CN113410465A

CN113410465A - Lithium-containing anti-perovskite material and application thereof

Info

Publication number: CN113410465A
Application number: CN202110668930.4A
Authority: CN
Inventors: 邓志; 陈典诚; 李帅; 赵予生
Original assignee: Southern University of Science and Technology
Current assignee: Southern University of Science and Technology
Priority date: 2021-06-17
Filing date: 2021-06-17
Publication date: 2021-09-17

Abstract

The application relates to a lithium-containing anti-perovskite material and application thereof, belonging to the technical field of electrode materials of lithium ion batteries. The general formula of the lithium-containing anti-perovskite material is as follows: li_xM_yA_z(ii) a Wherein M is a metal element or a metalloid element other than lithium, and M may be oxidized in the lithium-containing anti-perovskite material. M is a metal element, A includes anions of at least two valence states of-1, -2 and-3. Or, M is at least two metal elements, A includes an anion in at least one valence state from-1, 2, and-3. The lithium-containing anti-perovskite material is doped with different typesThe metal ions or metalloid ions, which are used as the positive electrode material, can increase the discharge capacity and make the cycle stability of the battery better.

Description

Lithium-containing anti-perovskite material and application thereof

Technical Field

The application relates to the technical field of electrode materials of lithium ion batteries, in particular to a lithium-containing anti-perovskite material and application thereof.

Background

The types of the anode and cathode materials of the lithium ion battery are various, but because the requirements of people on the battery performance are increasingly increased, the existing anode and cathode materials of the battery cannot meet the requirements at present, and therefore the battery and the electrode materials which are higher in energy density, longer in service life and safer need to be developed. Currently commercially available lithium battery positive electrode materials include LiCoO₂(α-NaFeO₂Layer-shaped structure), LiFePO₄(olivine type) and LiMn₂O₄(spinel type), etc., but the capacity is not more than 160mAh g^-1And face the drawback of short service life.

Disclosure of Invention

In order to overcome the defects in the prior art, the embodiment of the application provides a lithium-containing anti-perovskite material and application thereof, and the lithium-containing anti-perovskite material is used as a positive electrode material or a negative electrode material, so that the cycling stability of a battery can be improved.

In a first aspect, embodiments of the present application provide a lithium-containing anti-perovskite material, which has a general formula: li_xM_yA_z(ii) a Wherein M is a metal element or a metalloid element other than lithium, and M may be oxidized in the lithium-containing anti-perovskite material. M is a metal element, A includes anions of at least two valence states of-1, -2 and-3. Or, M is at least two metal elements, A includes an anion in at least one valence state from-1, 2, and-3.

In some embodiments of the present application, M comprises at least Na⁺、K⁺、Mg²⁺、Ca²⁺、Sr²⁺、Ba²⁺、Zn²⁺、Sc²⁺、Y³⁺、Al³⁺、Ga³⁺、Ti³⁺、Zr²⁺、V³⁺、V⁴⁺、Nb³⁺、Nb⁴⁺、Ta³⁺、Ta⁴⁺、Cr²⁺、Cr³⁺、Cr⁴⁺、Mo³⁺、Mo⁴⁺、W²⁺、Mn²⁺、Mn³⁺、Fe²⁺、Fe³⁺、Co²⁺、Co³⁺、Ni²⁺、Ni³⁺、Cu⁺、Cu²⁺、Si²⁺、Si⁴⁺、Sn²⁺、Sn³⁺、Sb³⁺One or more of (a).

A comprises an anion having a valence of-1, and the anion having a valence of-1 comprises F^-、Cl^-、Br^-、I^-、H^-、BF₄ ^-、BH₄ ^-、NO₂ ^-、NO₃ ^-、CN^-、ClO^-、ClO₃ ^-、ClO₄ ^-、NH₂ ^-、CH₃ ^-One or more of (a). Or/and, A comprises a-2 valent anion, the-2 valent anion comprising O^2-、S^2-、Se^2-、Te^2-、CO₃ ^2-、SO₃ ^2-、SO₄ ^2-、SeO₄ ^2-One or more of (a). Or/and, A comprises a-3 valent anion, the-3 valent anion comprising N^-3Or/and PO₄ ^3-。

In some embodiments of the present application, A comprises at least a-2 valent anion.

