Lithium borosilicate glass as electrolyte and electrode protective layer

Abstract

A lithium borosilicate composition, consisting essentially of a system of lithium oxide in combination with silicon oxide and boron oxide, wherein said lithium borosilicate comprises between 70-83 atomic % lithium based on the combined atomic percentages of lithium, boron and silicon, and wherein said lithium borosilicate is a glass, is disclosed.

Claims

1. A battery comprising a positive electrode, a negative electrode, and an electrolyte between said positive electrode and said negative electrode, wherein said positive electrode comprises a positive electrode active material selected from the group consisting of LiCoPO.sub.4, LiMnPO.sub.4, LiFePO.sub.4, LiNiPO.sub.4, Li.sub.2NiPO.sub.4F, Li.sub.2CoPO.sub.4F, LiMnPO.sub.4F, Li.sub.2CoSiO.sub.4, Li.sub.2MnSiO.sub.4, FeF.sub.3, LiMn.sub.0.8Fe.sub.0.1Ni.sub.0.1PO.sub.4, Li.sub.1-xVOPO.sub.4, and Li.sub.2FePO.sub.4F, and wherein said electrolyte is a lithium borosilicate composition consisting essentially of a system of lithium oxide in combination with silicon oxide and boron oxide, wherein said lithium borosilicate comprises between 70-83 atomic % lithium based on the combined atomic percentages of lithium, boron and silicon, and wherein said lithium borosilicate is a glass.

2. The battery of claim 1, wherein said negative electrode comprises a negative electrode active material selected from the group consisting of lithium, silicon, tin, magnesium, aluminum antimony, and carbon.

3. The battery of claim 1, wherein the negative electrode active material is lithium.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1. Open circuit voltage of a LMO/LiBSiO/Li cell measured every 5 seconds for 35 minutes.

(2) FIG. 2. Monitoring of the OCV at the top of charge for 15 minutes.

(3) FIG. 3. Cyclic voltammetry of a solid state cell comprised of an AlOPt substrate, LMO cathode, LiBSiO electrolyte, and Li metal anode. The cell was cycled 100 times between 3.6 and 4.25 V. The first three cycles were at 0.5 mV/s, while the remaining 97 cycles were performed at a scan rate of 0.25 mV/s.

(4) FIGS. 4A and 4B. Impedance of a solid state cell comprised of an AlOPt substrate, LMO cathode, LiBSiO electrolyte, and a Li metal anode. The measurement was performed at a potential of 3.8 V vs. Li/Li.sup.+ before, and after the battery was subjected to 10 constant current cycles between 3.8 and 4.25 V at a current value of 0.1 μA. The frequency range for the measurement was 261.0156 kHz to 0.1 Hz with seven data points per decade, and ac amplitude of 10 mV, and an average over 10 cycles per frequency was used to generate the point at each frequency. FIG. 4A shows data points over the entire experimental range. FIG. 4B shows data points below 40 kΩ.

(5) FIG. 5. Electronic conductivity (dotted lines with triangles) and ionic conductivity (solid lines with circles) of LiBSiO samples as a function of lithium content.

(6) FIG. 6. Utilization number (Y axis) of the 1st discharge of LiBSiO coated (open circles) vs uncoated (solid squares) LMO cathode samples as a function of the atomic percent Li in the LMO (X axis).

DETAILED DESCRIPTION OF THE INVENTION

(7) Electrolyte

(8) Electrolyte Composition

(9) Described herein is a lithium borosilicate (LiBSiO) glass electrolyte. The term “glass” means a non-crystalline or amorphous solid which, when characterized by X-ray diffraction or Raman spectroscopy, does not exhibit evidence of long-range structural order. The LiBSiO glass described herein is preferably a ternary system of lithium oxide, silicon oxide and boron oxide.

(10) As described herein, the lithium borosilicate glass comprises between 70-83 atomic % lithium based on the combined atomic percentages of lithium, boron and silicon (i.e. excluding the oxygen component). In a further embodiment, the lithium borosilicate glass comprises between 70 and 76 atomic % Li, based on Li, B and Si. In further embodiments, the lithium borosilicate glass comprises between 71 and 76 at. % Li, between 73 and 76 at. % Li, between 72 and 75 at. % Li, between 73 and 75 at. % Li, or between 79 and 83 at. % Li, each based on Li, B and Si. In all cases, it is understood that oxygen is present in amounts to form oxides and maintain charge neutrality.

(11) As described herein, the lithium borosilicate glass preferably comprises between 1-25 atomic % boron based on the combined atomic percentages of lithium, boron and silicon (i.e. excluding the oxygen component). Preferably, the lithium borosilicate glass comprises between 5 and 20 atomic % B, based on Li, B and Si. Preferably, the lithium borosilicate glass comprises between 7.5 and 15 at. % B, based on Li, B and Si. In all cases, it is understood that oxygen is present in amounts to form oxides and maintain charge neutrality.

(12) As described herein, the lithium borosilicate glass preferably comprises between 1-25 atomic % silicon based on the combined atomic percentages of lithium, boron and silicon (i.e. excluding the oxygen component). Preferably, the lithium borosilicate glass comprises between 5 and 20 atomic % Si, based on Li, B and Si. Preferably, the lithium borosilicate glass comprises between 6 and 17 at. % Si, based on Li, B and Si. In all cases, it is understood that oxygen is present in amounts to form oxides and maintain charge neutrality.

(13) As per B and Si, the ratio of B:Si may be 1:1+/−0.15. Based on components Li, B and Si, the LiBSiO electrolyte may comprise 74 at. % Li, 14 at. % Si, and 12 at. % B.

(14) The lithium borosilicate glass described herein may also be defined as a system of lithium oxide in combination with silicon oxide and/or boron oxide, wherein the mol % of said lithium borosilicate glass is between 70.9 mol % Li.sub.2O—0.0 mol % B.sub.2O.sub.3—29.1 mol % SiO.sub.2; 53.8 mol % Li.sub.2O—0.0 mol % B.sub.2O.sub.3—46.2 mol % SiO.sub.2; 83.0 mol % Li.sub.2O—17.0 mol % B.sub.2O.sub.3—0.0 mol % SiO.sub.2; and 70.0 mol % Li.sub.2O—30.0 mol % B.sub.2O.sub.3—0.0 mol % SiO.sub.2.

(15) Preferably, the mol % of lithium borosilicate glass is between 79.6 mol % Li.sub.2O—12.2 mol % B.sub.2O.sub.3—8.2 mol % SiO.sub.2; 60.3 mol % Li.sub.2O—12.1 mol % B.sub.2O.sub.3—27.6 mol % SiO.sub.2; 73.8 mol % Li.sub.2O—3.8 mol % B.sub.2O.sub.3—22.4 mol % SiO.sub.2; and 62.2 mol % Li.sub.2O—15.6 mol % B.sub.2O.sub.3 22.2 mol % SiO.sub.2.

