High energy density cylindrical cells

Abstract

A lithium-ion secondary battery comprising a positive electrode plate, a negative electrode plate, a separator and a non-aqueous electrolyte solution, the non-aqueous electrolyte solution comprising a mixture of at least one non-oxygenated lithium salt, at least one oxygenated lithium salt, at least one carbonate solvent, and, optionally, at least one non-carbonate solvent. The positive active material comprises one or more selected from the group consisting of LixNiaCobMncO2 and a doping and / or coating modified compound thereof wherein 0.95≤x≤1.2, 0<a≤1, 0≤b<1, 0≤c<1, and Lithium-rich Lithium Nickel Cobalt Manganese Oxide and a doping and / or coating modified compound thereof (LiwNixCoyMnzO2, where w>1.1, 0.1≤x≤0.2, 0.05≤y≤0.15, 0.5≤z≤0.6). The density of the non-aqueous electrolyte solution represented by p may range from 1.21 g / cm3 to 1.36 g / cm3. The lithium-ion secondary battery satisfies a relationship; 1.08 ≤ (m×C) / (ρ×Cap) < 1.44, wherein m represents a total mass of the non-aqueous electrolyte solution inside the lithium- ion secondary battery with a unit of g, p represents a density of the non-aqueous electrolyte solution with a unit of g / cm3, C represents a concentration of the at least one non-oxygenated lithium salt in the non-aqueous electrolyte solution with a unit of mol / L, Cap represents a rated capacity of the lithium-ion secondary battery with a unit of Ah. The electrolyte may have a mass per rated capacity of 1.25 g / Ah or less, and the rated capacity is measured using cyclic voltammetry over a range of 2.5 to 4.35 V over a 10 hour period at room temperature. Methods of manufacturing of a cylindrical battery are also provided.

Description

[0001] High Energy Density Cylindrical Cells

[0002] Technical Field

[0003] The invention relates to cylindrical batteries, and more particularly, to improving the energy density of cylindrical batteries while not adversely impacting the safety of cylindrical batteries.

[0004] Related Applications

[0005] This application claims the priority benefit of US Provisional Patent Application Ser. No. 63 / 704,514 filed 7 October 2024.

[0006] Introduction

[0007] Cylindrical batteries usually have a cylindrical metal battery case with a bottom for housing a power generating element. The opening of the battery case is sealed by a metal seal plate or seal assembly. FIG. 1 illustrates an example of a conventional cylindrical battery. A battery 100 is a lithium ion secondary battery, and a cylindrical can 102 contains an electrode assembly 110 which is obtained by spirally winding a positive electrode 104 having a positive electrode tab 114, a negative electrode 106 having a negative electrode tab 116, with a separator 108 interposed therebetween, and wherein the spiral winding is held together with a sealing tape. The opening of the cylindrical can 102 is sealed by a seal assembly or cap assembly 112. The cylindrical can 102 to which the electrode assembly 110 is coupled, typically using a weldment of the positive electrode tab 114 to the cap assembly 112 coupled to the top opening of the can, and a weldment of the negative electrode tab 116 to the bottom of the cylindrical can 102.

[0008] Such lithium ion secondary batteries may have cylindrical cans of varying diameters and heights, however standard sizes in use today include 1865 (18 millimeters in diameter and 65 millimeters tall), 2170 (21 millimeters in diameter and 70 millimeters tall) and 4680 (46 millimeters in diameter and 80 millimeters tall). The energy density of such standard sized cells increase with the volume of said cells, as the number of windings and total surface area of the electrode assembly increase accordingly. For example, it is known that the volume of the 4680 cylindrical cell is 550% larger than the volume of the 2170 cylindrical cell, and 800% larger than the that of the 1865 cylindrical cell. Such lithium ion secondary batteries designed for higher energy density in the 1865 cylindrical cell size generally have energy storage capacities up to around 3.2-3.5 Ah, and have been widely used for mobile devices such as notebook PCs, digital cameras, radios, power tools and the like, which require electric power with high capacity. Such lithium ion secondary batteries in the 2170 cylindrical cell size designed for higher energy density generally have energy storage capacities up to around 4.8-5.0 Ah. To derive the gravimetric or volumetric energy density, the energy storage capacity may be multiplied by the nominal voltage of each cell (typically 3.4-3.6V depending on materials) and divided by the weight of the cylindrical cell (Wh / kg) or the volume of the cylindrical cell (Wh / L), respectively. Current 2170 cylindrical cells have been limited to having a gravimetric energy density ranging from 260-280 Wh / kg, which is insufficient for many emerging applications and lightweighting efforts. Ultimately, such rechargeable batteries are connected in series or in parallel to provide a desired voltage or capacity, and are incorporated into battery packs having predetermined shapes, include safety devices and other features.

[0009] Wang et al. in U.S. Patent No. 11,031,622, incorporated herein by reference in its entirety, have taught a lithium-ion secondary battery, which comprises a positive electrode plate, a negative electrode plate, a separator and an electrolyte, the electrolyte comprises a lithium salt and an organic solvent; the lithium-ion secondary battery satisfies a relationship: 1.5 < (mxC) / (pxCap) < 6.5, m represents a total mass of the electrolyte inside the formed battery with a unit of g, p represents a density of the electrolyte with a unit of g / cm3, C represents a concentration of the lithium salt in the electrolyte with a unit of mol / L, Cap represents a rated capacity of the battery with a unit of Ah. According to Wang, the positive electrode plate comprises a positive current collector and a positive film, the positive film is provided on at least one surface of the positive current collector and comprises a positive active material, the positive active material comprises one or more selected from a group consisting of LixNiaCobMcO2 and a doping and / or coating modified compound thereof, M is one or two selected from a group consisting of Mn and Al, 0.95<x<1.2, 0<a<l, 0<b<l, 0<c<l, and preferably a+b+c=l. The negative electrode plate comprises a negative current collector and a negative film, the negative film is provided on at least one surface of the negative current collector and comprises a negative active material, the negative active material at least comprises graphite. Wang states that when the value of (m><C) / (pxCap) is less than 1.5 due to the mass of the electrolyte, m, inside the sealed battery being too small, there will be not enough electrolyte to be consumed during the long-term cycling process, the stability and the compactness of the solid electrolyte interphase (SEI) membrane on the surface of the negative active material will suffer, and the cycle life of the battery will be deteriorated.

[0010] While this relationship may be applied to any cell, Wang’s further teaching that m / Cap is between 2 g / Ah and 6 g / Ah cannot achieve capacity ratings exceeding 300 Wh / kg and / or 800 Wh / L. The invention may satisfy the relationship: (m*C) / (pxCap) < 1.5, preferably (m><C) / (pxCap) < 1.35, more preferably (m*C) / (px Cap) < 1.25, and 1.08 < (mxC) / (pxCap) < 1.22.

[0011] However, the present invention comprises both graphite and silicon as negative active materials, and further incorporates an artificial SEI membrane deposited on the surface of the negative active materials, which overcomes the cycle life issues taught by Wang.

[0012] Bhardwaj et al. in U.S. Patent No. 10,424,779, incorporated herein by reference in its entirety, teaches a cylindrical lithium ion battery providing a gravimetric energy density between 280 Wh / kg and 300 Wh / kg, having an anode comprising an anode material coupled to an anode current collector, wherein a weight percentage of silicon in the anode material is selected between 40% and 60%, and having lithium metal particles disposed on the anode. It is known in the art that data for volumetric capacity versus weight percentage of silicon in a battery anode can be used to determine a desired silicon weight percentage of an anode material so as to maximize or otherwise control a gravimetric energy density of the battery. The anode Bhardwaj is taught to include silicon at a weight percentage from 40% to 60%, however, based on a side reaction with conventional electrolytes, silicon anodes may expand or contract during the charge / discharge cycle. Such expansion and contraction may be a factor in relatively short cycle life for conventional silicon anode batteries (e.g., 300-400 cycles to 80% cell capacity), which is less than respective benchmarks of 500 cycles for consumer electronic devices and 1000 cycles for electric vehicles. Means of accommodating side reactions between silicon anodes and conventional electrolytes include additives into the electrolyte such as fluoroethylene carbonate (FEC), fluorinated cyclic carbonate, fluorinated linear carbonate, or fluorinated ether. In such a scenario, the additive may be incorporated into the electrolyte with a mass to volume ratio between 1 : 100 and 1 :20, which detracts from the attainable energy density of the cell, and increases the mass of the electrolyte, m, in the relationship according to Wang et al. As such, relying on energy density of silicon alone is insufficient to fully predict the final energy density of a cylindrical cell that achieves greater than 400, 500 or 1,000 or more charge / discharge cycles through the incorporation of electrolyte additives, if such a solution is able to achieve such high cycle numbers at all. Improvements to the energy density attainable in standard cylindrical cell sizes are still required, in particular widely produced cells having energy densities exceeding 300 Wh / kg or 800 Wh / L that are safe and achieve high cycle life. The present invention provides battery designs that provide capacity ratings exceeding 300 Wh / kg and / or 800 Wh / L while achieving high safety and at least 1,000 charge / discharge cycles.

[0013] Summary

[0014] The invention relates to cylindrical lithium-ion secondary batteries and methods for their manufacture. Namely, various embodiments described herein describe cylindrical lithium-ion secondary batteries: having nickel-rich cathode active materials and cathodes having a cathode active material content of 97.5% or greater; having silicon- and graphite-containing anode active materials and anodes having an anode active material content of at least 92.5%, and a Si:Graphite ratio of 1.68 to 2.71; and that provide a cycle life exceeding 500 cycles, cell energy density exceeding 300 Wh / kg and 800 Wh / L (measured at a 0.1 C-rate and at room temperature), and operable over a voltage range of 2.75-4.40V.

[0015] In one aspect, a method of manufacturing of a cylindrical battery is provided. The method includes forming a cathode on a first substrate. Forming the cathode on the first substrate includes coating a cathode current collector with a cathode material. The method also includes forming an anode on a second substrate. Forming the anode on the second substrate includes coating an anode current collector with an anode material. The anode material includes a first anode material comprising graphite and second anode material comprising silicon. The method includes slitting the first substrate and the second substrate according to a cylindrical battery form factor. The method also includes, after slitting the first substrate and the second substrate, forming a cathode electrode tab coupled to the cathode and an anode electrode tab coupled to the anode. The method also includes coupling the anode and the cathode to form a layered structure. The layered structure includes a separator arranged between the anode and the cathode. The method further includes winding the layered structure to form a rolled structure and placing the rolled structure in a container. The method further includes placing an electrolyte in the container and sealing the container with the rolled structure and electrolyte placed therein to form a battery.

[0016] In another aspect, a battery is provided. The battery includes a container, an electrolyte disposed in the container, and a structure disposed in the container. The structure has a rolled shape with a spiral cross-section. The battery includes a cathode comprising a cathode material disposed on a first substrate of the structure. The cathode includes the cathode material coupled to a cathode current collector. The battery includes an anode comprising an anode material disposed on a second substrate of the structure. The anode includes the anode material coupled to an anode current collector.

[0017] In one aspect, the invention provides a lithium-ion secondary battery comprising a positive electrode plate, a negative electrode plate, a separator and a non-aqueous electrolyte solution, the non-aqueous electrolyte solution comprising a mixture of at least one non-oxygenated lithium salt, at least one oxygenated lithium salt, at least one carbonate solvent, and, optionally, at least one non-carbonate solvent; the positive electrode plate comprising a positive current collector and a positive film, the positive film is provided on at least one surface of the positive current collector and comprises a positive active material, the positive active material comprises one or more selected from the group consisting of LixNiaCobMncO2 and a doping and / or coating modified compound thereof wherein 0.95<x<1.2, 0<a<l, 0<b<l, 0<c<l, and Lithium-rich Lithium Nickel Cobalt Manganese Oxide and a doping and / or coating modified compound thereof (LiwNixCoyMnzO2, where w>l.l, 0.1<x<0.2, 0.05<y<0.15, 0.5<z<0.6); the density of the nonaqueous electrolyte solution represented by p ranges from 1.21 g / cm3to 1.36 g / cm3; and further characterized by one or more of the following: wherein the lithium-ion secondary battery satisfies a relationship: 1.08 < (m*C) / (pxCap) < 1.44, wherein m represents a total mass of the non-aqueous electrolyte solution inside the lithium-ion secondary battery with a unit of g, p represents a density of the non-aqueous electrolyte solution with a unit of g / cm3, C represents a concentration of the at least one non-oxygenated lithium salt in the non-aqueous electrolyte solution with a unit of mol / L, Cap represents a rated capacity of the lithium-ion secondary battery with a unit of Ah; and / or wherein the electrolyte has a mass per rated capacity of 1.25 g / Ah or less, and the rated capacity is measured using cyclic voltammetry measured at a 0.1 C-rate or a 4 C-rate over a range of 2.5 to 4.35V over a 10 hour period at room temperature.

[0018] In another aspect, the invention provides a battery, as defined above, comprising: a cylindrical container; an electrolyte disposed in the cylindrical container; a structure disposed in the cylindrical container, wherein the structure has a rolled shape with a spiral cross-section; a cathode comprising a cathode material disposed on a first substrate of the structure, wherein the cathode comprises the cathode material coupled to a cathode current collector; an anode comprising a first anode material; a separator disposed between the anode and the cathode, wherein the separator comprises a polymeric material or a ceramic material; and wherein the battery provides a gravimetric energy density of at least 300 watt hours per kilogram and at least 800 watt hours per liter, measured at a 0.1 C-rate and at room temperature over a voltage range of 2.50-4.35V. Preferably, the anode comprises an anode material mixture comprising first anode material and a second anode material disposed on a second substrate of the structure, wherein the first anode material comprises graphite and the second anode material comprises silicon, wherein the anode comprises the anode material mixture coupled to an anode current collector, wherein the weight ratio of the first anode material to the second anode material is 1.68 to 2.79

[0019] In a further aspect, the invention provides a lithium ion rechargeable battery comprising: a cathode plate having a first face and a second face, and a cathode active material capable of occluding and releasing lithium ions disposed on both the first face and second face of the cathode plate, an anode plate having a first face and a second face, and a first anode active material and second anode active material capable of occluding and releasing lithium ions disposed on both the first face and the second face of the anode plate, a separator interposed between the cathode plate and the anode plate, and an electrolyte having lithium-ion conductivity; wherein the electrolyte comprises at least one oxygenated lithium salt selected from “LiFSI” (Lithium bisfluoro- sulfonylimide, LiF2S2NO4), “LiBETI” (lithium bisperfluoro-ethane-sulfonimide, LiN(C2F5SO2)2), “LiTFSI” (lithium (bis)trifluoro-methane-sulfonimide, LiN(CF3SO2)2, LiCF SCL, LiClCF SCLX “LiDFOB” (LiC2BO4F2), “LiTFOP” (LiC2PO4F4), “LiDFBOP” (LiC4PO4F2), “LiDFP” (LiPO2F2), LiN(C2F5SO2)2, “LiBOB” (LiC4BOg) and mixtures thereof; wherein the cathode active material comprises a first coating modification compound (CM1) comprising one or more cations at a total cation loading of less than or equal to 2,300 parts per million (ppm) relative to the cathode active material on a mass basis (CMlppm) and converted to moles by multiplying mass of CM1 by the molecular weight of the one or more cations of CM1 (CMlmoi), and wherein CM1 has a weighted average oxidation state (CMlos) of the one or more cations of CM1 as measured using X-ray photoelectron spectroscopy; wherein the first anode active material comprises a graphite material having a second coating modification compound (CM2) comprising one or more cations at a total cation loading of less than or equal to 1,200 parts per million (ppm) relative to the first anode active material on a mass basis (CM2ppm) and converted to moles by multiplying the mass of CM2 by the molecular weight(s) of the one or more cations of CM2 (CM2moi), and wherein CM2 has a weighted average oxidation state (CM2os) of the one or more cations of CM2 as measured using X-ray photoelectron spectroscopy; and wherein the second anode active material comprises a sili con-comprising material having a third coating modification compound (CM3) comprising one or more cations at a total cation loading of less than or equal to 1,600 parts per million (ppm) relative to the second anode active material on a mass basis (CM3ppm) and converted to moles by multiplying the mass of CM3 by the molecular weight(s) of the one or more cations of CM3 (CM3moi), and wherein CM3 has a weighted average oxidation state (CM3os) of the one or more cations of CM3 as measured using X-ray photoelectron spectroscopy; and wherein the total moles of the at least one oxygenated lithium salt(s) is within +50% to +200% of: [CMlmoi • CMlos / 2 + CM2moi • CM2os / 2 + CM3moi• CM3os / 2],

[0020] In yet another aspect, the invention provides a lithium secondary battery comprising: a positive electrode having a positive-electrode active material capable of occluding and releasing lithium ions, a negative electrode having a negative-electrode active material capable of occluding and releasing lithium ions, a separator interposed between the positive electrode and the negative electrode, and an electrolyte having lithium-ion conductivity; wherein the electrolyte comprises a non-aqueous electrolyte solution comprising a mixture of at least one non-oxygenated lithium salt (“NOLS”) having a mass of lithium defined as IUNOLS, at least one oxygenated lithium salt (“OLS”) having a mass of lithium defined as Liors, at least one carbonate solvent, and optionally at least one non-carbonate solvent, wherein the NOLS is present at a concentration of 1.3 M or above and 5.0 M or less in the non-aqueous electrolyte solution, and the ratio of the total mass of lithium in the non-aqueous electrolyte solution, LiEiectroiyte (defined as LINOLS + Liors) to the sum of the total mass of lithium in the non-aqueous electrolyte solution and mass of lithium in the positiveelectrode active material, LicAM, satisfies the relationship: where C represents a concentration of the NOLS in the electrolyte with a unit of mol / L and ranges from 1.3 < C < 5.0, 0.12 < A < 0.20, and B = 0.63.

