Lithium borosilicate glass as electrolyte and electrode protection layer

Abstract

Disclosed are lithium borosilicate compositions consisting essentially of a system of lithium oxide in combination with silicon oxide and boron oxide, wherein the lithium borosilicate comprises between 70 and 83 atomic percent lithium based on the total atomic percent of lithium, boron and silicon, and wherein the lithium borosilicate is a glass.

Description

[0001] This application is a divisional application of the invention patent application filed on June 12, 2017, with application number 201780037158.8 and invention title "Lithium borosilicate glass as an electrolyte and electrode protective layer". Invention Field

[0002] This invention relates to lithium borosilicate electrolytes and batteries containing the lithium borosilicate electrolyte. Background of the Invention

[0003] This invention relates to lithium borosilicate glass compositions, which are essentially composed of a system of lithium oxide combined with silicon oxide and / or boron oxide, and preferably essentially composed of a ternary system of lithium oxide, silicon oxide and boron oxide. Ren et al., in Journal of the American Ceramic Society, 98

[12] (2015)3603-3623, defined a series of properties required for an electrolyte if it is to be used in a solid-state battery. The electrolyte should have high lithium-ion conductivity at room temperature, negligible electronic conductivity (lithium-ion transference number close to one), a wide electrochemical window, and stability against adjacent electrodes. In addition, if lithium is used as the anode, the electrolyte must be lithium-stable.

[0004] One example of a solid-state electrolyte exhibiting some of these properties is lithium phosphorus oxynitride (LiPON). It displays high stability when in contact with lithium metal, possesses a sufficiently wide electrochemical window, and has negligible electronic conductivity. This makes it a successful candidate for use in thin-film solid-state batteries.

[0005] A significant challenge in the development of solid-state batteries is the identification of novel solid-state electrolytes that can be used to replace LiPON. The identification of new electrolytes with the desired properties is neither simple nor predictable. Furthermore, materials with the desired structure and ionic conductivity of a solid-state electrolyte may not necessarily prove stable when operating in a solid-state battery device.

[0006] This limits the design of new electrolyte materials for solid-state batteries and leads to a trial-and-error approach in materials design. Further research has been proposed to better understand the trends and mechanisms present in different types of lithium-ion conductors in order to facilitate the design of advanced lithium-ion conductors. (Bachman et al., Chemical Reviews, 116(2016)140-162.)

[0007] Having the composition Li 0.78 B 0.11 Si 0.11 and Li 0.77 B 0.18 Si0.05 Lithium borosilicate compounds and Li 0.78 B 0.06 Si 0.16 The nitrogen-doped variant has been disclosed in WO2015 / 104540, Vapor Deposition Method for Preparing Amorphous Lithium Containing Compounds. The material was synthesized according to the embodiments disclosed herein. The ionic conductivity is 3.2 × 10⁻⁶. -6 The material exhibits an amorphous structure with a strength of S / cm. A solid-state battery comprising a lithium borosilicate electrolyte, a lithium manganese oxide (LMO) cathode, and a tin oxide (SnO2) anode was fabricated. This disclosure does not provide any guidance regarding electrochemical stability as a function of potential, or regarding electrochemical stability and reactivity when in contact with lithium or operating in a solid-state battery device with a lithium anode. As proposed by Bachman et al., the behavior of a specific composition of lithium borosilicate cannot be predicted based on its structure and ionic conductivity. Invention Overview

[0008] According to a first aspect of the invention, an electrode is provided comprising an electrode active material; wherein the surface of the electrode is modified with a lithium borosilicate composition, wherein the lithium borosilicate composition is substantially composed of a system of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron and silicon, and wherein the lithium borosilicate is glass.

[0009] According to a second aspect of the invention, a battery is provided comprising a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein the surface of the positive electrode and / or the negative electrode is modified with a lithium borosilicate composition, wherein the lithium borosilicate composition is substantially composed of a system of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is glass.

[0010] According to a third aspect of the invention, a battery is provided comprising a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein the negative electrode comprises lithium, wherein the electrolyte is a lithium borosilicate composition, wherein the lithium borosilicate composition is substantially composed of a system of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is glass.

[0011] According to a fourth aspect of the invention, a battery is provided comprising a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein the electrolyte is a lithium borosilicate composition, wherein the lithium borosilicate composition is substantially composed of a system of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is glass, and wherein the battery has a full charge capacity of less than 0.5 μAh.

[0012] According to a fifth aspect of the invention, a battery is provided comprising a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein the positive electrode comprises a positive electrode active material selected from the group consisting of LiCoPO4 and LiNi. 0.5 Mn 1.5 O4, LiMnPO4, LiCoO2, LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2, LiFePO4, LiNiPO4, Li2NiPO4F, Li2CoPO4F, LiMnPO4F, Li2CoSiO4, Li2MnSiO4, FeF3, LiMn 0.8 Fe 0.1 Ni 0.1 PO4, Li 1-x VOPO4, and Li2FePO4F, wherein the electrolyte is a lithium borosilicate composition, wherein the lithium borosilicate composition is essentially composed of a system of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron and silicon, and wherein the lithium borosilicate is glass.

[0013] According to a sixth aspect of the invention, a battery is provided comprising: a positive electrode layer, a negative electrode layer, an electrolyte layer between the positive electrode layer and the negative electrode layer, and a layer of lithium borosilicate composition between the positive electrode layer and the electrolyte layer and / or between the negative electrode layer and the electrolyte layer, wherein the lithium borosilicate composition is substantially composed of a system of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron and silicon, and wherein the lithium borosilicate is glass.

[0014] According to a seventh aspect of the invention, a battery is provided comprising: a composite positive electrode layer comprising positive electrode active material particles, a negative electrode layer, an electrolyte layer between the positive electrode layer and the negative electrode layer, and a layer coated with a lithium borosilicate composition between the positive electrode active material particles and / or between the negative electrode layer and the electrolyte layer, wherein the lithium borosilicate composition is substantially composed of a system of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is glass.

[0015] According to an eighth aspect of the invention, a lithium borosilicate composition is provided, which is substantially composed of a system of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate composition contains lithium based on a total atomic percentage of lithium, boron and silicon between 81 and 83 atomic percent, and wherein the lithium borosilicate composition is a glass.

[0016] According to a ninth aspect of the present invention, a method for preparing a lithium borosilicate composition according to an eighth aspect of the present invention is provided, wherein the lithium borosilicate composition is formed by a vacuum deposition process, the method comprising:

[0017] For each component element of the lithium borosilicate glass, a separate vapor source is provided; wherein the vapor source comprises a lithium source, an oxygen source, a boron source, and a silicon source; and

[0018] Component elements from their individual vapor sources are co-deposited onto a heated substrate, where the component elements react to form a lithium borosilicate composition.

[0019] According to a tenth aspect of the present invention, a method for fabricating an electrode according to a first aspect of the present invention by a vacuum deposition process is provided, the method comprising:

[0020] a) Provide a first separate vapor source for each component element of the electrode; and

[0021] Component elements from their individual vapor sources are co-deposited onto a heated substrate, whereby the component elements react to form electrodes; and

[0022] b) Providing a second separate vapor source for each component element of the lithium borosilicate composition, wherein the second vapor source comprises a lithium source, an oxygen source, a boron source, and a silicon source; and

[0023] c) The component elements from a second separate vapor source are co-deposited onto the electrode of step a), wherein the component elements react on the electrode to form a lithium borosilicate composition.

[0024] According to an eleventh aspect of the present invention, a method for manufacturing a battery according to any one of the third to fifth aspects of the present invention is provided, wherein a lithium borosilicate glass electrolyte is formed by a vacuum deposition process, the method comprising:

[0025] A first vapor source is provided, which includes a separate vapor source for each component element in the compound for the first electrode layer; a second vapor source is provided, which includes a separate vapor source for each component element in the compound for the lithium borosilicate glass electrolyte layer; and a third vapor source is provided, which includes a separate vapor source for each component element in the compound for the second electrode layer.

[0026] The substrate is heated to a first temperature and component elements from the first vapor source are co-deposited onto the substrate, wherein the component elements react to form the first electrode layer;

[0027] Heating the substrate to a second temperature and co-depositing component elements from the second vapor source onto the first electrode layer, wherein the component elements react to form a lithium borosilicate glass electrolyte layer; and

[0028] The substrate is heated to a third temperature and component elements from a third separate vapor source are co-deposited onto the lithium borosilicate glass electrolyte layer, wherein the component elements react to form a second electrode layer.

[0029] According to a twelfth aspect of the present invention, a method for manufacturing a battery according to a second aspect of the present invention is provided, wherein an electrode with a lithium borosilicate surface modified by a vapor deposition process is formed, the method comprising:

[0030] For each component element of the lithium borosilicate glass, a separate vapor source is provided, comprising a lithium source, an oxygen source, a boron source, and a silicon source; and

[0031] Component elements from their individual vapor sources are co-deposited onto a heated substrate, where the component elements react to form a lithium borosilicate composition.

[0032] According to a thirteenth aspect of the invention, the use of lithium borosilicate compositions as defined herein as electrode protectants in batteries is provided.

[0033] As used herein, the term “battery” is considered synonymous with the term “cell” and is a device capable of generating electrical energy from a chemical reaction or promoting a chemical reaction by introducing electrical energy.

[0034] Lithium borosilicate composition

[0035] This document describes a lithium borosilicate composition, wherein the lithium borosilicate is substantially composed of a system of lithium oxide combined with silicon oxide and / or boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon. Typically, the lithium borosilicate is a glass. Preferably, the lithium borosilicate composition is substantially composed of a system of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is a glass.

[0036] Furthermore, the lithium borosilicate glass described herein is defined as a system combining lithium oxide with silicon oxide and / or boron oxide, wherein the mol% of the lithium borosilicate glass is between the following: 70.9 mol% Li₂O - 0.0 mol% B₂O₃ - 29.1 mol% SiO₂, 53.8 mol% Li₂O - 0.0 mol% B₂O₃ - 46.2 mol% SiO₂, 83.0 mol% Li₂O - 17.0 mol% B₂O₃ - 0.0 mol% SiO₂, and 70.0 mol% Li₂O - 30.0 mol% B₂O₃ - 0.0 mol% SiO₂. In another embodiment, the lithium borosilicate glass comprises between the following: 79.6 mol% Li₂O - 12.2 mol% B₂O₃ - 8.2 mol% SiO₂, 60.3 mol% Li₂O - 12.1 mol% B₂O₃ - 27.6 mol% SiO₂, 73.8 mol% Li₂O - 3.8 mol% B₂O₃ - 22.4 mol% SiO₂, and 62.2 mol% Li₂O - 15.6 mol% B₂O₃ - 22.2 mol% SiO₂. In another embodiment, the lithium borosilicate glass comprises between the following: 70.9 mol% Li₂O - 0.0 mol% B₂O₃ - 29.1 mol% SiO₂, 66.7 mol% Li₂O - 0.0 mol% B₂O₃ - 33.3 mol% SiO₂, 83.0 mol% Li₂O - 17.0 mol% B₂O₃ - 0.0 mol% SiO₂, and 75.0 mol% Li₂O - 25.0 mol% B₂O₃ - 0.0 mol% SiO₂.

[0037] In one aspect, the present invention relates to lithium borosilicate compositions, wherein the lithium borosilicate is substantially composed of a system of lithium oxide, silicon oxide, and boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon. Typically, the lithium borosilicate is a glass. In one embodiment, the present invention relates to lithium borosilicate compositions, wherein the lithium borosilicate is substantially composed of a system of lithium oxide, silicon oxide, and boron oxide, wherein the lithium borosilicate contains between 81 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon.

[0038] In one aspect, the present invention relates to lithium borosilicate compositions, wherein the lithium borosilicate is substantially composed of a ternary system of lithium oxide, silicon oxide, and boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon. Typically, the lithium borosilicate is a glass. In one embodiment, the present invention relates to lithium borosilicate compositions, wherein the lithium borosilicate is substantially composed of a ternary system of lithium oxide, silicon oxide, and boron oxide, wherein the lithium borosilicate contains between 81 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon.

[0039] It will be understood that trace amounts of other atoms may be present in the lithium borosilicate material according to the invention, provided that such amounts of other atoms do not affect the properties of the lithium borosilicate material. These trace amounts of other atoms may substitute for any one of Li, B, O, and / or Si, preferably B and / or Si.

[0040] Typical examples of materials in which Li, B, O, and / or Si (preferably B and / or Si) atoms can be substituted include N, S, Ge, Al, P, Ti, V, Zr, Pb, Ga, As, Sn, In, Sb, Bi, Nb, Ta, and W. Preferred examples of materials in which Li, B, O, and / or Si (preferably B and / or Si) atoms can be substituted include Al, Ti, Ge, P, V, W, S, and N.