In some embodiments of the present application, A comprises at least O^2-。

In some embodiments of the present application, the lithium-containing anti-perovskite material is Li_1.9Na_0.1Fe_0.6Co_0.2Mn_0.2OS or Li₂Co_0.5OCl_0.5Br_0.5。

In a second aspect, the present application provides a use of the above lithium-containing anti-perovskite material as a positive electrode material.

In a third aspect, the present application provides a lithium-containing anti-perovskite material having the general formula: li_xM_yA_z(ii) a Wherein M is a metal element or metalloid element other than lithium, and A comprises an anion in at least one valence state of-1, -2, and-3; and M in the lithium-containing anti-perovskite material can be reduced.

In bookIn some of the examples of this application, M comprises at least Ti⁴⁺、Zr³⁺、Zr⁴⁺、V³⁺、V⁴⁺、V⁵⁺、Nb²⁺、Nb³⁺、Nb⁴⁺、Nb⁵⁺、Ta²⁺、Ta³⁺、Ta⁵⁺、Cr²⁺、Cr³⁺、Cr⁴⁺、Cr⁵⁺、Cr⁶⁺、Mo⁴⁺、Mo⁶⁺、W³⁺、W⁴⁺、W⁵⁺、W⁶⁺、Mn³⁺、Mn⁴⁺、Mn⁵⁺、Mn⁶ ⁺、Mn⁷⁺、Fe³⁺、Co³⁺、Ni³⁺、Ni⁴⁺、Si⁴⁺、Sn⁴⁺、Sb⁵⁺One or more of (a).

A comprises an anion having a valence of-1, and the anion having a valence of-1 comprises F^-、Cl^-、Br^-、I^-、H^-、BF₄ ^-、BH₄ ^-、NO₂ ^-、NO₃ ^-、CN^-、ClO^-、ClO₃ ^-、ClO₄ ^-、NH₂ ^-、CH₃ ^-One or more of; or/and, A comprises a-2 valent anion, the-2 valent anion comprising O^2-、S^2-、Se^2-、Te^2-、CO₃ ^2-、SO₃ ^2-、SO₄ ^2-、SeO₄ ^2-One or more of; or/and, A comprises a-3 valent anion, the-3 valent anion comprising N^-3Or/and PO₄ ^3-。

In some embodiments of the present application, A comprises at least O^2-。

In some embodiments of the present application, the lithium-containing anti-perovskite material is Li₆V_1.5TiO₅Br₆Or Li₂V_0.5SO。

In a fourth aspect, the present application provides a use of the above lithium-containing anti-perovskite material as a negative electrode material.

The lithium-containing anti-perovskite material and the application thereof provided by the embodiment of the application have the beneficial effects that:

different types of metal ions or metalloid ions are doped in the lithium-containing anti-perovskite material and are used as a positive electrode material and a negative electrode material, so that the discharge capacity can be increased, and the cycling stability of the battery is better.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.

Fig. 1 is an XRD pattern of a lithium-containing anti-perovskite material provided in example 1 of the present application;

fig. 2 is an XRD pattern of the lithium-containing anti-perovskite material provided in example 2 of the present application;

fig. 3 is an XRD pattern of the lithium-containing anti-perovskite material provided in example 3 of the present application;

fig. 4 is an XRD pattern of the provided lithium-containing anti-perovskite material of example 4;

fig. 5 is an XRD pattern of the provided lithium-containing anti-perovskite material of comparative example 1;

fig. 6 is a discharge capacity cycle chart of a liquid-system half cell assembled by the positive electrode materials provided in example 1 and comparative example 1;

fig. 7 is a charge and discharge graph of an all-solid battery assembled with the positive electrode material provided in comparative example 1;

fig. 8 is a charge-discharge curve diagram of an all-solid-state battery assembled with the positive electrode material provided in example 2;

fig. 9 is a discharge capacity cycle chart of the liquid-based half cell assembled by the negative electrode materials provided in example 3 and example 4.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described below with reference to the drawings in the embodiments of the present application.

The embodiment of the application provides a lithium-containing anti-perovskite material, and the general formula of the lithium-containing anti-perovskite material is as follows: li_xM_yA_z(ii) a Wherein M is a metal element or a metalloid element other than lithium, and M may be oxidized in the lithium-containing anti-perovskite material. The lithium-containing anti-perovskite material and the application thereof are doped with metal ions or metalloid ions, and the M element can be oxidized, so that the lithium-containing anti-perovskite material can be used as a positive electrode material to improve the cycle stability of a battery.

