WO2021043296A1

WO2021043296A1 - Electrode and solid-state battery based on inorganic oxide particles

Info

Publication number: WO2021043296A1
Application number: PCT/CN2020/113647
Authority: WO
Inventors: 李长明; 辛民昌; 陈久存; 吴超; 辛程勋
Original assignee: 青岛九环新越新能源科技股份有限公司
Priority date: 2019-09-06
Filing date: 2020-09-06
Publication date: 2021-03-11
Also published as: CN112467091A

Abstract

Disclosed is an electrode based on inorganic oxide particles, the electrode comprising an electrode active layer, wherein inorganic oxide particles I for conducting ions are included in the electrode active layer. Further disclosed is a solid-state battery based on inorganic oxide particles, the solid-state battery comprising a positive electrode, a negative electrode, and a solid-state electrolyte layer located between the positive electrode and the negative electrode, wherein the electrode based on the inorganic oxide particles is used as the positive electrode and/or the negative electrode. In the electrode based on inorganic oxide particles of the present invention, by providing inorganic oxide particles I within an electrode active layer, the inorganic oxide particles I can conduct ions, so that the ions can be conducted to the inside of the electrode active layer by utilizing the inorganic oxide particles I, and therefore, the ion permeability in the electrode active layer can be effectively improved, and the interface resistance can be reduced.

Description

Electrode and solid-state battery based on inorganic oxide particles

Technical field

The invention belongs to the technical field of energy storage equipment, and specifically is an electrode and a solid-state battery based on inorganic oxide particles.

Background technique

Solid-state battery is a battery technology. Unlike lithium-ion batteries and lithium-ion polymer batteries commonly used today, solid-state batteries are batteries that use solid electrodes and solid electrolytes. The traditional liquid lithium battery is vividly called "rocking chair battery" by scientists. The two ends of the rocking chair are the positive and negative poles of the battery, and the middle is the electrolyte (liquid). Lithium ions are like excellent athletes, running back and forth on both ends of the rocking chair. During the movement of lithium ions from the first capacitor electrode to the second capacitor electrode and then to the first capacitor electrode, the charging and discharging process of the battery is completed. The principle of a solid-state battery is the same, except that its electrolyte is solid, with a density and structure that allows more charged ions to gather at one end, conduct a larger current, and then increase the battery capacity. Therefore, with the same amount of power, the volume of solid-state batteries will become smaller. Not only that, because there is no electrolyte in the solid-state battery, it will be easier to seal. When used in large equipment such as automobiles, there is no need to add additional cooling tubes, electronic controls, etc., which not only saves costs, but also effectively reduces weight.

Summary of the invention

In view of this, the purpose of the present invention is to provide an electrode and a solid-state battery based on inorganic oxide particles, which can effectively increase the ion permeability in the electrode and reduce the interface resistance.

In order to achieve the above objective, the present invention provides the following technical solutions:

The present invention first proposes an electrode based on inorganic oxide particles, which includes an electrode active layer containing inorganic oxide particles I for conducting ions.

Further, the particle size of the inorganic oxide particles I is less than or equal to the thickness of the electrode active layer.

Further, the inorganic oxide particles I include but are not limited to Li _1.5 Al _0.5 Ti _1.5 P ₃ O ₁₂ , Li _1.5 Al _0.5 Ge _1.5 P ₃ O ₁₂ , Li _6.5 La ₃ Zr _1.5 Ta _0.5 O ₁₂ , Li _6.5 La ₃ Zr _1.5 Nb _0.5 O ₁₂ , Li _6.28 Al _0.24 La ₃ Zr ₂ O ₁₂ , Li _6.40 Ga _0.20 La ₃ Zr ₂ O ₁₂ , Li _0.45 La _0.55 TiO ₃ or Li _x PO _y N _z .

Further, it also includes an electrode current collector; the side of the inorganic oxide particles I facing away from the electrode current collector exposes the electrode active layer; or, at least two of the inorganic oxide particles I contact each other and form Inorganic oxide particle group I, in the inorganic oxide particle group I, at least one of the inorganic oxide particles I exposes the electrode active layer.