(16) Preferably, the mol % of lithium borosilicate glass is between 70.9 mol % Li.sub.2O—0.0 mol % B.sub.2O.sub.3—29.1 mol % SiO.sub.2; 66.7 mol % Li.sub.2O—0.0 mol % B.sub.2O.sub.3—33.3 mol % SiO.sub.2; 83.0 mol % Li.sub.2O—17.0 mol % B.sub.2O.sub.3—0.0 mol % SiO.sub.2; and 75.0 mol % Li.sub.2O—25.0 mol % B.sub.2O.sub.3 0.0 mol % SiO.sub.2.

(17) Electrochemical Stability Against Lithium

(18) The lithium borosilicate glass as described herein is stable against lithium, where stability is characterized by an absence of evidence indicating detectable reaction or degradation Bates et al., Journal of the Electrochemical Society 144 [2] (1997) 524-533. The stability of lithium borosilicate glassy electrolyte has been measured using impedance spectroscopy and the time dependent open circuit voltage. Impedance spectroscopy has been used to demonstrate the comparability of the frequency dependent response of the battery before and after being subjected to cycling. The open circuit voltage has been measured after extended post-deposition storage and after being subjected to 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 leading to an inability to maintain a non-zero potential between said positive and negative electrodes.

(19) The inventors made the surprising discovery that a thin film battery comprising a LiBSiO electrolyte and a lithium anode can be cycled without evidence of deleterious reactions between the LiBSiO electrolyte and the anode material. Further, a stable open circuit voltage of the same thin film battery system was observed both before and after cycling of the battery. The technical effect of this discovery is that it facilitates the use of the LiBSiO electrolyte in solid state batteries configured with a deposited lithium anode or within lithium free cells whereby the lithium anode is formed in situ at the interface between the solid state LiBSiO electrolyte and the anode current collector.

(20) Accordingly, in one embodiment, the LiBSiO glass is in contact with lithium and is electrochemically stable.

(21) In another embodiment, the LiBSiO glass is stable against lithium and is chemically stable in contact with positive cathode active materials that are subjected to a potential of at least +3.9 V versus Li/Li.sup.+, at least +4.5 V versus Li/Li.sup.+, at least +5.5 V versus Li/Li.sup.+ or at least +6.0 V versus Li/Li.sup.+.

(22) Electrochemical Stability at High Voltage

(23) Electrochemical stability vs. high voltage is measured using cyclic voltammetry between two voltage limits where a current response as a function of potential is determined when a fixed rate change in potential as a function of time is applied across the sample electrodes. Electrochemical stability is characterized by a current response across the potential range that varies continuously with increasing or decreasing potential, which is to say at no point in the potential range does the current increase or decrease in magnitude independent of a change in potential value. Failure of the electrolyte during the test due to electrochemical instability would be observed as a continuously increasing magnitude of the current at a fixed potential value.

(24) The inventors further made the surprising discovery that the LiBSiO electrolytes described herein are electrochemically stable when configured between platinum and platinum, or platinum and nickel, between potentials ranging from 0 to 10 V. The technical effect of this discovery is that the LiBSiO electrolytes may be used in batteries operating at very high voltages and delivering high power densities.

(25) Accordingly, in another embodiment, the invention relates to a LiBSiO electrolyte that has electrochemical stability when subjected to a broad range of electrical potentials.

(26) In another embodiment, the lithium borosilicate glass is electrochemically stable in contact with a positive cathode active material subjected to a potential of 3.6-5 V; in a further embodiment a potential of 4.5-5 V; and in a further embodiment a potential of 5.5-8.5 V. In another embodiment, the lithium borosilicate glass is stable against lithium and is electrochemically stable in contact with a positive cathode active material subjected to a potential of 3.6-5V; in a further embodiment a potential of 4.5-5 V; and in a further embodiment a potential of 5.5-8.5 V.

(27) High Ionic Conductivity and Low Electronic Conductivity

(28) The inventors made the further surprising discovery that the electronic conductivities of the LiBSiO electrolytes as described herein are very low while the ionic conductivity is high. The technical effect of this discovery is that the electronic conductivity of the LiBSiO electrolytes as described herein is sufficiently low that they can be used for solid state batteries having very low theoretical capacity (<0.04 μAh), based on their ability to maintain the charged state, due to the very low electronic conductivity properties (<2.0×10.sup.−13 S/cm).

(29) Accordingly, in another embodiment, the invention relates to a LiBSiO electrolyte that has high ionic conductivity and low electronic conductivity. In a further embodiment, the LiBSiO electrolyte has an ionic conductivity of at least 1.0×10.sup.−6 S/cm and an electronic conductivity of less than 6.0×10.sup.−14 S/cm at 25° C. In a further embodiment, the LiBSiO electrolyte has an ionic conductivity of at least 1.0×10.sup.−6 S/cm and an electronic conductivity of less than 5.0×10.sup.−14 S/cm at 25° C. In a further embodiment, the LiBSiO electrolyte has an ionic conductivity of at least 1.0×10.sup.−6 S/cm and an electronic conductivity of less than 4×10.sup.−14 S/cm at 25° C. In a further embodiment, the LiBSiO electrolyte has an ionic conductivity of at least 1.0×10.sup.−6 S/cm and an electronic conductivity of less than 2.0×10.sup.−14 S/cm at 25° C.

(30) In a further embodiment, the LiBSiO electrolyte has an ionic conductivity of at least 3.0×10.sup.−6 S/cm and an electronic conductivity of less than 6.0×10.sup.−14 S/cm at 25° C. In a further embodiment, the LiBSiO electrolyte has an ionic conductivity of at least 3.0×10.sup.−6 S/cm and an electronic conductivity of less than 5.0×10.sup.−14 S/cm at 25° C. In a further embodiment, the LiBSiO electrolyte has an ionic conductivity of at least 3.0×10.sup.−6 S/cm and an electronic conductivity of less than 4×10.sup.−14 S/cm at 25° C. In a further embodiment, the LiBSiO electrolyte has an ionic conductivity of at least 3.0×10.sup.−6 S/cm and an electronic conductivity of less than 2.0×10.sup.−14 S/cm at 25° C.

(31) In a further embodiment, the LiBSiO electrolyte has an ionic conductivity of at least 5.0×10.sup.−6 S/cm and an electronic conductivity of less than 6.0×10.sup.−14 S/cm at 25° C. In a further embodiment, the LiBSiO electrolyte has an ionic conductivity of at least 5.0×10.sup.−6 S/cm and an electronic conductivity of less than 5.0×10.sup.−14 S/cm at 25° C. In a further embodiment, the LiBSiO electrolyte has an ionic conductivity of at least 5.0×10.sup.−6 S/cm and an electronic conductivity of less than 4×10.sup.−14 S/cm at 25° C. In a further embodiment, the LiBSiO electrolyte has an ionic conductivity of at least 5.0×10.sup.−6 S/cm and an electronic conductivity of less than 2.0×10.sup.−14 S/cm at 25° C.

(32) In another embodiment, the above LiBSiO electrolyte is stable against lithium. In another embodiment, the above LiBSiO electrolyte is electrochemically stable against lithium and electrochemically stable in contact with a positive cathode active material subjected to a potential of 3.6-5 V. In another embodiment, the above LiBSiO electrolyte is electrochemically stable against lithium and electrochemically stable in contact with a positive cathode active material subjected to a potential of 5.5-8.5 V.