Wherein M at least comprises Na⁺、K⁺、Mg²⁺、Ca²⁺、Sr²⁺、Ba²⁺、Zn²⁺、Sc²⁺、Y³⁺、Al³⁺、Ga³⁺、Ti³⁺、Zr²⁺、V³ ⁺、V⁴⁺、Nb³⁺、Nb⁴⁺、Ta³⁺、Ta⁴⁺、Cr²⁺、Cr³⁺、Cr⁴⁺、Mo³⁺、Mo⁴⁺、W²⁺、Mn²⁺、Mn³⁺、Fe²⁺、Fe³⁺、Co²⁺、Co³⁺、Ni² ⁺、Ni³⁺、Cu⁺、Cu²⁺、Si²⁺、Si⁴⁺、Sn²⁺、Sn³⁺、Sb³⁺One or more of (a).

A may be a monovalent anion; a may be a divalent anion; a may be a trivalent anion; a can contain both monovalent and divalent anions; a can contain both monovalent and trivalent anions; a can contain both divalent and trivalent anions; a may contain both monovalent anions, divalent anions, and trivalent anions.

If A is a monovalent anion, the monovalent anion comprises F^-、Cl^-、Br^-、I^-、H^-、BF₄ ^-、BH₄ ^-、NO₂ ^-、NO₃ ^-、CN^-、ClO^-、ClO₃ ^-、ClO₄ ^-、NH₂ ^-、CH₃ ^-One or more of (a). If A is a dianion, the dianion comprises O^2-、S^2-、Se^2-、Te^2-、CO₃ ^2-、SO₃ ^2-、SO₄ ^2-、SeO₄ ^2-One or more of (a). If A is a trivalent anion, the trivalent anion includes C^3-Comprising N^-3Or/and PO₄ ^3-。

Although in the foregoing, M includes one or more of the foregoing metal ions or metalloid ions; a includes one or more of the foregoing anions. However, in order to use the material as a positive electrode material, the battery can have better cycle stability.

M and A have a certain relation, so that the obtained positive electrode material has better performance.

In one embodiment, if M is a metal element (M is one of Na, K, Mg, Ca, Sr, Ba, Zn, Sc, Y, Al, Ga, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Si, Sn, Sb), A comprises anions in at least two valency states of-1, -2, and-3 (A is a monovalent and divalent anion; or, A is a monovalent and trivalent anion; or, A is a divalent and trivalent anion; or, A is a monovalent, divalent, and trivalent anion). That is, if a metal element is doped in the lithium-containing anti-perovskite material, the anion of the lithium-containing anti-perovskite material comprises two valence states or more, so that the cycling stability of the battery can be better.

In another embodiment, if M is at least two metal elements (M is at least two of Na, K, Mg, Ca, Sr, Ba, Zn, Sc, Y, Al, Ga, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Si, Sn, Sb), A comprises an anion in at least one of the valences-1, -2, and-3 (A is a monovalent anion; or A is a divalent anion; or, A is a trivalent anion; A is a monovalent and divalent anion; or, A is a monovalent and trivalent anion; or, A is a divalent and trivalent anion). That is, if two or two metal elements are doped in the lithium-containing anti-perovskite material, the anion of the lithium-containing anti-perovskite material is not particularly limited, and thus the cycling stability of the battery can be improved.

Alternatively, a comprises at least a-2 valent anion. For example: a comprises both-2 and-3 anions; or, A includes both-2 valent anions and-1 valent anions; or, A includes both anions having a valence of-2 and anions having a valence of-1 and-3.

Further, A comprises at least O^2-. For example: the lithium-containing anti-perovskite material may be Li_1.9Na_0.1Fe_0.6Co_0.2Mn_0.2OS or Li₂Co_0.5OCl_0.5Br_0.5It can be used as a positive electrode material.

In other embodiments, the lithium-containing anti-perovskite material may also be: li_0.5Ni(SO₄)F，Li_0.5Ni(SO₄)F_0.5Cl_0.5，LiCo(PO₄)F，LiCo(PO₄)F_0.5Cl_0.5，LiCoNI，Li₂FeOBr₂，Li₅FeO₂Br₃And the like, which can be synthesized by high-temperature solid-phase sintering, or synthesized by solvothermal method, or synthesized by high-temperature high-pressure method.

The lithium-containing anti-perovskite material can be used as a positive electrode material in a lithium ion battery containing electrolyte, and can also be used as a positive electrode material of an all-solid-state lithium ion battery.