The present invention also provides a solid-state battery based on inorganic oxide particles, including a positive electrode, a negative electrode, and a solid electrolyte layer located between the positive electrode and the negative electrode. The positive electrode and/or the negative electrode adopt the above-mentioned inorganic oxide-based Particle electrode.

Further, the solid electrolyte layer contains inorganic oxide particles II.

Further, the particle size of the inorganic oxide particles II is less than or equal to the thickness of the solid electrolyte layer.

Further, the inorganic oxide particles II include but are not limited to Li _1.5 Al _0.5 Ti _1.5 P ₃ O ₁₂ , Li _1.5 Al _0.5 Ge _1.5 P ₃ O ₁₂ , Li _6.5 La ₃ Zr _1.5 Ta _0.5 O ₁₂ , Li _6.5 La ₃ Zr _1.5 Nb _0.5 O ₁₂ , Li _6.28 Al _0.24 La ₃ Zr ₂ O ₁₂ , Li _6.40 Ga _0.20 La ₃ Zr ₂ O ₁₂ , Li _0.45 La _0.55 TiO ₃ or Li _x PO _y N _z .

Further, the solid electrolyte layer is exposed on both sides of the inorganic oxide particles II; or at least two of the inorganic oxide particles II are in contact with each other and form an inorganic oxide particle group II, the inorganic oxide particles In group II, at least two of the inorganic oxide particles II are respectively exposed on both sides of the solid electrolyte layer.

Further, the inorganic oxide particles II arranged in the solid electrolyte layer are in contact with the inorganic oxide particles I arranged in the positive electrode and/or the negative electrode to realize ion transmission.

The beneficial effects of the present invention are:

The electrode of the present invention is based on inorganic oxide particles. By arranging inorganic oxide particles I in the electrode active layer, the inorganic oxide particles I can conduct ions. In this way, the inorganic oxide particles I can conduct ions to the inside of the electrode active layer. It can effectively increase the ion permeability in the electrode active layer and reduce the interface resistance.

The solid-state battery based on inorganic oxide particles of the present invention has the following advantages:

1) Inorganic oxide particles I are arranged in the positive electrode and/or negative electrode, which can increase the ion permeability in the positive electrode and/or negative electrode and reduce the interface resistance;

2) Inorganic oxide particles II are arranged in the solid electrolyte layer. The inorganic oxide particles II can effectively separate the positive electrode and the negative electrode. In this way, the positive electrode and the negative electrode can be prevented from contacting and short-circuit, and the solid electrolyte layer can be made thinner and reduced. Small internal resistance

3) The inorganic oxide particles II arranged in the solid electrolyte layer are in contact and coordination with the inorganic oxide particles I arranged in the positive electrode and the negative electrode, that is, ion transport channels can be formed between the inorganic oxide particles I and the inorganic oxide particles II. , Enhance ion transmission efficiency.

Description of the drawings

In order to make the objectives, technical solutions and beneficial effects of the present invention clearer, the present invention provides the following drawings for illustration:

1 is a schematic structural diagram of an embodiment of a solid-state battery based on inorganic oxide particles of the present invention;

Figure 2 is a schematic diagram of the structure of an electrode based on inorganic oxide particles.

Description of reference signs:

1-positive electrode; 2-negative electrode; 3-solid electrolyte layer; 4-electrode active layer; 5-inorganic oxide particles I; 6-inorganic oxide particles II; 7-electrode current collector.

detailed description

The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention, but the examples given are not intended to limit the present invention.

As shown in FIG. 1, it is a schematic structural diagram of an embodiment of a solid-state battery based on inorganic oxide particles of the present invention. The solid-state battery based on inorganic oxide particles in this embodiment includes a positive electrode 1, a negative electrode 2, and a solid electrolyte layer 3 located between the positive electrode 1 and the negative electrode 2, and the positive electrode 1 and/or the negative electrode 2 are made of an electrode based on inorganic oxide particles. . Both the positive electrode 1 and the negative electrode 2 of this embodiment adopt electrodes based on inorganic oxide particles. Of course, it is also possible to use only the positive electrode 1 as an electrode based on inorganic oxide particles to increase the ion permeability of the positive electrode 1, or only the negative electrode 2 An electrode based on inorganic oxide particles is used to increase the ion permeability of the negative electrode 2.