[0041] In this regard, the term "consistent essentially of a system composed of lithium oxide combined with silicon oxide and / or boron oxide" means that the total amount of lithium, boron, and silicon atoms in the lithium borosilicate material (expressed as the molar percentage of the total amount of atoms excluding oxygen) is at least 90%, preferably at least 95%, preferably at least 97%, more preferably at least 98%, even more preferably at least 99%, still more preferably at least 99.5%, even more preferably at least 99.7%, still more preferably at least 99.8%, even more preferably at least 99.9%, still more preferably at least 99.9%. 9.95%, or even more preferably at least 99.97%, still more preferably at least 99.98%, even more preferably at least 99.99%, still more preferably at least 99.995%, even more preferably at least 99.997%, still more preferably at least 99.998%, even more preferably at least 99.999%, still more preferably at least 99.9995%, even more preferably at least 99.9997%, still more preferably at least 99.9998%, even more preferably at least 99.9999%, and most preferably 100%.

[0042] In one embodiment, the present invention relates to a lithium borosilicate composition, wherein the lithium borosilicate comprises a ternary system of lithium oxide, silicon oxide, and boron oxide, wherein the lithium borosilicate contains between 81 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon. Typically, the lithium borosilicate is a glass.

[0043] The inventors unexpectedly discovered that the lithium borosilicate glass described herein exhibits high ionic conductivity while also exhibiting low electronic conductivity. They also unexpectedly discovered that the lithium borosilicate glass described herein is particularly stable in contact with lithium at high voltages. These unexpectedly improved properties make the lithium borosilicate glass composition particularly suitable as a protective agent for electrodes, especially on the anode of batteries in which this composition is used as an anode coating. This was not anticipated in the art.

[0044] The inventors also unexpectedly discovered that lithium borosilicate glass, as described herein, is chemically / electrochemically stable in contact with lithium. These unexpectedly improved properties make lithium borosilicate glass compositions particularly suitable as electrolytes in contact with lithium metal. This was not predicted in the art.

[0045] The inventors also unexpectedly discovered that the lithium borosilicate glass described herein exhibits electrochemical stability under a wide range of potentials. In particular, the lithium borosilicate electrolyte is capable of operating at high voltages. This was not predicted in the art.

[0046] In one embodiment, the present invention provides a lithium borosilicate glass having a relative Li / Li ratio + The positive and negative cathode active materials are in contact with a potential of 3.6-8.5V, wherein the lithium borosilicate glass is electrochemically stable. In another embodiment, the lithium borosilicate glass is in contact with a positive cathode active material having a potential relative to Li / Li. + The positive and negative cathode active materials are in contact with a potential of 5-8.5V, wherein the lithium borosilicate glass is electrochemically stable. In another embodiment, the lithium borosilicate glass is in contact with a positive cathode active material having a potential relative to Li / Li + The positive cathode active material contacts a potential greater than 5.5V, wherein the lithium borosilicate glass is electrochemically stable.

[0047] In another embodiment, a lithium borosilicate glass is constructed between platinum and platinum electrodes having potentials between 0 and 10V, wherein the lithium borosilicate glass is electrochemically stable.

[0048] In another embodiment, a lithium borosilicate glass is constructed between platinum and nickel electrodes having potentials between 0 and 5V, wherein the lithium borosilicate glass is electrochemically stable.

[0049] In another embodiment, the lithium borosilicate glass has a strength of at least 1.0 × 10⁻⁶ at 25°C.-6 Ionic conductivity in S / cm.

[0050] In another embodiment, the present invention relates to a lithium borosilicate electrolyte having low electronic conductivity. In yet another embodiment, the lithium borosilicate glass has a conductivity of less than 2.0 × 10⁻⁶ at 25°C. -13 The electronic conductivity is S / cm. In another embodiment, the lithium borosilicate glass has an electronic conductivity of less than 8.5 × 10⁻⁶ S / cm. -14 Electron conductivity in S / cm.

[0051] In another embodiment, the lithium borosilicate glass is a thin film. In yet another embodiment, the film has a thickness between 40 nm and 15 micrometers.

[0052] Electrode with surface modified from lithium borosilicate composition

[0053] A first aspect of the invention provides an electrode comprising an electrode active material; wherein the surface of the electrode is modified with a lithium borosilicate composition, wherein the lithium borosilicate composition is substantially composed of a system of lithium oxide combined with silicon oxide and / or boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is glass. Preferably, the lithium borosilicate composition is substantially composed of a system of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is glass. Compared to an unmodified electrode, particularly but not only when operating in the presence of an adjacent liquid electrolyte material, the LiBSiO-surface-modified electrode has improved stability and / or improved cycling. In one embodiment, the LiBSiO-surface-modified electrode is a LiBSiO-surface-modified negative electrode. In another embodiment, the LiBSiO-surface-modified electrode is a LiBSiO-surface-modified positive electrode.

[0054] Battery containing lithium borosilicate surface-modified electrodes

[0055] A second aspect of the invention relates to a battery comprising a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein the surfaces of the positive electrode and / or the negative electrode are modified with the LiBSiO composition of the invention.

[0056] In one embodiment, the present invention relates to a battery comprising a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein the positive electrode and / or the negative electrode are coated with a layer of the LiBSiO composition of the present invention.

[0057] In one embodiment, the battery comprises a LiBSiO-surface-modified negative electrode. In another embodiment, the battery comprises a LiBSiO-surface-modified positive electrode.

[0058] According to the present invention, batteries comprising LiBSiO-surface-modified electrodes (particularly, but not only, negative electrodes) according to the invention have been found to be particularly advantageous. Without wishing to be bound by theory, it is believed that the properties of the LiBSiO compositions described herein make them particularly effective electrode protective layers on the electrodes of such batteries (especially lithium-ion batteries and especially lithium-ion batteries with liquid or polymer electrolytes).

[0059] In one embodiment, this aspect of the invention relates to a battery comprising a positive current collector, a positive electrode, an electrolyte, a negative electrode, and a negative current collector, wherein the surfaces of the positive and / or negative electrodes are modified with the LiBSiO composition of the present invention. In one embodiment, the battery comprises a LiBSiO-surface-modified negative electrode. In another embodiment, the battery comprises a LiBSiO-surface-modified positive electrode. In yet another embodiment, the battery is a lithium-ion secondary battery. In yet another embodiment, the lithium-ion secondary battery is a thin-film battery.

[0060] A battery containing a lithium borosilicate electrolyte and a lithium-containing negative electrode.

[0061] A third aspect of the invention relates to a battery comprising a positive electrode, a negative electrode, wherein the negative electrode comprises lithium and an electrolyte between the positive and negative electrodes, wherein the electrolyte is a lithium borosilicate composition, wherein the lithium borosilicate composition is substantially composed of a system of lithium oxide combined with silicon oxide and / or boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is glass. Preferably, the lithium borosilicate composition is substantially composed of a system of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is glass.

[0062] In one embodiment, the battery is a lithium-ion secondary battery. A lithium-ion secondary battery is defined herein as a device that directly converts the chemical energy contained in its active material into electrical energy through the reversible removal and insertion of lithium ions from the negative and positive electrodes, accompanied by their transport in the electrolyte and the associated electrons through an external circuit. The negative electrode may be implemented as an integral part of the battery structure before electrochemical cycling or during the first charge of the battery, because lithium is plated onto the surface of the negative current collector, which includes the interface with the electrolyte. In another embodiment, the positive electrode of the battery comprises a positive electrode active material selected from: LiCoPO4, LiNi 0.5Mn 1.5 O4, LiMnPO4, LiMn2O4, LiCoO2, LiNi 1 / 3 Mn 1 / 3Co 1 / 3 O2, LiFePO4, LiNiPO4, Li2NiPO4F, Li2CoPO4F, LiMnPO4F, Li2CoSiO4, Li2MnSiO4, FeF3, LiMn 0.8 Fe 0.1 Ni 0.1 PO4, LiVOPO4, Li2FePO4F.

[0063] In another embodiment, the battery further includes a negative electrode current collector and a positive electrode current collector. In another embodiment, the negative electrode current collector comprises a material selected from the group consisting of Pt, Ni, Mo, Cu, TiN, Al, Au, and stainless steel. In another embodiment, the positive electrode current collector material is selected from the group consisting of Pt, Ni, Mo, Al, Au, stainless steel, indium-doped tin oxide (ITO), and other conductive metal oxides.

[0064] In another embodiment, the battery is a solid-state battery. In yet another embodiment, the solid-state battery comprises: a substrate layer, a positive current collector layer, a positive electrode layer, a negative electrode layer, a negative current collector layer, and a lithium borosilicate glass electrolyte layer between the positive electrode layer and the negative electrode layer.

[0065] In another embodiment, the battery also includes a passivation layer (e.g., Si3N4) and / or an adhesion layer (e.g., TiO2) between the substrate and the current collector.

[0066] In another embodiment, the battery includes an encapsulation layer. In yet another embodiment, the encapsulation layer comprises AlN, Si3N4, SiO2, Al2O3, Al, Cu, and a parylene polymer. TM Polyimide, or copolymer (ethylene-co-methacrylic acid),

[0067] In another embodiment, the battery comprises a substrate material selected from the following: AlOPt (sapphire / TiO2 / Pt), SSTOP (Si / SiO2 / TiO2 / Pt), Si, SiO2, Si3N4, mica, and float glass.

[0068] In another embodiment, the battery is a thin-film battery. In yet another embodiment, the positive electrode is between 1 and 10 micrometers thick, preferably 2-8 micrometers thick. In yet another embodiment, the negative electrode is between 50 nm and 5 micrometers thick, preferably 0.15-3 micrometers thick. In yet another embodiment, the lithium borosilicate glass electrolyte layer is between 40 nm and 15 micrometers thick, preferably 0.4-5 micrometers thick.

[0069] In another embodiment, the battery has an open-circuit voltage between 1.0 and 8.5V in the state of charge. In yet another embodiment, the battery has an open-circuit voltage between 3.6 and 8.5V in the state of charge. In yet another embodiment, the battery has an open-circuit voltage between 5.5 and 8.5V in the state of charge.

[0070] In another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte having high ionic conductivity. In yet another embodiment, the lithium borosilicate glass electrolyte has a conductivity of at least 1.0 × 10⁻⁶ ions at 25°C. -6 Ionic conductivity in S / cm.

[0071] In another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte having low electronic conductivity. In yet another embodiment, the lithium borosilicate glass electrolyte has a conductivity of less than 2.0 × 10⁻⁶ at 25°C. -13 Electron conductivity in S / cm.

[0072] In another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte having high ionic conductivity and low electronic conductivity. In yet another embodiment, the lithium borosilicate glass electrolyte has a conductivity of at least 1.0 × 10⁻⁶ ions / mL at 25°C. -6 The ionic conductivity is less than 2.0 × 10⁻⁶ S / cm. -13 Electron conductivity in S / cm.

[0073] In another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte that is electrochemically stable to lithium. In yet another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte and a lithium anode. In yet another embodiment, the present invention relates to a lithium-free battery comprising a lithium borosilicate electrolyte.

[0074] In another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte capable of operating at high voltages. In another embodiment, the lithium borosilicate glass electrolyte is electrochemically stable at all potentials between 0 and 10 V. In yet another embodiment, the lithium borosilicate glass electrolyte is electrochemically stable at all potentials from 0 to 8 V.

[0075] In another embodiment, the lithium borosilicate glass electrolyte is in relation to Li / Li+ It is electrochemically stable at all potentials between 3.6 and 8.5 V.

[0076] In another embodiment, the battery has a full charge capacity between 0.04 and 5.0 μAh. In yet another embodiment, the battery has a full charge capacity of less than 0.5 μAh. In yet another embodiment, the battery has a full charge capacity of less than 0.1 μAh. In yet another embodiment, the battery has a full charge capacity of 2.0 μAh / cm². 2 and 300μAh / cm 2 The full charge capacity is between [a certain value]. In another embodiment, the full charge capacity is between 2 μAh / cm². 2 and 200μAh / cm 2 Between 2 μAh / cm². In another embodiment, the full charge capacity is between 2 μAh / cm². 2 and 100μAh / cm 2 Between 2 μAh / cm². In another embodiment, the full charge capacity is between 2 μAh / cm². 2 and 50μAh / cm 2 Between [specific values]. In another embodiment, the full charge capacity is between 100 μAh / cm². 2 and 300μAh / cm 2 Between. In another embodiment, the battery has a range of 3.25 μAh / cm. 2 and 650μAh / cm 2 The full charge capacity is between 21 μm and 2.7 nm, and the LiBSiO thickness is between 21 μm and 2.7 nm. In another embodiment, the battery has a capacity of 3.25 μAh / cm². 2 and 32.5 μAh / cm 2 The full charge capacity is between 21 μm and 55 nm, and the LiBSiO thickness is between 21 μm and 55 nm. In another embodiment, the battery has a capacity of 32.5 μAh / cm². 2 and 65μAh / cm 2 The full charge capacity is between 2.1 μm and 27 nm, and the LiBSiO thickness is between 2.1 μm and 27 nm. In another embodiment, the battery has a capacity of 65 μAh / cm². 2 and 650μAh / cm 2 The full charge capacity is between 1.3 μm and 2.7 nm and the LiBSiO thickness is between 1.3 μm and 2.7 nm.

[0077] Another embodiment provides a battery pack comprising at least two batteries of the present invention.