The following describes the preparation of the material:

if the lithium-containing anti-perovskite material is Li_1.9Na_0.1Fe_0.6Co_0.2Mn_0.2OS, one of the preparation methods may be: mixing raw material Li₂O powder and Na₂Mixing (such as ball milling) O powder, Fe powder, Co powder, Mn powder and S powder, and introducing into inert gas (nitrogen or/and argon) at 400 deg.C or higherPerforming heat treatment in a vacuum environment to obtain Li_1.9Na_0.1Fe_0.6Co_0.2Mn_0.2And an OS. Optionally, the heat treatment is carried out at 400-1500 ℃ for 2h or more. Illustratively, the temperature of the heat treatment is 400 ℃, 600 ℃, 800 ℃, 1000 ℃, 1200 ℃ or 1500 ℃; the time of the heat treatment is 0.5h, 1h, 2h, 4h or 8 h.

Further, if the raw material contains S powder or/and Se powder, the heat treatment can be performed under vacuum atmosphere with the vacuum degree of 10^-6-10 Pa. Illustratively, the degree of vacuum at the time of heat treatment is 10^-6Pa、10^-5Pa、10^-4Pa、10^-3Pa、10^-2Pa、10^-1Pa, 1Pa or 10 Pa.

If the lithium-containing anti-perovskite material is Li₂Co_0.5OCl_0.5Br_0.5One of the preparation methods can be as follows: mixing raw material Li₂O powder, CoCl₂Powder and CoBr₂After the powders are mixed (for example, ball milled) uniformly, heat treatment is carried out in an inert gas environment or a vacuum environment at a temperature of not less than 400 ℃ to obtain Li₂Co_0.5OCl_0.5Br_0.5. Optionally, the heat treatment is carried out at 400-1500 ℃ for 2h or more.

The embodiment of the application also provides a lithium-containing anti-perovskite material, and the general formula of the lithium-containing anti-perovskite material is as follows: li_xM_yA_z(ii) a Wherein M is a metal element or a metalloid element except lithium, and M in the lithium-containing anti-perovskite material can be reduced, so that the lithium-containing anti-perovskite material is doped with metal ions or metalloid ions, and the M element can be reduced, and the lithium-containing anti-perovskite material can be used as a negative electrode material to improve the cycling stability of the battery.

Wherein M comprises at least Ti⁴⁺、Zr³⁺、Zr⁴⁺、V³⁺、V⁴⁺、V⁵⁺、Nb²⁺、Nb³⁺、Nb⁴⁺、Nb⁵⁺、Ta²⁺、Ta³⁺、Ta⁵⁺、Cr²⁺、Cr³⁺、Cr⁴⁺、Cr⁵⁺、Cr⁶⁺、Mo⁴⁺、Mo⁶⁺、W³⁺、W⁴⁺、W⁵⁺、W⁶⁺、Mn³⁺、Mn⁴⁺、Mn⁵⁺、Mn⁶⁺、Mn⁷⁺、Fe³⁺、Co³⁺、Ni³ ⁺、Ni⁴⁺、Si⁴⁺、Sn⁴⁺、Sb⁵⁺One or more of (a).

A includes an anion in at least one valence state of-1, -2, and-3. A may be a monovalent anion; a may be a divalent anion; a may be a trivalent anion; a can contain both monovalent and divalent anions; a can contain both monovalent and trivalent anions; a can contain both divalent and trivalent anions; a may contain both monovalent anions, divalent anions, and trivalent anions.

Further, A comprises at least O^2-. For example: lithium-containing anti-perovskite materialThe material may be Li₆V_1.5TiO₅Br₆Or Li₂V_0.5SO, which may be used as a negative electrode material.

In other embodiments, the lithium-containing anti-perovskite material may also be: li_0.2CoOCl、Li₂Ti_0.5SO、LiNi(SO₄)F、LiNi(PO₄) Cl, etc., which may be synthesized by high temperature solid phase sintering, or by solvothermal synthesis, or by high temperature high pressure synthesis.

The lithium-containing anti-perovskite material can be used as a negative electrode material in a lithium ion battery containing electrolyte, and can also be used as a negative electrode material of an all-solid-state lithium ion battery.

