CN111326709A - Electrode active material with coating in multilayer system and lithium ion battery cell - Google Patents

Electrode active material with coating in multilayer system and lithium ion battery cell Download PDF

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CN111326709A
CN111326709A CN201911272433.1A CN201911272433A CN111326709A CN 111326709 A CN111326709 A CN 111326709A CN 201911272433 A CN201911272433 A CN 201911272433A CN 111326709 A CN111326709 A CN 111326709A
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active material
coating
electrode active
layer
solid electrolyte
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E.乔赫勒
D.A.韦伯
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Volkswagen AG
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to an electrode active material for a lithium ion battery, comprising active material particles (1) which have a first coating (2) consisting of a solid electrolyte, wherein the active material particles (1) have a second coating (3) consisting of an electron-conducting material, which is applied to the first coating (2), and wherein the first coating (2) is applied to the active material in a thickness which allows electron transport through the first coating (2), and to a secondary battery comprising the electrode active material according to the invention and to the use of the electrode active material for producing a battery cell, in particular for producing a traction battery for vehicles. Advantageously, with the electrode active material for lithium ion batteries according to the invention, it is possible to increase the efficiency of the anode and cathode active materials at voltages >4.2V, in particular at 4.9V, and to improve the service life and the high current carrying capacity.

Description

Electrode active material with coating in multilayer system and lithium ion battery cell
Technical Field
The invention relates to a coating for an electrode active material of a lithium ion battery, in particular for use in an electric vehicle as a traction battery, having the features of the preamble of claim 1.
Prior Art
Coated electrode active materials are known in the art. German application publication DE 3443455 a1 describes a galvanic cell with a polymer electrode. As the electrode support, an aluminum substrate may be used, the surface of which includes a usual oxide protective layer. The aluminum substrate can furthermore be coated with an electron-conducting material, for example graphite or metal. Electrode materials comprising lithium ions are not mentioned.
Between the active material of the electrode material, in particular of the cathode, and the electrolyte in a lithium-ion battery cell>An undesirable side reaction occurs at a high voltage of 4.2V because the cathode active material is in direct contact with the electrolyte. The result of the side reaction is cation release from the cathode active material, which leads to a degradation of the power of the cathode active material and thus to a reduction of the overall efficiency of the lithium-ion battery cell. Particularly in the cathode active material LiNi0.5Mn1.5O4Nickel and manganese ions are dissolved out of the structure at a voltage of 4.9V, diffuse through the separator to the anode and metal deposition occurs there.
It also results therefrom that direct contact between the cathode active material and the electrolyte occurs in the lithium ion battery cell, leading to decomposition of the electrolyte, in particular at high voltages > 4.2V. The efficiency of the lithium ion battery cell is reduced.
It is therefore absolutely necessary to protect the cathode active material and the electrolyte from the above-mentioned degradation mechanism or degradation effect in order to stably maintain or extend the service life of the lithium ion battery cell.
Furthermore, an electrolyte for a lithium secondary battery is known from european patent document EP 2472662B 1, said electrolyte comprising a lithium salt, a non-aqueous organic solvent and a vitamin selected from vitamin G, B4、B5、H、M、D2、Bx、D3And K1The additive of (1). According to the above document, the cathode may have a thin film on the surface thereof, the thin film being formed by oxidation of the additive by the primary application of voltage.
Electrode materials for lithium ion batteries are also known, which are either pre-coated with a polymer coating as a protective layer for the active material, in particular to prevent oxidation, or in which a solid electrolyte is applied, in particular for the cathode active material, as disclosed, for example, in U.S. patent application No. US2017/0018760 a1 or in german application publication No. DE 102015217749 a 1.
In all the coated electrode materials known to date, the coating serves either as a protection for the sensitive active material or at the same time as a lithium ion conductor.
A disadvantage here, however, is that the electron transport is impeded because the known coatings cannot conduct electrons. The solid electrolyte is a simple ionic conductor, not an electronic conductor. Furthermore, in view of the direct contact between the electrode active material and the solid electrolyte, the electrolyte is caused to decompose especially at high pressure, which results in a decrease in the efficiency of the lithium ion battery.
Disclosure of Invention
The object of the present invention is therefore to provide an improved electrode active material which has good protection of the active material and at the same time also good electronic conductivity. Improved efficiency, higher high-voltage loadability (load capacity) and improved service life of lithium ion batteries should therefore be achieved.