[0021] In a further aspect, the invention provides a lithium ion rechargeable battery comprising: a cathode plate having a first face and a second face, and a cathode active material capable of occluding and releasing lithium ions disposed on both the first face and second face of the cathode plate, an anode plate having a first face and a second face, and an anode active material capable of occluding and releasing lithium ions disposed on both the first face and the second face of the anode plate, a separator interposed between the cathode plate and the anode plate, and an electrolyte having lithium-ion conductivity; wherein the cathode active material comprises LixNiaMnbCocCMldO2 where CM1 represents one or more cations of a first coating modification compound thereon where preferably a + b + c = 1 and d < 2,300 parts per million (ppm) relative to the cathode active material on a mass basis, and satisfies the formula of either:

[0022] 1) 0.95 < x < 1.2, 0.80 < a < 1, 0 < b < 0.1, 0 < c < 0.1; or

[0023] 2) x > 1.1, 0.1 < a < 0.2, 0.05 < b < 0.15, 0.5 < c < 0.6; wherein the anode comprises a first anode active material comprising a graphite material having second coating modification compound thereon (CM2), where CM2 represents one or more cations of a second coating modification compound, wherein the cations of CM2 comprise less than 1,200 parts per million relative to the first anode material on a mass basis, and a second anode active material comprising silicon and carbon and a third coating modification compound thereon (CM3), where CM3 represents one or more cations of a third coating modification compound, wherein the cations of CM3 comprise less than 1,600 parts per million relative to the second anode material on a mass basis; wherein the cathode active material, the first anode active material and the second anode active material have a measurable specific surface area using the BET technique and wherein the parts per million of the cations of CM1 on a mass basis as measured using ICP-OES satisfies the relationship 620 ppm < CMld / SA < 1150 ppm, where SA is the specific surface area of the cathode active material in units of m2 / g; and wherein the molar average Pauling electronegativity (known constants) of the one or more cations of CM1 is between 1.22 and 1.66, and / or range from 0.21 to 0.65 below the molar average electronegativity of the cations of the cathode active material (1.87 for Formula 1 wherein a = 0.8, b = 0.1 and c = 0.1). Surface area of the powders is measured before the powder is applied to the electrode, before the electrode is assembled into the battery

[0024] In another aspect, the invention provides a lithium ion rechargeable battery comprising: a cathode plate having a first face and a second face, and a cathode active material capable of occluding and releasing lithium ions disposed on both the first face and second face of the cathode plate, an anode plate having a first face and a second face, and an anode active material capable of occluding and releasing lithium ions disposed on both the first face and the second face of the anode plate, a separator interposed between the cathode plate and the anode plate, and an electrolyte having lithium-ion conductivity; wherein the cathode active material comprises LixNiaMnbCocCMldCh where CM1 represents one or more cations of a first coating modification compound thereon where preferably a + b + c = 1 and d < 2,300 parts per million (ppm) relative to the cathode active material on a mass basis, and satisfies the formula of either:

[0025] 1) 0.95 < x < 1.2, 0.80 < a < 1, 0 < b < 0.1, 0 < c < 0.1; or

[0026] 2) x > 1.1, 0.1 < a < 0.2, 0.05 < b < 0.15, 0.5 < c < 0.6; wherein the anode comprises a first anode active material comprising a graphite material having second coating modification compound thereon (CM2), wherein the cations of CM2 comprise less than 1,200 parts per million relative to the first anode material on a mass basis, and a second anode active material comprising silicon and carbon and a third coating modification compound thereon (CM3), wherein the cations of CM3 comprise less than 1,600 parts per million relative to the second anode material on a mass basis; wherein the cathode active material, the first anode active material and the second anode active material have a measurable specific surface area using the BET technique and wherein the parts per million of the cations of CM1 on a mass basis as measured using ICP-OES satisfies the relationship 620 ppm < CMld / SA < 1150 ppm, where SA is the specific surface area of the cathode active material in units of m2 / g; and wherein the first ionization of each of the one or more cations of CM1 is 745 kJ / mol or lower, which is the approximate threshold that will allow the first ionization energy of the one or more cations of CM1 to remain below that of Ni, Mn and Co cations of the Ni-rich cathode active material (approximately 750 kJ / mol or higher).

[0027] In yet another aspect, the invention provides a lithium ion rechargeable battery comprising: a cathode plate having a first face and a second face, and a cathode active material capable of occluding and releasing lithium ions disposed on both the first face and second face of the cathode plate, an anode plate having a first face and a second face, and an anode active material capable of occluding and releasing lithium ions disposed on both the first face and the second face of the anode plate, a separator interposed between the cathode plate and the anode plate, and an electrolyte having lithium-ion conductivity; wherein the electrolyte comprises at least one oxygenated lithium salt selected from “LiFSI” (Lithium bisfluoro-sulfonylimide, LiF2S2NO4), “LiBETI” (lithium bisperfluoro-ethane-sulfonimide, LiN^FsSCh^), “LiTFSI” (lithium (bis)trifluoro-methane-sulfonimide, LiN(CF3SO2)2, LiCFsSCh, LiC(CF3SO2)3, “LiDFOB” (LiC2BO4F2), “LiTFOP” (LiC2PO4F4), “LiDFBOP” (LiC4PO4F2), “LiDFP” (LiPO2F2), LiN(C2FsSO2)2, “LiBOB” (LiC BOg) and mixtures thereof; wherein the cathode active material comprises a first coating modification compound (CM1) comprising one or more cations at a total cation loading of less than or equal to 2,300 parts per million (ppm) relative to the cathode active material on a mass basis (CMlppm) and converted to moles by multiplying mass of CM1 by the molecular weight of the one or more cations of CM1 (CMlmoi), and wherein CM1 has a weighted average oxidation state (CMlos) of the one or more cations of CM1 as measured using X-ray photoelectron spectroscopy; wherein the anode active material comprises a second coating modification compound (CM2) comprising one or more cations at a total cation loading of less than or equal to 1,600 parts per million (ppm) relative to the anode active material on a mass basis (CM2ppm) and converted to moles by multiplying the mass of CM2 by the molecular weight(s) of the one or more cations of CM2 (CM2moi), and wherein CM2 has a weighted average oxidation state (CM2os) of the one or more cations of CM2 as measured using X-ray photoelectron spectroscopy; and wherein the total moles of the at least one oxygenated lithium salt(s) is within ± 50% of [CMlmoi ■ CMlos / 2 + CM2moi• CM2os / 2],

[0028] In another aspect, the invention provides a lithium ion rechargeable battery comprising: a cathode plate having a first face and a second face, and a cathode active material capable of occluding and releasing lithium ions disposed on both the first face and second face of the cathode plate, an anode plate having a first face and a second face, and a first anode active material and second anode active material capable of occluding and releasing lithium ions disposed on both the first face and the second face of the anode plate, a separator interposed between the cathode plate and the anode plate, and an electrolyte having lithium-ion conductivity; wherein the electrolyte comprises at least one oxygenated lithium salt selected from “LiFSI” (Lithium bisfluoro- sulfonylimide, LiF2S2NO4), “LiBETI” (lithium bisperfluoro-ethane-sulfonimide, LiN(C2FsSO2)2), “LiTFSI” (lithium (bis)trifluoro-methane-sulfonimide, LiN(CFsSO2)2, LiCFsSCh, LiC(CF3SO2)s, “LiDFOB” (LiC2BO4F2), “LiTFOP” (LiC2PO4F4), “LiDFBOP” (LiC4PO4F2), “LiDFP” (LiPO2F2), LiN(C2F5SO2)2, “LiBOB” (LiC4BOs) and mixtures thereof; wherein the cathode active material comprises a first coating modification compound (CM1) comprising one or more cations at a total cation loading of less than or equal to 2,300 parts per million (ppm) relative to the cathode active material on a mass basis (CMlppm) and converted to moles by multiplying mass of CM1 by the molecular weight of the one or more cations of CM1 (CMlmoi), and wherein CM1 has a weighted average oxidation state (CMlos) of the one or more cations of CM1 as measured using X-ray photoelectron spectroscopy; wherein the first anode active material comprises a graphite material having a second coating modification compound (CM2) comprising one or more cations at a total cation loading of less than or equal to 1,200 parts per million (ppm) relative to the first anode active material on a mass basis (CM2ppm) and converted to moles by multiplying the mass of CM2 by the molecular weight(s) of the one or more cations of CM2 (CM2moi), and wherein CM2 has a weighted average oxidation state (CM2os) of the one or more cations of CM2 as measured using X-ray photoelectron spectroscopy; and wherein the second anode active material comprises a silicon-comprising material having a third coating modification compound (CM3) comprising one or more cations at a total cation loading of less than or equal to 1,600 parts per million (ppm) relative to the second anode active material on a mass basis (CM3ppm) and converted to moles by multiplying the mass of CM3 by the molecular weight(s) of the one or more cations of CM3 (CM3moi), and wherein CM3 has a weighted average oxidation state (CM3os) of the one or more cations of CM3 as measured using X-ray photoelectron spectroscopy; and wherein the total moles of the at least one oxygenated lithium salt(s) is within -50% to 200% (or within ± 50%) of: [CMlmoi• CMlos / 2 + CM2moi• CM2os / 2 + CM3moi• CM3os / 2],