[0078] A battery having a full-charge capacity of less than 0.5 μAh, the battery comprising a lithium borosilicate electrolyte.

[0079] A fourth aspect of the invention relates to a battery comprising a positive electrode, a negative electrode, and an electrolyte between the positive and negative electrodes, wherein the electrolyte is a lithium borosilicate composition, wherein the lithium borosilicate composition is substantially composed of a system of lithium oxide combined with silicon oxide and / or boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is glass, and wherein the battery has a full charge capacity of less than 0.5 μAh. Preferably, the lithium borosilicate composition is substantially composed of a system of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is glass.

[0080] In one embodiment, the battery is a lithium-ion secondary battery. A lithium-ion secondary battery is defined herein as a device that directly converts the chemical energy contained in its active material into electrical energy through the reversible removal and insertion of lithium ions from the negative and positive electrodes, accompanied by their transport in the electrolyte and the associated electrons through an external circuit. The negative electrode may be implemented as an integral part of the battery structure before electrochemical cycling or during the first charge of the battery, because lithium is plated onto the surface of the negative current collector, which includes the interface with the electrolyte. In another embodiment, the positive electrode of the battery comprises a positive electrode active material selected from: LiCoPO4, LiNi 0.5 Mn 1.5 O4, LiMnPO4, LiMn2O4, LiCoO2, LiNi 1 / 3 Mn 1 / 3Co 1 / 3 O2, LiFePO4, LiNiPO4, Li2NiPO4F, Li2CoPO4F, LiMnPO4F, Li2CoSiO4, Li2MnSiO4, FeF3, LiMn 0.8 Fe 0.1 Ni 0.1 PO4, LiVOPO4, Li2FePO4F. In another embodiment, the negative electrode of the battery comprises a negative electrode active material selected from the following: lithium, silicon, tin, magnesium, aluminum, antimony, indium, titanium, nickel, cobalt, chromium, germanium, zinc, oxygen, carbon, vanadium, niobium, bismuth, tungsten, sulfur, and iron.

[0081] In another embodiment, the positive electrode comprises a positive electrode active material selected from the following: LiCoPO4, LiNi 0.5 Mn 1.5 O4, LiMnPO4, LiMn2O4, LiCoO2, LiNi 1 / 3 Mn 1 / 3 Co 1 / 3O2, LiFePO4, LiNiPO4, Li2NiPO4F, Li2CoPO4F, LiMnPO4F, Li2CoSiO4, Li2MnSiO4, FeF3, LiMn 0.8 Fe 0.1 Ni 0.1 PO4, LiVOPO4, Li2FePO4F, and the negative electrode contain negative electrode active materials selected from the following: lithium, silicon, tin, magnesium, and aluminum.

[0082] In another embodiment, the battery further includes a negative electrode current collector and a positive electrode current collector. In another embodiment, the negative electrode current collector comprises a material selected from the group consisting of Pt, Ni, Mo, Cu, TiN, Al, Au, and stainless steel. In another embodiment, the positive electrode current collector material is selected from the group consisting of Pt, Ni, Mo, Al, Au, stainless steel, indium-doped tin oxide (ITO), and other conductive metal oxides.

[0083] In another embodiment, the battery is a solid-state battery. In yet another embodiment, the solid-state battery comprises: a substrate layer, a positive current collector layer, a positive electrode layer, a negative electrode layer, a negative current collector layer, and a lithium borosilicate glass electrolyte layer between the positive electrode layer and the negative electrode layer.

[0084] In another embodiment, the battery also includes a passivation layer (e.g., Si3N4) and / or an adhesion layer (e.g., TiO2) between the substrate and the current collector.

[0085] In another embodiment, the battery includes an encapsulation layer. In yet another embodiment, the encapsulation layer comprises AlN, Si3N4, SiO2, Al2O3, Al, Cu, and a parylene polymer. TM ), polyimide, or poly(ethylene-co-methacrylic acid)

[0086] In another embodiment, the battery comprises a substrate material selected from the following: AlOPt (sapphire / TiO2 / Pt), SSTOP (Si / SiO2 / TiO2 / Pt), Si, SiO2, Si3N4, mica, and float glass.

[0087] In another embodiment, the battery is a thin-film battery. In yet another embodiment, the positive electrode is between 1 and 10 μm thick, preferably 2-8 μm thick. In yet another embodiment, the negative electrode is between 50 nm and 5 μm thick, preferably 0.15-3 μm thick. In yet another embodiment, the lithium borosilicate glass electrolyte layer is between 40 nm and 15 μm thick, preferably 0.4-5 μm thick.

[0088] In another embodiment, the battery has an open-circuit voltage between 1.0 and 8.5V in the state of charge. In yet another embodiment, the battery has an open-circuit voltage between 3.6 and 8.5V in the state of charge. In yet another embodiment, the battery has an open-circuit voltage between 4.6 and 8.5V in the state of charge. In yet another embodiment, the battery has an open-circuit voltage between 5.5 and 8.5V in the state of charge.

[0089] In another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte having high ionic conductivity. In yet another embodiment, the lithium borosilicate glass electrolyte has a conductivity of at least 1.0 × 10⁻⁶ ions at 25°C. -6 Ionic conductivity in S / cm.

[0090] In another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte having low electronic conductivity. In yet another embodiment, the lithium borosilicate glass electrolyte has a conductivity of less than 2.0 × 10⁻⁶ at 25°C. -13 Electron conductivity in S / cm.

[0091] In another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte having high ionic conductivity and low electronic conductivity. In yet another embodiment, the lithium borosilicate glass electrolyte has a conductivity of at least 1.0 × 10⁻⁶ ions / mL at 25°C. -6 The ionic conductivity is less than 2.0 × 10⁻⁶ S / cm. -13 Electron conductivity in S / cm.

[0092] In another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte that is electrochemically stable to lithium. In yet another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte and a lithium anode. In yet another embodiment, the present invention relates to a lithium-free battery comprising a lithium borosilicate electrolyte.

[0093] In another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte capable of operating at high voltages. In another embodiment, the lithium borosilicate glass electrolyte is electrochemically stable at all potentials between 0 and 10 V. In yet another embodiment, the lithium borosilicate glass electrolyte is electrochemically stable at all potentials from 0 to 8 V.

[0094] In another embodiment, the lithium borosilicate glass electrolyte is in relation to Li / Li + It is electrochemically stable at all potentials between 3.6 and 8.5 V.

[0095] In another embodiment, the battery has a full charge capacity of less than 0.1 μAh. In yet another embodiment, the battery has a capacity of 2.0 μAh / cm².2 and 300μAh / cm 2 The full charge capacity is between [a certain value]. In another embodiment, the full charge capacity is between 2 μAh / cm². 2 and 200μAh / cm 2 Between 2 μAh / cm². In another embodiment, the full charge capacity is between 2 μAh / cm². 2 and 100μAh / cm 2 Between 2 μAh / cm². In another embodiment, the full charge capacity is between 2 μAh / cm². 2 and 50μAh / cm 2 Between [specific values]. In another embodiment, the full charge capacity is between 100 μAh / cm². 2 and 300μAh / cm 2 between.

[0096] Another embodiment provides a battery pack comprising at least two batteries of the present invention.

[0097] A battery containing a lithium borosilicate electrolyte and a high-voltage positive electrode.

[0098] The fifth aspect relates to a battery comprising a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein the positive electrode comprises a positive electrode active material selected from the group consisting of LiCoPO4 and LiNi. 0.5 Mn 1.5 O4, LiMnPO4, LiCoO2, LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2, LiFePO4, LiNiPO4, Li2NiPO4F, Li2CoPO4F, LiMnPO4F, Li2CoSiO4, Li2MnSiO4, FeF3, LiMn 0.8 Fe 0.1 Ni 0.1 PO4, Li 1-x The electrolyte is a lithium borosilicate composition, wherein the lithium borosilicate composition is substantially composed of a system of lithium oxide combined with silicon oxide and / or boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is a glass. Preferably, the lithium borosilicate composition is substantially composed of a system of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is a glass.

[0099] In one embodiment, the battery is a lithium-ion secondary battery. A lithium-ion secondary battery is defined herein as a device that directly converts the chemical energy contained in its active material into electrical energy through the reversible removal and insertion of lithium ions from the negative and positive electrodes, accompanied by their transport in the electrolyte and the passage of associated electrons through an external circuit. The negative electrode may be implemented as an integral part of the battery structure before electrochemical cycling or during the first charge of the battery, as lithium is plated onto the surface of a negative current collector comprising the interface with the electrolyte. In another embodiment, the negative electrode of the battery comprises a negative electrode active material selected from the following: lithium, silicon, tin, magnesium, aluminum, antimony, indium, titanium, nickel, cobalt, chromium, germanium, zinc, oxygen, carbon, vanadium, niobium, bismuth, tungsten, sulfur, and iron.

[0100] In another embodiment, the positive electrode comprises a positive electrode active material selected from the following: LiCoPO4, LiNi 0.5 Mn 1.5 O4, LiMnPO4, LiCoO2, LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2, LiFePO4, LiNiPO4, Li2NiPO4F, Li2CoPO4F, LiMnPO4F, Li2CoSiO4, Li2MnSiO4, FeF3, LiMn 0.8 Fe 0.1 Ni 0.1 PO4, LiVOPO4, Li2FePO4F, and the negative electrode contain negative electrode active materials selected from the following: lithium, silicon, tin, magnesium, and aluminum.

[0101] In another embodiment, the battery further includes a negative electrode current collector and a positive electrode current collector. In another embodiment, the negative electrode current collector comprises a material selected from the group consisting of Pt, Ni, Mo, Cu, TiN, Al, Au, and stainless steel. In another embodiment, the positive electrode current collector material is selected from the group consisting of Pt, Ni, Mo, Al, Au, stainless steel, indium-doped tin oxide (ITO), and other conductive metal oxides.

[0102] In another embodiment, the battery is a solid-state battery. In yet another embodiment, the solid-state battery comprises: a substrate layer, a positive current collector layer, a positive electrode layer, a negative electrode layer, a negative current collector layer, and a lithium borosilicate glass electrolyte layer between the positive electrode layer and the negative electrode layer.

[0103] In another embodiment, the battery also includes a passivation layer (e.g., Si3N4) and / or an adhesion layer (e.g., TiO2) between the substrate and the current collector.

[0104] In another embodiment, the battery includes an encapsulation layer. In yet another embodiment, the encapsulation layer comprises AlN, Si3N4, SiO2, Al2O3, Al, Cu, and a parylene polymer. TM ), polyimide, or poly(ethylene-co-methacrylic acid)

[0105] In another embodiment, the battery comprises a substrate material selected from the following: AlOPt (sapphire / TiO2 / Pt), SSTOP (Si / SiO2 / TiO2 / Pt), Si, SiO2, Si3N4, mica, and float glass.

[0106] In another embodiment, the battery is a thin-film battery. In yet another embodiment, the positive electrode is between 1 and 10 micrometers thick, preferably 2-8 micrometers thick. In yet another embodiment, the negative electrode is between 50 nm and 5 micrometers thick, preferably 0.15-3 micrometers thick. In yet another embodiment, the lithium borosilicate glass electrolyte layer is between 40 nm and 15 micrometers thick, preferably 0.4-5 micrometers thick.

[0107] In another embodiment, the battery has an open-circuit voltage between 1.0 and 8.5V in the state of charge. In yet another embodiment, the battery has an open-circuit voltage between 3.6 and 8.5V in the state of charge. In yet another embodiment, the battery has an open-circuit voltage between 4.6 and 8.5V in the state of charge. In yet another embodiment, the battery has an open-circuit voltage between 5.5 and 8.5V in the state of charge.

[0108] In another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte having high ionic conductivity. In yet another embodiment, the lithium borosilicate glass electrolyte has a conductivity of at least 1.0 × 10⁻⁶ ions at 25°C. -6 Ionic conductivity in S / cm.

[0109] In another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte having low electronic conductivity. In yet another embodiment, the lithium borosilicate glass electrolyte has a conductivity of less than 2.0 × 10⁻⁶ at 25°C. -13 Electron conductivity in S / cm.

[0110] In another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte having high ionic conductivity and low electronic conductivity. In yet another embodiment, the lithium borosilicate glass electrolyte has a conductivity of at least 1.0 × 10⁻⁶ ions / mL at 25°C. -6 The ionic conductivity is less than 2.0 × 10⁻⁶ S / cm. -13 Electron conductivity in S / cm.

[0111] In another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte that is electrochemically stable to lithium. In yet another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte and a lithium anode. In yet another embodiment, the present invention relates to a lithium-free battery comprising a lithium borosilicate electrolyte.

[0112] In another embodiment, the present invention relates to a battery comprising a lithium borosilicate electrolyte capable of operating at high voltages. In another embodiment, the lithium borosilicate glass electrolyte is electrochemically stable at all potentials between 0 and 10 V. In yet another embodiment, the lithium borosilicate glass electrolyte is electrochemically stable at all potentials from 0 to 8 V.

[0113] In another embodiment, the lithium borosilicate glass electrolyte is in relation to Li / Li + It is electrochemically stable at all potentials between 3.6 and 8.5 V.