The object is achieved according to the invention by an electrode active material having the features of claim 1.
The present invention includes an electrode active material for a lithium ion battery, the electrode active material including active material particles having a first coating layer composed of a solid electrolyte.
According to the invention, the active material particles have a second coating of an electron-conducting material, which is applied to the first coating, and the first coating (2) is applied to the active material with a thickness that allows electron transport through the first coating (2) to take place, or the first coating is applied to the active material with a thickness such that electron transport through the first coating or in other words electron transport through the first coating can take place.
Coatings with only a conventional solid electrolyte electrically insulate the electrode particles from each other, because the solid electrolyte is a pure ionic conductor and does not conduct electrons.
Advantageously, with the electrode active material according to the invention, which can be both a cathode material and an anode material, it is possible to achieve ionic and electronic contact of the anode and cathode active material particles with one another in order to conduct lithium ions and at the same time transport electrons to the current arrester.
This is achieved in the first aspect of the invention in that the solid electrolyte layer of the first coating layer is very thin, yet thick enough to protect the active material particles. The solid electrolyte layer may be, for example, as thin as one atomic layer to several atomic layers. For electron transition through solid electrolytes
Figure BDA0002314560430000031
The transmission coefficient of (a) should thus be very high, i.e. as close to 1 as possible.
A second aspect of the invention consists in depositing a second layer on the first layer, which second layer can conduct electrons very well. The second layer may have a lower fermi energy and a lower work function (otherwise known as work function).
The efficiency of the anode and cathode active materials at voltages >4.2V, in particular at 4.9V, is increased due to the at least double coating of the anode and cathode active materials in a multilayer system by means of a high-voltage-stable solid electrolyte as a first coating and an electron-conducting layer using tunneling effect as a second coating.
This is because material dissolution and electrolyte decomposition are avoided. Thus improving the efficiency of the lithium ion battery cell. The improved efficiency of the lithium-ion battery cell is, in particular, a longer service life and a high current carrying capacity.
In one embodiment of the present invention, the first coating layer is formed of a solid electrolyte including a solid electrolyte material selected from the group consisting of: NASICON solid electrolytes, particularly LATP or LAGP; and (anti) perovskites, especially LLTO or Li3OCl。
The deposition may be achieved by physical, wet chemical or mechanical means. Deposition or coating (application) methods are generally known to the person skilled in the art. For example, Atomic Layer Deposition (ALD), Molecular Layer Deposition (MLD), Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD), electron beam deposition, laser deposition, plasma deposition, radio frequency sputtering, micro-emulsion deposition, continuous ionic layer deposition, aqueous phase deposition, solid phase diffusion, sputter coating, sol-gel coating, or powder coating.
By selecting the solid electrolyte as the first coating layer, it can be ensured that, depending on the type of the electron, the cathode or the anode material, very good ionic conductivity and at the same time good protection of the electrode active material are achieved. By utilizing the tunneling effect and thus the electron conductivity, the decomposition of the solid electrolyte material due to high voltage is suppressed.
In one embodiment of the invention, the second coating is comprised of an electron conducting material selected from the group consisting of: graphite; titanium; zirconium; boron; vanadium oxide; titanium oxide; niobium oxide; lithium metal alloys, especially Zn-Li, Sn-Li, Al-Li; lithium metal oxides, especially Li2ZrO3、Li3.5Al2O3、Li4Ti5O12(ii) a And lithium metal fluorides, especially Li3AlF6、Li2AlF4、Li3VF6。
The material conducts electrons very well and has a low fermi energy. In addition, it has a low work function WA. The deposition may be achieved by physical, wet chemical or mechanical means.
In another embodiment of the electrode material according to the invention, the electrode active material of the active material particles is LiNi0.5Mn1.5O4。
By this design, a significant improvement in the high-voltage stability and thus a longer service life of the battery comprising this material can be achieved, in particular for the cathode active material.
In a further preferred embodiment of the invention, the first coating has a layer thickness of 0.05nm to 100nm, in particular 0.1nm to 80nm, and preferably 0.5nm to 50 nm.