[0029] In any of its aspects, the invention can be further characterized by one or any combination of the following: wherein the negative electrode plate comprises a negative current collector and a negative film, the negative film is provided on at least one surface of the negative current collector and comprises a first negative active material and a second negative active material, the first negative active material at least comprises graphite, the second negative active material at least comprises silicon; wherein a coating weight of the negative film per unit area on one surface of the negative current collector is 0.006 g / cm2-0.015 g / cm2; wherein the coating weight of the negative film per unit area on one surface of the negative current collector is 0.008 g / cm2-0.010 g / cm2; wherein a pressing density of the negative film is 1.5 g / cm3-1.9 g / cm3; wherein the lithium- ion secondary battery satisfies a relationship: 1.08 < (mxC) / (p*Cap) < 1.44; wherein the concentration of the lithium salt in the electrolyte represented by C is 1.3 mol / L-5.0 mol / L; wherein the concentration of the lithium salt in the electrolyte represented by C is 1.5 mol / L-3.0 mol / L; wherein m / Cap is 1.0 g / Ah-1.25 g / Ah or wherein m / Cap is 1.12 g / Ah-1.22 g / Ah; wherein a pressing density of the positive film is 3.4 g / cm3-3.6 g / cm3; wherein a+b+c=l ; wherein the battery is a cylindrical cell; wherein the battery is a pouch cell; wherein the battery is a prismatic cell; wherein the negative film comprises from 0.10 mass% to 0.20 mass% carbon nanotubes, and the positive film comprises from 0.6 mass% to 1.1 mass% carbon nanotubes; wherein the cathode material comprises at least one of Nickel-rich Lithium Nickel Cobalt Manganese Oxide and a doping and / or coating modified compound thereof (LixNiaCobMncO2, 0.95<x<1.2, 0.8<a<l, 0<b<0.1, 0<c<0.1) or Lithium-rich Lithium Nickel Cobalt Manganese Oxide and a doping and / or coating modified compound thereof (LiwNixCoyMnzO2, where w>l. l, 0.1<x<0.2, 0.05<y<0.15, 0.5<z<0.6); wherein the second anode material comprises at least one of silicon carbide, silicon monoxide, silicon dioxide, or a silicon carbon composite; wherein a weight ratio of the first anode material to the second anode material is 1.81 to 2.75, 2.13 to 2.72 or 2.50 to 2.71; further comprising a cathode electrode tab or tabs coupled to the cathode and an anode electrode tab or tabs coupled to the anode; wherein the cathode electrode and / or anode electrode are tables; wherein the cylindrical container is at least 18 millimeters in diameter and 65 millimeters in length and has a capacity of at least 3.7 amp hours, at least 21 millimeters in diameter and 70 millimeters in length and has a capacity of at least 5.6 amp hours, or at least 46 millimeters in diameter and at least 80 millimeters in length; wherein the battery is configured to be charged and discharged over a cell voltage between 2.5 volts and 4.35 volts, and wherein the battery maintains a capacity of at least 4.48 amp hours after 500 charge and discharge cycles at a 0.1 C-rate and at room temperature, or after 1,000 charge and discharge cycles at a 0.1 C-rate and at room temperature; wherein the container comprises steel or a steel alloy; wherein the container comprises aluminum or an aluminum alloy; wherein the battery provides a gravimetric energy density of 300-355 watt hours per kilogram, 305-345 watt hours per kilogram, or 302-308 watt hours per kilogram, measured at a 0.1 C-rate and at room temperature over a voltage range of 2.50-4.35V; a pack or module comprising the battery; wherein the cathode active material comprises LixNLMnbCocCh where preferably a + b + c = 1, and satisfies the Formula of either: 1) 0.95 < x < 1.2, 0.80 < a < 1, 0 < b < 0.1, 0 < c < 0.1; or 2) x > 1.1, 0.1 < a < 0.2, 0.05 < b < 0.15, 0.5 < c < 0.6; wherein the electrolyte further comprises at least one non-oxygenated lithium salt, at least one oxygenated lithium salt, at least one carbonate solvent, and optionally at least one non-carbonate solvent, wherein the nonoxygenated lithium salt is present at a concentration of 1.3 M or above and 5.0 M or less in the electrolyte; wherein the weight loading of the cathode active material and CM1 comprises at least 97.5% of the material disposed on each of the first face and second face of the cathode plate; wherein the cathode active material has a measurable specific surface area using the BET technique (“SA”) and wherein CMlppmon a mass basis as measured using ICP-OES satisfies the relationship 620 ppm < CMlppm / SA < 1150 ppm, where SA is the specific surface area of the cathode active material in units of m2 / g; wherein the sum of all Coating Modification Compounds (CMlppm+ CM2ppm+ CM3ppm) as measured using ICP-OES ranges from 500 to 3,000 ppm, or ranges from 650 to 2,600 ppm, or ranges from 800 to 2,400 ppm; wherein the positive-electrode active material comprises at least one of: Nickel-rich Lithium Nickel Cobalt Manganese Oxide and a doping and / or coating modified compound thereof (LixNiaCobMncO2, 0.95<x<1.2, 0.8<a<l, 0<b<0.1, 0<c<0.1) or Lithium-rich Lithium Nickel Cobalt Manganese Oxide and a doping and / or coating modified compound thereof (LiwNixCoyMnzO2, where w>l . 1, 0.1<x<0.2, 0.05<y<0.15, 0.5<z<0.6); the negative-electrode active material contains a mixture containing a graphite material and a sili con-comprising material, wherein the ratio of the graphite material to the silicon-comprising material is 1.68 to 2.79, or 1.81 to 2.75, or 1.96 to 2.74, or 2.13 to 2.72, or 2.50 to 2.71; wherein the at least one non-oxygenated lithium salt, NOLS, is selected from one or more of LiPFe, LiBF4, LiSbFe, and LiAsFe, and mixtures thereof; wherein the at least one oxygenated lithium salt, OLS, is selected from “LiFSI” (Lithium bisfluoro-sulfonylimide, LiF2S2NO4), “LiBETF’ (lithium bisperfluoro-ethane-sulfonimide, LiN(C2F5SO2)2), “LiTFSI” (lithium (bis)trifluoro-methane- sulfonimide, LiN(CF3SO2)2, LiCF3SO3, LiC(CF3SO2)3, “LiDFOB” (LiC2BO4F2), “LiTFOP” (UC2PO4F4), “LiDFBOP” (LiC4PO4F2), “LiDFP” (LiPO2F2), LiN(C2F5SO2)2, “LiBOB” (LiC4BO8) and mixtures thereof; wherein the at least one carbonate solvent is selected from butylene carbonate, 2,3-butylene carbonate, iso-butylene carbonate, dimethyl carbonate, ethylene carbonate, ethyl methyl carbonate, fluoroethylene carbonate, difluoroethylene carbonate, propylene carbonate, and mixtures thereof; wherein the optional at least one non-carbonate solvent is selected from ' / -butyrolactone, sulfolane, butanedinitrile, malononitrile, glutaronitrile, adiponitrile, suberonitrile, sebaconitrile, and mixtures thereof; wherein each non-oxygenated lithium salt, NOLS, and each oxygenated lithium salt, OLS, can be further described as consisting of a positively charged lithium cation and a negatively-charged anion, the total mass of all positively charged lithium cations of all non-oxygenated lithium salt(s), LiNots, and all oxygenated lithium salt(s), Lions, in the non-aqueous electrolyte solution defines LiEiectroiyte; wherein the nonoxygenated lithium salt is present at a concentration of 1.3 M or above and 5.0 M or less, or 1.5 M or above and 3.0 M or less in the non-aqueous electrolyte solution; wherein the battery comprises a cylindrical container having dimensions of at least 18 millimeters in diameter and 65 millimeters in length, or at least 21 millimeters in diameter and 70 millimeters in length, or at least 46 millimeters in diameter and at least 80 millimeters in length; wherein the weight percentage of the at least one oxygenated lithium salt comprises 2 percent or less of the total weight of the nonaqueous electrolyte solution; wherein the mass of boron relative to the total mass of lithium in the non-aqueous electrolyte solution is at most 0.06-LiEiedroiyte, and / or the mass of phosphorous relative to the total mass of lithium in the non-aqueous electrolyte solution is at least 429-LiEiectroiyte., and / or the mass of fluorine relative to the total mass of lithium in the non-aqueous electrolyte solution is at least 1633-LiEiectroiyte; wherein the positive-electrode active material is a cathode active material and comprises LixNiaMnbCocCMldO2 where CM1 represents one or more cations of a first coating modification compound thereon where preferably a + b + c = 1 and d < 2,300 parts per million (ppm) relative to the cathode active material on a mass basis, and satisfies the Formula of either: 1) 0.95 < x < 1.2, 0.80 < a < 1, 0 < b < 0.1, 0 < c < 0.1; or 2) x > 1.1, 0.1 < a < 0.2, 0.05 < b < 0.15, 0.5 < c < 0.6; wherein the graphite material having second coating modification compound thereon (CM2), where CM2 represents one or more cations of a second coating modification compound, wherein the cations of CM2 comprise less than 1,200 parts per million relative to the graphite material on a mass basis, and a silicon-comprising material and a third coating modification compound thereon (CM3), where CM3 represents one or more cations of a third coating modification compound, wherein the cations of CM3 comprise less than 1,600 parts per million relative to the silicon-comprising material on a mass basis; wherein the positive electrode active material, the graphite material and the silicon-comprising material have a measurable specific surface area using the BET technique and wherein the parts per million of the cations of CM1 on a mass basis as measured using ICP-OES satisfies the relationship 620 ppm < CMla / SA < 1150 ppm, where SA is the specific surface area of the cathode active material in units of m2 / g; wherein the graphite material comprises natural graphite and CM2 ranges from 25 to 350 ppm, or 30 to 75 ppm, or 250 to 350 ppm; or wherein the graphite material comprises synthetic or artificial graphite, and CM2 ranges from 600 to 1200 ppm, or 700 to 1100 ppm, or 800 to 900 ppm; wherein CM1, CM2 and / or CM3 further comprise lithium within each coating modification compound, provided that the loading of lithium is not included in the satisfying criteria calculation provided herein for CM1, CM2 or CM3; wherein the cations of CM1 comprise one or more of Y (1.22), Hf (1.30), Mg (1 .31), Zr (1.33), Sc (1.36), Ta (1.50), Ti (1 .54), Nb (1 .60), Al (1 .61 ), TI (1.62), V (1 .63), Zn (1.65) and Cr (1.66), wherein the Pauling Electronegativity of each cation is listed in parentheses; wherein the cations of CM1 satisfy the relationship 100 < CMlppm / PE < 900, preferably 150 < CMlPPm / PE < 780, and sometimes 200 < CMlppm / PE < 560; wherein the first anode material comprises natural graphite and CM2 ranges from 25 to 350 ppm, or 30 to 75 ppm, or 250 to 350 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.60 to 1.66; or wherein the first anode material comprises synthetic or artificial graphite, and CM2 ranges from 600 to 1200 ppm, or 700 to 1100 ppm, or 800 to 900 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.60 to 1.66; wherein CM2 ranges from 450 to 1,600 ppm, or 500 to 1,500 ppm, or 600 to 1,400 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.22 to 1.60; wherein CM3 ranges from 25 to 350 ppm, or 80 to 275 ppm, or 150 to 240 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.60 to 1.66; wherein CM3 ranges from 450 to 1,600 ppm, or 500 to 1,500 ppm, or 600 to 1,400 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.22 to 1.60; wherein CM1, CM2 and / or CM3 further comprise lithium within each coating modification compound, provided that the loading and electronegativity of lithium is not included in the satisfying criteria calculation provided herein for CM1, CM2 or CM3; wherein the cations of CM1 having a first ionization energy of 745 kJ / mol or lower, are selected from one or more of Y, Hf, Mg, Zr, Sc, Ti, Nb, Al, V and Cr; wherein the first anode material comprises natural graphite and CM2 ranges from 25 to 350 ppm, or 30 to 75 ppm, or 250 to 350 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.60 to 1.66; or wherein the first anode material comprises synthetic or artificial graphite, and CM2 ranges from 400 to 1200 ppm, or 500 to 1100 ppm, or 600 to 900 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.60 to 1.66; wherein CM2 ranges from 450 to 1,600 ppm, or 500 to 1,500 ppm, or 600 to 1,400 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.22 to 1.60; wherein CM3 ranges from 25 to 350 ppm, or 80 to 275 ppm, or 150 to 240 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.60 to 1.66; wherein CM3 ranges from 450 to 1,600 ppm, or 500 to 1,500 ppm, or 600 to 1,400 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.22 to 1.60; wherein CM1, CM2 and / or CM3 further comprise lithium within each coating modification compound, provided that the loading and electronegativity of lithium is not included in the satisfying criteria calculation provided herein for CM1, CM2 or CM3; wherein the ratio of the first anode active material to the second anode active material is 1.68 to 2.79, or 1.81 to 2.75, or 1.96 to 2.74, or 2.13 to 2.72, or 2.50 to 2.71; wherein the weight loading of the cathode active material and CM1 comprises at least 97.5% of the material disposed on each of the first face and second face of the cathode plate; wherein the ratio of the first anode active material to the second anode active material is 1.68 to 2.79, or 1.81 to 2.75, or 1.96 to 2.74, or 2.13 to 2.72, or 2.50 to 2.71; wherein the weight loading of the cathode active material and CM1 comprises at least 97.5% of the material disposed on each of the first face and second face of the cathode plate; wherein the cathode active material comprises LixNiaMnbCocCh where preferably a + b + c = 1, and satisfies the Formula of either: 1) 0.95 < x < 1.2, 0.80 < a < 1, 0 < b < 0.1, 0 < c < 0.1; or 2) x > 1.1, 0.1 < a < 0.2, 0.05 < b < 0.15, 0.5 < c < 0.6; wherein the electrolyte further comprises at least one nonoxygenated lithium salt, at least one oxygenated lithium salt, at least one carbonate solvent, and optionally at least one non-carbonate solvent, wherein the non-oxygenated lithium salt is present at a concentration of 1.3 M or above and 5.0 M or less in the electrolyte; wherein the weight loading of the cathode active material and CM1 comprises at least 97.5% of the material disposed on each of the first face and second face of the cathode plate; wherein the cathode active material has a measurable specific surface area using the BET technique (“SA”) and wherein CMlppmon a mass basis as measured using ICP-OES satisfies the relationship 620 ppm < CMlppm / SA < 1150 ppm, where SA is the specific surface area of the cathode active material in units of m2 / g; wherein the sum of all Coating Modification Compounds (CMlppm + CM2ppm) as measured using ICP- OES ranges from 500 to 3,000 parts per million (ppm), or ranges from 650 to 2,600 ppm, or ranges from 800 to 2,400 ppm; wherein the electrolyte further comprises at least one non-oxygenated lithium salt, at least one oxygenated lithium salt, at least one carbonate solvent, and optionally at least one non-carbonate solvent, wherein the non-oxygenated lithium salt is present at a concentration of 1.3 M or above and 5.0 M or less in the electrolyte; wherein the weight loading of the cathode active material and CM1 comprises at least 97.5% of the material disposed on each of the first face and second face of the cathode plate; wherein the cathode active material has a measurable specific surface area using the BET technique (“SA”) and wherein CMlppmon a mass basis as measured using ICP-OES satisfies the relationship 620 ppm < CMlppm / SA < 1150 ppm, where SA is the specific surface area of the cathode active material in units of m2 / g; wherein the sum of all Coating Modification Compounds (CMlppm+ CM2ppm+ CM3ppm) as measured using ICP-OES ranges from 500 to 3,000 ppm, or ranges from 650 to 2,600 ppm, or ranges from 800 to 2,400 ppm; wherein one or any combination of the Coating Modification Compounds are formed by atomic layer deposition; battery pack comprising the lithium-ion secondary battery according to any of the descriptions herein; wherein the ratio of Li in the electrolyte to total Li in the cell is in the range of 0.13 to 0.54 and non-oxygenated Li salt concentration is in the range of 1 to 5 mol / L; and wherein non-oxygenated Li salt concentration (defined as x) is in the range of 1 to 5 mol / L and the ratio of Li in the electrolyte to total Li in the cell (defined as y) is in the range of y = 0.20x°'63to 0.12x°'63.

[0030] Throughout the descriptions, a coating modification compound may alternatively be described as a coating modification composition.

[0031] The invention is further elucidated in the examples below. In some preferred embodiments, the invention may be further characterized by any selected descriptions from the examples, for example, within ±30%, ±20% (or within ±10%) of any of the values in any of the examples, tables or figures; however, the scope of the present invention, in its broader aspects, is not intended to be limited by these examples. All ranges are inclusive and combinable. For example, when a range of “1 to 5’ is recited, the recited range should be construed as including ranges “1 to 4”, “1 to 3”, “1-2”, “1-2 & 4-5”, “1-3 & 5”, “2-5”, any of 1, 2, 3, 4, or 5 individually, and the like.

[0032] Brief Description of the Drawings

[0033] Fig. 1 is a schematic representation of a cylindrical battery.

[0034] Fig. 2 shows a cross-sectional image of the spirally-wound electrode assembly.

[0035] Fig. 3 shows cross-sectional SEM images of the assembled cathode electrodes

[0036] Fig. 4 shows a diagram of the inventive region (encompassed by dotted lines) of percentage of lithium in the battery derived from the electrolyte, versus the concentration of non-oxygenated lithium salt in the electrolyte.

[0037] Fig. 5 shows a graph of cumulative energy derived from 5.65 Ah cells cycled at different states of charge and charging rates.

[0038] Detailed Description of the Invention A conventional cylindrical lithium rechargeable battery comprises an anode plate coated on both sides by a layer comprising anode active material, a separator, and a cathode plate coated on both sides with a cathode active material, are stacked and one end of the stacked structure is coupled to a bar-shaped winding axis. The structure is then wound into the shape of a cylinder and taped to form an electrode assembly. An exemplary cross-sectional image of the electrode assembly showing the spirally-wound electrode-separator-electrode stacked structure is provided in Figure 2. Next, the taped electrode assembly is inserted into the cylindrical can. Then, an electrolyte is injected into the cylindrical can and a cap assembly is coupled to the top of the cylindrical can, to complete the manufacture of a substantially cylindrical, sealed lithium-ion battery.

[0039] A cylindrical lithium rechargeable battery typically comprises: a cathode plate having a first face and a second face, and a cathode active material capable of occluding and releasing lithium ions disposed on both the first face and second face of the cathode plate, an anode plate having a first face and a second face, and an anode active material capable of occluding and releasing lithium ions disposed on both the first face and the second face of the anode plate, a separator interposed between the cathode plate and the anode plate, an electrolyte having lithium- ion conductivity, wherein the cathode plate, anode plate and separator interposed therebetween is wound into the shape of a cylinder to form an electrode assembly, and taped to form a taped electrode assembly, and inserted into a cylindrical can; wherein the cathode active material comprises LixNiaMnbCocCMldCL where CM1 represents a first coating modification compound thereon, 0.95 < x < 1.2, 0.80 < a < 1, 0 < b < 0.1, 0 < c < 0.1, and preferably a + b + c = 1 and d < 2,000 parts per million; or Lithium-rich Lithium Nickel Cobalt Manganese Oxide, LixNiaCobMncCMldO2, where x > 1.1, 0.1 < a < 0.2, 0.05 < b < 0.15, 0.5 < c < 0.6 and d < 2,000 parts per million; wherein the anode comprises a first anode active material comprising a graphite material having coating modification compound thereon of less than 2,000 parts per million, and a second anode active material comprising silicon and carbon and a coating modification compound thereon of less than 2,000 parts per million, and the ratio of the first anode active material to the second anode active material is 1.68 to 2.79, or 1.81 to 2.75, or 1.96 to 2.74, or 2.13 to 2.72, or 2.50 to 2.71; and wherein the cycle life of the battery exceeds 500 cycles, the energy density of the battery exceeds 300 Wh / kg and 800 Wh / L (measured at a 0.1 C-rate and at room temperature), and the battery is operable over a voltage range of 2.75-4.40V. A cylindrical lithium rechargeable battery according to the present invention comprises: a cathode plate having a first face and a second face, and a cathode active material capable of occluding and releasing lithium ions disposed on both the first face and second face of the cathode plate, an anode plate having a first face and a second face, and an anode active material capable of occluding and releasing lithium ions disposed on both the first face and the second face of the anode plate, a separator interposed between the cathode plate and the anode plate, an electrolyte having lithium-ion conductivity, wherein the cathode plate, anode plate and separator interposed therebetween is wound into the shape of a cylinder to form an electrode assembly, and taped to form a taped electrode assembly, and inserted into a cylindrical can; wherein the cathode active material comprises LixNiaMnbCocCMldCh where CM1 represents a first coating modification compound thereon, 0.95 < x < 1.2, 0.80 < a < 1, 0 < b < 0.1, 0 < c < 0.1, and preferably a + b + c = 1 and d < 2,000 parts per million; or Lithium-rich Lithium Nickel Cobalt Manganese Oxide, LixNiaCobMncCMldO2, where x > 1.1, 0.1 < a < 0.2, 0.05 < b < 0.15, 0.5 < c < 0.6 and d < 2,000 parts per million; wherein the anode comprises a first anode active material comprising a graphite material having second coating modification compound thereon of less than 1 ,200 parts per million, and a second anode active material comprising silicon and carbon and a third coating modification compound thereon of less than 1,600 parts per million, and the ratio of the first anode active material to the second anode active material is 1.68 to 2.79, or 1.81 to 2.75, or 1.96 to 2.74, or 2.13 to 2.72, or 2.50 to 2.71; and wherein the cylindrical lithium rechargeable battery satisfies the relationship: (m><C) / (pxCap) < 1.5, preferably (mxC) / (pxCap) < 1.35, more preferably (mxC) / (pxCap) < 1.25, and 1.08 < (mxC) / (pxCap) < 1.22, where m represents a total mass of the electrolyte inside the formed battery with a unit of g, p represents a density of the electrolyte with a unit of g / cm3, C represents a concentration of the lithium salt in the electrolyte with a unit of mol / L, Cap represents a rated capacity of the battery with a unit of Ah.