As shown in FIG. 2, the electrode based on inorganic oxide particles of this embodiment includes an electrode active layer 4, and the electrode active layer 4 contains inorganic oxide particles I5 for conducting ions.

Further, the particle size of the inorganic oxide particles I5 is less than or equal to the thickness of the electrode active layer 4, the particle size of the inorganic oxide particles I5 in this embodiment is equal to the thickness of the electrode active layer 4, and the mass of all the inorganic oxide particles I5 in this embodiment The ratio to the total mass of the electrode active layer 4 is less than or equal to 50%, so as to prevent the inorganic oxide particles I5 from excessively affecting the energy density of the electrode active layer 4.

Further, the inorganic oxide particles I5 include but are not limited to Li _1.5 Al _0.5 Ti _1.5 P ₃ O ₁₂ , Li _1.5 Al _0.5 Ge _1.5 P ₃ O ₁₂ , Li _6.5 La ₃ Zr _1.5 Ta _0.5 O ₁₂ , Li _6.5 La ₃ Zr _1.5 Nb _0.5 O ₁₂ , Li _6.28 Al _0.24 La ₃ Zr ₂ O ₁₂ , Li _6.40 Ga _0.20 La ₃ Zr ₂ O ₁₂ , Li _0.45 La _0.55 TiO ₃ or Li _x PO _y N _z .

Further, the solid electrolyte layer 3 contains inorganic oxide particles II6, and the particle size of the inorganic oxide particles II6 is less than or equal to the thickness of the solid electrolyte layer 3. The particle size of the inorganic oxide particles II6 of this embodiment is equal to the thickness of the solid electrolyte layer 3. Since the ceramic material used in the inorganic oxide particles II6 can be used to transport ions, the ratio between the mass of the inorganic oxide particles II6 and the total mass of the solid electrolyte layer 3 may not be particularly limited. The gelatinous material used in the solid electrolyte layer 3 On the one hand, the solid electrolyte material can be used to transport ions, and on the other hand, it can fill the space between the inorganic oxide particles II6. Therefore, the solid electrolyte layer 3 is obtained by curing the inorganic oxide particles II6 and the colloidal solid electrolyte material.

Further, the inorganic oxide particles II6 include but are not limited to Li _1.5 Al _0.5 Ti _1.5 P ₃ O ₁₂ , Li _1.5 Al _0.5 Ge _1.5 P ₃ O ₁₂ , Li _6.5 La ₃ Zr _1.5 Ta _0.5 O ₁₂ , Li _6.5 La ₃ Zr _1.5 Nb _0.5 O ₁₂ , Li _6.28 Al _0.24 La ₃ Zr ₂ O ₁₂ , Li _6.40 Ga _0.20 La ₃ Zr ₂ O ₁₂ , Li _0.45 La _0.55 TiO ₃ or Li _x PO _y N _z .

Furthermore, the electrode of this embodiment further includes an electrode current collector 7; the side of the inorganic oxide particles I5 facing away from the electrode current collector 7 exposes the electrode active layer 4; or, at least two inorganic oxide particles I5 contact each other and form Inorganic oxide particle group I, in the inorganic oxide particle group I, at least one inorganic oxide particle I exposes the electrode active layer 4, that is, the inorganic oxide particle I5 exposes the electrode active layer 4 to facilitate ion conduction to the electrode active layer 4 internal. The side of the inorganic oxide particles I5 facing away from the electrode current collector 7 of this embodiment exposes the electrode active layer 4.

The solid electrolyte layer 3 is exposed on both sides of the inorganic oxide particles II6; or at least two inorganic oxide particles II6 are in contact with each other to form an inorganic oxide particle group II. In the inorganic oxide particle group II, there are at least two inorganic oxide particles. The oxide particles II are respectively exposed on both sides of the solid electrolyte layer. In this way, ions can be directly conducted between the positive electrode 1 and the negative electrode 2 through the inorganic oxide particles II6, without the need to transfer the ions between the ceramic material and other solid electrolyte materials, which can effectively improve the ion transmission efficiency. The solid electrolyte layer 3 is exposed on both sides of the inorganic oxide particles II6 of this embodiment.