In this way, the aim is achieved that the tunnel effect is exploited, i.e. that electrons cross a path from the cathode active material to the second coating layer, which is electronically conductive, despite the presence of an electrically insulating solid electrolyte layer between the cathode active material and the second coating layer.
In other words, the first coating has a layer thickness of preferably from one to several atomic layers and is applied by means of physical, wet-chemical or mechanical methods.
The second coating may be applied by physical, wet chemical or mechanical means.
The method for coating the electrode active material particles may be adjusted according to the manufacturing process. As a suitable method thereof, for example, physical or chemical vapor deposition, Atomic Layer Deposition (ALD), Molecular Layer Deposition (MLD), Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD), electron beam deposition, laser deposition, plasma deposition, radio frequency sputtering, micro-emulsion deposition, continuous ionic layer deposition, aqueous phase deposition, solid phase diffusion, sputter coating, sol-gel coating, or powder coating may be mentioned.
Suitable electrode active materials are all substances known for lithium ion batteries. For example, but not limited to, the following list may be listed:
suitable oxide electrode active material for cathodeThe materials are as follows: LiNiCoAlO2；LiNiCoMnO2(NMC)；LiMn2-xMxO4Wherein M ═ Ni, Fe, Co, or Ru, and x ═ 0 to 0.5; and LiCoO2(LCO)。
Suitable anode active materials are, for example, the following: v2O5，LiVO3，Li3VO4And Li4Ti5O12(LTP)。
Furthermore, compounds containing phosphates are suitable as electrode materials, for example Li for cathodes3V2(PO4)3Or LiMPO4Where M is 1/4(Fe, Co, Ni, Mn), or LiM for anodes2(PO4)3Or mixtures thereof, wherein M ═ Zr, Ti, Hf.
In a further embodiment of the invention, a third coating of a solid electrolyte is applied to the second coating, and optionally a fourth coating of an electron-conducting material is applied to the third coating.
The order of the two layers is preserved, but more coating is applied. Thereby, improvement (improvement) of the high voltage stability and long-term durability of the electrode material according to the present invention can be achieved again. The invention is not limited to a two-layer or four-layer multilayer coating. Likewise, within the scope of the invention, further coating layers are applied in the same sequence, wherein a solid electrolyte layer or an electron-conducting layer is to be provided as an outer layer in each case optionally.
Another technical solution of the present invention resides in a secondary battery including the electrode active material according to the present invention.
The technical solution according to the invention is also the use of the electrode active material according to the invention as described above for producing a battery cell, in particular for producing a battery cell for a traction power battery for a vehicle.
Drawings
There are numerous possibilities for designing and improving electrode active materials. For this purpose reference is made primarily to the dependent claims of claim 1. The preferred embodiments of the invention are explained in more detail below with the aid of the figures and the associated description. In the drawings:
fig. 1 shows a very schematic representation of a cross section of an electrode material, and shows a detail of a particle of such an electrode material according to the invention,
figure 2 shows in a very schematic representation the energy curve of the coated active material according to the invention under applied voltage,
FIG. 3 shows, in a very schematic representation, a cross-sectional view of an electrode material particle with a multilayered coating according to a further aspect of the invention, an
Fig. 4 shows a cross-sectional view of an electrode material particle with a multilayered coating according to a further aspect of the invention in a very schematic illustration.
Detailed Description
Fig. 1 schematically shows a cross section of an electrode material according to the invention and an enlarged detail thereof. An electrode active material for a lithium ion battery includes active material particles 1 having a first coating layer 2 composed of a solid electrolyte. According to the invention, the active material particles 1 have a second coating 3 of an electron-conducting material, which is applied to the first coating 2. The first coating layer 2 is applied to the active material 1 at such a thickness that electron transport through the first coating layer 2 is allowed to take place.
Suitable oxide electrode active materials for the cathode are, for example: LiNiCoAlO2；LiNiCoMnO2(NMC)；LiMn2-xMxO4Wherein M ═ Ni, Fe, Co, or Ru, and x ═ 0 to 0.5; and LiCoO2(LCO)。
Suitable anode active materials are, for example, the following: v2O5、LiVO3、Li3VO4And Li4Ti5O12(LTP)。
Furthermore, compounds containing phosphates are suitable as electrode materials, for example Li for cathodes3V2(PO4)3Or LiMPO4Where M is 1/4(Fe, Co, Ni, Mn), or LiM for anodes2(PO4)3Or mixtures thereof, wherein M ═ Zr, Ti, Hf.
