pass rate is higher. In particular, LATP is coated on the positive and negative electrodes and assembled into a semi-solid battery, and its acupuncture passes 100%. Assembled into an all-solid-state battery, its acupuncture pass rate is 100%, and the volume expansion of the 150°C~30min hot box is small. As shown in Example 32 and Comparative Example 7, it can be seen that after coating the silicon-carbon negative electrode, its expansion rate is greatly reduced. Comparing Example 6 with Comparative Example 5 and Comparative Example 12, their excellent thermal safety performance may be attributed to the lithium replenishment of the battery by the LATP material. Under extreme conditions, the high lithium content LATP (lithium content of Example 6 is 1.9, lithium content of Comparative Example 5 is 1.4, and lithium content of Comparative Example 12 is 0) can replenish lithium for the positive electrode material and stabilize the positive electrode lattice.

The above is a detailed introduction to the battery, hydrophobic powder material and preparation method thereof provided in the embodiments of the present application. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea; at the same time, for technicians in this field, according to the ideas of the present application, there will be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims (10)

1. A powder material having spherical particles, characterized in that: The chemical formula of the powder material is Li _a M _{b N c} R _d P _e T _f O _g ; Wherein, M is selected from at least one of In, Sc, B, Ga, Nb, Y, Zr, Al, Ni, Co, Mn, Mg, Ca, Sr, Cu, Zn, Fe, Na, and K; Wherein, N is selected from at least one of Ti, Zr, Hf, Si, Ge, and Sn; R is selected from at least one of Nb, Ti, Zr, Hf, As, Sb, Si, Ge, and Sn, and R and N are selected from different elements; T is selected from at least one of S, Se, N, F, Cl, Br, and I; The primary particles and/or secondary particles of the powder material are spheroids; the spheroids have a first short axis, a second short axis and a long axis; the long axis is perpendicular to the plane where the first short axis and the second short axis are located; the dimensions of the spheroids at the first short axis, the second short axis and the long axis are x, y, z, respectively, wherein 1≤z/x＜2, 1≤z/y＜2. 2. The powder material according to claim 1, characterized in that: The dimension z of the spheroid on the major axis ranges from 0.01 μm ≤ z ≤ 100 μm. 3. The powder material according to claim 2, characterized in that: The dimension x of the spheroid at the first minor axis ranges from 0.01 μm ≤ x ≤ 100 μm. 4. The powder material according to claim 3, characterized in that: The value range of the dimension y of the spheroid at the second minor axis is 0.01 μm≤y≤100 μm. 5. The powder material according to any one of claims 1 to 4, characterized in that: The dimension z of the spheroid on the major axis ranges from 0.014 μm ≤ z ≤ 32 μm; The dimension x of the spheroid at the first minor axis is in the range of 0.014 μm ≤ x ≤ 32 μm; The value range of the dimension y of the spheroid at the second minor axis is 0.014 μm≤xy≤32 μm. 6. The powder material according to any one of claims 1 to 4, characterized in that: The dimension z of the spheroid on the major axis ranges from 0.014 μm ≤ z ≤ 11 μm; The dimension x of the spheroid at the first minor axis is in the range of 0.014 μm ≤ x ≤ 11 μm; The dimension y of the spheroid at the second minor axis ranges from 0.014 μm ≤ y ≤ 11 μm. 7. The powder material according to any one of claims 1 to 4, characterized in that: The average particle size of the powder material ranges from 0.1 to 30 μm. 8. The powder material according to any one of claims 1 to 4, characterized in that: Wherein, in the Li _a M _b N _c R _d P _e T _f O _g , 1＜a≤6, 0＜b＜1, 0＜c＜2, 0＜d＜3, 0＜e＜3, 0<f<8, 0<g<12. 9. The powder material according to any one of claims 1 to 4, characterized in that: The ionic conductivity of the powder material ranges from 10E ^-6 to 5E ^-2 S/cm. 10. A method for preparing a powder material, characterized in that: The preparation method comprises the following steps: Step 1: providing raw materials to be mixed corresponding to each element according to the chemical formula of the powder material: Li _a M b _{N c} R _d P _e T _f O _g ; Step 2: Mixing the multiple raw materials to be mixed provided in step 1 to obtain a precursor material; Step 3: heat-treating the precursor material obtained in step 2 to obtain a heat-treated product; Step 4: crushing, ball milling, drying and sieving the heat-treated product obtained in step 3 to obtain the powder material; Wherein, M is selected from at least one of In, Sc, B, Ga, Nb, Y, Zr, Al, Ni, Co, Mn, Mg, Ca, Sr, Cu, Zn, Fe, Na, and K; Wherein, N is selected from at least one of Ti, Zr, Hf, Si, Ge, and Sn; R is selected from at least one of Nb, Ti, Zr, Hf, As, Sb, Si, Ge, and Sn, and R and N are selected from different elements; T is selected from at least one of S, Se, N, F, Cl, Br, and I; Among them, the primary particles and/or secondary particles of the powder material are spheroids; the spheroids have a first short axis, a second short axis and a long axis; the long axis is perpendicular to the plane where the first short axis and the second short axis are located; the dimensions of the spheroids at the first short axis, the second short axis and the long axis are x, y, z, respectively, wherein 1≤z/x＜2, 1≤z/y＜2.