[0040] Cathode

[0041] The cathode plate of the invention provides a cathode active layer composition, comprising a cathode active material that is provided to at least one surface of a cathode current collector, and typically both opposing surfaces of the cathode current collector. The cathode active material comprises lithium nickel cobalt manganese composite oxide primary particles, which are formed into lithium nickel cobalt manganese composite oxide secondary particles prior to the fabrication of the batery. A mass average primary particle diameter of the lithium nickel cobalt manganese composite oxide mixture is typically in a range of 0.2 micrometers or more and 2 micrometers or less. A mass average secondary particle diameter of the lithium nickel cobalt manganese composite oxide mixture is in a range of 4 micrometers or more and 20 micrometers or less, preferably 16 micrometers or less, and sometimes 12 micrometers or less. The positive electrode active material layer includes one or more solid particulate-type conductive additives and one or more binder materials, in a range of 2.5% or less based on a weight of the positive electrode active material layer of 97.5% or more. The cathode active material comprises LixNiaMnbCocCMldO2 where CM1 represents a first coating modification compound thereon, 0.95 < x < 1.2, 0.80 < a < 1, 0 < b

[0042] < 0.1, 0 < c < 0.1, and preferably a + b + c = 1 (Ni-rich NMC) and d < 2,000 parts per million; or Lithium-rich Lithium Nickel Cobalt Manganese Oxide, LixNiaCobMncCMldO2, where x > 1.1, 0.1

[0043] < a < 0.2, 0.05 < b < 0.15, 0.5 < c < 0.6 and d < 2,000 parts per million. The thickness of the cathode active layer composition ranges from at least 50 microns to 80 microns in thickness per surface of the cathode current collector, however it is known in the art that increasing the layer thickness per surface increases resistance and can sacrifice power density as energy density is increased.

[0044] It has been determined that a cathode layer thickness of 60 micrometers to 65 micrometers provides suitable performance for a cathode plate having a cathode active material loading of at least 97.5%, on an aluminum-based current collector having a thickness of 8 to 14 micrometers, preferably 10 to 12 micrometers, and sometimes 12 micrometers, achieves the objective of producing a cylindrical lithium rechargeable battery having an energy density of > 300 Wh / kg in a 2170 cell format. Such a cell would require a porosity of less than or equal to less 25%, preferably less than or equal to 23%, and a density of greater than 3.5 g / cm3, to produce a cathode active area exceeding 1,230 cm2, preferably exceeding 1,235 cm2, and oftentimes exceeding 1,237.5 cm2, and also be able to achieve a volumetric energy density exceeding 800 Wh / L. The inventive cylindrical lithium rechargeable battery having an energy density of greater than 300 Wh / kg should have a total weight of less than 65 grams, preferably less than 64 grams, and more preferably less than 63.5 grams, when using the Ni-rich LixNiaMnbCocCMldO2 cathode as described above. A design capacity preferably exceeds 5.25 Ah, more preferably at least 5.50 Ah (typically measured using a 0.1C rate in a half coin cell at room temperature, and downwardly adjusted by a derating percentage thereof). Figure 3A depicts an uncycled cathode plate having a cathode active material loading of 97.5% and a porosity of 28%. Figure 3B depicts an uncycled cathode plate having an ALD-coated cathode active material loading of 97.5% and a porosity of 23%.

[0045] In order to achieve a sufficiently high energy density at the prescribed cell weight and a derating percentage of 90%, the Ni-rich NMC cathode active material may demonstrate a first delithiation capacity exceeding 240 mAh / g over a voltage range of 2.5V to 4.45V (typically measured using a 0.1C rate in a half coin cell), and a first cycle efficiency exceeding 93%. In turn, this would allow the cathode areal capacity to be equal to or greater than 4.6 mAh / cm2, and a cathode capacity of 5.69 mAh prior to any adjustment by a derating percentage thereof. The total loading of the cathode layer is preferably equal to or greater than 21.0 mg / cm2, wherein the cathode active material comprises at least 97.5% of the mass of the cathode layer. It is important to note that the conventional anode to cathode ratio (N / P ratio) used in the industry is 1.1, which is calculated by multiplying this ratio by the cathode areal capacity, to achieve the target anode areal capacity, which for example is 5.06 mAh / cm2for a cathode areal capacity of 4.60 mAh / cm2.

[0046] Anode

[0047] The anode plate of the invention provides an anode active layer having an anode areal capacity defined by multiplying the N / P ratio by the cathode areal capacity, wherein the anode active layer composition comprises: a mixture of a first anode active material powder and a second anode active material powder; wherein the first anode active material powder comprises a graphite powder comprising a surface comprising a second coating modification compound (“CM2”) comprising lithium, aluminum, zirconium and / or titanium cations; wherein the second anode active material powder comprises a silicon-carbon composite powder (particles comprising silicon and carbon within each particle) and comprising a third coating modification compound (“CM3”) comprising lithium, aluminum, zirconium and / or titanium cations disposed over the silicon-carbon particles. In some preferred embodiments, the cation loading on the second anode active material powder is at least 50% greater than the cation loading on the first anode active material powder; and in some preferred embodiments, at least 2X greater, in some embodiments in the range of at least 50% greater to 4X or less or 3X or less. A graphite anode active material powder has the conventional meaning in the art; typically a powder that comprises at least 90 mass% C, preferably at least 95 mass% C; small amounts of oxygen and other elements are sometimes present. A silicon-carbon anode active material powder also has its conventional meaning. The silicon of the silicon-carbon anode active material powder is in the form of elemental silicon, silicon oxide or an alloy comprising greater than 50 atomic percent silicon. The carbon of the silicon-carbon anode active material powder is primarily elemental carbon and can be in graphitic or non-graphitic form. Throughout this disclosure, “primarily” has the conventional meaning of greater than 50%. The mass ratio of Si / C in silicon-carbon anode active material particles is typically in the range of 2 to 0.7, or 1.5 to 1.0. Ultimately, the silicon fraction of the second anode active material powder can be calculated in order to define a silicon fraction within the anode layer on the anode plate, the balance of mass being derived from the weights of: the first anode active material, the silicon fraction of the second anode active material, the non-silicon fraction of the second anode active material, the solid conductive additive(s) and the binder(s).

[0048] Preferably, the cell energy density is at least 300 Wh / kg and / or at least 800 Wh / L, a siliconcarbon anode active material fraction within the anode layer on the anode plate ranges from 20 to 35 wt%, preferably 25-35 wt%, and in some cases is 25 to 26 wt%. The weight of the first anode active material ranges from 58 to 72 wt%, preferably 62 to 68.5 wt%, and in some cases is 66 to 68 wt%, and in some cases is 67.4 to 68 wt%; The conductive additive(s) range from 1.0 to 1.5 wt%, preferably 1.2 to 1.4 wt%, or 1.23 to 1.33 wt%; the binder(s) range from 5 to 7 wt%, preferably 5.8 to 6.4 wt%, and in some cases 6.0 to 6.1 wt%.

[0049] In another example of the invention, the cell energy density is at least 300 Wh / kg and / or at least 800 Wh / L, the anode current collector comprises a copper foil has a thickness of 6 microns, and the thickness of the anode layer applied to each side of the anode current collector is 55 to 60 microns and has a density of at least 1.5 g / cm3. The weight percentage of the second anode active material particle is at least 25% and the first lithiation capacity (typically measured using a 0.1C rate in a half coin cell at room temperature) is at least 770 mAh / g, and sometimes at least 774 mAh / g, with a first cycle efficiency of at least 92%. Preferably, the anode areal capacity is at least 5.4 mAh / cm2, provided that the N / P atio is 1.1 as is a typical value in the art. However, as mentioned previously, an anode areal capacity as low as 5.1 mAh / cm2could achieve the energy density objectives of the invention albeit at a risk of reduced cycle life caused by operating at the extremes of the invention.

[0050] Coating Modification Compounds The coating modification compounds CM1 , CM2 and CM3 provide at least two important functions in the cylindrical lithium rechargeable batteries described herein. First, CM1, CM2 and CM3 provide a structural protection means for the cathode active material, the first anode active material, and the second active material, respectively, that maintains the structural integrity of each of the cathode active material and anode active materials over a wider operating voltage range than what is feasible for conventional cylindrical lithium rechargeable batteries. Second, CM1, CM2 and CM3 are designed to provide a uniform interface with which an electrolyte can physically and / or chemically interact, reversibly or irreversibly, during cycling of the cylindrical lithium rechargeable battery.

[0051] The coating modification compound disposed on the cathode active material can also function to improve the adhesion between the binder or binders of the cathode plate and one or more of the cathode active material, a conductive additive or additives, and the cathode current collector; the coating modification compound disposed on each of the anode active materials can also function to improve the adhesion between the binder or binders of the anode plate and one or more of the first anode active material, the second anode active material, a conductive additive or additives, and the anode current collector.

[0052] The coating modification compounds CM1, CM2 and CM3 preferably primarily comprise anion elements consisting of O and / or N, and are preferably primarily in the form of oxide, nitride or oxynitride layers when initially provided to the cylindrical lithium rechargeable battery prior to the addition of the electrolyte.

[0053] Individual coating modification layers have become ubiquitous in the art as a means of protecting individual electrode active materials, however the inventors have unexpectedly discovered there is a relationship between the sum of the loading of all coating modification layers in the cell on both the cathode plate, here CM1, and the anode plate, here CM2 and CM3, and specifically how they relate to the electrolyte composition selected for the inventive cylindrical lithium rechargeable battery described herein. Preferably, the cumulative mass of the cations of all coating modification compounds (CM1 + CM2 + CM3) as measured using ICP-OES range from 500 to 3,000 parts per million (ppm), or ranges from 650 to 2,600 ppm, or ranges from 800 to 2,400 ppm. In general, the mass of the cations of the coating modification compound on the cathode active material (CM1) ranges from 100 to 300 ppm for surface areas ranging from 0.35 to 0.60 m2 / g, 300 to 600 for surface areas ranging from 0.60 to 1.00 m2 / g, 600 to 1,725 for surface areas ranging from 1.00 to 1.50 m2 / g, and 1,725 to 2,300 for surface areas ranging from 1.50 to 2.00 m2 / g. Preferably, the cathode active material comprises LixNiaMnbCocCMldCh where CM1 represents the cation loading of the coating modification compound on the Ni-rich NMC, 0.95 < x < 1.2, 0.80 < a < l, 0 <b < 0.1, 0 < c < 0.1, and preferably a + b + c = 1 and d satisfies the equation 620 ppm < CMld / SA < 1150 ppm, where CMld is the loading of the cation of the coating modification compound in parts per million, and SA is the specific surface area of the cathode active material expressed in units of m2 / g. By way of example, if the surface area of the cathode active material is 1.2 in units of m2 / g (as measured using BET) and the coating modification compound is aluminum oxide (AI2O3) or aluminum oxyhydroxide (A1OOH), the equation 620 ppm < CMld / 1.2 < 1150 ppm is satisfied for CMld within a range of 744 to 1,725 ppm. Whether the coating modification compound CM1 comprises aluminum oxide, aluminum oxyhydroxide or a mixture thereof, in order to satisfy the above relationship, the loading of the cation of CM1 (here aluminum) as measured using ICP-OES would be required to fall within the range of 744 to 1,725 ppm.

[0054] It is preferable for the Pauling electronegativity of the one or more cations of CM1 to range between 1.22 and 1.66, which are values that range from approximately 0.21 to 0.65 below the molar average electronegativity of the cations of the Ni-rich cathode active material (1.87 for NMC-811). The cations that satisfy this range include Y (1.22), Hf (1.30), Mg (1.31), Zr (1.33), Sc (1.36), Ta (1.50), Ti (1.54), Nb (1.60), Al (1.61), TI (1.62), V (1.63), Zn (1.65) and Cr (1.66).

[0055] It is also preferable for the one or more of CM1 to have a first ionization energy that is 745 kJ / mol or lower, which is the approximate threshold that will allow the first ionization energy of the one or more cations of CM1 to remain below that of Ni, Mn and Co cations of the Ni-rich cathode active material (approximately 750 kJ / mol or higher). The cations that satisfy both the electronegativity and first ionization energy criteria include Y, Hf, Mg, Zr, Sc, Ti, Nb, Al, V and Cr. As such, it is preferable that CM1 is comprised of at least one cation selected from the group Y, Hf, Mg, Zr, Sc, Ti, Nb, Al, V and Cr, wherein the stoichiometric weighted electronegativity of the one or more cations of CM1 ranges between 1.22 and 1.66.

[0056] Alternatively, or in addition to, the ppm loading per surface area criteria stated previously, it is preferable that for the array of preferred CM1 cations listed above, having a Pauling Electronegativity (PE) ranging from 1.22 to 1.66, satisfy the relationship 100 < CMlppm / PE < 900, preferably 150 < CMlppm / PE < 780, and sometimes 200 < CMlppm / PE < 560. With regard to the mass of the coating modification compound on the first anode active material, CM2, and second anode active material, CM3, it is preferable that one or both of CM2 and CM3 range from 25 to 350 ppm, or 80 to 275 ppm, or 150 to 240 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.60 to 1.66. It is also preferable that one or both of CM2 and CM3 range from 450 to 1,600 ppm, or 500 to 1,500 ppm, or 600 to 1,400 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.22 to 1.60. CM1 , CM2 and CM3 may further comprise lithium within each coating modification compound, provided that the loading and electronegativity of lithium is not included in the satisfying criteria calculation provided herein for CM1, CM2 or CM3.

[0057] Unless specified to the contrary, “ppm” refers to the composition of a material as measured by ICP-OES (Inductively Coupled Plasma - Optical Emission Spectroscopy) of the powder. So, for example, the phrase “a coating modification compound comprises 100 to 300 ppm of ZrO2,” means that when the powder is measured by ICP-OES it indicates 100 to 300 ppm of Zr, and the stable compound of ZrO2 is presumed if the coating modification compound is in the form of zirconium oxide. Unless stated otherwise, this value is for the entire powder; however, knowledge of the synthesis or characterization of the coated particle can be conducted to specify the distribution of Zr (or any element of interest) in the particles.

[0058] Binder

[0059] In general, irrespective of size and format, a lithium rechargeable battery is composed of a positive electrode, a negative electrode, an electrolyte, and a separator. The positive electrode and the negative electrode each are generally composed of an electrode current collector and an electrode active material layer formed on the electrode current collector, wherein the electrode active material layer is prepared by coating the electrode current collector with a non-aqueous or an aqueous electrode slurry composition including the electrode active material, conductive additive(s), and binder(s), which is coated at a controllable thickness, dried, and then roll pressing the coated, dried electrode current collector to a desired porosity.

[0060] A binder used in each of the positive or negative electrode active material layers is not particularly limited, and for example, the following materials may be mentioned. Thermoplastic polymers such as polyethylene, polypropylene, polyethylene terephthalate (PET), poly ether nitrile, polyacrylic acid, polyacrylonitrile, polyimide, polyamide, cellulose, carboxymethyl cellulose (CMC) and any salt thereof, an ethylene-vinyl acetate copolymer, polyvinylidene chloride, styrene-butadiene rubber (SBR), isoprene rubber, butadiene rubber, ethylene-propylene rubber, an ethylene-propylene-diene copolymer, a styrene-butadiene-styrene block copolymer and a hydrogen-added product thereof, and a styrene-isoprene-styrene block copolymer and a hydrogen- added product thereof, fluorine resins such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a tetrafluoroethylene-hexafluoropropylene copolymer (FEP), a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PF A), an ethylene-tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), an ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polyvinyl fluoride (PVF), vinylidene fluoride-based fluorine rubber such as vinylidene fluoride-hexafluoropropylene-based fluorine rubber (VDF-HFP -based fluorine rubber), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene-based fluorine rubber (VDF-HFP-TFE-based fluorine rubber), vinylidene fluoride-pentafluoropropylene-based fluorine rubber (VDF-PFP-based fluorine rubber), vinylidene fluoride-pentafluoropropylene- tetrafluoroethylene-based fluorine rubber (VDF-PFP-TFE-based fluorine rubber), vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene-based fluorine rubber (VDF-PFMVE- TFE-based fluorine rubber), and vinylidene fluoride-chlorotrifluoroethylene-based fluorine rubber (VDF-CTFE-based fluorine rubber), an epoxy resin, and the like are exemplified. These binders may be used singly, or two or more kinds thereof may be used concurrently.