Preferably, the electrode active material of the active material particles 1 may be LiNi0.5Mn1.5O4。
In other words, the coating of the anode and cathode active material particles is also achieved with the first coating 2, which is a very thin, ion-conducting, solid electrolyte layer, of the order of one to several atomic layers. Since the solid electrolyte layer itself cannot conduct electrons, this layer 2 is applied very thinly, so that the tunnel effect can be used.
High-voltage-stable hybrid or non-hybrid solid electrolytes, i.e. NASICON types such as LATP, LAGP or such as LLTO or Li3The (anti-) perovskites of OCl are deposited on anode or cathode active material particles 1.
Without being limited thereto, the following exemplary descriptions are of specific compounds which are suitable for use as solid electrolytes in the indicated range:
oxides, e.g. Li7-xLa3Zr2AlxO12Wherein x is 0 to 0.5, or Li7La3Zr2-xTaxO12Wherein x is 0 to 0.5,
lithium aluminium titanium phosphates, e.g. Li1+xMxTi2-x(PO4)3Wherein x is 0 to 7, and M is al (latp), Fe, Y or Ge,
lanthanum lithium zirconate, where doping with tantalum, aluminum and iron may additionally be used,
lithium phosphorus sulfide (Lithiumphosphorusulfide), which may be doped with germanium and selenium, for example Li7P3S11、Li10P3S12、Li10MxP3-xS12Wherein M ═ Ge, Se, and x ═ 0 to 1, wherein M ═ ayBzWherein a ═ Si, Ge, and B ═ Sn, Si, and wherein y ═ 0 to 0.5, and z ═ 1-y.
The first coating 2 can preferably have a layer thickness of 0.05nm to 100nm, in particular 0.1nm to 80nm, and preferably 0.5nm to 50 nm.
An important second aspect of the invention consists in depositing on the first coating 2 a layer 3, said layer 3 being capable of conducting electrons very well and having a low fermi energy (see E3 in fig. 2) and a low work function (see WA (3) in fig. 2), such as graphite and metals (titanium, boron, zirconium, etc.), metal oxides (VO), etc2、TiO、NbO2Etc.), lithium metal alloys (Zn-Li, Sn-Li, Al-Li, etc.), lithium metal oxides (Li)2ZrO3、Li3.5Al2O3、Li4Ti5O12Etc.) or lithium metal fluoride (Li)3AlF6、Li2AlF4、Li3VF6Etc.).
Further, lithium ions cross a path from the active material or the solid electrolyte by means of tunneling via the electron conductive material, respectively.
The efficiency of the anode and cathode active materials at voltages >4.2V, in particular at 4.9V, is improved due to the coating of the anode and cathode active materials in a multilayer system, by means of a high-voltage stable solid electrolyte and an electron conducting layer using tunneling effect.
This is because material dissolution and electrolyte decomposition are avoided. Thus improving the efficiency of the lithium ion battery cell. The improved efficiency of the lithium-ion battery cell is, in particular, a longer service life and a high current carrying capacity.
The multi-layered coating layer consisting of the solid electrolyte 2 and the electron conductive material 3 on the anode and cathode active materials 1 can conduct electrons in addition to lithium ions and is stable at high voltage. This has the result, inter alia, that one or more of the following advantages are achieved:
protection of the electrolyte against decomposition by high voltages.
Protection of cathode active materials, in particular LiNi0.5Mn1.5O4No material dissolution occurs at high temperature and high voltage.
-avoiding structural changes of the cathode active material during cell cycling of the battery.
-using the tunneling effect of a non-electronically conductive solid electrolyte;
-improving the efficiency of the cathode active material, the electrode and the lithium ion battery cell consisting thereof.
Both coatings 2 and 3 are applied to the active material particles 1 by means of suitable methods known to the person skilled in the art of manufacturing lithium-ion battery cells, for example vapor deposition or the like. For example, Atomic Layer Deposition (ALD), Molecular Layer Deposition (MLD), Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD), electron beam deposition, laser deposition, plasma deposition, radio frequency sputtering, micro-emulsion deposition, continuous ionic layer deposition, aqueous phase deposition, solid phase diffusion, sputter coating, sol-gel coating, or powder coating.