[0114] In another embodiment, the battery has a full charge capacity between 0.04 and 5.0 μAh. In yet another embodiment, the battery has a full charge capacity of less than 0.5 μAh. In yet another embodiment, the battery has a full charge capacity of less than 0.1 μAh. In yet another embodiment, the battery has a full charge capacity of 2.0 μAh / cm². 2 and 300μAh / cm 2 The full charge capacity is between [a certain value]. In another embodiment, the full charge capacity is between 2 μAh / cm². 2 and 200μAh / cm 2 Between 2 μAh / cm². In another embodiment, the full charge capacity is between 2 μAh / cm². 2 and 100μAh / cm 2 Between 2 μAh / cm². In another embodiment, the full charge capacity is between 2 μAh / cm². 2 and 50μAh / cm 2 Between [specific values]. In another embodiment, the full charge capacity is between 100 μAh / cm². 2 and 300μAh / cm 2 between.

[0115] Another embodiment provides a battery pack comprising at least two batteries of the present invention.

[0116] Method for preparing lithium borosilicate compositions

[0117] A ninth aspect provides a method for preparing a lithium borosilicate composition as defined herein. In one embodiment, the lithium borosilicate composition is formed by a vacuum deposition process. In another embodiment, the lithium borosilicate composition is formed by a physical vapor deposition process.

[0118] In one embodiment, the present invention relates to a method for producing a lithium borosilicate electrolyte that is electrochemically stable to lithium. In another embodiment, the battery comprises a lithium anode.

[0119] In another embodiment, the present invention relates to a method for producing a lithium borosilicate electrolyte capable of operating at high voltages. In another aspect, the battery is suitable for longer cycling durations.

[0120] In another embodiment, the present invention relates to a method for producing a lithium borosilicate electrolyte having low electronic conductivity. In yet another embodiment, the battery has low capacity.

[0121] Method for fabricating lithium borosilicate surface-modified electrodes

[0122] The tenth aspect provides a method for fabricating a LiBSiO-surface-modified electrode. The method is not particularly limited as long as it provides a desired LiBSiO-surface-modified electrode with improved stability or improved electrode cycling. Examples of this method include PVD as described herein. In one embodiment, the method is a method for fabricating a LiBSiO-surface-modified negative electrode. In another embodiment, the method is a method for fabricating a LiBSiO-surface-modified positive electrode. In one embodiment, the LiBSiO coating is prepared by physical vapor deposition (PVD).

[0123] Method for manufacturing batteries containing lithium borosilicate electrolyte

[0124] The eleventh aspect of the present invention relates to a method for manufacturing a battery comprising a lithium borosilicate electrolyte.

[0125] In one embodiment, the present invention relates to a method for manufacturing a battery comprising a lithium borosilicate electrolyte that is electrochemically stable to lithium. In another embodiment, the battery comprises a lithium anode.

[0126] In another embodiment, the present invention relates to a method of manufacturing a battery comprising a lithium borosilicate electrolyte capable of operating at high voltages. In another aspect, the battery is suitable for longer cycling durations.

[0127] In another embodiment, the present invention relates to a method for manufacturing a battery comprising a lithium borosilicate electrolyte having low electronic conductivity. In yet another embodiment, the battery has a low capacity.

[0128] Method for fabricating batteries containing lithium borosilicate surface-modified electrodes

[0129] Another aspect provides a method for fabricating a battery comprising electrodes, wherein the surface of the electrodes is modified with the LiBSiO material of the present invention. In one embodiment, the method is a method for fabricating a battery comprising a LiBSiO-surface-modified negative electrode. In another embodiment, the method is a method for fabricating a battery comprising a LiBSiO-surface-modified positive electrode. In yet another embodiment, the battery is a lithium-ion secondary battery. In yet another embodiment, the lithium-ion secondary battery is a thin-film battery. Brief description of the attached diagram

[0130] Figure 1 The open-circuit voltage of the LMO / LiBSiO / Li cell was measured every 5 seconds over a 35-minute period.

[0131] Figure 2 OCV monitoring during the first 15 minutes of charging.

[0132] Figure 3 Cyclic voltammetry was performed on a solid-state battery cell comprising an AlOPt substrate, an LMO cathode, a LiBSiO electrolyte, and a Li metal anode. The cell was cycled 100 times between 3.6 and 4.25 V. The first three cycles were performed at 0.5 mV / s, and the remaining 97 cycles were performed at a scan rate of 0.25 mV / s.

[0133] Figure 4A and 4B Impedance of a solid-state battery cell comprising an AlOPt substrate, an LMO cathode, a LiBSiO electrolyte, and a Li metal anode. Impedance relative to Li / Li before and after 10 constant-current cycles at 0.1 μA between 3.8 and 4.25 V. + Measurements were performed at a potential of 3.8V. The frequency range of the measurements was from 261.0156kHz to 0.1Hz, with seven data points per decade and an AC amplitude of 10mV. The average of more than 10 cycles was used to generate the points at each frequency. Figure 4A Displays data points across the entire experimental range. Figure 4B Display data points with an impedance less than 40kΩ.

[0134] Figure 5 Electronic conductivity (dashed line with triangles) and ionic conductivity (solid line with circles) of LiBSiO samples as lithium content varies.

[0135] Figure 6 The utilization number (Y-axis) of the first discharge is compared between LiBSiO coated (hollow circle) and uncoated (solid square) LMO cathode samples, with the percentage of Li atoms in LMO (X-axis) varying. Detailed description of the invention

[0136] electrolytes

[0137] Electrolyte composition

[0138] This article describes lithium borosilicate (LiBSiO) glass electrolyte. The term "glass" refers to an amorphous or non-crystalline solid that does not exhibit long-range structural order when characterized by X-ray diffraction or Raman spectroscopy. The LiBSiO glass described herein is preferably a ternary system of lithium oxide, silicon oxide, and boron oxide.

[0139] As described herein, lithium borosilicate glass comprises lithium with a total atomic percentage between 70 and 83 atomic percent based on lithium, boron, and silicon (i.e., excluding oxygen components). In another embodiment, lithium borosilicate glass comprises Li with a total atomic percentage between 70 and 76 atomic percent based on Li, B, and Si. In yet another embodiment, lithium borosilicate glass comprises Li with a total atomic percentage between 71 and 76 atomic percent, Li with a total atomic percentage between 73 and 76 atomic percent, Li with a total atomic percentage between 72 and 75 atomic percent, Li with a total atomic percentage between 73 and 75 atomic percent, or Li with a total atomic percentage between 79 and 83 atomic percent, each based on Li, B, and Si. In all cases, it should be understood that oxygen is present in an amount necessary to form oxides and maintain electrical neutrality.

[0140] As described herein, lithium borosilicate glasses preferably contain boron in a total atomic percentage between 1 and 25 atomic percent based on lithium, boron, and silicon (i.e., excluding oxygen components). Preferably, lithium borosilicate glasses contain boron in a total atomic percentage between 5 and 20 atomic percent based on Li, B, and Si. More preferably, lithium borosilicate glasses contain boron in a total atomic percentage between 7.5 and 15 atomic percent based on Li, B, and Si. In all cases, it should be understood that oxygen is present in an amount necessary to form oxides and maintain electrical neutrality.

[0141] As described herein, lithium borosilicate glasses preferably contain silicon with a total atomic percentage of lithium, boron, and silicon (i.e., excluding oxygen components) between 1 and 25 atomic percent. Preferably, lithium borosilicate glasses contain Si with a total atomic percentage of Li, B, and Si between 5 and 20 atomic percent. More preferably, lithium borosilicate glasses contain Si with a total atomic percentage of Li, B, and Si between 6 and 17 atomic percent. In all cases, it should be understood that oxygen is present in an amount necessary to form oxides and maintain electrical neutrality.

[0142] Based on B and Si, the B:Si ratio can be 1:1 + / - 0.15. Based on the components Li, B, and Si, the LiBSiO electrolyte can contain 74 atomic% Li, 14 atomic% Si, and 12 atomic% B.

[0143] The lithium borosilicate glass described herein can also be defined as a system combining lithium oxide with silicon oxide and / or boron oxide, wherein the mol% of the lithium borosilicate glass is between: 70.9 mol% Li₂O - 0.0 mol% B₂O₃ - 29.1 mol% SiO₂, 53.8 mol% Li₂O - 0.0 mol% B₂O₃ - 46.2 mol% SiO₂, 83.0 mol% Li₂O - 17.0 mol% B₂O₃ - 0.0 mol% SiO₂, and 70.0 mol% Li₂O - 30.0 mol% B₂O₃ - 0.0 mol% SiO₂.

[0144] Preferably, the mol% of lithium borosilicate glass is between the following: 79.6 mol% Li₂O - 12.2 mol% B₂O₃ - 8.2 mol% SiO₂, 60.3 mol% Li₂O - 12.1 mol% B₂O₃ - 27.6 mol% SiO₂, 73.8 mol% Li₂O - 3.8 mol% B₂O₃ - 22.4 mol% SiO₂, and 62.2 mol% Li₂O - 15.6 mol% B₂O₃ - 22.2 mol% SiO₂.

[0145] Preferably, the mol% of lithium borosilicate glass is between the following: 70.9 mol% Li₂O - 0.0 mol% B₂O₃ - 29.1 mol% SiO₂, 66.7 mol% Li₂O - 0.0 mol% B₂O₃ - 33.3 mol% SiO₂, 83.0 mol% Li₂O - 17.0 mol% B₂O₃ - 0.0 mol% SiO₂, and 75.0 mol% Li₂O - 25.0 mol% B₂O₃ - 0.0 mol% SiO₂.

[0146] Electrochemical stability of lithium

[0147] As described herein, lithium borosilicate glass is stable to lithium, characterized by the absence of any indication of detectable reaction or degradation (Bates et al., Journal of the Electrochemical Society 144[2](1997) 524-533). The stability of the lithium borosilicate glass electrolyte was measured using impedance spectroscopy and time-dependent open-circuit voltage. Impedance spectroscopy was used to demonstrate the comparability of the frequency-dependent response of the battery before and after cycling. Open-circuit voltage was measured after extended post-deposition storage and after cycling to demonstrate the integrity of the electrolyte and its ability to withstand the electrochemical potential difference between the cathode and anode without sustaining detectable reaction or degradation leading to mechanical or chemical failure, resulting in the inability to maintain a non-zero potential between the positive and negative electrodes.

[0148] The inventors unexpectedly discovered that thin-film batteries containing a LiBSiO electrolyte and a lithium anode can be cycled without any signs of harmful reactions between the LiBSiO electrolyte and the anode material. Furthermore, a stable open-circuit voltage was observed in the same thin-film battery system both before and after cycling. The technical benefit of this discovery is that it facilitates the use of LiBSiO electrolyte in solid-state batteries constructed with deposited lithium anodes or in lithium-free cells, thereby forming the lithium anode in situ at the interface between the solid LiBSiO electrolyte and the anode current collector.

[0149] Therefore, in one embodiment, the LiBSiO glass is in contact with lithium and is electrochemically stable.

[0150] In another embodiment, the LiBSiO glass is stable to lithium and chemically stable in contact with a cathode active material subjected to a potential of: relative to Li / Li + At least +3.9V, relative to Li / Li + At least +4.5V, relative to Li / Li + At least +5.5V, or relative to Li / Li + At least +6.0V.

[0151] Electrochemical stability at high voltage

[0152] Electrochemical stability relative to high voltage is measured using cyclic voltammetry between two voltage limits. In cyclic voltammetry, the current response as a function of potential is measured when a time-varying, fixed-rate potential change is applied across the sample electrode. Electrochemical stability is characterized by a continuous change in current response with increasing or decreasing potential across the potential range; that is, there are no points within the potential range where an increase or decrease in current amplitude is independent of the change in potential value. Since electrochemical instability occurs during the test due to electrolyte failure, it will be considered as a continuous increase in current amplitude at a fixed potential value.

[0153] The inventors also unexpectedly discovered that the LiBSiO electrolyte described herein is electrochemically stable when constructed between platinum and platinum or platinum and nickel at potentials ranging from 0 to 10 V. The technical advantage of this discovery is that the LiBSiO electrolyte can be used in batteries that operate at very high voltages and deliver high energy densities.

[0154] Therefore, in another embodiment, the present invention relates to a LiBSiO electrolyte that has electrochemical stability when subjected to a wide range of potentials.

[0155] In another embodiment, the lithium borosilicate glass is electrochemically stable in contact with positive and negative cathode active materials subjected to potentials of 3.6-5V, 4.5-5V in another embodiment, and 5.5-8.5V in another embodiment. In yet another embodiment, the lithium borosilicate glass is stable to lithium and is electrochemically stable in contact with positive and negative cathode active materials subjected to potentials of 3.6-5V, 4.5-5V in another embodiment, and 5.5-8.5V in another embodiment.

[0156] High ionic conductivity and low electronic conductivity

[0157] The inventors also unexpectedly discovered that the LiBSiO electrolyte, as described herein, exhibits very low electronic conductivity and high ionic conductivity. The technical advantage of this discovery is that the electronic conductivity of the LiBSiO electrolyte, as described herein, is sufficiently low to result in a very low electronic conductivity property (<2.0 × 10⁻⁶). -13 Based on their ability to maintain a state of charge, they can be used in solid-state batteries with very low theoretical capacity (<0.04μAh).