[0061] However, the amount of the binder contained in the positive electrode active material layer should be particularly limited in order to maximize the loading of the cathode active material applied to the cathode plate (e.g. 97.5% or greater), provided at minimum the binder or binders can maintain the cathode layer comprising the active material and conductive additive materials in a bound state. The amount of the binder is preferably from 0.5 to 1.5% by weight and more preferably from 1.0 to 1.3% by weight with respect to the active material layer. The present inventors have determined that when one or more of the aforementioned coating modification compounds is disposed between the cathode active material and the binder of the cathode layer, it is beneficial to utilize a first PVDF binder having a lower molecular weight, and a second PVDF binder having a higher molecular weight, wherein the ratio between the first binder and the second binder is within a range of 4:1 to 7: 1, preferably 5:1 to 6: 1, and in some cases the ratio between the first binder and the second binder is 5.5 ± 0.2. Preferred molecular weights (in kiloDaltons) for the lower molecular weight binder range from 500 to 800, preferably 600 to 750, and sometimes 670 to 700. Preferred molecular weights (in kiloDaltons) for the higher molecular weight binder range from 1,000 to 1,500, preferably 1,000 to 1,300. In these embodiments, the mass of the coating modification compound, d, on the cathode active material satisfies the equation 620 ppm < d / SA < 1105 ppm, where d is the loading of the coating modification compound in parts per million, and SA is the specific surface area of the cathode active material expressed in units of m2 / g.

[0062] Conductive Additive

[0063] In the cylindrical lithium rechargeable battery according to the present invention, each of the positive electrode active material layer and negative electrode active material layer contains at least one conductive additive, preferably two or more conductive additives. Here, the term “conductive additive” refers to a solid particulate-type additive that is blended into each electrode active material slurry order to improve the conductivity of the respective electrode active material layer. Conventionally, conductive additives are carbon-based and can be categorized in geometrical terms. Using the nomenclature of Kim et al. in US 11,831,006, which is incorporated by reference in its entirety, two categories are a point-type conductive agent, e.g. a traditional powder that may appear spherical or of a general spheroidal shape when observed using a scanning electron microscope, and a linear or line-type conductive agent, e.g. that may appear linear or rectangular and generally having a first dimension that is substantially larger than a second dimension positioned orthogonally to the first dimension, when observed using a scanning electron microscope. Non-limiting examples of point-type conductive additives may include carbon materials such as carbon black including ketjen black, LITX® HP carbon black, SuperP® Li carbon black, Timcal Super C65 carbon black, Timrex® SFG6, acetylene black, graphene or graphite. Non-limiting examples of linear conductive additives may include carbon materials such as carbon nanotubes (CNTs) or carbon nanofibers (CNFs). CNTs may consist of single- walled or multiwalled configurations, where the latter comprises a plurality of CNTs positioned concentric to one another in a single linear or rectangular image.

[0064] Irrespective of the choice of conductive additives, the electron network within each of the positive and negative electrode active material layers is effectively formed when each electrode active material layer contains a conductive additive, which can contribute to the improvement in output characteristics of the cylindrical lithium secondary battery with high active material loading. Based on differences between the particle sizes, inherent electrical conductivity, binder(s), coating modification compounds and properties, electrode thickness, active material loadings, porosity, etc., it is beneficial to independently optimize the conductive additive or additives used within each electrode active material layer.

[0065] Kim teaches a line-type conductive additive at a weight percentage of 0.1% to 0.5% is beneficial when using a plurality of PVDF binders having a weight-average molecular weight of between 100 and 1,000 kiloDaltons. However, the teachings of Kim were devoid of coating modification compounds that modify the electrical conductivity of the electrode active materials and flow properties of the materials, which impact the ability to mix and disperse conductive additives amongst the coating modification compound coated active electrode materials. For instance, it was determined experimentally that Kim’s teachings of incorporating a line-type conductive additive at a weight percentage of 0.1% to 0.5% was insufficient for the cylindrical lithium rechargeable battery of the present invention. Due to the high cathode loading within the cathode plate of the cylindrical lithium rechargeable battery of the present invention, and the coating modification compounds, one of the required features is that the conductive additive contained in the positive electrode active material layer comprises at least two or more kinds of carbon materials, the first carbon material comprising a line-type additive and the second carbon material comprising a point-type additive, and the line-type conductive additive must have a loading higher than the range taught by Kim. The cathode plate of the cylindrical lithium rechargeable battery of the present invention comprising a cathode active material loading of at least 97 wt%, preferably at least 97.5 wt%, and a coating modification compound, comprises a line-type additive and a point-type additive, wherein the weight percentage of the line-type additive ranges from 0.5% to 1.0%, and the weight percentage of the point-type additive ranges from 0.2% to 0.5%, provided the loading of the line-type additive is greater than the loading of the point-type additive, and wherein the mass of the coating modification compound on the cathode active material ranges from 100 to 300 ppm for surface areas ranging from 0.35 to 0.60 m2 / g, 300 to 600 for surface areas ranging from 0.60 to 1.00 m2 / g, and 600 to 1,000 for surface areas ranging from 1.00 to 1.50 m2 / g. It was determined that the cylindrical lithium rechargeable battery of the present invention was only able to achieve at least 500 charge / discharge cycles, preferably at least 1,000 charge / discharge cycles, over a cycling range of 2.50V to 4.40V. Atomic or Molecular Layer Deposition for the Coating Modification Compound

[0066] Atomic layer-controlled growth techniques permit the deposition of coatings of about 0.1 to about 5 angstroms in thickness per reaction cycle, and thus provide a means of extremely fine control over surface coverage or coating thickness. Thicker coatings can be prepared by repeating the reaction sequence to sequentially deposit additional layers of the coating material until the desired coating thickness is achieved. The coating modification compound is preferably applied using an Atomic Layer Deposition (ALD) or Molecular Layer Deposition (MLD) process. In the ALD / MLD process, the coating-forming reaction is conducted as a series of (typically) two halfreactions. In each of these half-reactions, a single reagent (precursor) is introduced into contact with the substrate surface. Conditions are such that the reagent is in the form of a gas. In most cases, the reagent reacts with functional groups on the surface of the substrate and becomes bound to the substrate. Because the reagent is a gas, it permeates into pores in the substrate and deposits onto the interior surfaces of the pores as well as onto the exterior surfaces of the substrate. This precursor is designed to react with the surface at all of the available surface sites but not react with itself. In this way, the first reaction occurs to form a single monolayer, or sub -monol ay er, and creates a new surface functionality. Excess amounts of the reagent are then removed, which helps to prevent the growth of undesired, larger inclusions of the coating material. Each remaining halfreaction is then conducted in turn, each time introducing a first reagent, allowing it to react at the surface of the substrate, and removing excess reagent before introducing the next reagent. Usually, an inert carrier gas is used to introduce the reagents, and the reaction chamber is usually swept with the carrier gas between successive reagent introductions to help remove excess reagents and gaseous reaction products. A vacuum may be pulled during and between successive dosing of reagents, to further remove excess reagents and gaseous reaction products.

[0067] After exposure to the first precursor, the surface is then exposed to the second precursor, also typically dispersed in an inert carrier gas. This precursor is designed to react with the functional groups put down in the first reaction step. This reaction also happens until all of the available surface sites are reacted. The second precursor also does not react with itself. Any excess of the second precursor is also removed in an optional inert gas purge step. If the gases are metered properly, the purge step may be unnecessary. This may be at least a 4-step process (precursor 1, purge, precursor 2, purge) to deposit one monolayer of the film which is being grown. This is not meant to imply only a single precursor because some ALD and MLD processes use multiple reactants in a step, for example APTES / H2O / O3 for depositing SiCh. This process is repeated as many times as is necessary to build up the desired film thickness. The ALD / MLD process may start with a “linker” agent, or pre-treatment gas (such as ozone), that facilitates covalent bonding to the surface, or it may end with a terminating agent that may be hydrophobic, hydrophilic, or otherwise engineered for a specific purpose.

[0068] One of many benefits of using ALD / MLD to apply a coating modification compound is that the loading (in parts per million) of the compound applied is controllable and repeatable, generally scaling with the surface area of the underlying substrate. Several techniques are useful for monitoring the progress of the reaction while applying the appropriate parts per million loading. For example, vibrational spectroscopic studies can be performed using transmission Fourier transform infrared techniques. The deposited coatings can be examined using in situ spectroscopic ellipsometry. Atomic force microscopy studies can be used to characterize the roughness of the coating relative to that of the surface of the substrate. X-ray photoelectron spectroscopy and x-ray diffraction can be used to do depth-profiling and ascertain the crystallographic structure of the coating. Some ALD coatings are aluminum oxide and / or titanium oxide coatings. "Aluminum oxide" is used herein to designate a coating that is made up substantially entirely of aluminum and oxygen atoms, without reference to the specific stoichiometry. In many cases, it is expected that an aluminum oxide coating will correspond somewhat closely to the empirical structure of alumina, i.e., AI2O3, although deviations from this structure are common and may be substantial. "Titanium oxide" is used herein to designate a coating that is made up substantially entirely of titanium and oxygen atoms, without reference to the specific stoichiometry. In most cases, it is expected that a titanium oxide coating will correspond closely to the empirical structure of titania, i.e., TiCL, although deviations from this structure are common and may be substantial. Similarly, considerations apply to understanding the other formulations described herein; although in some embodiments, the invention can be more specifically defined by the use of terms such as “consisting.” The coating modification compound may comprise any coating that can be applied by molecular or atomic layer deposition. Some well-known coatings that can be applied to the metallic or other material core substrate may comprise: oxides or mixed oxides (e.g., AI2O3, TiCL. ZnO, ZrO2, SiO2, HfO2, Ta2O5, LiNbxOy), nitrides (e.g., TiN, TaN, W2N, TiY2N), sulfides (e.g., ZnS, CdS, SnS, WS2, M0S2, ZnIn2S4), and phosphides (e.g., GaP, InP, Feo.5Coo 5P). Some lesser known materials that can be applied to the core substrate may comprise: transition metals (e.g., of Al, Cu, Co, W, Cr, Fe, Zn, Zr, Pt, Pd), metal fluorides (e.g., AIF3, MgF2, Z11F2), oxy fluorides and oxy nitrides of transition metals, lanthanides in either elemental, oxide, fluoride, nitride, boride, or sulfide form (e.g., Y, YN, La2O3, LaF3, Nb, Dy3O3, Nd, LaBe, La2S3etc), borides (e.g., Tifh), carbides (e.g., B4C, WC), silanes, silicides and other silicon containing materials, carbon- containing materials including, but limited to, polymers (e.g., polyamides, polyethylenes, polyamides, polyureas, polyurethanes), hydrocarbons, polymers or fragments of amino acids or other biological -related molecules and polymers, and other materials), fluorinated polymers (e.g., fluoro or perfluoro- polyamides, -polyethylenes, -polyamides, -polyureas, -urethanes, - hydrocarbons). This coating is highly uniform over the substrate; preferably, there is no more than a 20%, more preferably no more than 10%, or no more than 5% variation in coating thickness over the surface of the substrate. This high level of uniformity is a characteristic of the ALD / MLD process.

[0069] Electrolyte

[0070] The electrolyte of the cylindrical lithium secondary battery comprises a non-aqueous electrolyte solution comprising a mixture of at least one non-oxygenated lithium salt, at least one oxygenated lithium salt, at least one carbonate solvent, and optionally at least one non-carbonate solvent. The non-oxygenated lithium salt may be included in a concentration of 1.3 M or above and 5.0 M or less in the non-aqueous electrolyte solution, and is selected from one or more of LiPFe, LiBF4, LiSbFe, and LiAsFe, and mixtures thereof. The oxygenated lithium salt is at least one selected from “LiFSF’ (Lithium bisfluoro-sulfonylimide, LiF2S2NO4), “LiBETI” (lithium bisperfluoro-ethane-sulfonimide, LiN^FsSCh ), “LiTFSI” (lithium (bis)trifluoro-methane- sulfonimide, LiN(CF3SO2)2, LiCF3SO3, LiC(CF3SO2)3, “LiDFOB” (LiC2BO4F2), “LiTFOP” (LiC2PO4F4), “LiDFBOP” (LiC4PO4F2), “LiDFP” (LiPO2F2), LiN(C2F5SO2)2, “LiBOB” (LiC4BO8) and mixtures thereof. Each non-oxygenated lithium salt and oxygenated lithium salt can be further described as consisting of a positively charged lithium cation and a negatively-charged anion. For example, LiDFOB can be described as consisting of a Li+cation and a BF2C2O4‘ anion. The carbonate solvent is selected from butylene carbonate, 2,3 -butylene carbonate, iso-butylene carbonate, dimethyl carbonate, ethylene carbonate, ethyl methyl carbonate, fluoroethylene carbonate, difluoroethylene carbonate, propylene carbonate, vinylene carbonate, and mixtures thereof. The optional non-carbonate solvent is selected from y-butyrolactone, sulfolane, butanedinitrile, malononitrile, glutaronitrile, adiponitrile, suberonitrile, sebaconitrile, mixtures thereof.

[0071] Typically, the majority of the composition of the electrolyte mixture of the cylindrical lithium secondary battery consists of the carbonate solvent. On a mass percentage basis, the carbonate solvent selected from butylene carbonate, 2,3-butylene carbonate, iso-butylene carbonate, dimethyl carbonate, ethylene carbonate, ethyl methyl carbonate, fluoroethylene carbonate, difluoroethylene carbonate, propylene carbonate, vinylene carbonate, and mixtures thereof, comprises: at least 50% by mass and at most 85% by mass; between 65% by mass and 84% by mass; between 75% by mass and 82% by mass; or for a molarity of the non-oxygenated lithium salt of 1.5M, between 80.5% by mass and 81% by mass. However, as the molarity of the nonoxygenated lithium salt increases to 3M, 4M or even 5M, composition of the electrolyte mixture of the cylindrical lithium secondary battery shifts to lower percentages by mass of the carbonate solvent. For a molarity of the non-oxygenated lithium salt of 5M, for example, the mass percentage of the carbonate solvent relative to the total electrolyte mass could be between 45% by mass to 49% by mass. The role of the solvent is well established in the art and a minimum threshold is oftentimes required for robust performance and longevity. For any electrolyte mixture a consideration is to be able to quantify the positively charged lithium cations and negatively- charged anions of the non-oxygenated lithium salt(s) and oxygenated lithium salt(s).

[0072] The positively charged lithium cations and negatively-charged anions of the nonoxygenated lithium salt(s) and oxygenated lithium salt(s) of the electrolyte mixture of the cylindrical lithium secondary battery can be quantified based on the composition of the electrolyte mixture, and the molarity, volume, mass and / or density of each constituent component.

[0073] The lithium content of the cathode active material(s) and optionally the anode active material(s) are also known inputs of the cylindrical lithium secondary battery, and can also be quantified in terms of moles, mass and atomic weight. The amount of lithium ions that can be occluded into and released from the active materials, sometimes referred to as reversible lithium, can be estimated based upon the intended charging and discharging profiles, including charge rates, discharge rates, temperatures, N / P ratio and other considerations known to one of ordinary skill in the art. For example, a particular charging profile may only release 50% of the lithium content of a cathode material, while the remaining 50% is retained within the cathode material and does not factor into the amount of reversible lithium that participates in the current that is generated by the cylindrical lithium secondary battery. Then, amongst the example 50% of the lithium content released from the cathode material, and the lithium cations of the non-oxygenated lithium salt(s) and oxygenated lithium salt(s) of the electrolyte mixture, sometimes referred to as the lithium inventory, further irreversible lithium is removed from the equation as evidenced by the difference between the charge and discharge capacity, which in percentage form is known as Coulombic Efficiency. The maximum lifetime and state of health of the cylindrical lithium secondary battery is limited by the Coulombic Efficiency of the system, but gradual depletion of the constituent components of the electrolyte mixture, loss of lithium inventory to the Cathode Electolyte Interface (CEI) layer of the cathode active material, Solid Electrolyte Interface (SEI) layer of the anode active material, and other lithium sinks, are known to further impact the lifetime and state of health of lithium ion batteries.