The energy curves of the anode or cathode active material particles 1, of the solid electrolyte 2 and of the electron conductor 3 are schematically shown in fig. 2.
The effect of the invention is to exploit the tunnel effect, i.e. the electrons cross the path from the cathode active material 1 to the second coating 3, which is electronically conductive, despite the presence of the electrically insulating solid electrolyte layer 2 between the cathode active material 1 and the second coating 3.
When a voltage is applied on both sides of the potential barrier (barrier), for example in the operating case of a battery, the fermi levels E1 and E3 differ from each other by eV, because electrons are extracted on the right side 3. A void state for the electrons of the left side 1 is thus formed on the right side 3, whereby tunneling, i.e. electron transport through the non-electron-conducting layer 2, is easily obtained.
Fig. 3 schematically shows a cross-sectional view of an anode or cathode active material particle 1 according to the invention with a multilayer system of a solid electrolyte layer 2 and an electron conductor layer 3, wherein the outermost layer is always the solid electrolyte layer 2.
Fig. 4 schematically shows a cross-sectional view of an anode or cathode active material particle 1 according to the invention with a multilayer system of a solid electrolyte layer 2 and an electron conductor layer 3, wherein the outermost layer is always the electron conductor layer 3.
The sequence of the solid electrolyte layer 2 and the electron conductor layer 3 can be extended in this case as desired until the desired protection against degradation of the cathode active material and the electrolyte is achieved, but no insulating effect is yet established.
Since the coating of the anode and cathode active materials 1 is carried out in a multilayer system, by means of a high-voltage-stable solid electrolyte 2 and an electron-conducting layer 3 using tunneling effect, the efficiency of the anode and cathode active materials at voltages >4.2V, in particular at 4.9V, is increased.
This is because material dissolution and electrolyte decomposition are avoided. Thus improving the efficiency of the lithium ion battery cell. The improved efficiency of the lithium-ion battery cell is, in particular, a longer service life and a high current carrying capacity.
List of reference numerals
1 electrode active material particles
2 first coating
3 second coating layer

Claims (10)

1. An electrode active material for a lithium ion battery, comprising active material particles (1) having a first coating layer (2) of a solid electrolyte, characterized in that the active material particles (1) have a second coating layer (3) of an electron-conducting material, which is applied on the first coating layer (2), and wherein the first coating layer (2) is applied on the active material at a thickness which allows electron transport through the first coating layer (2) to take place.
2. The electrode active material according to claim 1, wherein the first coating layer (2) is composed of a solid electrolyte comprising a solid electrolyte material selected from the group consisting of: NASICON solid electrolytes, particularly LATP or LAGP; and (anti) perovskites, especially LLTO or Li3OCl。
3. The electrode active material according to claim 1 or 2, characterized in that the second coating layer (3) is composed of an electron-conducting material selected from: graphite; titanium; zirconium; boron(ii) a Vanadium oxide; titanium oxide; niobium oxide; lithium metal alloys, especially Zn-Li, Sn-Li, Al-Li; lithium metal oxides, especially Li2ZrO3、Li3.5Al2O3、Li4Ti5O12(ii) a And lithium metal fluorides, especially Li3AlF6、Li2AlF4、Li3VF6。
4. An electrode active material according to any one of the preceding claims, wherein the electrode active material of the active material particles is LiNi0.5Mn1.5O4。
5. The electrode active material according to any one of the preceding claims, characterized in that the first coating (2) has a layer thickness of 0.05nm to 100nm, in particular 0.1nm to 80nm, and preferably 0.5nm to 50 nm.
6. Electrode active material according to one of the preceding claims, characterized in that the first coating (2) has a layer thickness of a maximum of a plurality of atomic layers and is applied by means of a physical, wet-chemical or mechanical method.
7. Electrode active material according to any of the preceding claims, characterized in that the second coating (3) is applied by means of a physical, wet-chemical or mechanical method.
8. Electrode active material according to one of the preceding claims, characterized in that a third coating of solid electrolyte (2) is applied on the second coating (3).
9. A secondary battery comprising the electrode active material according to any one of the preceding claims.
10. Use of an electrode active material according to any one of the preceding claims 1 to 9 for the manufacture of a battery cell, in particular for the manufacture of a traction power battery for a vehicle.
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