[0158] Therefore, in another embodiment, the present invention relates to a LiBSiO electrolyte having high ionic conductivity and low electronic conductivity. In another embodiment, the LiBSiO electrolyte has a conductivity of at least 1.0 × 10⁻⁶ ions at 25 °C. -6 The ionic conductivity S / cm is less than 6.0 × 10⁻⁶. -14 The electronic conductivity is S / cm. In another embodiment, the LiBSiO electrolyte has an electronic conductivity of at least 1.0 × 10⁻⁶ S / cm. -6 Ionic conductivity of S / cm is less than 5.0 × 10⁻⁶. -14 The electronic conductivity is S / cm. In another embodiment, the LiBSiO electrolyte has an electronic conductivity of at least 1.0 × 10⁻⁶ S / cm. -6 The ionic conductivity of S / cm is less than 4 × 10 -14 The electronic conductivity is S / cm. In another embodiment, the LiBSiO electrolyte has an electronic conductivity of at least 1.0 × 10⁻⁶ S / cm. -6 The ionic conductivity is less than 2.0 × 10⁻⁶ S / cm. -14 Electron conductivity in S / cm.

[0159] In another embodiment, the LiBSiO electrolyte has a strength of at least 3.0 × 10⁻⁶ at 25 °C. -6 The ionic conductivity S / cm is less than 6.0 × 10⁻⁶. -14 The electronic conductivity is S / cm. In another embodiment, the LiBSiO electrolyte has an electronic conductivity of at least 3.0 × 10⁻⁶ S / cm. -6Ionic conductivity of S / cm is less than 5.0 × 10⁻⁶. -14 The electronic conductivity is S / cm. In another embodiment, the LiBSiO electrolyte has an electronic conductivity of at least 3.0 × 10⁻⁶ S / cm. -6 The ionic conductivity of S / cm is less than 4 × 10 -14 The electronic conductivity is S / cm. In another embodiment, the LiBSiO electrolyte has an electronic conductivity of at least 3.0 × 10⁻⁶ S / cm. -6 The ionic conductivity is less than 2.0 × 10⁻⁶ S / cm. -14 Electron conductivity in S / cm.

[0160] In another embodiment, the LiBSiO electrolyte has a strength of at least 5.0 × 10⁻⁶ at 25 °C. -6 The ionic conductivity S / cm is less than 6.0 × 10⁻⁶. -14 The electronic conductivity is S / cm. In another embodiment, the LiBSiO electrolyte has an electronic conductivity of at least 5.0 × 10⁻⁶ S / cm. -6 Ionic conductivity of S / cm is less than 5.0 × 10⁻⁶. -14 The electronic conductivity is S / cm. In another embodiment, the LiBSiO electrolyte has an electronic conductivity of at least 5.0 × 10⁻⁶ S / cm. -6 The ionic conductivity of S / cm is less than 4 × 10 -14 The electronic conductivity is S / cm. In another embodiment, the LiBSiO electrolyte has an electronic conductivity of at least 5.0 × 10⁻⁶ S / cm. -6 The ionic conductivity is less than 2.0 × 10⁻⁶ S / cm. -14 Electron conductivity in S / cm.

[0161] In another embodiment, the above-described LiBSiO electrolyte is stable to lithium. In another embodiment, the above-described LiBSiO electrolyte is electrochemically stable to lithium and is electrochemically stable in contact with positive and negative cathode active materials subjected to a potential of 3.6-5V. In another embodiment, the above-described LiBSiO electrolyte is electrochemically stable to lithium and is electrochemically stable in contact with positive and negative cathode active materials subjected to a potential of 5.5-8.5V.

[0162] Lithium borosilicate surface-modified electrode

[0163] Degradation of electrode active materials can be induced by reaction with electrolytes, electrolyte solutions, or atmospheres, by mechanical stress, or by other means. For example, lithium metal is highly reactive. Reactions occur during battery cycling with Li-based electrodes due to the reduction of solvents, active materials, or impurities in the electrolyte. These and other reactions lead to electrode degradation, capacity loss, consumption of electrolyte and active materials, and ultimately, battery failure. Additional failure modes include capacity loss due to the growth of dendritic lithium at the surface of the lithium anode (caused by uneven current density provided by surface defects), cell destruction due to the generation of separated lithium, and cell destruction through electrode short circuits. This process can be mitigated by placing a solid electrolyte at the interface between the lithium and liquid electrolyte. Materials with high ionic conductivity and low electronic conductivity are required; they must be stable in contact with lithium and usable as a protective coating for the electrodes. Batteries also require electrodes with improved stability and cycling performance.

[0164] Therefore, a second aspect of the invention provides an electrode whose surface is modified with a LiBSiO material as described herein. The LiBSiO-surface-modified electrode exhibits improved stability and / or improved cycling performance compared to an uncoated electrode. In one embodiment, the LiBSiO-surface-modified electrode is a LiBSiO-surface-modified negative electrode. In another embodiment, the LiBSiO-surface-modified electrode is a LiBSiO-surface-modified positive electrode.

[0165] As used herein, the terms “surface modified” and “the surface thereof modified” mean that at least a portion of the electrode surface is in mechanical or chemical contact with the LiBSiO composition described herein.

[0166] There are no particular limitations on the electrode active material of the electrode, as long as the material allows LiBSiO to attach to its surface and is capable of storing and releasing lithium ions. Examples of electrode active materials include, but are not limited to, those described elsewhere in this specification. In a preferred embodiment, the negative electrode active material is lithium metal.

[0167] In some embodiments, the electrode is a lithium intercalation electrode. As used herein, the term "intercalation" refers to the reversible inclusion or insertion of molecules or ions into a compound having a layered structure. Thus, a lithium intercalation electrode can be an electrode in which lithium ions can be reversibly included or inserted into a layered structure (e.g., graphite).

[0168] In some embodiments, the electrode is coated with a LiBSiO material layer as described herein. In some embodiments, a lithium borosilicate composition as described herein is provided as a layer on the electrode surface.

[0169] In some embodiments, the surface of the electrode is coated with a LiBSiO material layer as described herein. This coating can be achieved by first casting an electrode containing the electrode active material (and optionally carbon additives, polymer binders, and / or solvents) onto a current collector, and then curing and drying the electrode. The surface of the cast electrode can then have a protective layer of LiBSiO material deposited thereon. In some embodiments, LiBSiO completely coats the surface of the electrode. In some embodiments, LiBSiO partially covers the surface of the electrode.

[0170] In some embodiments, the electrode comprises particles of electrode active material, wherein the particles are coated with a LiBSiO material layer as described herein. This can be achieved by coating each particle of the active material entirely with a protective LiBSiO material. The protected particles may then optionally be mixed with carbon additives, polymer binders, and / or solvents to form a slurry. The slurry may then be cast onto a conductive current collector.

[0171] There are no particular limitations on the thickness of the LiBSiO coating, as long as stability or electrode cycling is improved. In one embodiment, the thickness of the LiBSiO coating is between 2 nm and 100 nm. In another embodiment, this range is between 2 nm and 50 nm.

[0172] In one embodiment, the LiBSiO-surface-modified electrode comprises a LiBSiO-coating layer that coats the surface of the electrode and through which lithium ions are mobile. In one embodiment, the electrode surface is completely coated with LiBSiO. In another embodiment, the electrode surface in contact with an electrolyte (especially a non-solid electrolyte) is coated with LiBSiO.

[0173] Battery

[0174] The inventors unexpectedly discovered that the lithium borosilicate glass described herein possesses 1) high ionic conductivity combined with low electronic conductivity, and 2) high ionic conductivity with highly reducing electrodes (e.g., metallic lithium anodes) and highly oxidizing electrodes (e.g., in relation to Li / Li). + Li charging at 4.2V 0.5 The CoO2 cathode contact is electrochemically stable, and 3) is electrochemically stable at high voltage.

[0175] Therefore, a third aspect of the invention relates to a battery comprising a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein the negative electrode comprises lithium, and wherein the electrolyte is a lithium borosilicate composition as described herein. Therefore, a fourth aspect of the invention relates to a battery comprising a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein the electrolyte is a lithium borosilicate composition as described herein, and wherein the battery has a full charge capacity of less than 0.5 μAh. Therefore, a fifth aspect of the invention relates to a battery comprising a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein the positive electrode comprises a positive electrode active material selected from the group consisting of LiCoPO4, LiNi. 0.5 Mn 1.5 O4, LiMnPO4, LiCoO2, LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2, LiFePO4, LiNiPO4, Li2NiPO4F, Li2CoPO4F, LiMnPO4F, Li2CoSiO4, Li2MnSiO4, FeF3, LiMn 0.8 Fe 0.1 Ni 0.1 PO4, Li 1-x VOPO4 and Li2FePO4F, wherein the electrolyte is a lithium borosilicate composition as described herein.

[0176] In another embodiment, the battery further includes a positive electrode current collector and a negative electrode current collector. In another embodiment, the battery further includes a substrate. In another embodiment, the battery is also sealed.

[0177] In one embodiment, the battery is a lithium-ion battery. In another embodiment, the battery is a lithium-ion rechargeable battery. In yet another embodiment, the thin-film battery is an all-solid-state battery. In yet another embodiment, the battery is a thin-film battery comprising a positive electrode, an electrolyte, and a negative electrode.

[0178] In one embodiment, the battery includes multiple positive electrodes and multiple negative electrodes, for example, in the form of a stack. An electrolyte in contact with the electrodes provides ionic conductivity through spacers between electrodes of opposite polarity. The battery typically includes current collectors associated with the negative and positive electrodes, respectively. The stacks of electrodes, their associated current collectors, and spacers are typically placed within a container containing a lithium borosilicate electrolyte.

[0179] In one embodiment, the battery is an improved lithium-ion battery comprising a negative electrode, a positive electrode, and a lithium borosilicate electrolyte, wherein the positive electrode comprises a high-voltage positive electrode active material having the following electrochemical potential relative to Li / Li+ At least 3.5V, relative to Li / Li + At least 4.0V, relative to Li / Li + At least 4.5V, relative to Li / Li + At least 5.5V, or relative to Li / Li + Between 6.0 and 8.5V.

[0180] Lithium-ion batteries with a lithium borosilicate electrolyte and a high-voltage positive electrode as described herein allow for the development of high-energy / power-density lithium-ion batteries. Furthermore, the lithium borosilicate electrolyte as described herein exhibits very high ionic conductivity and low electronic conductivity, thus providing improved performance such as higher power and energy as well as stable low capacity. Another important aspect of the electrolyte properties for high-voltage operation is reduction and oxidation stability. Improved reduction and oxidation stability enhances the battery life and cycle performance of this invention.

[0181] An improved battery system with a lithium borosilicate electrolyte and a high-voltage positive electrode is provided, which can be used to fabricate high-energy and high-power lithium-ion batteries. It features a high voltage ratio relative to Li / Li + Positive electrode active materials (cathode materials) with potentials in the range of approximately 3.6 to 8.5 V provide excellent performance for bonding with LiBSiO electrolyte.

[0182] negative electrode

[0183] The negative electrode active material is used as the counter electrode to the positive electrode. The composition of the positive and negative electrode active materials determines the battery potential during discharge, which is the difference between the potentials of their respective half-reactions.

[0184] The negative electrode active material used in the battery of this invention can be selected from Li4Ti5O. 12 Si, Ge, Sn, Sb, Al, Mg, Bi, Si-M (M = Mg, Al, Sn, Zn, Ag, Fe, Ni, Mn), InSb, metal oxides including TiO2, vanadium oxides and molybdenum oxides, Ti and Nb oxides (MgTi2O5, TiNb2O7), SnO, SnO2, Sb oxides, or germanates.

[0185] The negative electrode active material used in the battery of the present invention may be lithium or a lithified transition metal oxide, such as lithium titanium oxide. The negative electrode active material may be a lithium metal alloy, including LiSi, LiSb, or LiGe. The negative electrode active material may also be a carbon-containing material (e.g., activated carbon), a tin-containing material, a silicon-containing material, or other materials capable of reversibly intercalating lithium ions.

[0186] Negative electrode active materials also include graphite, synthetic graphite, coke, fullerene, niobium pentoxide, tin alloy, silicon (including amorphous silicon), titanium oxide, tin oxide, and lithium titanium oxide.

[0187] Negative electrode active materials containing all-carbon materials include graphite, synthetic graphite, coke, fullerenes, carbon nanotubes, other graphitic carbons, and combinations thereof. Graphitic carbon refers to any all-carbon material containing a large number of graphene sheet regions.

[0188] In one embodiment, the negative electrode active material comprises lithium metal or an alloy thereof, and the battery is a rechargeable (secondary) lithium-ion battery. In another embodiment, the negative electrode may comprise a lithium-aluminum alloy or a layer of metallic lithium. In yet another embodiment, the negative electrode is lithium. In yet another embodiment, the negative electrode is a lithium-free anode. In yet another embodiment, the negative electrode is a lithium-air anode.