[0074] An objective of the cylindrical lithium secondary battery of the present invention is to maximize the lifetime and state of health of the battery, while also maximizing the lithium inventory provided to the cell in order to maximize the area under the curve of a plot of energy density on the y-axis, and charge / discharge cycles on the x-axis. Ordinarily, lithium secondary batteries of the prior art can be charged and discharged over a higher voltage window to increase the initial lithium inventory of the cell, however this leads to faster degradation of the cell and does not materially benefit the area under the curve of a plot of energy density on the y-axis, and charge / discharge cycles on the x-axis. The composition and quantity of the negatively-charged anions of the non-oxygenated lithium salt(s) and oxygenated lithium salt(s) of the electrolyte mixture of the cylindrical lithium secondary battery are known to be able to marginally improve the area under the curve of a plot of energy density on the y-axis, and charge / discharge cycles on the x-axis. However, these typically would not be sufficient to overcome structural degradation phenomena inherent to the active materials of the battery that typically originate at the cathode / CEI and / or anode / SEI interfaces. Further increasing the oxygenated lithium salt(s) of the electrolyte mixture can further improve the early area under the curve of a plot of energy density on the y- axis, and charge / discharge cycles on the x-axis, however this a) decreases the initial lithium cations present in the electrolyte mixture due to the oxygenated lithium salts having a higher molecular weight than the non-oxygenated lithium salts, and b) decreases the amount of solvent that can be devoted toward maximizing the Coulombic Efficiency of the cell over time. A known long-term failure mechanism of batteries of the prior art is dry-out of the electrolyte mixture, which rapidly degrades the cell and signals the end of life of the cell.

[0075] A lithium rechargeable battery according to the present invention may comprise: a cathode plate having a first face and a second face, and a cathode active material capable of occluding and releasing lithium ions disposed on both the first face and second face of the cathode plate, an anode plate having a first face and a second face, and an anode active material capable of occluding and releasing lithium ions disposed on both the first face and the second face of the anode plate, a separator interposed between the cathode plate and the anode plate, an electrolyte having lithium- ion conductivity; wherein the cathode active material comprises LixNiaMnbCocCh where 0.95 < x < 1.2, 0.80 < a < 1, 0 < b < 0.1, 0 < c < 0.1, and preferably a + b + c = 1; wherein the anode comprises a first anode active material comprising a graphite material and a second anode active material comprising silicon and carbon; wherein the electrolyte comprises a non-aqueous electrolyte solution comprising a mixture of at least one non-oxygenated lithium salt, at least one oxygenated lithium salt, at least one carbonate solvent, and optionally at least one non-carbonate solvent, wherein the non-oxygenated lithium salt is present at a concentration of 1.0 M or above and 5.0 M or less in the non-aqueous electrolyte solution, and the ratio of the total mass of lithium in the non-aqueous electrolyte solution, LiEiectroiyte to the sum of the total mass of lithium in the non-aqueous electrolyte solution and mass of lithium in the cathode active material comprises LixNiaMnbCocCh where 0.95 < x < 1.2, LICAM, satisfies the relationship: where C represents a concentration of the lithium salt in the electrolyte with a unit of mol / L and ranges from 1.0 < C < 5.0, 0.12 < A < 0.20, and B = 0.63. In general, the ratio of the total mass of lithium provided in the non-aqueous electrolyte solution, LiEiectroiyte to the sum of the total mass of lithium in the cylindrical lithium secondary battery geometrical shape can be depicting as having an upper boundary of O.2O*C0 63over the range 1.0 < C < 5.0, and a lower boundary of 0.12*C°63over the range 1.0 < C < 5.0. In many cases, in order to achieve a cell energy density exceeding 300 Wh / kg and / or 800 Wh / L, C is at least 1.3, and sometimes at least 1.5. In some embodiments, the ratio of the total mass of lithium provided in the non-aqueous electrolyte solution, LiEiectroiyte to the sum of the total mass of lithium in the cylindrical lithium secondary battery geometrical shape can be depicting as having an upper boundary of O.16*C0 63over the range 1.3 < C < 3.0, and a lower boundary of O.13*C0 63over the range 1.3 < C < 3.0.

[0076] The ratio of the total mass of lithium provided in the non-aqueous electrolyte solution, LiEiectroiyte to the sum of the total mass of lithium in the lithium secondary batteries of the prior art typically range in value from 25% to 35% for 1.0 < C < 1.4. For example, Wang et al. teach in Example 4 of US 11,031,622, a battery having a coating weight of 0.086 g / cm2NMC523, a total mass of injected electrolyte of 300g at a lithium salt concentration, C, of 1.14 mol / L in a battery having a rated capacity of 108 Ah. Based on the known values of mass and density, the ratio of lithium provided in the non-aqueous electrolyte solution, LiEiectroiyte to the sum of the total mass of lithium is 27.26% (Referenced as 1 in Figure 4), substantially higher than that of the inventive battery. Wang et al. also teach in Comparative Example 2 of US 11,031,622, a battery having a coating weight of 0.007 g / cm2NMC523, a total mass of injected electrolyte of 740 g at a lithium salt concentration, C, of 1.4 mol / L in a battery having a rated capacity of 200 Ah. Based on the known values of mass and density, the ratio of lithium provided in the non-aqueous electrolyte solution, LiEiectroiyte to the sum of the total mass of lithium is 32.95% (Referenced as 2 in Figure 4), substantially higher than that of the inventive battery. Applying the C0 63factor to the examples of Wang leads to values of A ranging from 0.25 to 0.27. Similarly, Yamamoto et al. teach in US 8,568,925 a pouch-type battery having an areal capacity of 3.0 mAh / cm2, an electrode area of 20 mm x 20 mm, and 0.5 grams of electrolyte having a non-oxygenated salt concentration of 1.0 mol / L. Applying the C0 63factor to the example of Yamamoto also leads to value of A of 0.27 (Referenced as 3 in Figure 4). As such the geometrical considerations of the cell (cylindrical, prismatic, pouch, etc.) are immaterial to the relationship between LiEiectroiyte to the sum of the total mass of lithium in the cells.

[0077] In Fig. 4, the region encompassed by the dotted line represents a preferred region defining the preferred ratio of Li in electrolyte to total lithium in a cell. Thus, lower amounts of electrolytes are required and a higher concentration electrolyte is enabled because of the protection afforded by the ALD coatings.

[0078] Anionic Exchange of the Coating Modification Compound

[0079] The total moles of lithium cations provided in the non-aqueous electrolyte solution has a direct bearing on the total moles of anions dissociated from the salt compounds from which the lithium cations were derived. It is well established that the CEI and SEI layers that form within a lithium secondary battery are both complex and may change over time depending on the use profile of the battery. Unexpectedly however, the present inventors have also determined that there can be a critical interplay between the Coating Modification Compounds of the inventive lithium secondary battery and the positively charged lithium cations and / or negatively-charged anions of the non-oxygenated lithium salt(s) and oxygenated lithium salt(s) of the electrolyte mixture of the cylindrical lithium secondary battery. Especially when the inventive lithium secondary batteries are charged and discharged over a higher voltage window to increase the initial lithium inventory of the cell, in particular a voltage window from 2.50 V or lower to 4.35 V or higher. The inventive cell can achieve capacity ratings exceeding 300 Wh / kg and / or 800 Wh / L, while having a greater area under the curve of a plot of energy density on the y-axis, and charge / discharge cycles on the x-axis than a cell of the prior art. The electrolyte of the inventive lithium secondary battery comprises a non-aqueous electrolyte solution comprising a mixture of at least one non-oxygenated lithium salt, at least one oxygenated lithium salt, at least one carbonate solvent, and optionally at least one non-carbonate solvent, each as defined herein. The amount of the at least one oxygenated lithium salt is 5.0 weight percent or lower (on the basis of the mass of the non-aqueous electrolyte solution), typically 4.0 weight percent or lower, oftentimes 3.0%, 2.5% or 2.0% or lower. A technical feature of the at least one oxygenated lithium salt, is that a respective dissociated anion of an oxygenated lithium salt may undergo an exchange reaction with one or more Coating Modification Compounds of the inventive battery. For example, the oxygenated lithium salt LiPCEF dissociates into a Li+ cation, which contributes to the Li total moles of lithium cations provided in the non-aqueous electrolyte solution, LiEiectroiyte, while the anion (PC^)’, or subcomponents thereof, may undergo an exchange reaction with one or more of CM1 of the cathode active material, CM2 of the first anode active material, and CM3 of the second anode active material. For CM1, CM2 and / or CM3 comprising a metal oxide having a hydroxylated surface species, the anion (PO2F2)' itself may interact with the metal of the metal oxide to form a phosphate or fluorophosphate species, or a terminal fluorine atom of the anion may exchange with a terminal hydrogen of the hydroxylated surface and form a metal oxyfluoride. In general, the CEI layer that forms on CM1 (“CEECM1”) has a higher propensity of including anionic species from the non-oxygenated lithium salt(s) and the at least one oxygenated lithium salt(s), while CM2 and CM3 and the SEI layers that form thereon (“SEECM2” and “SEECM3”, respectively) have a higher propensity of including both anionic species and Li+ cations, which can slightly detract from the lithium inventory, yet improve the ionic conductivity of the SEI / CM2 and SEI-CM3 layers. The degree of Li+ cation incorporation into the CEI / CM 1, SEI / CM2 and / or SEVCM3 is operating voltage and formation process dependent.

[0080] The inventors have empirically observed that the charge transfer resistance of the CEVCM1, SEI / CM2 and / or SE1 / CM3 layers is lower than the CEI and SEI layers of an equivalent cell devoid of CM1, CM2 and CM3. Additionally, it has also been observed that the charge transfer resistance of the CEVCM1, SEECM2 and / or SEECM3 layers in a battery containing the one or more oxygenated lithium salt(s) is also lower than the resistance of the CEVCM1, SEI / CM2 and / or SEI / CM3 layers of an equivalent cell devoid of the one or more oxygenated lithium salt(s). A useful technique to measure charge transfer resistance is Electrochemical Impedance Spectroscopy (EIS). If any of CM1, CM2 or CM3 are too thick, the overall charge transfer resistance of the cell increases. If the concentration of the anionic species of the at least one oxygenated lithium salt(s) is substantially higher than the total amount of CM1 + CM2 + CM3, then the anionic exchange between the anionic species of the non-aqueous electrolyte solution and the Coating Modification Compounds may over-react and destabilize one or more of CM1, CM2 and CM3. As described previously, it is preferable for the cumulative mass of the cations of all Coating Modification Compounds (CM1 + CM2 + CM3) as measured using ICP-OES range from 500 to 3,000 parts per million (ppm), or ranges from 650 to 2,600 ppm, or ranges from 800 to 2,400 ppm. As the ICP- OES measurement pertains to the cationic species alone, the concentration window of the anionic species of the lithium salts of the electrolyte solution corresponds to the anionic component of the Coating Modification Compounds, which is driven by the oxidation state of the cations. For example, if the Coating Modification Compound on the cathode active material, CM1, comprises 850 parts per million of aluminum applied in the form of aluminum oxide, the composition of the aluminum oxide may be AI2O3 due to the Al oxidation state of +3. As such, the anionic species may be ideally represented a multiple of 1.5 times the molar content of the 850 parts per million of aluminum measured using ICP-OES. If the total amount of cathode active material in a 21700 cylindrical cell is 27.21 grams, then 850 ppm Al would correspond to a mass of aluminum of 0.023 grams, or 0.000857 moles of aluminum. Using a multiplier of 1.5 for the anionic species, would correspond to 0.00128 moles of exchangeable material attributable to CM1. The total moles of exchangeable material can be calculated similarly for CM2 and CM3, based on the mass of the first anode active material and the mass of the second anode active material in the battery, the respective parts per million of CM2 and CM3, and the respective oxidation state multiplier for the respective anionic species. For example, if the Coating Modification Compound on the first anode active material, CM2, comprises 1200 parts per million of zirconium applied in the form of zirconium oxide, the composition of the zirconium oxide may be ZrCh due to the Zr oxidation state of +4. As such, the anionic species may be represented a multiple of 2.0 times the molar content of the 1200 parts per million of zirconium measured using ICP-OES. If the total amount of first anode active material in a 21700 cylindrical cell is 7.13 grams, then 1200 ppm Zr would correspond to a mass of zirconium of 0.0085 grams, or 0.000094 moles of zirconium. Using a multiplier of 2.0 for the anionic species, would correspond to 0.00018 moles of exchangeable material attributable to CM2.

[0081] If for example, the total moles of cations in CM1 equals 0.000857 moles of a +3 oxidation state element, CM2 equals 0.000094 moles of a +4 oxidation state element and CM3 equals 0.0001 moles of a +5 oxidation state element, it is preferable for the total moles of the at least one oxygenated lithium salt(s) fall within a range of 50% to 200% of [0.000857 * 1.5 + 0.000094 * 2.0 + 0.0001 * 2.5], or 0.00096 to 0.00344 moles to obtain the unique benefits discovered by the inventors. If the number of moles of oxygenated lithium salt(s) exceeds 200%, the total moles of the sum of masses of CM1 + CM2 + CM3, the weight of the cell is unnecessarily increased, thereby reducing the total energy density of the cell in Wh / kg. If the number of moles of oxygenated lithium salt(s) is less than 50% of the total moles of the sum of masses of CM1 + CM2 + CM3, the anion exchange of one or more of CM1, CM2 or CM3 by the oxygenated lithium salt(s) is insufficient and detrimental etching of one or more of CM1, CM2 or CM3 can occur. For example by HF generated from released oxygen loss from the cathode active material that reacts with the non-oxygenated lithium salt(s).

[0082] It is conventional knowledge to one of ordinary skill in the art that lithium ion batteries exhibit reduced cycle life at higher discharging rates and higher depth of discharge. The typical measurement of End of Life (“EOL”) in some industries such as the automotive industry, is the number of cycles required to achieve a capacity that is 80% of a battery’ s initial capacity. One can add the discharge energy provided by a battery when cycling between an upper cutoff voltage (UCV) and lower cutoff voltage (LCV) for the number of cycles until the battery reaches EOL, and produce a Cumulative Discharge Energy (typically measured in kWh) for any battery cell. In the inventive battery cell, the baseline State of Charge (“SOC”) is defined as cycling between an LCV of 2.50V (0% SOC) and an UCV of 4.35V (100% SOC). A Relative State of Charge for a particular experiment can be selected by increasing the LCV and / or reducing the UCV to define an experimental SOC relative to the 100% SOC values. An SOC of 10% can be obtained by reducing the UCV from 4.35V to 4.18V, and when paired with an LCV of 2.50V a Relative SOC of 90% is obtained; an SOC of 90% can be obtained by increasing the LCV from 2.50V to 2.58V, and when paired with a UCV of 4.35V a Relative SOC of 90% is also obtained; an SOC of 80% can be obtained by increasing the LCV from 2.50V to 2.78V, and when paired with a UCV of 4.18V (10% SOC) a Relative SOC of 70% is also obtained. The number of cycles required to achieve EOL (80% of initial discharge capacity) for any Relative SOC is a straightforward measurement using cyclic voltammetry at any particular charging and discharging rate (C-rate).

[0083] For the inventive cell in which the total moles of the at least one oxygenated lithium salt(s) falls within a range of 50% to 200% of the total moles of anion present within CM1+CM2+CM3 (oxygen, in the case of metal oxides), it has been unexpectedly observed that the Cumulative Discharge Energy per cycle to EOL does not align with conventional teachings of the effect of higher rate and higher SOC cycling on the Cumulative Discharge Energy obtained per cycle to EOL. As mentioned previously, higher C-rate and higher SOC cycling are known to decrease cycle life, as these are known methods of increasing stress levels to reduce the time required to achieve EOL. For example, Saxena et al. discuss an Acceleration Factor that can predict how increasing C-rate will accelerate the capacity fade trend of lithium ion batteries. As such, it is widely accepted that the Cumulative Discharge Energy per cycle to EOL will always decrease with increasing Relative SOC and increasing C-Rate.