Further, the inorganic oxide particles II6 arranged in the solid electrolyte layer 3 are in contact with the inorganic oxide particles I5 arranged in the positive electrode 1 and/or the negative electrode 2 to achieve ion transmission. In this way, the positive electrode 1 and the negative electrode 2 can transmit ions through the ion transmission channel constructed between the inorganic oxide particles I5 and the inorganic oxide particles II6, and can also transmit ions through other solid electrolyte materials, and the ion transmission efficiency is higher.

The present invention is a solid-state battery based on inorganic oxide particles. By arranging inorganic oxide particles I in the electrode active layer, the inorganic oxide particles I can conduct ions. In this way, the inorganic oxide particles I can conduct ions to the inside of the electrode active layer. It can effectively increase the ion permeability in the electrode active layer and reduce the interface resistance.

The solid-state battery based on inorganic oxide particles in this embodiment also has the following advantages:

The above-mentioned embodiments are only preferred embodiments for fully explaining the present invention, and the protection scope of the present invention is not limited thereto. Equivalent substitutions or alterations made by those skilled in the art on the basis of the present invention are all within the protection scope of the present invention. The protection scope of the present invention is subject to the claims.

Claims

An electrode based on inorganic oxide particles, comprising an electrode active layer, characterized in that the electrode active layer contains inorganic oxide particles I for conducting ions.
The electrode based on inorganic oxide particles according to claim 1, wherein the particle diameter of the inorganic oxide particles I is less than or equal to the thickness of the electrode active layer.
The electrode based on inorganic oxide particles according to claim 1, wherein the inorganic oxide particles I include but are not limited to Li 1.5 Al 0.5 Ti 1.5 P 3 O 12 , Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 , Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 , Li 6.5 La 3 Zr 1.5 Nb 0.5 O 12 , Li 6.28 Al 0.24 La 3 Zr 2 O 12 , Li 6.40 Ga 0.20 La 3 Zr 2 O 12 , Li 0.45 La 0.55 Made of TiO 3 or Li x PO y N z.
The electrode based on inorganic oxide particles according to claim 1, further comprising an electrode current collector; the side of the inorganic oxide particles I facing away from the electrode current collector exposes the electrode active layer; or At least two of the inorganic oxide particles I are in contact with each other and form an inorganic oxide particle group I. In the inorganic oxide particle group I, at least one of the inorganic oxide particles I exposes the electrode active layer .
A solid state battery based on inorganic oxide particles, comprising a positive electrode, a negative electrode, and a solid electrolyte layer located between the positive electrode and the negative electrode, characterized in that: the positive electrode and/or the negative electrode adopt any one of claims 1 to 4 The described electrode is based on inorganic oxide particles.
The solid-state battery based on inorganic oxide particles according to claim 5, wherein the solid electrolyte layer contains inorganic oxide particles II.
The solid-state battery based on inorganic oxide particles according to claim 5, wherein the particle size of the inorganic oxide particles II is less than or equal to the thickness of the solid electrolyte layer.
The solid-state battery based on inorganic oxide particles according to claim 5, wherein the inorganic oxide particles II include but are not limited to Li 1.5 Al 0.5 Ti 1.5 P 3 O 12 , Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 , Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 , Li 6.5 La 3 Zr 1.5 Nb 0.5 O 12 , Li 6.28 Al 0.24 La 3 Zr 2 O 12 , Li 6.40 Ga 0.20 La 3 Zr 2 O 12 , Li 0.45 La 0.55 Made of TiO 3 or Li x PO y N z.
The solid-state battery based on inorganic oxide particles according to claim 5, wherein the solid electrolyte layer is exposed on both sides of the inorganic oxide particles II; or at least two of the inorganic oxide particles II are in contact with each other Together and form an inorganic oxide particle group II, in the inorganic oxide particle group II, at least two of the inorganic oxide particles II are respectively exposed on both sides of the solid electrolyte layer.
The solid-state battery based on inorganic oxide particles according to claim 9, characterized in that: the inorganic oxide particles II arranged in the solid electrolyte layer and the inorganic oxide particles II arranged in the positive electrode and/or negative electrode The oxide particles I contact together and realize ion transmission.