[0189] In some embodiments, the electrode is a lithium intercalation electrode. As used herein, the term "intercalation" refers to the reversible inclusion or insertion of molecules or ions into a compound having a layered structure. Thus, a lithium intercalation electrode can be an electrode in which lithium ions can be reversibly included or inserted into a layered structure (e.g., graphite).

[0190] positive electrode

[0191] A positive electrode active material is used as the counter electrode to the negative electrode. In some embodiments, the positive electrode may include a material having a relative Li / Li ratio. + Positive electrode active material with a potential greater than 3.6V.

[0192] The positive electrode active material of the battery of the present invention includes lithium-ionized transition metal compounds, such as lithium nickel manganese oxide, lithium nickel vanadium oxide, lithium cobalt vanadium oxide, or lithium cobalt phosphate, such as Li₂NiMn₃O₈, LiNiVO₄, LiCoVO₄, LiCoPO₄, etc. Other examples include lithium nickel phosphate, lithium nickel fluorophosphate, and lithium cobalt fluorophosphate, namely LiNiPO₄, Li₂NiPO₄F, Li₂CoPO₄F, etc. The lithium content typically varies depending on the charge state of the battery. The positive electrode active material may contain other oxygen-containing materials, such as oxides, manganates, nickelates, vanadates, phosphates, or fluorophosphates. The positive electrode active material may have the formula Li x M y N z O, where M is selected from the group consisting of Ni, Mn, V, and Co, and N is a heteroatom substance different from M, such as Ni, Mn, V, Co, or P. N can be omitted. The positive electrode active material can also be fluorinated, for example, as a fluorophosphate.

[0193] In one embodiment, the positive electrode active material of the battery of the present invention is selected from the following: LiCoO2, FeS2, LiCoPO4, LiFePO4, Li2FeS2, Li2FeSiO4, LiMn2O4, LiMnPO4, LiNiPO4, LiV3O8, LiV6O 13 , LiVOPO4, LiVOPO4F, Li3V2(PO4)3, MnO2, MoS3, S, TiS2, TiS3, V2O5, V6O 13 LiNi 0.5 Mn 1.5 O4 and LiMnNiCoAlO2.

[0194] In another embodiment, the positive electrode active material of the battery of the present invention is a high-voltage positive electrode active material. In yet another embodiment, the high-voltage positive electrode active material is selected from the following: LiCoPO4, LiNi 0.5 Mn 1.5 O4, LiMnPO4, LiMn2O4, LiCoO2, LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2, LiFePO4, LiNiPO4, Li2NiPO4F, Li2CoPO4F, LiMnPO4F, Li2CoSiO4, Li2MnSiO4, FeF3, LiMn 0.8 Fe 0.1 Ni0.1PO4, Li 1-x VOPO4 and Li2FePO4F.

[0195] In another embodiment, the positive electrode comprises a positive electrode active material having the following chemical formula:

[0196] Li x M 1-(d+t+q+r) D d T t Q q R r (XO4)

[0197] in:

[0198] M is a metal cation selected from Fe, Mn, Co, Ti, Ni or mixtures thereof;

[0199] D is selected from Mg 2+ Ni 2+ Co 2+ Zn 2+ Cu 2+ and Ti 2+ Metals with an oxidation state of +2;

[0200] T is a metal with a +3 oxidation state selected from Al 3+ , Ti 3+ , Cr 3+ , Fe 3+ , Mn 3+ , Ga 3+ , Zn 3+ , and V 3+ ;

[0201] Q is a metal with a +4 oxidation state selected from Ti 4+ , Ge 4+ , Sn 4+ , and V 4+ ;

[0202] R is a metal with a +5 oxidation state selected from V 5+ , Nb 5+ , and Ta 5+ ;

[0203] X comprises Si, S, P, V or a mixture thereof;

[0204] 0 ≤ x ≤ 1; and

[0205] 0 ≤ d, t, q, r ≤ 1, where at least one of d, t, q, and r is not 0.

[0206] In another embodiment, the positive electrode active material comprises a positive electrode active material comprising an ordered olivine electrode compound selected from LiFePO4, LiMnPO4, LiCoPO4, LiNiPO4, a mixed transition metal compound such as Li 1-2x Fe 1-x Ti x PO4 or LiFe 1-x Mn x PO4 (where 0 < x < 1), or other compounds having the general formula LiMPO4 and an ordered olivine structure.

[0207] Generally, "isovalent substitution" refers to the substitution of one element at a given crystal site with an element having a similar charge. For example, Mg 2+ is considered to be isovalent with Fe 2+ , and V 5+ is isovalent with P 5+ . Similarly, the VO4 3- tetrahedron can replace the PO4 3- tetrahedron. "Heterovalent substitution" refers to the substitution of one element at a given crystal site with an element having a different valence or charge. An example of heterovalent substitution would be Cr 2+ or Ti at the Fe 3+ site4+ Another example would be in Fe. 2+ Li at the site + These positive electrode active materials typically possess an olivine structure based on iron or manganese derivatives, with the general formula:

[0208] Li x+y M 1-(y+d+t+q+r) D d T t Q q R r [PO4] 1-(p+s+v) [SO4] p [SiO4] s [VO4] v

[0209] in

[0210] M can be Fe 2+ or Mn 2+ or mixtures thereof;

[0211] D can be a metal in the +2 oxidation state, preferably Mg. 2+ Ni 2+ Co 2+ Zn 2+ Cu 2+ , or Ti 2+ ;

[0212] T can be a metal in the +3 oxidation state, preferably Al. 3+ Ti 3+ Cr 3+ Fe 3+ Mn 3+ Ga 3+ Zn 3+ 、 or V 3+ ;

[0213] Q can be a metal in the +4 oxidation state, preferably Ti. 4+ 、Ge 4+ Sn 4+ 、 or V 4+ ;

[0214] R can be a metal in the +5 oxidation state, preferably V. 5+ 、Nb 5+ 、or Ta 5+ ;

[0215] In this alternative implementation, M, D, T, Q, and R are present at octahedral sites. Additional coefficients can be defined as follows: x represents the degree of embedding during the operation of the electrode material; y represents the initial Fe... 2+ The fraction of lithium ions at the site; d represents the initial Fe2+ The fraction of divalent ions (labeled D) at the site; t represents the initial Fe 2+ The fraction of trivalent ions (labeled T) at the site; q represents the initial Fe 2+ The fraction of tetravalent ions (labeled Q) at the site; r represents the initial Fe 2+ The fraction of pentavalent ions (labeled R) at the site; p represents the initial P 5+ Hexavalent sulfur at the site (as discrete SO4) 2- The fraction of tetrahedrons; s represents the initial P 5+ Tetravalent silicon at the site (as discrete SiO4) 2- The fraction of tetrahedron; and v represents the initial value of P. 5+ The fraction of pentavalent vanadium ions at the site.

[0216] The conditions of site occupancy and electroneutrality imply the following:

[0217] 0≤x≤1;

[0218] y+d+t+q+r≤1;

[0219] P+s+v<1; and

[0220] 3 + sp = x - y + t + 2q + 3r.

[0221] x, y, d, t, q, r, p, s, and v can be between 0 (zero) and 1 (one), wherein at least one of y, d, t, q, r, p, s, or v is not 0. In a preferred embodiment, y, d, t, q, r, and v can vary between 0 (zero) and 0.2 ({fraction(2 / 10)}) and r and s can vary between 0 (zero) and 0.5 (1 / 2). In some embodiments, the electrode is a lithium intercalation electrode. As used herein, the term "intercalation" refers to the reversible inclusion or insertion of molecules or ions into a compound having a layered structure. Thus, a lithium intercalation electrode can be an electrode in which lithium ions can be reversibly included or inserted into a layered structure (e.g., graphite).

[0222] The battery of the present invention can contain the Li x+y M 1-(y+d+t+q+r) D d T t Q q R r [PO4] 1-(p+s+v) [SO4] p [SiO4] s [VO4] vThe positive electrode of the material contains an embedded material with fast diffusion kinetics. The phrase "fast diffusion kinetics" is generally understood in the art to mean that the material can maintain a specific current of at least 10 mA per gram of material and a capacity utilization of greater than 80% at the operating temperature. Preferably, the embedded material with fast diffusion kinetics can be a sheet-like dichalcogenide, vanadium oxide (VO₂O₃), or similar material. x (where 2.1 ≤ x ≤ 2.5), or NASICON-related materials such as Li3Fe2(PO4)3 or Li 3-x Fe 2-x Ti x (PO4)3 (where x represents Ti) 4+ Fe replacement 3+ (the degree).

[0223] When discharged from 8.5 volts to 1 volt, the positive electrode active material described herein can have a discharge specific capacity of at least about 50 mAh / g at a discharge rate of C / 3 during the 10th discharge cycle at room temperature.

[0224] current collector

[0225] The current collector (electron collector) can be a conductive component, comprising a metal, a conductive polymer, or other conductive material. The current collector of the battery of the present invention may comprise metals such as Cu, Pt, Au, Al, Ni, Fe, Ti, Mo, stainless steel, or other metals or alloys. The electron collector may have additional layers to reduce corrosion, for example comprising additional layers of tungsten (W), platinum (Pt), palladium (Pd), titanium carbide (TiC), thallium carbide (TaC), titanium oxide (e.g., TiO2 or Ti4O7), copper phosphide (Cu2P3), nickel phosphide (Ni2P3), iron phosphide (FeP), etc., or may contain particles of such materials.

[0226] Electrochemical stability

[0227] Batteries can be expected to operate at high voltages to provide higher capacity and / or greater power output. The improved lithium borosilicate glass electrolyte described herein significantly improves the properties of high-voltage batteries. For example, batteries can exhibit longer cycle life.

[0228] For high-voltage operation, another important aspect of the electrolyte is its reduction and oxidation stability. Improved reduction and oxidation stability improves the cycle performance of the corresponding battery. The lithium borosilicate glass electrolyte described herein shows no eventual reaction (reduction or oxidation) at the battery's operating voltage. The lithium borosilicate glass electrolyte possesses, for example, the ability to operate with lithium or carbon elemental negative electrode active materials at high voltages. The improved electrolyte described herein effectively improves the cycle performance of lithium-ion batteries operating at high charging voltages greater than 4.45V.

[0229] Therefore, in another embodiment, the present invention relates to a battery comprising a lithium borosilicate glass electrolyte capable of operating at high voltages. In another embodiment, the high-voltage battery comprises a lithium borosilicate glass electrolyte capable of operating at voltages up to 4.45V, at least 5V, at least 5.5V, at least 6V, at least 7V, at least 8V, at least 9V, or at least 10V. In another embodiment, the lithium borosilicate glass electrolyte has a voltage greater than 1.0 × 10⁻⁶ at 25°C. -6 The ionic conductivity is measured in S / cm. In another embodiment, the lithium borosilicate glass electrolyte is lithium-stabilized. In another embodiment, the lithium borosilicate glass electrolyte is 0.05-15 micrometers thick, 0.3-4 micrometers thick, or 2-4 micrometers thick. In yet another embodiment, the battery includes a lithium anode or is a lithium-free battery.

[0230] High ionic and low electronic conductivity

[0231] In another embodiment, the present invention provides a battery comprising a lithium borosilicate glass electrolyte having high ionic conductivity and low electronic conductivity. In one embodiment, the lithium borosilicate glass electrolyte has a conductivity greater than 1.0 × 10⁻⁶. -6 The ionic conductivity is less than 8.6 × 10⁻⁶ S / cm. -14 The electronic conductivity is S / cm. In another embodiment, the battery has an electronic conductivity greater than 1.0 × 10⁻⁶. -6 The ionic conductivity is less than 8.6 × 10⁻⁶ S / cm. -14 The battery exhibits an electronic conductivity of S / cm and is capable of operating at voltages up to 4.45V, at least 5V, at least 5.5V, at least 6V, at least 7V, at least 8V, at least 9V, or at least 10V. In another embodiment, the battery has an electronic conductivity greater than 1.0 × 10⁻⁶. -6 The ionic conductivity is less than 8.6 × 10⁻⁶ S / cm. -14 It exhibits an electronic conductivity of S / cm and can operate at voltages up to 4.45V, and may include a lithium anode or be a lithium-free battery. In other embodiments, the battery is an all-solid-state battery, a thin-film battery, or a lithium-ion battery.

[0232] In another embodiment, the battery comprising a lithium borosilicate glass electrolyte has a strength greater than 1.0 × 10⁻⁶. -6 The ionic conductivity is less than 8.6 × 10⁻⁶ S / cm. -14 The battery exhibits an electronic conductivity of S / cm and a full charge capacity between 0.04 and 5 μAh. In another embodiment, the battery has a full charge capacity of less than 0.5 μAh. In yet another embodiment, the battery has a full charge capacity of less than 0.1 μAh.