[0084] A series of 5.65 Ah cells were produced and cycled over a range of Relative SOCs and at a low charging rate (C / 3) and a higher charging rate (1C). The 5.65 Ah cells weighed 65.5g and resulted in an energy density of 301 Wh / kg. The total ppm of CM1+CM2+CM3 was 1,950 of AI2O3, which resulted in an anion ppm of 2,925. Based on the distribution of CM1, CM2 and CM3 over the specific mass of each of the cathode active materal, first anode active material and second anode active material, a total of 0.000763 moles of anion were present due to CM1, CM2 and CM3. An electrolyte comprising a 1.5M LiPFe non-oxygenated lithium salt and up to 2 wt% of an oxygenated lithium salt was used to prepare the 5.65 Ah cell having an energy density of greater than 300 Wh / kg. The total moles of anion present in the non-oxygenated lithium salt was 0.001496, which is a ratio of 196% of the moles of the anion present within CM1, CM2 and CM3. Additional non-oxygenated lithium salt would have been disadvantageous as the energy density of the inventive cell would have decreased to below 300 Wh / kg. Less than 0.000381 moles of nonoxygenated lithium salt would not have provided the unexpected benefit to Cumulative Discharge Energy per Cycle to EOL with respect to Relative State of Charge and increasing C-rate used.

[0085] Figure 5 shows the Cumulative Discharge Energy per cycle to EOL for four sets of Relative State of Charge experiments. As the Relative SOC increases, the Cumulative Discharge Energy to EOL per cycle increases. For example, at 1C and 100% Relative SOC the 5.65 Ah cell produced a Cumulative Discharge Energy of 9.15 kWh over 576 cycles, for a value of 15.89 Wh / cycle; at C / 3 and 70% Relative SOC, the 5.65 Ah cell produced a Cumulative Discharge Energy of 27.05 kWh over 2,200 cycles, for a value of 12.29 Wh / cycle. As would be expected of slower cycling, cycling the same 5.65 Ah cell at C / 3 and 100% Relative SOC the 5.65 Ah cell produced a Cumulative Discharge Energy of 11.87 kWh over 684 cycles, for a higher value of 17.35 Wh / cycle. Whereas cycling the 5.65 Ah cell to 70% Relative SOC at the higher rate of 1C, produced a Cumulative Discharge Energy of 19.16 kWh over 1,400 cycles, for a value of 13.69 Wh / cycle.

[0086] Examples:

[0087] Example 1

[0088] (A) Production of Positive Electrode

[0089] A positive electrode comprising Li(Nio.8Mno.iCoo.i)02 as the positive electrode active material, a first conductive additive - a point-type conductive additive a second conductive additive - a linetype conductive additive, a first PVDF binder having a lower molecular weight (600 to 750 kiloDaltons), and a second PVDF binder having a higher molecular weight (1,000 to 1,300 kiloDaltons) were combined together at a mass ratio of 97.5:0.5:0.7:1.1:0.2. N-methylpyrrolidone (NMP) was used as the solvent to prepare a positive electrode slurry having a solid content of 70%. The positive electrode slurry was applied to a positive electrode current collector (Al) having a thickness of 12 pm and dried in a vacuum oven at 130° C. for 6 hours. Thereafter, the current collector was rolled between rolls heated to 60° C. under a pressure of 10 MPa to produce a positive electrode having a final active material layer thickness of 64 pm, a porosity of 23%, a density of 3.52 g / cm3, and a loading amount of the positive electrode active material layer of 22.55 mg / cm2. The total content of the remaining components (the conductive material and the binder) excluding the positive electrode active material in the positive electrode active material layer was 2.5 wt % with respect to the total weight of the positive electrode active material layer.

[0090] (B) Production of Negative Electrode

[0091] A negative electrode comprising natural graphite as the first negative electrode active material, a silicon / graphite composite material as the second negative electrode active material, a first conductive additive - a point-type conductive additive a second conductive additive - a line-type conductive additive, a first binder comprising PAA, a second binder comprising SBR, and a third binder comprising CMC, were combined together at a mass ratio of 67.7:25.0: 1.2:0.12:4.5:1.3:0.18. The solids were mixed with distilled water to prepare a negative electrode slurry. The prepared slurry was applied to a negative electrode current collector (Cu) having a thickness of 6 pm and dried in a vacuum oven at 100° C for 12 hours. Thereafter, the current collector was rolled between rolls heated to 60° C. under a pressure of 10 MPa to produce a negative electrode having a final active material layer thickness of 57 pm, a porosity of 30%, a density of 1.51 g / cm3, and a loading amount of the active material layer of 8.12 mg / cm2. The total content of the remaining components (the conductive material and the binder) excluding the negative electrode active materials in the negative electrode active material layer was 5.0 wt % with respect to the total weight of the negative electrode active material layer.

[0092] (C) Preparation of a Nonaqueous Electrolyte

[0093] In a nonaqueous solvent obtained by mixing EC, EMC and DMC in a volume ratio of 10:40:50, LiPFe was dissolved as an electrolyte salt at a concentration of 1.2 mol / L, and up to 2.0 mass % of oxygenated lithium salt(s) were added thereto as an additive, thereby obtaining a nonaqueous electrolyte of Example 1.

[0094] (D) Assembly of a Secondary Cylindrical Battery

[0095] The positive electrode and the negative electrode were wound along with a porous polyethylene separator having a thickness 14 pm and a width of 6.6 cm, to form an electrode assembly. The electrode assembly was inserted into an aluminum case, and then the case lid was laser-welded. The nonaqueous electrolyte described above was injected into the case through an electrolyte solution filling hole provided in the case, and then the electrolyte solution filling hole was sealed, thereby obtaining a secondary cylindrical battery.

[0096] Example 2

[0097] The steps of A, C and D of Example 1 were followed, except step B included:

[0098] A negative electrode comprising natural graphite as the first negative electrode active material, a silicon / graphite composite material as the second negative electrode active material, a first conductive additive - a point-type conductive additive a second conductive additive - a line-type conductive additive, a first binder comprising PAA, and a second binder GB2000, were combined together at a mass ratio of 81 :14:0.44:0.06:3.5: 1.0. The solids were mixed with distilled water to prepare a negative electrode slurry. The prepared slurry was applied to a negative electrode current collector (Cu) having a thickness of 8 pm and dried in a vacuum oven at 100° C for 12 hours. Thereafter, the current collector was rolled between rolls heated to 60° C. under a pressure of 10 MPa to produce a negative electrode having a final active material layer thickness of 57 pm, a porosity of 30%, a density of 1.51 g / cm3, and a loading amount of the active material layer of 8.12 mg / cm2. The total content of the remaining components (the conductive material and the binder) excluding the negative electrode active materials in the negative electrode active material layer was 5.0 wt % with respect to the total weight of the negative electrode active material layer.

[0099] Example 3

[0100] The steps of A, B and D of Example 1 were followed, except step C included:

[0101] In a nonaqueous solvent obtained by mixing EC, EMC and DMC in a volume ratio of 10:40:50, LiPFe was dissolved as an electrolyte salt at a concentration of 1.3 mol / L, 10% by mass of FEC was used, and up to 2.0 mass % of oxygenated lithium salt(s) were added thereto as an additive, thereby obtaining a nonaqueous electrolyte of Example 3.

[0102] Example 4

[0103] The steps of A, B and D of Example 1 were followed, except step C included:

[0104] In a nonaqueous solvent obtained by mixing EC, EMC and DMC in a volume ratio of 20: 10:70, LiPFe was dissolved as an electrolyte salt at a concentration of 1.3 mol / L, 10% by mass of FEC was used, and up to 2.0 mass % of oxygenated lithium salt(s) were added thereto as an additive, thereby obtaining a nonaqueous electrolyte of Example 4.

[0105] Example 5

[0106] The steps of A, B and D of Example 1 were followed, except step C included:

[0107] In a nonaqueous solvent obtained by mixing EC, EMC and DMC in a volume ratio of 20: 10:70, LiPFe was dissolved as an electrolyte salt at a concentration of 1.5 mol / L, 10% by mass of FEC was used, and up to 2.0 mass % of oxygenated lithium salt(s) were added thereto as an additive, thereby obtaining a nonaqueous electrolyte of Example 5.

[0108] Example 6

[0109] The steps of A, B and D of Example 1 were followed, except step C included:

[0110] In a nonaqueous solvent obtained by mixing EC, EMC and DMC in a volume ratio of 20: 10:70, LiPFe was dissolved as an electrolyte salt at a concentration of 1.75 mol / L, 10% by mass of FEC was used, and up to 2.0 mass % of oxygenated lithium salt(s) were added thereto as an additive, thereby obtaining a nonaqueous electrolyte of Example 6.

[0111] Example 7

[0112] The steps of A, B and D of Example 1 were followed, except step C included:

[0113] In a nonaqueous solvent obtained by mixing EC, EMC and DMC in a volume ratio of 20: 10:70, LiPFe was dissolved as an electrolyte salt at a concentration of 2.0 mol / L, 10% by mass of FEC was used, and up to 2.0 mass % of oxygenated lithium salt(s) were added thereto as an additive, thereby obtaining a nonaqueous electrolyte of Example 7.

[0114] Example 8

[0115] The steps of A, B and D of Example 1 were followed, except step C included:

[0116] In a nonaqueous solvent obtained by mixing EC, EMC and DMC in a volume ratio of 20: 10:70, LiPFe was dissolved as an electrolyte salt at a concentration of 1.5 mol / L, 5% by mass of FEC was used, and up to 2.0 mass % of oxygenated lithium salt(s) were added thereto as an additive, thereby obtaining a nonaqueous electrolyte of Example 8. Example 9

[0117] The steps of A, B and D of Example 1 were followed, except step C included:

[0118] In a nonaqueous solvent obtained by mixing EC, EMC and DMC in a volume ratio of 20: 10:70, LiPFe was dissolved as an electrolyte salt at a concentration of 1.5 mol / L, 10% by mass of FEC was used, and up to 2.0 mass % of oxygenated lithium salt(s) were added thereto as an additive, and 0.25% by mass of a non-carbonate solvent was added thereto as an additive, thereby obtaining a nonaqueous electrolyte of Example 9.

[0119] Example 10

[0120] The steps of A, B and D of Example 1 were followed, except step C included:

[0121] In a nonaqueous solvent obtained by mixing EC, EMC and DMC in a volume ratio of 20: 10:70, LiPFe was dissolved as an electrolyte salt at a concentration of 3 mol / L, 10% by mass of a mixture of FEC and VC was used, up to 2.0 mass % of oxygenated lithium salt(s) were added thereto as an additive, and 0.25% by mass of a non-carbonate solvent was added thereto as an additive, thereby obtaining a nonaqueous electrolyte of Example 10.

[0122] Example 11

[0123] The steps of A, B and D of Example 1 were followed, except step C included:

[0124] In a nonaqueous solvent obtained by mixing EC, EMC and DMC in a volume ratio of 20: 10:70, LiPFe was dissolved as an electrolyte salt at a concentration of 5 mol / L, 10% by mass of a mixture of FEC and VC was used, and up to 2.0 mass % of oxygenated lithium salt(s) were added thereto as an additive, and 0.25% by mass of a non-carbonate solvent was added thereto as an additive, thereby obtaining a nonaqueous electrolyte of Example 11.

[0125] Example 12

[0126] The steps B and D of Example 1 and step C of Example 9 were followed, except step A included:

[0127] A positive electrode comprising Lithium-rich Lithium Nickel Cobalt Manganese Oxide (LiwNixCoyMnzO2, where w>l. l, 0.1<x<0.2, 0.05<y<0.15, 0.5<z<0.6) as the positive electrode active material, a first conductive additive - a point-type conductive additive a second conductive additive - a line-type conductive additive, a first PVDF binder having a lower molecular weight (600 to 750 kiloDaltons), and a second PVDF binder having a higher molecular weight (1,000 to 1,300 kiloDaltons) were combined together at a mass ratio of 97.5:0.5:0.7:1.1 :0.2. N- methylpyrrolidone (NMP) was used as the solvent to prepare a positive electrode slurry having a solid content of 70%. The positive electrode slurry was applied to a positive electrode current collector (Al) having a thickness of 12 pm and dried in a vacuum oven at 130° C. for 6 hours. Thereafter, the current collector was rolled between rolls heated to 60° C. under a pressure of 10 MPa to produce a positive electrode having a final active material layer thickness of 64 pm, a porosity of 23%, a density of 3.52 g / cm3, and a loading amount of the positive electrode active material layer of 22.55 mg / cm2. The total content of the remaining components (the conductive material and the binder) excluding the positive electrode active material in the positive electrode active material layer was 2.5 wt % with respect to the total weight of the positive electrode active material layer.

[0128] Effect of Non-Oxygenated Lithium Salt concentration on cycle life

[0129] Examples 13a-13j

[0130] The steps of Example 1 were followed, and further incorporated a coating modification compound (CM1) applied to two different cathode active materials comprising Li(Nio.8Mno.iCoo.i)02, one having a specific surface area of 0.50 m2 / g and another having a specific surface area of 0.85 m2 / g. An array of CM1 loadings were applied by repeating the steps as outlined in PCT / US24 / 13596 entitled “Large Scale System for Atomic Layer Deposition”, which is incorporated herein by reference in its entirety. For these examples, trimethylaluminum and water were used as precursors to produce aluminum oxide coatings resulting in a range of loadings (measured using ICP-OES in parts per million with respect to the total mass of the coated cathode active material). The Pauling Electronegativity (PE) constant known for aluminum is 1.61. In each case, cells were constructed for cycle life testing using cyclic voltammetry and measured at a 0.1 C-rate and at room temperature over a voltage range of 2.50-4.35V. The reported cycle life shown in the table below equates to the point at which the cell capacity reduced to a level of 80% of the starting capacity for that cell, rounded to the nearest five cycles.

[0131] Examples 14a-14j

[0132] The steps of Example 4 were followed, using the coated cathode materials of Examples 13a- 13j . In each case, cells were constructed for cycle life testing using cyclic voltammetry and measured at a 0.1 C-rate and at room temperature over a voltage range of 2.50-4.35V. The reported cycle life shown in the table below equates to the point at which the cell capacity reduced to a level of 80% of the starting capacity for that cell, rounded to the nearest five cycles. Examples 15a-15j

[0133] The steps of Example 5 were followed, using the coated cathode materials of Examples 13a-13j.

[0134] In each case, cells were constructed for cycle life testing using cyclic voltammetry and measured at a 0.1 C-rate and at room temperature over a voltage range of 2.50-4.35V. The reported cycle life shown in the table below equates to the point at which the cell capacity reduced to a level of 80% of the starting capacity for that cell, rounded to the nearest five cycles.

[0135] Examples 16a-16j

[0136] The steps of Example 7 were followed, using the coated cathode materials of Examples 13a-13j.

[0137] In each case, cells were constructed for cycle life testing using cyclic voltammetry and measured at a 0.1 C-rate and at room temperature over a voltage range of 2.50-4.35V. The reported cycle life shown in the table below equates to the point at which the cell capacity reduced to a level of 80% of the starting capacity for that cell, rounded to the nearest five cycles. Effect of CM1 Cation on cycle life at 0.1 C and 4C rates

[0138] Examples 17a-17j

[0139] The steps of Example 5 were followed, and further incorporated a coating modification compound (CM1) applied to the cathode active material comprising Li(Nio.8Mno.iCoo i)02 having a specific surface area of 0.85 m2 / g, and emulating the process to produce the material of Example 13i (here Example 17b), using known precursors for the deposition of an array of oxide layers comprising certain cation elements, each having a Pauling Electronegativity constant stated previously. In each case, cells were constructed for cycle life testing using cyclic voltammetry and measured at a 0.1 C-rate or a 4 C-rate at room temperature over a voltage range of 2.50-4.35V. The reported cycle life shown in the table below equates to the point at which the cell capacity reduced to a level of 80% of the starting capacity for that cell, rounded to the nearest five cycles.