(33) Lithium Borosilicate Surface-Modified Electrode

(34) Degradation of an electrode active material can be caused by reactions with an electrolyte, electrolyte solution or atmosphere; by mechanical stress; or otherwise. For example, lithium metal is highly reactive. Reactions occur during cycling of a battery with a Li-based electrode due to reduction of solvents, active species, or impurities in the electrolyte. These and other reactions lead to the degradation of the electrodes, loss of electrode capacity, consumption of electrolyte and active materials, and eventual battery failure. An additional failure mode is the growth of dendritic lithium at the surface of the lithium anode (due to non-uniform current densities provided by surface defects) leading to capacity loss, arising from generation of detached lithium, and cell death by shorting of the electrodes, a process which may be mitigated by the placement of a solid state electrolyte at the interface between the lithium and the liquid electrolyte. There is need for a material with a high ion conductivity, a low electronic conductivity, that is stable in contact with lithium, and can be used as a protective coating for an electrode. There is further a need for a battery with electrodes having improved stability and cycling.

(35) Accordingly, a second aspect the invention provides an electrode a surface of which is modified by a LiBSiO material as described herein. The LiBSiO-surface-modified electrode has improved stability and/or improved cycling over 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.

(36) As used herein, the term “surface-modified” and “a surface of which is modified by” means that at least a portion of a surface of the electrode is in mechanical or chemical contact with the LiBSiO composition described herein.

(37) The electrode active material of the electrode is not particularly limited as long as the material allows the LiBSiO to attach a surface thereto, and is capable of storing and releasing lithium ions. Examples of the electrode active material includes, but is not limited to, those described elsewhere in the instant specification. In a preferred embodiment, the negative electrode active material is lithium metal.

(38) In some embodiments, the electrode is a lithium intercalation electrode. As used herein, the term “intercalation” refers to the reversible inclusion or insertion of a molecule or ion into compounds with layered structures. Therefore, a lithium intercalation electrode may be an electrode in which lithium ions may be reversibly included or inserted into a layered structure, e.g. graphite.

(39) In some embodiments, the electrode is coated with a layer of LiBSiO material as described herein. In some embodiments, the lithium borosilicate composition described herein is provided as a layer on the surface of the electrode.

(40) In some embodiments, a surface of the electrode is coated with a layer of LiBSiO material as described herein. This coating may be achieved by first casting an electrode comprising electrode active material (and optionally carbon additive, polymer binder and/or solvent) on a current collector, and then curing and drying the electrode. The surface of the cast electrode may then have a protective layer of the LiBSiO material deposited thereon. In some embodiments, the LiBSiO entirely coats the surface of the electrode. In some embodiments, the LiBSiO partially covers the surface of the electrode.

(41) In some embodiments, the electrode comprises particles of electrode active material, wherein the particles are coated with a layer of the LiBSiO material as described herein. This may be achieved by coating the entirety of each particle of active material with the protective LiBSiO material. The protected particles may then be optionally mixed with carbon additive, polymer binder and/or solvent and formed into a slurry. The slurry may then be cast onto an electronically conducting current collector.

(42) The thickness of the LiBSiO-coat layer is not particularly limited as long as it improves stability or improves cycling of the electrode. In one embodiment, the thickness of the LiBSiO-coat layer is between 2 nm to 100 nm. In a further embodiment, the range is between 2 nm to 50 nm.

(43) In one embodiment, the LiBSiO-surface-modified electrode comprises a LiBSiO-coat layer that coats a surface of the electrode and through which lithium ions may move. In one embodiment, the electrode surface is entirely coated with LiBSiO. In another embodiment, an electrode surface that is in contact with an electrolyte (especially a non-solid state electrolyte) is coated with LiBSiO.

(44) Battery

(45) The inventors made the surprising discoveries that the lithium borosilicate glass as described herein has 1) a high ionic conductivity coupled with low electronic conductivity, 2) is electrochemically stable in contact with very reducing electrodes, such as a metallic lithium anode, and very oxidizing electrodes, such as a charged Li.sub.0.5CoO.sub.2 cathode at 4.2 V versus Li/Li.sup.+, and 3) is electrochemically stable at high voltages.

(46) Accordingly, a third aspect of the invention relates to a battery comprising a positive electrode, a negative electrode, and an electrolyte between said positive electrode and said negative electrode, wherein said negative electrode comprises lithium, and wherein said electrolyte is a lithium borosilicate composition as described herein. Accordingly, a fourth aspect of the invention relates to a battery comprising a positive electrode, a negative electrode, and an electrolyte between said positive electrode and said negative electrode, wherein said electrolyte is a lithium borosilicate composition as described herein, and wherein said battery has a fully charged capacity that is less than 0.5 μAh. Accordingly, a fifth aspect of the invention relates to a battery comprising a positive electrode, a negative electrode, and an electrolyte between said positive electrode and said negative electrode, wherein said positive electrode comprises a positive electrode active material selected from the group consisting of LiCoPO.sub.4, LiNi.sub.0.5Mn.sub.1.5O.sub.4, LiMnPO.sub.4, LiCoO.sub.2, LiNi.sub.1/3Mn.sub.1/3CO.sub.1/3O.sub.2, LiFePO.sub.4, LiNiPO.sub.4, Li.sub.2NiPO.sub.4F, Li.sub.2CoPO.sub.4F, LiMnPO.sub.4F, Li.sub.2CoSiO.sub.4, Li.sub.2MnSiO.sub.4, FeF.sub.3, LiMn.sub.0.8Fe.sub.0.1Ni.sub.0.1PO.sub.4, Li.sub.1-xVOPO.sub.4, and Li.sub.2FePO.sub.4F, and wherein said electrolyte is a lithium borosilicate composition as described herein.

(47) In a further embodiment, the battery further comprises a positive electrode current collector and a negative electrode current collector. In a further embodiment, the battery further comprises a substrate. In a further embodiment, the battery is further encapsulated.

(48) In one embodiment, the battery is a lithium ion battery. In a further embodiment, the battery is lithium ion secondary battery. In a further embodiment, the thin film battery is an all-solid state battery. In a further embodiment, the battery is a thin film battery comprising a positive electrode, an electrolyte and a negative electrode.

(49) In one embodiment, the battery comprises multiple positive electrodes and multiple negative electrodes, such as in a stack. Electrolyte in contact with the electrodes provides ionic conductivity through the separator between electrodes of opposite polarity. The battery generally comprises current collectors associated respectively with a negative electrode and a positive electrode. The stack of electrodes with their associated current collectors and separator are generally placed within a container with the lithium borosilicate electrolyte.

(50) 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 active material having an electrochemical potential of at least 3.5 V versus Li/Li.sup.+; at least 4.0 V versus Li/Li.sup.+; at least 4.5 V versus Li/Li.sup.+; at least 5.5 V versus Li/Li.sup.+; or between 6.0-8.5 V versus Li/Li.sup.+.