[0233] Batteries containing lithium borosilicate surface-modified electrodes

[0234] One aspect of the invention relates to a battery comprising a positive electrode, a negative electrode, and an electrolyte between the positive and negative electrodes, wherein the surfaces of the positive and / or negative electrodes are modified with a LiBSiO composition described herein. The LiBSiO composition may consist substantially of a system of lithium oxide combined with silicon oxide and / or boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is glass. Preferably, the lithium borosilicate composition consists substantially of a system of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 70 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is glass. In one embodiment, the battery comprises a LiBSiO-surface-modified negative electrode. In another embodiment, the battery comprises a LiBSiO-surface-modified positive electrode.

[0235] In one embodiment, the battery includes a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein the positive electrode and / or the negative electrode are coated with a LiBSiO composition layer of the present invention.

[0236] In one embodiment, the present invention provides a battery comprising a positive current collector, a positive electrode comprising a positive electrode active material, an electrolyte, a negative electrode comprising a negative electrode active material, and a negative current collector, wherein the surfaces of the positive and / or negative electrodes are modified with the LiBSiO material described herein. In one embodiment, the battery comprises a LiBSiO-surface-modified negative electrode. In another embodiment, the battery comprises a LiBSiO-surface-modified positive electrode. In yet another embodiment, the battery comprises both a LiBSiO-surface-modified negative electrode and a LiBSiO-surface-modified positive electrode. In still another embodiment, the battery is a lithium-ion secondary battery. In yet another embodiment, the lithium-ion secondary battery is a thin-film battery.

[0237] In one embodiment, the present invention provides a battery comprising a positive current collector, a positive electrode comprising a positive electrode active material, an electrolyte, a negative electrode comprising a negative electrode active material, and a negative current collector, wherein the positive electrode and / or negative electrode are coated with the LiBSiO material of the present invention, for example, according to the first aspect. In one embodiment, the battery comprises a LiBSiO-coated negative electrode. In another embodiment, the battery comprises a LiBSiO-coated positive electrode. In yet another embodiment, the battery comprises both a LiBSiO-coated negative electrode and a LiBSiO-coated positive electrode. In still another embodiment, the battery is a lithium-ion secondary battery. In yet another embodiment, the lithium-ion secondary battery is a thin-film battery.

[0238] The electrolyte may comprise an organic electrolyte, a liquid electrolyte, an ionic liquid, a gel electrolyte, a room-temperature molten salt, or a solid electrolyte. If the electrolyte is a liquid or a gel, it is preferably a non-aqueous electrolyte. In one embodiment, the electrolyte is an organic electrolyte. In another embodiment, the electrolyte is a liquid electrolyte. In yet another embodiment, the liquid electrolyte is a non-aqueous electrolyte. In another embodiment, the electrolyte is a gel electrolyte. In yet another embodiment, the electrolyte is a molten salt electrolyte. In yet another embodiment, the electrolyte is a solid electrolyte.

[0239] In another embodiment, the liquid non-aqueous electrolyte comprises a lithium salt and a non-aqueous solvent. Examples of lithium salts include LiPF6, LiBF4, lithium bis(trifluoromethanesulfonyl)amine (LiTFSA, LiN(CF3SO2)2), LiCF3SO3, LiC4F9SO3, LiC(CF3SO2)3, LiClO4, lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)amine (LiFSA, LiN(SO2F)2), and LiCF3CO2. The non-aqueous solvent is capable of dissolving the lithium salt. Examples of non-aqueous solvents include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, 1,3-dioxolane, nitromethane, N,N-dimethylformamide, dimethyl sulfoxide, sulfolane, vinylene carbonate, and γ-butyrolactone.

[0240] In some embodiments, the electrolyte comprises additives. Electrolyte additives can readily and economically modify the electrode-electrolyte interface. In some embodiments, the electrolyte comprises additives selected from: 4-(trifluoromethyl)-1,3-dioxolane-2-one (TFM-EC), tris(hexafluoro-isopropyl) phosphate (HFip), 3-hexylthiophene, LiDFOB, tris(trimethylsilyl) phosphate (TMSP), tris(trimethylsilyl) borate (TMSB), and combinations thereof.

[0241] Methods for producing lithium borosilicate

[0242] The ninth aspect provides a method for fabricating the lithium borosilicate glass described herein. In one embodiment, the lithium borosilicate glass is formed by a vacuum deposition process. In another embodiment, the lithium borosilicate glass is formed by a physical vapor deposition process.

[0243] Physical vapor deposition processes are generally known to those skilled in the art. In the present invention, the process generally involves using a physical process (such as heating) to prepare a vapor comprising the component elements Li, B, Si, and O, and then depositing the vapor onto a substrate. In one embodiment, the physical vapor deposition process is carried out at a temperature between 100 and 400 °C, preferably between 150 and 300 °C, and more preferably between 200 and 250 °C.

[0244] In one embodiment, at 4.0 x 10 -4 and 6.7 x 10 -3 Pa (between 3 x 10 -6 and 5 x 10 -5 Torr), preferably at 2.7 x 10 -3 and 4.7 x 10 -3 Pa (between 2 x 10 -5 and 3.5 x 10 -5 Torr), the physical vapor deposition process is carried out.

[0245] In one embodiment, the oxygen source can be an ozone source of oxygen, an atomic source of oxygen, or a molecular source of oxygen.

[0246] In one embodiment, the present invention relates to a method for fabricating a lithium borosilicate electrolyte that is electrochemically stable to lithium. In a further embodiment, the battery comprises a lithium anode.

[0247] In another embodiment, the present invention relates to a method for fabricating a lithium borosilicate electrolyte capable of operating at high voltages. In a further aspect, the battery is suitable for longer-term cycling.

[0248] In another embodiment, the present invention relates to a method for fabricating a lithium borosilicate electrolyte having a low electron conductivity. In a further embodiment, the battery has a low capacity.

[0249] Method for fabricating a lithium borosilicate-coated electrode

[0250] Another aspect provides a method for fabricating a LiBSiO-surface modified electrode. There is no particular limitation on the method for fabricating the LiBSiO-surface modified electrode of the present invention as long as the method can provide the desired LiBSiO-surface modified electrode with improved stability or improved electrode cycling. Examples of the method include PVD as described herein. In one embodiment, the method is a method for fabricating a LiBSiO-surface modified negative electrode. In another embodiment, the method is a method for fabricating a LiBSiO-surface modified positive electrode. In one embodiment, the LiBSiO coating is prepared by physical vapor deposition (PVD).

[0251] Method for fabricating a battery comprising a lithium borosilicate glass electrolyte

[0252] Another aspect of the invention relates to a method for manufacturing a battery comprising a lithium borosilicate glass electrolyte.

[0253] In another embodiment, thin-film batteries are prepared by sequentially forming component films in an all-solid state.

[0254] Method for fabricating a battery containing lithium borosilicate coated electrodes

[0255] Another aspect provides a method for fabricating a battery comprising electrodes, wherein the surface of the electrodes is modified with the LiBSiO material described herein. In one embodiment, the method is a method for fabricating a battery comprising a LiBSiO-surface-modified negative electrode. In another embodiment, the method is a method for fabricating a battery comprising a LiBSiO-surface-modified positive electrode. In yet another embodiment, the battery is a lithium-ion secondary battery. In yet another embodiment, the lithium-ion secondary battery is a thin-film battery. Example

[0256] Example 1 - Preparation of LiBSiO Electrolyte

[0257] According to an embodiment of the present invention, lithium borosilicate materials are formed from the component elements lithium, oxygen, and two glass-forming elements boron and silicon using the method disclosed in WO2015 / 104540 entitled "Vapour Deposition Method for Preparing Amorphous Lithium-Containing Compounds" (the entire contents of which are incorporated herein by reference). This is achieved by providing a vapor source for each component element of the compound and [the vapor source is then described as being from 2.7 x 10⁻⁶]. -3 Up to 4.3x10 -3 Pa(2x10 -5 Up to 3.2x10 -5 Component elements from a vapor source were co-deposited onto a substrate heated to 225°C under pressure. The component elements reacted on the substrate to form an amorphous lithium borosilicate compound. The prepared compound had the composition described in Example 5 below.

[0258] Deposition was performed in a physical vapor deposition (PVD) system previously described in the literature (Guerin, S. and Hayden, BE, Journal of Combinatorial Chemistry 8 (2006) 66-73). All samples were deposited using an oxygen plasma source as the atomic oxygen source. Oxide materials (lithium silicate and lithium borate) require the highest oxidation states of both silicon and boron (4+ and 3+, respectively), and therefore the use of atomic oxygen instead of molecular oxygen eliminates the decomposition step required to break O2 into 2O and provides highly reactive material to oxidize silicon and boron to their highest oxidation states (as required in materials Li4SiO4 and Li3BO3). Lithium was deposited using a Knudsen cell source. Both silicon and boron were deposited using an electron gun (E-Gun) source.

[0259] Other vacuum deposition methods can be used to fabricate cathode, anode, current collector, and first barrier layer materials. These may include, but are not limited to, physical vapor deposition, chemical vapor deposition (CVD), RF sputtering, molecular beam epitaxy solid-state reaction, pulsed laser deposition (PLD), sol-gel, and atomic layer deposition (ALD).

[0260] In the case of this invention, a battery can be constructed by sequentially depositing suitable compounds onto a suitable conductive substrate. For example, a layered structure of a thin-film battery can be provided by sequentially depositing an anode layer (e.g., Li metal from a Li evaporation source), an electrolyte layer (e.g., lithium borosilicate prepared using the methods disclosed herein), a cathode layer (e.g., LMO from a component evaporation source), and a conductive top layer.

[0261] Example 2 - Electrochemical stability of LiBSiO electrolyte

[0262] A thin-film battery was fabricated using a platinum cathode current collector, a LiMn₂O₄ cathode, a lithium borosilicate glass electrolyte, and a Li anode. The stability of the lithium borosilicate glass electrolyte was illustrated in three ways.

[0263] Example 3 - Stability of Lithium Anode

[0264] First, the battery was cycled between 3.6 and 4.25 V using linear sweep voltammetry at rates between 0.5 and 0.25 mV / s, and then harmful reactions between the electrolyte and the anode material were observed. After 100 cycles, no indication of harmful reactions between the electrolyte and the anode material was found in the current versus potential curve.

[0265] Example 4 - Stable OCV

[0266] Secondly, the stable open-circuit voltage (OCV) of the same thin-film battery system was observed before and after cycling. The range of open-circuit voltage at the beginning of the lifetime (measured 40 days after anode deposition on LiBSiO solid electrolyte) relative to Li / Li was determined. + From 2.36 to 2.92 V. If lithium reacts with the solid electrolyte in a persistent manner, it eventually consumes LiBSiO in the formation of a continuous pathway between the anode and cathode, resulting in a measured OCV of 0 V.

[0267] After undergoing 10 galvanostatic cycles between 3.8 and 4.25 volts at 0.1 μA, 12 cyclic voltammetric cycles, and 23 galvanostatic cycles between 3.8 and 4.25 V at 0.2 μA, the relative Li / Li ratio was observed. + The stable end-of-life (EOL) OCV is 4.15V.

[0268] After the cycle was completed, the open-circuit voltage of the LMO / LiBSiO / Li cell was measured every 5 seconds for 35 minutes. Figure 1 The final stage involves monitoring OCV for 15 minutes after the start of charging. Figure 2 The dispersion observed in the data in the right figure is due to measurement interruptions caused by external disturbances.

[0269] like Figure 3 As shown, cyclic voltammetry was performed on a solid-state cell comprising an AlOPt (sapphire, titanium, or titanium dioxide (20 nm), platinum (100 nm)) substrate, an LMO cathode, a LiBSiO electrolyte, and a Li metal anode. The cell was cycled 100 times between 3.6 and 4.25 V. The first three cycles were performed at 0.25 mV / s, and the remaining 97 cycles were performed at a scan rate of 0.5 mV / s. It is evident that the characteristic curve of the potential-dependent current did not change as observed in the data set reflecting behavior from the start to the end of the cycle. The capacity reduction associated with the decrease in current amplitude is a sign of cycle-related aging effects, but does not necessarily indicate degradation or instability related to incompatibility between the electrolyte and the electrode; rather, it may be related to the intrinsic stability of the cathode material under the applied cycling conditions.

[0270] Example 5 - Impedance

[0271] Bates et al., Journal of the Electrochemical Society 144[2](1997)524-533, used impedance as a measure of stability, in which a comparison was made between the impedances of LiPON sandwiched between platinum electrodes or between a lithium electrode and a platinum electrode.

[0272] Using a method similar to that described in Bates et al.'s paper, the Li / Li ratio was compared before and after 10 cycles of constant current at 0.1 μA between 3.8 and 4.25 V. + Impedance was measured on a LiBSiO electrolyte sample (72.6 mol% Li₂O - 6.8 mol% B₂O₃ - 20.6 mol% SiO₂) at a potential of 3.8 V. The frequency range used in this paper is from 261.0156 kHz to 0.1 Hz, with seven data points per carry and an AC amplitude of 10 mV. Figure 4A As shown in B, in the high-frequency range of the data set ( Figure 4A The impedance spectra collected before and after the cycle are almost or no different, as shown by the data points below 40 kΩ on the vertical and horizontal axes in the figure. Figure 4B The data provided by [the source] are within this frequency range, reflecting the contribution of the electrolyte and the interface between the electrolyte and the electrode. Therefore, the reproducibility of the data before and after cycling indicates the stability of the interface between the LiBSiO solid electrolyte and the adjacent lithium anode.