The following describes the preparation of the material: if the lithium-containing anti-perovskite material is Li₆V_1.5TiO₅Br₆One of the preparation methods can be as follows: raw materials of LiBr powder and VO₂Powder and TiO₂After the powders are mixed (for example, ball milled) uniformly, heat treatment is carried out in an inert gas environment or a vacuum environment at a temperature of not less than 400 ℃ to obtain Li₆V_1.5TiO₅Br₆. Optionally, the heat treatment is carried out at 400-1500 ℃ for 2h or more.

If the lithium-containing anti-perovskite material is Li₂V_0.5SO, one of the preparation methods may be: mixing raw materials V powder and Li₂Mixing O powder and S powder (such as ball milling), and heat treating at 400 deg.C or above in inert gas or vacuum to obtain Li₂V_0.5And (3) SO. Optionally, the heat treatment is carried out at 800-1500 ℃ for 2h or more.

In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

Example 1

Mixing raw material Li₂O powder and Na₂Weighing O powder, Fe powder, Co powder, Mn powder and S powder according to a stoichiometric ratio, ball-milling at a rotation speed of 500rpm for more than 30min, uniformly mixing, performing heat treatment at 650 ℃ in a vacuum tube furnace, preserving heat for more than 2h, taking out a sealing tube after heat preservation, and putting the sealing tube into cold water for quenching treatment to obtain Li_1.9Na_0.1Fe_0.6Co_0.2Mn_0.2OS。

FIG. 1 is Li_1.9Na_0.1Fe_0.6Co_0.2Mn_0.2The XRD pattern of OS, as can be seen from fig. 1, the lithium-containing anti-perovskite material is a cubic anti-perovskite phase.

Example 2

Mixing raw material Li₂O powder, CoCl₂Powder and CoBr₂Weighing the powder according to a stoichiometric ratio, ball-milling at a rotation speed of 500rpm for more than 30min, uniformly mixing, performing heat treatment at 700 ℃ in a vacuum tube furnace, preserving heat for more than 2h, taking out a sealing tube after heat preservation, putting the sealing tube into cold water for quenching treatment to obtain Li₂Co_0.5OCl_0.5Br_0.5。

FIG. 2 is Li₂Co_0.5OCl_0.5Br_0.5As can be seen from fig. 2, the lithium-containing anti-perovskite material is a cubic anti-perovskite phase.

Example 3

Mixing raw materials V powder and Li₂Weighing O powder and S powder according to a stoichiometric ratio, ball-milling at a rotation speed of 500rpm for more than 30min, uniformly mixing, carrying out heat treatment at 850 ℃ in a vacuum tube furnace, keeping the temperature for more than 2h, taking out a sealing tube after the heat preservation is finished, and putting the sealing tube into cold water for quenching treatment to obtain Li₂V_0.5SO。

FIG. 3 is Li₂V_0.5XRD pattern of SO, it can be seen from fig. 3 that the lithium-containing anti-perovskite material is a cubic anti-perovskite phase.

Example 4

Raw materials LiBr powder and VO₂Powder and TiO₂Weighing the powder according to stoichiometric ratio, ball milling at 500rpm for more than 30min, mixing, heat treating at 850 deg.C in vacuum tube furnace, maintaining for more than 2 hr, taking out the sealed tube, and placing in cold waterQuenching treatment is carried out to obtain Li₆V_1.5TiO₅Br₆。

FIG. 4 is Li₆V_1.5TiO₅Br₆As can be seen from fig. 4, the lithium-containing anti-perovskite material is a composite phase of a cubic anti-perovskite phase and a layered anti-perovskite phase.

Comparative example 1

Mixing raw material Li₂Weighing O powder, Fe powder and S powder according to a stoichiometric ratio, ball-milling at the rotation speed of 500rpm for more than 30min, uniformly mixing, carrying out heat treatment at 800 ℃ in a vacuum tube furnace, preserving heat for more than 2h, taking out a sealing tube after heat preservation, and putting the sealing tube into cold water for quenching treatment to obtain Li₂FeOS。

FIG. 4 is Li₂The XRD pattern of FeOS, as can be seen from FIG. 5, the lithium-containing anti-perovskite material is a cubic anti-perovskite phase.