(51) A Li-ion battery with a lithium borosilicate electrolyte as described herein and a high voltage positive electrode allows development of a high energy/power density Li-ion battery. Furthermore, lithium borosilicate electrolytes as described herein have very high ionic conductivity, and low electrical conductivity so can provide improved performance, such as higher power and energy as well as stable low capacity. For high voltage operation, another significant aspect of the electrolyte properties is the reductive and oxidative stability. The improved reductive and oxidative stability improves cycling performance and life of the battery of the invention.

(52) Improved battery systems are provided with a lithium borosilicate electrolyte and a high voltage positive electrode that can be used to produce a high energy and high power Li-ion battery. The positive electrodes having positive electrode active materials (cathode materials) with a potential in the range of about 3.6 to 8.5 V vs Li/Li.sup.+ provide excellent performance in conjunction with a LiBSiO electrolyte.

(53) Negative Electrode

(54) Negative electrode active materials are used as the counter-electrode for the positive electrodes. The compositions of the positive electrode active material and the negative electrode active material determine the potential of the battery during discharge, which is the difference between the potentials of the respective half reactions.

(55) The negative electrode active material used in the battery of the present invention may be selected from Li.sub.4Ti.sub.5O.sub.12, Si, Ge, Sn, Sb, Al, Mg, Bi, Si-M (M=Mg, Al, Sn, Zn, Ag, Fe, Ni, Mn), InSb, metal oxides including; TiO.sub.2, vanadium and molybdenum oxides, Ti, Nb oxides (MgTi.sub.2O.sub.5, TiNb.sub.2O.sub.7), SnO, SnO.sub.2, Sb oxides, or germanates.

(56) The negative electrode active material used in the battery of the present invention may be lithium or a lithiated 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 (such as activated carbon) capable of reversibly intercalating lithium ions, a tin containing material, a silicon-containing material, or other material.

(57) Negative electrode active materials further include graphite, synthetic graphite, coke, fullerenes, niobium pentoxide, tin alloys, silicon (including amorphous silicon), titanium oxide, tin oxide, and lithium titanium oxide.

(58) Negative electrode active materials comprising elemental carbon materials include graphite, synthetic graphite, coke, fullerenes, carbon nanotubes, other graphitic carbon and combinations thereof. Graphitic carbon refers to any elemental carbon material comprising substantial domains of graphene sheets.

(59) 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 a further embodiment, the negative electrode may comprise a layer of lithium metal, or a lithium-aluminum alloy. In another embodiment, the negative electrode is lithium. In another embodiment, the negative electrode is a lithium free anode. In another embodiment, the negative electrode is a lithium air anode.

(60) In some embodiments, the electrode is a lithium intercalation electrode. As used herein, the term “intercalation” refers to the reversible inclusion or insertion of a molecule or ion into compounds with layered structures. Therefore, a lithium intercalation electrode may be an electrode in which lithium ions may be reversibly included or inserted into a layered structure, e.g. graphite.

(61) Positive Electrode

(62) Positive electrode active materials are used in the counter-electrode for the negative electrodes. The positive electrode may, in some embodiments, include a positive active material having a potential greater than 3.6 V vs Li/Li.sup.+.

(63) A positive electrode active material of a battery of the present invention include a lithiated transition metal compound, such as a lithium nickel manganese oxide, lithium nickel vanadium oxide, lithium cobalt vanadium oxide, or lithium cobalt phosphate, for example Li.sub.2NiMn.sub.3O.sub.8, LiNiVO.sub.4, LiCoVO.sub.4, LiCoPO.sub.4, and the like. Other examples include lithium nickel phosphate, lithium nickel fluorophosphate, and lithium cobalt fluorophosphate; i.e. LiNiPO.sub.4, Li.sub.2NiPO.sub.4F, Li.sub.2CoPO.sub.4F, and the like. The lithium content typically varies depending on the state of charge of the battery. The positive active material may comprise other oxygen-containing materials, such as an oxide, manganate, nickelate, vanadate, phosphate, or fluorophosphate. The positive active material may have the formula Li.sub.xM.sub.yN.sub.zO, where M is selected from a group consisting of Ni, Mn, V, and Co, and N is a heteroatomic species different from M, such as Ni, Mn, V, Co, or P. N can be omitted. The positive active material may also be fluorinated, for example as a fluorophosphate.

(64) In one embodiment, the positive electrode active material of a battery of the present invention is selected from the group consisting of LiCoO.sub.2, FeS.sub.2, LiCoPO.sub.4, LiFePO.sub.4, Li.sub.2FeS.sub.2, Li.sub.2FeSiO.sub.4, LiMn.sub.2O.sub.4, LiMnPO.sub.4, LiNiPO.sub.4, LiV.sub.3O.sub.8, LiV.sub.8O.sub.13, LiVOPO.sub.4, LiVOPO.sub.4F, Li.sub.3V.sub.2(PO.sub.4).sub.3, MnO.sub.2, MoS.sub.3, S, TiS.sub.2, TiS.sub.3, V.sub.2O.sub.5, V.sub.6O.sub.13, LiNi.sub.0.5Mn.sub.1.5O.sub.4, and LiMnNiCoAlO.sub.2.

(65) In another embodiment, the positive electrode active material of a battery of the present invention is high voltage positive electrode active materials. In a further embodiment, the high voltage positive electrode active material is selected from the group consisting of LiCoPO.sub.4, LiNi.sub.0.8Mn.sub.1.8O.sub.4, LiMnPO.sub.4, LiMn.sub.2O.sub.4, LiCoO.sub.2, LiNi.sub.1/3Mn.sub.1/3CO.sub.1/3O.sub.2, LiFePO.sub.4, LiNiPO.sub.4, Li.sub.2NiPO.sub.4F, Li.sub.2CoPO.sub.4F, LiMnPO.sub.4F, Li.sub.2CoSiO.sub.4, Li.sub.2MnSiO.sub.4, FeF.sub.3, LiMn.sub.0.8Fe.sub.0.1Ni.sub.0.1PO.sub.4, Li.sub.1-xVOPO.sub.4 and Li.sub.2FePO.sub.4F.

(66) In another embodiment, the positive electrode comprises a positive electrode active material having a chemical formula:
Li.sub.xM.sub.1−(d+t+q+r)D.sub.dT.sub.tQ.sub.qR.sub.r(XO.sub.4)

(67) wherein:

(68) M is a cation of a metal selected from the group consisting of Fe, Mn, Co, Ti, Ni or mixtures thereof;

(69) D is a metal having a +2 oxidation state selected from the group consisting of Mg.sup.2+, Ni.sup.2+, Co.sup.2+, Zn.sup.2+, Cu.sup.2+, and Ti.sup.2+;

(70) T is a metal having a +3 oxidation state selected from the group consisting of Al.sup.3+, Ti.sup.3+, Cr.sup.3+, Fe.sup.3+, Mn.sup.3+, Ga.sup.3+, Zn.sup.3+, and V.sup.3+;

(71) Q is a metal having a +4 oxidation state selected from the group consisting of Ti.sup.4+; Ge.sup.4+; Sn.sup.4+, and V.sup.4+;

(72) R is a metal having a +5 oxidation state selected from the group consisting of V.sup.5+; Nb.sup.5+, and Ta.sup.5+;

(73) X comprises Si, S, P, V or mixtures thereof;

(74) 0≤x≤1; and

(75) 0≤d, t, q, r≤1, where at least one of d, t, q, and r is not 0.