[0273] Third, the impedance was compared before and after cycling and showed that it remained largely unchanged across the frequency range that reflects contributions from the electrolyte and the interface between the electrolyte and adjacent electrodes.

[0274] The technical advantage of this discovery is that it facilitates the use of lithium borosilicate glass compositions in solid-state batteries constructed with lithium anodes in a deposited state and in lithium-free cells, thereby forming a lithium anode in situ at the interface between the solid lithium borosilicate electrolyte and the anode current collector.

[0275] Example 6 - Electrochemical stability at high voltage

[0276] Many lithium borosilicate compositions were prepared as shown below, where the values ​​of Li, B, and Si are atomic percentages of Li:B:Si:

[0277] 1.Li=80.9, B=7.56, Si=11.5

[0278] 2.Li=79.6, B=13.7, Si=6.7

[0279] 3.Li=78.5, B=9.6, Si=11.87

[0280] 4.Li=77.73, B=10.07, Si=12.19

[0281] 5.Li=76.89, B=10.55, Si=12.56

[0282] 6.Li=76.14, B=10.98, Si=12.88

[0283] 7.Li=75.30, B=11.46, Si=13.24

[0284] 8.Li=74.54, B=11.89, Si=13.58

[0285] 9.Li=73.16, B=12.62, Si=14.22

[0286] 10.Li=71.86, B=13.31, Si=14.83

[0287] 11.Li=70.41, B=14.07, Si=15.51

[0288] 12.Li=69.12, B=14.76, Si=16.12;

[0289] Oxygen is present in an amount that forms oxides and maintains electrical neutrality.

[0290] When deposited on a platinum-coated substrate (serving as the bottom electrode) and with the top electrode deposited on a lithium borosilicate electrolyte composed of nickel or platinum, the LiBSiO composition exhibits electrochemical stability across a potential range from 0 to 5 V. A representative sample was selected, tested, and found to exhibit electrochemical stability across a potential range from 0 to 10 V.

[0291] The technical advantage of this discovery is that it enables the use of the material in solid-state battery compositions that deliver high energy density at very high voltages, as described herein, for lithium borosilicate compositions.

[0292] Example 7 - Electronic conductivity and ionic conductivity

[0293] For a range of compositions in the LiBSiO system, electronic and ionic conductivity were measured as a function of lithium content (approximately 69-79% lithium based on the composition of Li, B, and Si). Ionic conductivity was determined from impedance measurements performed using a Solartron 1260 frequency response analyzer at 1 MHz and 1 Hz with a 100 mV AC potential (integrated for one second per frequency, seven frequency points per ten measurements). Conductivity was calculated by fitting the experimental data using an equivalent circuit model constructed in the ZView software program to determine the real part of the resistance associated with the thin-film electrolyte, which was then combined with a geometric factor to determine ionic conductivity. Electronic conductivity was determined using a Keithley 2636 series digital source meter. A 1 V DC potential was applied across the electrodes of the sample for 65 hours, where steady-state current, applied voltage, and geometric factor were used to calculate electronic conductivity. Electronic conductivity was measured within a Faraday cage shell. The electronic conductivity was 1.84 × 10⁻⁶. -14 and 4.40×10 -14 The S / cm range is between 8.74 × 10⁻⁶, while the ionic conductivity is between 8.74 × 10⁻⁶. -7 and 5.72×10 -6 Between S / cm.

[0294] The technical advantage of this discovery is that the electronic conductivity is sufficiently low, resulting from a very low electronic conductivity property (<7×10⁻⁶). -14 Based on their ability to maintain the state of charge (S / cm), LiSBiO glass electrolytes can be used in solid-state batteries with very low theoretical capacity (<0.5μAh).

[0295] Example 8 - Utilization of cathode material coated with LiBSiO

[0296] Figure 6The utilization number (Y-axis) of the first discharge is shown as a comparison of LiBSiO-coated (hollow circular) and uncoated (solid circular) LMO cathode samples, varying with the atomic percentage of Li in LMO (X-axis). Data from curves generated by a 10x10 Pt electrode array shows discrete LMO regions deposited on the electrodes with lithium contents between 18.38 and 48.43 atomic % (determined by the Li and Mn composition of the LMO film). The LMO active cathode material deposited on the Pt current collector below was elementally deposited onto a substrate maintained at 450°C, with lithium and manganese flux sourced from a Knudsen cell and oxygen supplied via a plasma source with an O2 flow rate of 3.5 sccm and a power of 500 W. The substrate containing an array of individual LMO sample regions was treated at 550°C for 2 hours under O2 before the LiBSiO coating was deposited on the test samples. The LiBSiO film was deposited on seven out of ten rows, while the remaining three rows remained uncoated. Electrochemical tests on the electrode array were performed using an internal potentiostat via cyclic voltammetry. The voltage range was between 3.25 V and 4.75 V, and the scan rate was 0.104 mV / sec. The reference electrode was a 0.5 mm thick lithium foil, and the electrolyte consisted of 1 M LiPF6 in EC:DMC (1:1). Data used to generate the images were processed as follows: first, all compositional equivalent sites on the sample were averaged (7 per composition for those with LiBSiO, and 3 per composition for those without LiBSiO, unless null values ​​were present due to electrode failure), and then the average of all values ​​falling within one standard deviation of this average was taken.

[0297] All publications mentioned in the foregoing specification are incorporated herein by reference. Various modifications and variations of the methods and systems described herein will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in conjunction with specific preferred embodiments, it should be understood that the claimed invention should not be unduly limited to these specific embodiments. In fact, various modifications to the modes of carrying out the invention that will be apparent to those skilled in the art of chemistry and materials science or related fields are intended to fall within the scope of the following claims.

Claims

1. A battery comprising a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein the negative electrode comprises lithium, and wherein the electrolyte is a lithium borosilicate composition. The lithium borosilicate composition is essentially composed of a system combining lithium oxide, silicon oxide, and boron oxide. The lithium borosilicate contains between 81 and 83 atomic percent lithium, based on the total atomic percentage of lithium, boron, and silicon, and the lithium borosilicate is glass.

2. A battery comprising a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein the electrolyte is a lithium borosilicate composition. The lithium borosilicate composition is essentially a system composed of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 81 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is glass. The battery described therein has a full charge capacity of less than 0.5 μAh.

3. A battery comprising a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein the positive electrode comprises a positive electrode active material selected from the group consisting of LiCoPO4 and LiNi. 0.5 Mn 1.5 O4, LiMnPO4, LiMn2O4, LiCoO2, LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2, LiFePO4, LiNiPO4, Li2NiPO4F, Li2CoPO4F, LiMnPO4F, Li2CoSiO4, Li2MnSiO4, FeF3, LiMn 0.8 Fe 0.1 Ni 0.1 PO4, Li 1-x VOPO4 and Li2FePO4F, wherein the electrolyte is a lithium borosilicate composition. The lithium borosilicate composition is essentially composed of a system combining lithium oxide with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 81 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron, and silicon, and wherein the lithium borosilicate is glass. The negative electrode contains a negative electrode active material, which is lithium.

4. A battery comprising a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein the positive electrode comprises a positive electrode active material selected from the following: LiCoPO4, LiMnPO4, LiFePO4, LiNiPO4, Li2NiPO4F, Li2CoPO4F, LiMnPO4F, Li2CoSiO4, Li2MnSiO4, FeF3, LiMn 0.8 Fe 0.1 Ni 0.1 PO4, Li 1-x VOPO4 and Li2FePO4F, wherein the electrolyte is a lithium borosilicate composition, which is essentially composed of a system of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 81 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron and silicon, and wherein the lithium borosilicate is glass.

5. A battery comprising a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein the positive electrode comprises an electrolyte having the formula Li x M y N z The positive electrode active material of O, wherein M is selected from Ni, V and Co, and N is a heteroatom material different from M, selected from Ni, V, Co and P, and wherein the electrolyte is a lithium borosilicate composition, which is essentially composed of a system of lithium oxide combined with silicon oxide and boron oxide, wherein the lithium borosilicate contains between 81 and 83 atomic percent lithium based on the total atomic percentage of lithium, boron and silicon, and wherein the lithium borosilicate is glass.

6. The battery of any one of claims 1-5, wherein the lithium borosilicate composition comprises a ternary system of lithium oxide, silicon oxide and boron oxide, wherein the lithium borosilicate contains lithium between 81 and 83 atomic percent based on the total atomic percentage of lithium, boron and silicon, and wherein the lithium borosilicate is glass.

7. The battery of any one of claims 1-5, wherein the lithium borosilicate composition contains between 7.5 and 15 atomic percent boron, based on the total atomic percentage of lithium, boron, and silicon.

8. The battery of any one of claims 1-5, wherein the lithium borosilicate composition contains between 6 and 17 atomic percent silicon based on the total atomic percentage of lithium, boron, and silicon.

9. The battery of any one of claims 1-5, wherein the battery is a lithium-ion secondary battery.

10. The battery of claim 1 or 2, wherein the positive electrode comprises a positive electrode active material selected from the group consisting of LiCoPO4, LiNi 0.5 Mn 1.5 O4, LiMnPO4, LiMn2O4, LiCoO2, LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2, LiFePO4, LiNiPO4, Li2NiPO4F, Li2CoPO4F, LiMnPO4F, Li2CoSiO4, Li2MnSiO4, FeF3, LiMn 0.8 Fe 0.1 Ni 0.1 PO4, Li 1-x VOPO4 and Li2FePO4F.

11. The battery of any one of claims 2-5, wherein the negative electrode comprises a negative electrode active material selected from lithium, silicon, tin, magnesium, aluminum, antimony and carbon.

12. The battery of claim 2, 4 or 5, wherein the negative electrode active material is lithium.

13. The battery of claim 2, wherein the negative electrode active material is lithium-free.

14. The battery of claim 1 or 2, wherein the positive electrode comprises a positive electrode active material selected from the group consisting of LiCoPO4, LiNi 0.5 Mn 1.5 O4, LiMnPO4, LiMn2O4, LiCoO2, LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2, LiFePO4, LiNiPO4, Li2NiPO4F, Li2CoPO4F, LiMnPO4F, Li2CoSiO4, Li2MnSiO4, FeF3, LiMn 0.8 Fe 0.1 Ni 0.1 PO4, Li 1-x VOPO4 and Li2FePO4F; and wherein the negative electrode comprises a negative electrode active material selected from the following: lithium, silicon, tin, magnesium, and aluminum.

15. The battery according to any one of claims 1-5 further comprises a negative electrode current collector and a positive electrode current collector.

16. The battery of claim 15, wherein the negative electrode current collector comprises a negative electrode current collector material selected from the group consisting of Pt, Ni, Mo, Cu, TiN, Al, Au and stainless steel; and wherein the positive electrode current collector material is selected from the group consisting of Pt, Ni, Mo, Al, Au and ITO.

17. The battery of any one of claims 1-5, wherein the battery is a solid-state battery.

18. The solid-state battery of claim 17, wherein the battery is a stacked battery.

19. The battery of any one of claims 1-5, wherein the battery is sealed.

20. The battery of any one of claims 1-5, wherein the positive electrode is between 1 and 10 μm thick.

21. The battery of any one of claims 1-5, wherein the negative electrode is between 0.5 and 5 μm thick.

22. The battery of any one of claims 1-5, wherein the lithium borosilicate glass electrolyte layer has a thickness between 0.3 and 15 μm.

23. The battery of any one of claims 1-5, wherein the battery has an open-circuit voltage greater than 4.5 V.

24. The battery of any one of claims 1-5, wherein the lithium borosilicate glass electrolyte has a strength of at least 2.0 × 10⁻⁶ at 25°C. -6 Scm -1 Its ionic conductivity is less than 8 × 10⁻⁶ at 25°C. -14 Electron conductivity in S / cm.

25. The battery of any one of claims 1-5, wherein the lithium borosilicate glass electrolyte has a strength of at least 3.0 × 10⁻⁶ at 25°C. -6 The ionic conductivity is S / cm and less than 6 × 10⁻⁶ at 25°C. -14 Electron conductivity in S / cm.

26. The battery of any one of claims 1-5, wherein the lithium borosilicate glass electrolyte has a strength of at least 3.0 × 10⁻⁶ at 25°C. -6 The ionic conductivity is S / cm and less than 5 × 10⁻⁶ at 25°C. -14 Electron conductivity in S / cm.

27. The battery of any one of claims 1-5, wherein the lithium borosilicate glass electrolyte is electrochemically stable at a potential between 0 and 10 V.

28. The battery of claim 1 or 2, wherein the positive electrode comprises a positive electrode active material having an electrochemical potential of at least 3.6 V relative to lithium.

29. The battery of claim 1 or any one of claims 3-5, wherein the battery has a fully charged capacity of less than 0.5 μAh.

30. The battery of any one of claims 1-5, wherein the battery has a full charge capacity of less than 0.1 μAh.

31. The battery of claim 30, wherein the battery has a full charge capacity of less than 0.05 μAh.

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