Experimental example 1

With Li in example 1_1.9Na_0.1Fe_0.6Co_0.2Mn_0.2OS is a positive electrode material assembly liquid system half cell: li prepared in example 1_1.9Na_0.1Fe_0.6Co_0.2Mn_0.2Mixing O positive electrode powder, a conductive agent (Super P) and a binder (polyvinylidene fluoride, PVDF, Poly (1,1-difluoroethylene)) according to a ratio of 7:2:1, uniformly dispersing the mixture into a solvent (N, N-Dimethylformamide, DMF, N, N-Dimethylformamide), uniformly coating the mixture on a current collector aluminum foil in a spinning mode, evaporating the solvent to dryness, mixing the solvent with a lithium battery diaphragm, a metal lithium negative electrode and a lithium battery electrolyte (ethylene carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1: 1), and adding LiClO₄Concentration in the electrolyte is 1M) assembly liquid system half cell.

With Li in comparative example 1₂FeOS is a positive electrode material assembly liquid system half cell: li prepared in comparative example 1₂Mixing FeOS positive electrode powder, a conductive agent (Super P) and a binder (polyvinylidene fluoride, PVDF, Poly (1,1-difluoroethylene)) according to a ratio of 7:2:1, uniformly dispersing the mixture into a solvent (N, N-Dimethylformamide, DMF, N, N-Dimethylformamide), uniformly coating the mixture on a current collector aluminum foil in a spinning mode, and after the solvent is evaporated to dryness, uniformly coating the mixture with a lithium battery diaphragm and a metal lithium negative electrodeWith lithium electrolyte (ethylene carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1: 1) and LiClO was added₄Concentration in the electrolyte is 1M) assembly liquid system half cell.

The discharge capacity cycling graphs of the assembled liquid-based half-cells of example 1 and comparative example 1 were respectively examined as shown in fig. 6, and it can be seen from fig. 6 that Li was provided in comparison with Li provided in comparative example 1₂FeOS as a positive electrode material for a battery, Li provided in example 1 was used_1.9Na_0.1Fe_0.6Co_0.2Mn_0.2The OS is used as a positive electrode material of the battery, and the obtained liquid-system half battery has better cycling stability.

With Li in example 2₂Co_0.5OCl_0.5Br_0.5As a positive electrode material, Li₃OCl is electrolyte, and lithium metal negative electrode assembly solid-state battery: li prepared in example 2₂Co_0.5OCl_0.5Br_0.5As a positive electrode material, in Li₃And one side of the OCl electrolyte sheet, the metal lithium foil and the copper current collector are arranged on the other side, and the two sides are pressurized and sealed to assemble the solid-state battery.

With Li in comparative example 1₂FeOS as the positive electrode material, Li₃OCl is electrolyte, and lithium metal negative electrode assembly solid-state battery: li prepared in comparative example 1₂FeOS as anode material and placed in Li₃And one side of the OCl electrolyte sheet, the metal lithium foil and the copper current collector are arranged on the other side, and the two sides are pressurized and sealed to assemble the solid-state battery.

The charge and discharge curves of the all-solid batteries assembled in example 2 and comparative example 1 were examined separately as shown in fig. 7 and 8, and as can be seen from fig. 7 and 8, compared to Li provided in comparative example 1₂FeOS as a positive electrode material for a battery, Li provided in example 2 was used₂Co_0.5OCl_0.5Br_0.5As a positive electrode material of the battery, the obtained all-solid-state battery has higher working voltage and higher energy density.

With Li in example 3₂V_0.5SO is a negative electrode material assembly liquid system half cell: li prepared in example 3₂V_0.5SO negative electrode powder, conductive agent (Super P) and adhesive (Super P)Polyvinylidene fluoride, PVDF and Poly (1,1-difluoroethylene)) are uniformly mixed and dispersed into a solvent (N, N-Dimethylformamide, DMF, N, N-Dimethylformamide) according to the proportion of 7:2:1, uniformly coated on a current collector copper foil in a spinning way, and after the solvent is evaporated to dryness, the current collector copper foil, a lithium battery diaphragm, a lithium metal negative electrode and a lithium battery electrolyte (ethylene carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1: 1) are added, and LiClO is added₄Concentration in the electrolyte is 1M) assembly liquid system half cell.

With Li in example 4₆V_1.5TiO₅Br₆Assembling a liquid-based half cell for a negative electrode material: li prepared in example 4₆V_1.5TiO₅Br₆Uniformly mixing and dispersing the negative electrode powder, a conductive agent (Super P) and a binder (polyvinylidene fluoride, PVDF, Poly (1,1-difluoroethylene)) in a solvent (N, N-Dimethylformamide, DMF, N, N-Dimethylformamide) according to a ratio of 7:2:1, uniformly coating the mixture on a current collector copper foil in a spinning mode, drying the solvent to dryness, then uniformly coating the dried solvent on a lithium battery diaphragm, a metal lithium negative electrode and a lithium battery electrolyte (ethylene carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1:1, and adding LiClO₄Concentration in the electrolyte is 1M) assembly liquid system half cell.