(76) In another embodiment, the positive electrode active material comprises a positive electrode active material comprises an ordered olivine electrode compound selected from LiFePO.sub.4, LiMnPO.sub.4, LiCoPO.sub.4, LiNiPO.sub.4, mixed transition-metal compounds such as Li.sub.1-2xFe.sub.1-xTi.sub.xPO.sub.4 or LiFe.sub.1-xMn.sub.xPO.sub.4, where 0<x<1, or other compounds having the general formula LiMPO.sub.4 and an ordered olivine structure.

(77) In general, “isocharge substitutions” refers to substitution of one element on a given crystallographic site with an element having a similar charge. For example, Mg.sup.2+ is considered similarly isocharge with Fe.sup.2+, and V.sup.5+ is similarly isocharge with P.sup.5+. Likewise, PO.sub.4.sup.3− tetrahedra can be substituted with VO.sub.4.sup.3− tetrahedra. “Aliovalent substitution” refers to substitution of one element on a given crystallographic site with an element of a different valence or charge. One example of an aliovalent substitution would be Cr.sup.3+ or Ti.sup.4+ on an Fe.sup.2+ site. Another example would be Li.sup.+ on a Fe.sup.2+ site. These positive electrode active materials will generally have an olivine structure based on iron or manganese derivatives whose general formula is:
Li.sub.x+yM.sub.1−(y+d+t+q+r)D.sub.dT.sub.tQ.sub.qR.sub.r[PO.sub.4].sub.1−(p+s+v)[SO.sub.4].sub.p[SiO.sub.4].sub.s[VO.sub.4].sub.v

(78) where

(79) M may be Fe.sup.2+ or Mn.sup.2+ or mixtures thereof;

(80) D may be a metal in the +2 oxidation state, preferably Mg.sup.2+, Ni.sup.2+, Co.sup.2+, Zn.sup.2+, Cu.sup.2+, or Ti.sup.2+;

(81) T may be a metal in the +3 oxidation state, preferably Al.sup.3+, Ti.sup.3+, Cr.sup.3+, Fe.sup.3+ Ga.sup.3+, Zn.sup.3+, or V.sup.3+;

(82) Q may be a metal in the +4 oxidation state, preferably Ti.sup.4+, Ge.sup.4+, Sn.sup.4+, or V.sup.4+;

(83) R may be a metal in the +5 oxidation state, preferably V.sup.5+, Nb.sup.5+, or Ta.sup.5+;

(84) In this further embodiment, M, D, T, Q and R reside in octahedral sites. The additional coefficients may be defined as follows: x represents the degree of intercalation during operation of the electrode material; y represents the fraction of lithium ions on the initial Fe.sup.2+ sites; d represents the fraction of divalent ions (noted as D) on the initial Fe.sup.2+ sites; t represents the fraction of trivalent ions (noted as T) on the initial Fe.sup.2+ sites; q represents the fraction of tetravalent ions (noted as 0) on the initial Fe.sup.2+ sites; r represents the fraction of pentavalent ions (noted as R) on the initial Fe.sup.2+ sites; p represents the fraction of hexavalent sulfur (as discrete SO.sub.4.sup.2− tetrahedra) on the initial P.sup.5+ sites; s represents the fraction of tetravalent silicon (as discrete SiO.sub.4.sup.2− tetrahedra) on the initial P.sup.5+ sites; and v represents the fraction of pentavalent vanadium ions on the initial P.sup.5÷ sites.

(85) The conditions for site occupancy and electroneutrality imply the following:
0≤x≤1;
y+d+t+q+r≤1;
P+s+v<1; and
3+s−p=x−y+t+2q+3r.

(86) x, y, d, t, q, r, p, s, and v may be between 0 (zero) and 1 (one), with at least one of y, d, t, q, r, p, s, or v differing from 0. In a preferred embodiment y, d, t, q, r, and v may vary between 0 (zero) and 0.2 ( 2/10) and r and s may vary between 0 (zero) and 0.5 (½). In some embodiments, the electrode is a lithium intercalation electrode. As used herein, the term “intercalation” refers to the reversible inclusion or insertion of a molecule or ion into compounds with layered structures. Therefore, a lithium intercalation electrode may be an electrode in which lithium ions may be reversibly included or inserted into a layered structure, e.g. graphite.

(87) The battery of the invention may contain an intercalation material with fast diffusion kinetics in the positive electrode containing the Li.sub.x+yM.sub.1−(y+d+t+q+r)D.sub.dT.sub.tQ.sub.qR.sub.r[PO.sub.4].sub.1−(p+s+v)[SO.sub.4].sub.p[SiO.sub.4].sub.s[VO.sub.4].sub.v material described. The phrase “fast diffusion kinetics” is generally understood in the art as referring to a material able to sustain a specific current of at least 10 mA per gram of material with more than 80% utilization of the capacity at the temperature of operation. Preferably, the intercalation material with fast diffusion kinetics may be a lamellar dichalcogenide, a vanadium oxide VO.sub.x where 2.1≤x≤2.5, or a NASICON-related material such as Li.sub.3Fe.sub.2(PO.sub.4).sub.3 or Li.sub.3-xFe.sub.2-xTi.sub.x(PO.sub.4).sub.3 where x represents the degree of substitution of Fe.sup.3+ by Ti.sup.4+.

(88) The positive electrode active materials described herein can have a specific discharge capacity of at least about 50 mAh/g at a discharge rate of C/3 at the 10th discharge cycle at room temperature when discharged from 8.5 volts to 1 volts.

(89) Current Collector

(90) A current collector (electron collector) can be an electrically conductive member comprising a metal, conducting polymer, or other conducting material. A current collector for a battery of the present invention may comprise a metal such as Cu, Pt, Au, Al, Ni, Fe, Ti, Mo, stainless steel, or other metal or alloy. The electron collector may have an additional layer to reduce corrosion, for example an additional layer comprising tungsten (W), platinum (Pt), palladium (Pd), titanium carbide (TiC), tantalum carbide (TaC), titanium oxide (for example, TiO.sub.2 or Ti.sub.4O.sub.7), copper phosphide (Cu.sub.2P.sub.3), nickel phosphide (Ni.sub.2P.sub.3), iron phosphide (FeP), and the like, or may comprise particles of such materials.

(91) Electrochemical Stability

(92) It may be desirable to operate a battery at high voltages to provide for higher capacity and/or to provide greater power output. With an improved lithium borosilicate glass electrolyte described herein, the properties of the high voltage batteries can be significantly improved. For example, the battery can have a longer cycle life.

(93) For high voltage operation, another significant aspect of the electrolyte is the reductive and oxidative stability. The improved reductive and oxidative stability improves cycling performance of the corresponding battery. The lithium borosilicate glass electrolytes described herein do not react terminally (reduce or oxidize) at the operational voltages of the battery. The lithium borosilicate glass electrolytes have the capability of operating at high voltages, for example, against lithium or elemental carbon negative electrode active materials. The improved electrolytes described herein can be effective to improve the cycling performance of lithium ion batteries in operation at high charge voltages above 4.45 V.

(94) Accordingly, in another embodiment, the invention relates to a battery comprising a lithium borosilicate glass electrolyte that is capable of operation at high voltages. In a further embodiment, the high voltage battery comprises a lithium borosilicate glass electrolyte that is capable of operation at up to 4.45 V, at least 5 V, at least 5.5 V, at least 6 V, at least 7 V, at least 8 V, at least 9 V or at least 10 V. In a further embodiment, the lithium borosilicate glass electrolyte has an ionic conductivity of greater than 1.0×10.sup.−6 S/cm at 25° C. In a further embodiment, the lithium borosilicate glass electrolyte is stable against lithium. In a further embodiment, the lithium borosilicate glass electrolyte is between 0.05-15 microns thick, between 0.3-4 microns thick, or between 2-4 microns thick. In a further embodiment, the battery comprises a lithium anode or is a lithium free battery.

(95) High Ionic and Low Electronic Conductivity

(96) In another embodiment, the invention provides for a battery comprising a lithium borosilicate glass electrolyte that has a high ionic conductivity and a low electronic conductivity. In one embodiment, the lithium borosilicate glass electrolyte has an ionic conductivity of greater than 1.0×10.sup.−6 S/cm and an electronic conductivity of less than 8.6×10.sup.−14 S/cm. In a further embodiment, the battery has an ionic conductivity of greater than 1.0×10.sup.−6 S/cm and an electronic conductivity of less than 8.6×10.sup.−14 S/cm and is capable of operation at up to 4.45 V, at least 5 V, at least 5.5 V, at least 6 V, at least 7 V, at least 8 V, at least 9 V or at least 10 V. In a further embodiment, the battery has an ionic conductivity of greater than 1.0×10.sup.−6 S/cm and an electronic conductivity of less than 8.6×10.sup.−14 S/cm and is capable of operation at up to 4.45 V and comprises a lithium anode or is a lithium free battery. In a further embodiment, the battery is an all solid state, thin film, lithium ion battery.

(97) In another embodiment, the battery comprising a lithium borosilicate glass electrolyte has an ionic conductivity of greater than 1.0×10.sup.−6 S/cm and an electronic conductivity of less than 8.6×10.sup.−14 S/cm and has a fully charged capacity that is between 0.04-5 μAh. In a further embodiment, the battery has a fully charged capacity that is less than 0.5 μAh. In a further embodiment, the battery has a fully charged capacity that is less than 0.1 μAh.

(98) Battery Comprising a Lithium Borosilicate Surface-Modified Electrode

(99) One aspect of the invention relates to a battery comprising a positive electrode, a negative electrode, and an electrolyte between said positive electrode and said negative electrode, wherein a surface of the positive electrode and/or negative electrode is modified by a LiBSiO composition described herein. The LiBSiO composition may consist essentially of a system of lithium oxide in combination with silicon oxide and/or boron oxide, wherein said lithium borosilicate comprises between 70-83 atomic % lithium based on the combined atomic percentages of lithium, boron and silicon, and wherein said lithium borosilicate is a glass. Preferably, the lithium borosilicate composition consists essentially of a system of lithium oxide in combination with silicon oxide and boron oxide, wherein said lithium borosilicate comprises between 70-83 atomic % lithium based on the combined atomic percentages of lithium, boron and silicon, and wherein said lithium borosilicate is a 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.

(100) In one embodiment, the battery comprises a positive electrode, a negative electrode, and an electrolyte between said positive electrode and said negative electrode, wherein the positive electrode and/or negative electrode is coated with a layer of a LiBSiO composition of the present invention.

(101) In one embodiment, the 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 a surface of the positive electrode and/or negative electrode is modified by a LiBSiO material as 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 another embodiment, the battery comprises a LiBSiO-surface-modified negative electrode and a LiBSiO-surface-modified positive electrode. In a further embodiment, the battery is a lithium ion secondary battery. In another embodiment, the lithium ion secondary battery is a thin-film battery.

(102) In one embodiment, the 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 is coated with a LiBSiO material of the present invention, e.g., 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 another embodiment, the battery comprises a LiBSiO-coated negative electrode and a LiBSiO-coated positive electrode. In a further embodiment, the battery is a lithium ion secondary battery. In another embodiment, the lithium ion secondary battery is a thin-film battery.

(103) The electrolyte may comprise an organic electrolyte, liquid electrolyte, an ionic liquid, a gel electrolyte, room temperature molten salt, or a solid electrolyte. If the electrolyte is a liquid or gel, then preferably it is a non-aqueous electrolyte. In one embodiment, the electrolyte is an organic electrolyte. In another embodiment, the electrolyte is a liquid electrolyte. In a further embodiment, the liquid electrolyte is a non-aqueous electrolyte. In another embodiment, the electrolyte is a gel electrolyte. In another embodiment, the electrolyte is a molten salt electrolyte. In another embodiment, the electrolyte is a solid electrolyte.

(104) In a further embodiment the liquid, non-aqueous electrolyte comprises a lithium salt and a non-aqueous solvent. Examples of lithium salts include LiPF.sub.6, LiBF.sub.4, lithium bis(trifluoromethanesulfonyl)amide (LiTFSA, LiN(CF.sub.3SO.sub.2).sub.2), LiCF.sub.3SO.sub.3, LiC.sub.4F.sub.9SO.sub.3, LiC(CF.sub.3SO.sub.2).sub.3, LiClO.sub.4, lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)amide (LiFSA, LiN(SO.sub.2F).sub.2), and LiCF.sub.3CO.sub.2. The non-aqueous solvent is capable of dissolving the lithium salt. Examples of the non-aqueous solvent include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, 1,3-dioxolane, nitromethane, N,N-dimethyl formamide, dimethyl sulfoxide, sulfolane, vinylene carbonate, and γ-butyrolactone.

(105) In some embodiments, the electrolyte comprises an additive. The electrolyte additive may modify the electrode-electrolyte interface easily and economically. In some embodiment, the electrolyte comprises an additive selected from the group consisting of 4-(trifluoromethyl)-1,3-dioxolan-2-one (TFM-EC), tris(hexafluoro-iso-propyl)phosphate (HFip), 3-hexylthiophene, LiDFOB, tris(trimethylsilyl)phosphate (TMSP), tris(trimethylsilyl)borate (TMSB), and combinations thereof.

(106) Methods of Making Lithium Borosilicate

(107) A ninth aspect provides for a method of making the lithium borosilicate glass described herein. In one embodiment, the lithium borosilicate glass is formed by a vacuum deposition process. In a further embodiment, the lithium borosilicate glass is formed by a physical vapor deposition process.