The discharge capacity cycling graphs of the assembled liquid-based half-cells of examples 3 and 4 were respectively measured as shown in fig. 9, and it can be seen from fig. 9 that the anti-perovskite cubic phase Li provided in example 3 is compared with that provided in example 3₂V_0.5SO as a negative electrode Material for a Battery, the anti-perovskite cubic/layered composite phase Li provided in example 4 was used₆V_1.5TiO₅Br₆The obtained liquid-system half-cell has better cycle stability as a negative electrode material of the cell.

The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

Claims

1. A lithium-containing anti-perovskite material, wherein the general formula of the lithium-containing anti-perovskite material is: li_xM_yA_z(ii) a Wherein M is a metal element or a metalloid element other than lithium, and M may be oxidized in the lithium-containing anti-perovskite material;

m is a metal element, A comprises anions in at least two valence states of-1, -2 and-3;

or, M is at least two metal elements, A includes an anion in at least one valence state from-1, 2, and-3.

2. The lithium-containing anti-perovskite material of claim 1, wherein M comprises Na⁺、K⁺、Mg²⁺、Ca²⁺、Sr²⁺、Ba²⁺、Zn²⁺、Sc²⁺、Y³⁺、Al³⁺、Ga³⁺、Ti³⁺、Zr²⁺、V³⁺、V⁴⁺、Nb³⁺、Nb⁴⁺、Ta³⁺、Ta⁴⁺、Cr²⁺、Cr³⁺、Cr⁴⁺、Mo³⁺、Mo⁴⁺、W²⁺、Mn²⁺、Mn³⁺、Fe²⁺、Fe³⁺、Co²⁺、Co³⁺、Ni²⁺、Ni³⁺、Cu⁺、Cu²⁺、Si²⁺、Si⁴⁺、Sn²⁺、Sn³⁺、Sb³⁺One or more of;

3. The lithium-containing anti-perovskite material of claim 2, wherein a comprises at least a-2 valent anion; or/and, A comprises at least O^2-。

4. The lithium-containing anti-perovskite material of claim 3, wherein the lithium-containing anti-perovskite material is Li_1.9Na_0.1Fe_0.6Co_0.2Mn_0.2OS or Li₂Co_0.5OCl_0.5Br_0.5。

5. Use of a lithium-containing anti-perovskite material as defined in any one of claims 1 to 4 as a positive electrode material.

6. A lithium-containing anti-perovskite material, wherein the general formula of the lithium-containing anti-perovskite material is: li_xM_yA_z(ii) a Wherein M is a metal element or metalloid element other than lithium, and A comprises an anion in at least one valence state of-1, -2, and-3; and M in the lithium-containing anti-perovskite material can be reduced.

7. The lithium-containing anti-perovskite material of claim 6, wherein M comprises Ti⁴⁺、Zr³⁺、Zr⁴⁺、V³⁺、V⁴⁺、V⁵⁺、Nb²⁺、Nb³⁺、Nb⁴⁺、Nb⁵⁺、Ta²⁺、Ta³⁺、Ta⁵⁺、Cr²⁺、Cr³⁺、Cr⁴⁺、Cr⁵⁺、Cr⁶⁺、Mo⁴⁺、Mo⁶⁺、W³⁺、W⁴⁺、W⁵⁺、W⁶⁺、Mn³⁺、Mn⁴⁺、Mn⁵⁺、Mn⁶⁺、Mn⁷⁺、Fe³⁺、Co³⁺、Ni³⁺、Ni⁴⁺、Si⁴⁺、Sn⁴⁺、Sb⁵⁺One or more of;

8. The lithium-containing anti-perovskite material of claim 7, wherein a comprises at least a-2 valent anion;

or/and, A comprises at least O^2-。

9. The lithium-containing anti-perovskite material of claim 8, wherein the lithium-containing anti-perovskite material is Li₆V_1.5TiO₅Br₆Or Li₂V_0.5SO。

10. Use of a lithium-containing anti-perovskite material as defined in any one of claims 6 to 9 as a negative electrode material.