(108) Physical vapour deposition processes are generally known to those skilled in the art. In the present invention, the process typically comprises the use of a physical process (such as heating) to produce a vapour including the component elements Li, B, Si and O, which is then deposited on the substrate. In one embodiment, the physical vapour deposition process is carried out at a temperature of between 100 and 400° C., preferably 150 to 300° C., and more preferably 200 to 250° C.

(109) In one embodiment, the physical vapour deposition process is carried out at a pressure of between 4.0×10.sup.−4 and 6.7×10.sup.−3 Pa (3×10.sup.−6 and 5×10.sup.−5 Torr), preferably between 2.7×10.sup.−3 and 4.7×10.sup.−3 Pa (2×10.sup.−5 and 3.5×10.sup.−5 Torr).

(110) In one embodiment, the oxygen source may be an ozone source of oxygen, an atomic source of oxygen or molecular source of oxygen.

(111) In one embodiment, the invention relates to a method of making a lithium borosilicate electrolyte that is electrochemically stable against lithium. In a further embodiment, the battery comprises a lithium anode.

(112) In another embodiment, the invention relates to a method of making a lithium borosilicate electrolyte that is capable of operation at high voltages. In a further aspect, the battery is suitable for longer term cycling.

(113) In another embodiment, the invention relates to a method of making a lithium borosilicate electrolyte that has low electronic conductivity. In a further embodiment, the battery has a low capacity.

(114) Method of Making a Lithium Borosilicate Coated Electrode

(115) A further aspect provides for a method of making a LiBSiO-surface-modified electrode. The method of making the LiBSiO-surface-modified electrode of the invention is not particularly limited as long as the method is able to provide a desired LiBSiO-surface-modified electrode that improves stability or improves cycling of the electrode. Examples of the method include PVD as described herein. In one embodiment, the method is a method of making a LiBSiO-surface-modified negative electrode. In another embodiment, the method is a method of making a LiBSiO-surface-modified positive electrode. In one embodiment, the LiBSiO coating is produced by physical vapour deposition (PVD).

(116) Methods of Making a Battery Comprising a Lithium Borosilicate Glass Electrolyte

(117) A further aspect of the invention relates to a method of making a battery comprising a lithium borosilicate glass electrolyte.

(118) In another embodiment, the thin film battery is produced by sequentially forming films of constituents in all-solid state.

(119) Method of Making a Battery Comprising a Lithium Borosilicate Coated Electrode

(120) A further aspect provides for a method of making a battery comprising an electrode the surface of which is modified with a LiBSiO material described herein. In one embodiment, the method is a method of making a battery comprising a LiBSiO-surface-modified negative electrode. In another embodiment, the method is a method of making a battery comprising a LiBSiO-surface-modified positive electrode. In a further embodiment, the battery is a lithium ion secondary battery. In another embodiment, the lithium ion secondary battery is a thin-film battery.

EXAMPLES

Example 1—Preparing a LiBSiO Electrolyte

(121) In accordance with embodiments of the invention, lithium borosilicate material was 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’, incorporated herein by reference in its entirety. Lithium borosilicate was fabricated by providing a vapour source of each component element of the compound and co-depositing the component elements from the vapour sources onto a substrate heated to 225° C. at a pressure from 2.7×10.sup.−3 to 4.3×10.sup.−3 Pa (2×10.sup.−5 to 3.2×10.sup.−5 Torr). The component elements reacted on the substrate to form the amorphous lithium borosilicate compound. The compounds produced had the compositions described in Example 5 below.

(122) The deposition was carried out in a physical vapour deposition (PVD) system which was previously described in the literature (Guerin, S. and Hayden, B. E., Journal of Combinatorial Chemistry 8 (2006) 66-73). All samples were deposited utilizing an oxygen plasma source as a source of atomic oxygen. The oxide materials, lithium silicate and lithium borate, require the highest oxidation states of both silicon and boron (4+ and 3+ respectively), and the use of atomic oxygen rather than molecular oxygen therefore removes the dissociation step required to break O.sub.2 to 20 and provides a highly reactive species to oxidize silicon and boron into their highest oxidation states, as required in the materials Li.sub.4SiO.sub.4 and Li.sub.3BO.sub.3. Lithium was deposited from a Knudsen cell source. Silicon and boron were both deposited from electron gun (E-Gun) sources.

(123) The use of other vacuum deposition methods may be used for the fabrication of the cathode, anode, current collectors and first barrier layer materials. This may include but is not limited to physical vapour deposition, chemical vapour deposition (CVD), RF sputtering, molecular beam epitaxy solid state reaction, pulsed laser deposition (PLD), sol-gel, and atomic layer deposition (ALD).

(124) In the case of the present invention a battery could be constructed by sequential deposition of an appropriate chemical compound onto a suitable, electrically conductive substrate. For example, sequential deposition of an anode layer (e.g., Li metal from a Li evaporation source), an electrolyte layer (e.g., lithium borosilicate prepared using the method disclosed herein), a cathode layer (e.g., LMO from component evaporation sources), and an electrically conductive top layer could be carried out to provide the layered structure of a thin film battery.

Example 2—Electrochemical Stability of LiBSiO Electrolyte

(125) A thin film battery was made with a platinum cathode current collector, a LiMn.sub.2O.sub.4 cathode, a lithium borosilicate glass electrolyte, and an Li anode. The stability of the lithium borosilicate glass electrolyte was exemplified in three ways.

Example 3—Stability Against Lithium Anode

(126) 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 observed for deleterious reactions between the electrolyte and the anode materials. After 100 cycles, there was no evidence in the profile of the current as a function of potential to suggest the presence of deleterious reactions between the electrolyte and the anode materials.

Example 4—Stable OCV

(127) Second, a stable open circuit voltage (OCV) of the same thin film battery system was observed both before and after cycling of said battery. The open circuit voltage at beginning of life, measured 40 days after the deposition of the anode on the LiBSiO solid state electrolyte was determined to range from 2.36 to 2.92 V vs. Li/Li.sup.+. Had the lithium reacted in a persistent fashion with the solid state electrolyte it would eventually have consumed the LiBSiO in formation of a continuous pathway between the anode and the cathode leading to a measured OCV of 0 V.

(128) A stable end of life (EOL) OCV of 4.15 V vs. Li/Li.sup.+ was observed after being subjected to 10 constant current cycles between 3.8 and 4.25 voltage at a current of 0.1 μA, 12 cycles of cyclic voltammetry, and 23 constant current cycles between 3.8 and 4.25 V at a current of 0.2 μA.

(129) The open circuit voltage of a LMO/LiBSiO/Li cell was measured every 5 seconds for 35 minutes (FIG. 1) subsequent to completion of cycling, the final stage of which was monitoring of the OCV at the top of charge for 15 minutes (FIG. 2). The scatter observed in the data in the figure to the right was due to disruption of the measurement by external perturbations.

(130) As shown in FIG. 3, cyclic voltammetry was performed on a solid state cell comprised of a AlOPt (sapphire, titanium or titania (20 nm), platinum (100 nm)) substrate, LMO cathode, 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 at 0.25 mV/s, while the remaining 97 cycles were performed at a scan rate of 0.5 mV/s. It can be seen that the characteristic profile of the potential dependent current does not change as within the set of data reflecting the behavior from beginning to the end of cycling. A decrease in capacity associated with reduction in current magnitude is symptomatic of cycling related aging effects but does not imply degradation or instability related to incompatibility between the electrolyte and the electrodes, but could relate to the intrinsic stability of the cathode material when subjected to the applied cycling conditions.

Example 5—Impedance

(131) The application of impedance as a measure of stability was used by Bates et al., Journal of the Electrochemical Society, 144 [2] (1997) 524-533 where a comparison between the impedance of LiPON as sandwiched between platinum electrodes or one lithium and one platinum electrode was made.

(132) Impedance, in a method similar to that described in Bates et al., was measured on a LiBSiO electrolyte 72.6 mol % Li.sub.2O—6.8 mol % B.sub.2O.sub.3—20.6 mol % SiO.sub.2 sample at a potential of 3.8 V vs. Li/Li.sup.+ before and after 10 constant current cycles at 0.1 μA between 3.8 and 4.25 V. Here a frequency range between 261.0156 kHz to 0.1 Hz with seven data points per decade, and an AC amplitude of 10 mV was used. As demonstrated in FIGS. 4A and B, there is little or no difference between the impedance spectra collected before and after cycling in the high frequency regime (FIG. 4A) of the data set as provided by data points below 40 kΩ (FIG. 4B) on the ordinate and abscissa axes of the plots. It is in this frequency range that the data reflect the contribution from the electrolyte and the interfaces between the electrolyte and the electrodes. As such the reproducibility of the data before and after cycling is indicative of the stability of the interface between the LiBSiO solid state electrolyte and the neighboring lithium anode.

(133) Third, the impedance was compared before and after cycling and shown to be largely unchanged in the frequency range which reflects the contribution from the electrolyte and the interfaces between the electrolyte and the neighboring electrodes.

(134) The technical effect of this discovery is that it facilitates the use of the lithium borosilicate glass compositions as described herein in solid state batteries configured with as deposited lithium anodes and within lithium free cells whereby the lithium anode is formed in situ at the interface between the solid state lithium borosilicate electrolyte and the anode current collector.

Example 6—Electrochemical Stability at High Voltage

(135) A number of lithium borosilicate compositions were made as shown below where the values of Li, B and Si are the atomic percent with regards to Li:B:Si:

(136) 1. Li=80.9, B=7.56, Si=11.5

(137) 2. Li=79.6, B=13.7, Si=6.7

(138) 3. Li=78.5, B=9.6, Si=11.87

(139) 4. Li=77.73, B=10.07, Si=12.19

(140) 5. Li=76.89, B=10.55, Si=12.56

(141) 6. Li=76.14, B=10.98, Si=12.88

(142) 7. Li=75.30, B=11.46, Si=13.24

(143) 8. Li=74.54, B=11.89, Si=13.58

(144) 9. Li=73.16, B=12.62, Si=14.22

(145) 10. Li=71.86, B=13.31, Si=14.83

(146) 11. Li=70.41, B=14.07, Si=15.51

(147) 12. Li=69.12, B=14.76, Si=16.12;

(148) with oxygen present in amounts to form oxides and maintain charge neutrality.

(149) The LiBSiO compositions exhibited electrochemical stability across potentials ranging from 0 to 5 V when deposited on top of a platinum coated substrate, acting as the bottom electrode, with the top electrode being deposited on top of the lithium borosilicate electrolyte and composed of either nickel or platinum. One representative sample was selected and tested and found to exhibit electrochemical stability across potentials ranging from 0 to 10 V.

(150) The technical effect of this discovery is that for the lithium borosilicate compositions as described herein, it may be possible to use the materials in solid state battery compositions operating at very high voltages delivering high power densities.

Example 7—Electronic and Ionic Conductivities

(151) The electronic and ionic conductivities for a range of compositions in the LiBSiO system were measured as a function of lithium content (approx. 69-79% lithium as based on components Li, B and Si). Ionic conductivity values were determined from impedance measurements performed using a Solartron 1260 frequency response analyzer between 1 MHz and 1 Hz using a 100 mV ac potential, one second integration per frequency, with seven frequency points measured per decade. Conductivity values were calculated by fitting of 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 used in combination with the geometric factor to determine the ionic conductivity. Electronic conductivity values were determined using a Keithley Series 2636 sourcemeter. A DC potential of 1 V was applied across the samples' electrodes for 65 hours with the steady state current, applied voltage, and geometric factor used to calculate the electronic conductivity values. Measurement of the electronic conductivity values was carried out in a Faraday cage enclosure. The electronic conductivity was between 1.84×10.sup.−14 and 4.40×10.sup.−14 S/cm and ionic conductivity was between 8.74×10.sup.−7 and 5.72×10.sup.−6 S/cm.

(152) The technical effect of this discovery is that the electronic conductivity is sufficiently low that the LiBSiO glass electrolytes can be used in solid state batteries having very low theoretical capacity (<0.5 μAh), based on their ability to maintain the charged state, due to the very low electronic conductivity properties (<7×10.sup.−14 S/cm).

Example 8—Utilization of Cathode Material Coated with LiBSiO

(153) FIG. 6 show the utilization number (Y axis) of the 1st discharge of LiBSiO coated (open circles) vs uncoated (solid circles) LMO cathode samples as a function of the atomic percent Li in the LMO (X axis), Data from which the plot was produced from a 10×10 array of Pt electrodes on to which discrete fields of LMO having lithium contents between 18.38 and 48.43 at. % lithium, as determined from the Li and Mn components of the LMO films were deposited. The LMO active cathode material deposited on the underlying Pt current collectors was deposited from the elements onto a substrate maintained at 450° C., with the lithium and the manganese fluxes originating from Knudsen cell sources and the oxygen supplied by a plasma source with a flow rate of O.sub.2 of 3.5 sccm and a power of 500 W. The substrate comprising the array of individual LMO sample fields were treated under O.sub.2 to 550° C. for two hours prior to the deposition of the LiBSiO coating on the test samples. The LiBSiO film was deposited on seven of the ten rows while the fields of the three remaining rows remained uncoated. The array of electrodes was subjected to electrochemically testing by cyclic voltammetry using an in-house potentiostat. The voltage range was between 3.25 V and 4.75 V, with a scan rate of 0.104 mV/sec. The counter-reference electrode was a piece of 0.5 mm thick lithium foil and the electrolyte comprised 1 M LiPF.sub.6 in EC:DMC (1:1). The data used to generate the graph were processed by first averaging all compositionally equivalent sites on the sample (seven per composition for those with LiBSiO and three per composition without LiBSiO unless null values were present due to electrode failure), then by taking the average of all values falling within one standard deviation of that average.

(154) All publications mentioned in the above specification are herein incorporated by reference. Various modifications and variations of the described methods and system of the present invention will be apparent to those skilled in the art without departing from the scope and spirit of the present invention. Although the present invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in chemistry and materials science or related fields are intended to be within the scope of the following claims.