[0140] Effect of CM2 Loading on cycle life at 0.1 C and 4C rates for two CM2 cations

[0141]

[0142] Effect of CM3 Loading on cycle life at 0.1 C and 4C rates for three CM3 cations, based on the materials of Examples 15c (CM1 = 310) and 18e (CM2 = 222)

Claims

What is claimed:

1. A lithium-ion secondary battery comprising a positive electrode plate, a negative electrode plate, a separator and a non-aqueous electrolyte solution, the non-aqueous electrolyte solution comprising a mixture of at least one non-oxygenated lithium salt, at least one oxygenated lithium salt, at least one carbonate solvent, and, optionally, at least one non-carbonate solvent; the positive electrode plate comprising a positive current collector and a positive film, the positive film is provided on at least one surface of the positive current collector and comprises a positive active material, the positive active material comprises one or more selected from the group consisting of LixNiaCobMncO2 and a doping and / or coating modified compound thereof wherein 0.95<x<1.2, 0<a<l, 0<b<l, 0<c<l, and Lithium-rich Lithium Nickel Cobalt Manganese Oxide and a doping and / or coating modified compound thereof (LiwNixCoyMnzO2, where w>l. l, 0.1<x<0.2, 0.05<y<0.15, 0.5<z<0.6); the density of the non-aqueous electrolyte solution represented by p ranges from 1.21 g / cm3to 1.36 g / cm3; and further characterized by one or more of the following: wherein the lithium-ion secondary battery satisfies a relationship: 1.08 < (m*C) / (pxCap) < 1.44, wherein m represents a total mass of the non-aqueous electrolyte solution inside the lithium-ion secondary battery with a unit of g, p represents a density of the non-aqueous electrolyte solution with a unit of g / cm3, C represents a concentration of the at least one non-oxygenated lithium salt in the non-aqueous electrolyte solution with a unit of mol / L, Cap represents a rated capacity of the lithium-ion secondary battery with a unit of Ah; and / or wherein the electrolyte has a mass per rated capacity of 1.25 g / Ah or less, and the rated capacity is measured using cyclic voltammetry measured at a 0.1 C-rate over a range of 2.5 to 4.35V over a 10 hour period at room temperature.

2. The lithium-ion secondary battery according to claim 1, wherein the negative electrode plate comprises a negative current collector and a negative film, the negative film is provided on at least one surface of the negative current collector and comprises a first negative active material and a second negative active material, the first negative active material at least comprises graphite, the second negative active material at least comprises silicon.

3. The lithium-ion secondary battery according to claim 2, wherein a coating weight of the negative fdm per unit area on one surface of the negative current collector is 0.006 g / cm2-0.015 g / cm2.

4. The lithium-ion secondary battery according to any of the above claims, wherein the coating weight of the negative fdm per unit area on one surface of the negative current collector is 0.008 g / cm2-0.010 g / cm2.

5. The lithium-ion secondary battery according to any of the above claims, wherein a pressing density of the negative fdm is 1.5 g / cm3-1.9 g / cm3.

6. The lithium-ion secondary battery according to any of the above claims, the lithium-ion secondary battery satisfies a relationship: 1.08 < (m*C) / (pxCap) < 1.44.

7. The lithium-ion secondary battery according to any of the above claims, wherein the concentration of the lithium salt in the electrolyte represented by C is 1.3 mol / L-5.0 mol / L.

8. The lithium-ion secondary battery according to any of the above claims, wherein the concentration of the lithium salt in the electrolyte represented by C is 1.5 mol / L-3.0 mol / L.

9. The lithium-ion secondary battery according to any of the above claims, wherein m / Cap is 1.0 g / Ah- 1.25 g / Ah.

10. The lithium-ion secondary battery according to any of the above claims, wherein m / Cap is 1.12 g / Ah- 1.22 g / Ah.

11. The lithium-ion secondary battery according to any of the above claims, wherein a pressing density of the positive fdm is 3.4 g / cm3-3.6 g / cm3.

12. The lithium-ion secondary battery according to any of the above claims, wherein a+b+c=l .

13. The lithium-ion secondary battery according to any of the above claims, wherein the battery is a cylindrical cell.

14. The lithium-ion secondary battery according to any of the above claims, wherein the battery is a pouch cell.

15. The lithium-ion secondary battery according to any of the above claims, wherein the battery is a prismatic cell.

16. The lithium-ion secondary battery according to any of the above claims, wherein the negative film comprises from 0.10 mass% to 0.20 mass% carbon nanotubes, and the positive film comprises from 0.6 mass% to 1.1 mass% carbon nanotubes.

17. A battery pack comprising the lithium-ion secondary battery according to any of the above claims.

18. A battery, comprising the lithium-ion secondary battery according to any of the above claims, comprising: a cylindrical container; an electrolyte disposed in the cylindrical container; a structure disposed in the cylindrical container, wherein the structure has a rolled shape with a spiral cross-section; a cathode comprising a cathode material disposed on a first substrate of the structure, wherein the cathode comprises the cathode material coupled to a cathode current collector; an anode comprising a first anode material; a separator disposed between the anode and the cathode, wherein the separator comprises a polymeric material or a ceramic material; and wherein the battery provides a gravimetric energy density of at least 300 watt hours per kilogram and at least 800 watt hours per liter, measured at a 0.1 C-rate and at room temperature over a voltage range of 2.50-4.35V.

19. The battery of claim 18, wherein the cathode material comprises at least one of Nickel- rich Lithium Nickel Cobalt Manganese Oxide and a doping and / or coating modified compound thereof (LixNiaCobMncO2, 0.95<x<1.2, 0.8<a<l, 0<b<0.1, 0<c<0.1) or Lithium-rich Lithium Nickel Cobalt Manganese Oxide and a doping and / or coating modified compound thereof (LiwNixCoyMnzO2, where w>l.l, 0.1<x<0.2, 0.05<y<0.15, 0.5<z<0.6).

20. The battery of any of claims 18-19, wherein the second anode material comprises at least one of: silicon carbide, silicon monoxide, silicon dioxide, or a silicon carbon composite.

21. The battery of claim 20, wherein a weight ratio of the first anode material to the second anode material is 1.81 to 2.75, 2.13 to 2.72 or 2.50 to 2.71.

22. The battery of claim 21, further comprising a cathode electrode tab or tabs coupled to the cathode and an anode electrode tab or tabs coupled to the anode.

23. The battery of claim 21, wherein the cathode electrode and / or anode electrode are tabless.

24. The battery of claim 21, wherein the cylindrical container is at least 18 millimeters in diameter and 65 millimeters in length and has a capacity of at least 3.7 amp hours, at least 21 millimeters in diameter and 70 millimeters in length and has a capacity of at least 5.6 amp hours, or at least 46 millimeters in diameter and at least 80 millimeters in length.

25. The battery of claim 24, wherein the battery is configured to be charged and discharged over a cell voltage between 2.5 volts and 4.35 volts, and wherein the battery maintains a capacity of at least 4.48 amp hours after 500 charge and discharge cycles at a 0.1 C-rate and at room temperature, or after 1,000 charge and discharge cycles at a 0.1 C-rate and at room temperature.

26. The battery of claim 21, wherein the container comprises steel or a steel alloy27. The battery of claim 21, wherein the container comprises aluminum or an aluminum alloy.

28. The battery of claim 21 , wherein the battery provides a gravimetric energy density of 300- 355 watt hours per kilogram, 305-345 watt hours per kilogram, or 302-308 watt hours per kilogram, measured at a 0.1 C-rate and at room temperature over a voltage range of 2.50-4.35 V.

29. A pack or module comprising the battery of claim 28.

30. A lithium ion rechargeable battery comprising: a cathode plate having a first face and a second face, and a cathode active material capable of occluding and releasing lithium ions disposed on both the first face and second face of the cathode plate, an anode plate having a first face and a second face, and a first anode active material and second anode active material capable of occluding and releasing lithium ions disposed on both the first face and the second face of the anode plate, a separator interposed between the cathode plate and the anode plate, and an electrolyte having lithium-ion conductivity; wherein the electrolyte comprises at least one oxygenated lithium salt selected from “LiFSI” (Lithium bisfluoro-sulfonylimide, LiF2S2NO4), “LiBETI” (lithium bisperfluoro-ethane- sulfonimide, LiN(C2F5SO2)2), “LiTFSI” (lithium (bis)trifluoro-methane-sulfonimide, LiN(CF3SO2)2, LiCF3SO3, LiC(CF3SO2)3, “LiDFOB” (LiC2BO4F2), “LiTFOP” (LiC2PO4F4), “LiDFBOP” (LiC4PO4F2), “LiDFP” (LiPO2F2), LiN(C2F5SO2)2, “LiBOB” (LiC4BO8) and mixtures thereof; wherein the cathode active material comprises a first coating modification compound (CM1) comprising one or more cations at a total cation loading of less than or equal to 2,300 parts per million (ppm) relative to the cathode active material on a mass basis (CMlppm) and converted to moles by multiplying mass of CM1 by the molecular weight of the one or more cations of CM1 (CMlmoi), and wherein CM1 has a weighted average oxidation state (CMlos) of the one or more cations of CMl as measured using X-ray photoelectron spectroscopy; wherein the first anode active material comprises a graphite material having a second coating modification compound (CM2) comprising one or more cations at a total cation loading of less than or equal to 1,200 parts per million (ppm) relative to the first anode active material on a mass basis (CM2ppm) and converted to moles by multiplying the mass of CM2 by the molecular weight(s) of the one or more cations of CM2 (CM2moi), and wherein CM2 has a weighted averageoxidation state (CM2os) of the one or more cations of CM2 as measured using X-ray photoelectron spectroscopy; and wherein the second anode active material comprises a silicon-comprising material having a third coating modification compound (CM3) comprising one or more cations at a total cation loading of less than or equal to 1,600 parts per million (ppm) relative to the second anode active material on a mass basis (CM3ppm) and converted to moles by multiplying the mass of CM3 by the molecular weight(s) of the one or more cations of CM3 (CM3moi), and wherein CM3 has a weighted average oxidation state (CM3os) of the one or more cations of CM3 as measured using X-ray photoelectron spectroscopy; and wherein the total moles of the at least one oxygenated lithium salt(s) is within +50% to +200% of: [CMlmoi• CMlos / 2 + CM2moi■ CM2os / 2 + CM3moi• CM3os / 2],31. The lithium ion rechargeable battery of claim 30, wherein the cathode active material comprises LixNiaMnbCocO2 where preferably a + b + c = 1, and satisfies the Formula of either:1) 0.95 < x < 1.2, 0.80 < a < 1, 0 < b < 0.1, 0 < c < 0.1; or2) x > 1.1, 0.1 < a < 0.2, 0.05 < b < 0.15, 0.5 < c < 0.6.

32. The lithium ion rechargeable battery of claim 30, wherein the electrolyte further comprises at least one non-oxygenated lithium salt, at least one oxygenated lithium salt, at least one carbonate solvent, and optionally at least one non-carbonate solvent, wherein the non-oxygenated lithium salt is present at a concentration of 1.3 M or above and 5.0 M or less in the electrolyte.

33. The lithium ion rechargeable battery of claim 30, wherein the ratio of the first anode active material to the second anode active material is 1.68 to 2.79, or 1.81 to 2.75, or 1.96 to 2.74, or 2.13 to 2.72, or 2.50 to 2.71.

34. The lithium ion rechargeable battery of claim 30, wherein the weight loading of the cathode active material and CM1 comprises at least 97.5% of the material disposed on each of the first face and second face of the cathode plate.

35. The lithium ion rechargeable battery of claim 30, wherein the cathode active material has a measurable specific surface area using the BET technique (“SA”) and wherein CMlppmon a mass basis as measured using ICP-OES satisfies the relationship 620 ppm < CMlppm / SA < 1150 ppm, where SA is the specific surface area of the cathode active material in units of m2 / g.

36. The lithium ion rechargeable battery of claim 30, wherein the sum of all Coating Modification Compounds (CMlppm+ CM2ppm+ CM3ppm) as measured using ICP-OES ranges from 500 to 3,000 ppm, or ranges from 650 to 2,600 ppm, or ranges from 800 to 2,400 ppm.

37. A lithium secondary battery comprising: a positive electrode having a positive-electrode active material capable of occluding and releasing lithium ions, a negative electrode having a negative-electrode active material capable of occluding and releasing lithium ions, a separator interposed between the positive electrode and the negative electrode, and an electrolyte having lithium-ion conductivity, wherein the electrolyte comprises a non-aqueous electrolyte solution comprising a mixture of at least one non-oxygenated lithium salt (“NOLS”) having a mass of lithium defined as LINOLS, at least one oxygenated lithium salt (“OLS”) having a mass of lithium defined as LioLs, at least one carbonate solvent, and optionally at least one non-carbonate solvent, wherein the NOLS is present at a concentration of 1.3 M or above and 5.0 M or less in the non-aqueous electrolyte solution, and the ratio of the total mass of lithium in the non-aqueous electrolyte solution, LiEiectroiyte (defined as LINOLS + Lio s) to the sum of the total mass of lithium in the non-aqueous electrolyte solution and mass of lithium in the positive-electrode active material, LICAM, satisfies the relationship:where C represents a concentration of the NOLS in the electrolyte with a unit of mol / L and ranges from 1.3 < C < 5.0, 0.12 < A < 0.20, and B = 0.63.

38. The lithium ion secondary battery of claim 37, wherein the at least one non-oxygenated lithium salt, NOLS, is selected from one or more of LiPFe, LiBF4, LiSbFe, and LiAsFe, and mixtures thereof.

39. The lithium ion secondary battery of claim 37, wherein the at least one oxygenated lithium salt, OLS, is selected from “LiFSI” (Lithium bisfluoro-sulfonylimide, LiF2S2NO4), “LiBETI” (lithium bisperfluoro-ethane-sulfonimide, LiN^FsSCh^), “LiTFSI” (lithium (bis)trifluoro- methane-sulfonimide, LiN(CF3SO2)2, LiCF3SO3, LiC(CF3SO2)3, “LiDFOB” (LiC2BO4F2), “LiTFOP” (LiC2PO4F4), “LiDFBOP” (LiC4PO4F2), “LiDFP” (LiPO2F2), LiN(C2F5SO2)2, “LiBOB” (LiC4BOs) and mixtures thereof.

40. The lithium ion secondary battery of claim 37, wherein the at least one carbonate solvent is selected from butylene carbonate, 2,3 -butylene carbonate, iso-butylene carbonate, dimethyl carbonate, ethylene carbonate, ethyl methyl carbonate, fluoroethylene carbonate, difluoroethylene carbonate, propylene carbonate, and mixtures thereof.

41. The lithium ion secondary battery of claim 37, wherein the optional at least one noncarbonate solvent is selected from y-butyrolactone, sulfolane, butanedinitrile, malononitrile, glutaronitrile, adiponitrile, suberonitrile, sebaconitrile, and mixtures thereof.

42. The lithium ion secondary battery of claim 37, wherein each non-oxygenated lithium salt, NOLS, and each oxygenated lithium salt, OLS, can be further described as consisting of a positively charged lithium cation and a negatively-charged anion, the total mass of all positively charged lithium cations of all non-oxygenated lithium salt(s), LINOLS, and all oxygenated lithium salt(s), LioLs, in the non-aqueous electrolyte solution defines LiEiectroiyte.

43. The lithium ion secondary battery of claim 37, wherein the non-oxygenated lithium salt is present at a concentration of 1.3 M or above and 5.0 M or less, or 1.5 M or above and 3.0 M or less in the non-aqueous electrolyte solution.

44. The lithium ion secondary battery of claim 37, wherein the battery comprises a cylindrical container having dimensions of at least 18 millimeters in diameter and 65 millimeters in length, or at least 21 millimeters in diameter and 70 millimeters in length, or at least 46 millimeters in diameter and at least 80 millimeters in length.

45. The lithium ion secondary battery of claim 37, wherein the weight percentage of the at least one oxygenated lithium salt comprises 2 percent or less of the total weight of the non-aqueous electrolyte solution.

46. The lithium ion secondary battery of claim 37, wherein the mass of boron relative to the total mass of lithium in the non-aqueous electrolyte solution is at most 0.06-LiEiectroiyte, and / or the mass of phosphorous relative to the total mass of lithium in the non-aqueous electrolyte solution is at least 429-LiEiectroiyte., and / or the mass of fluorine relative to the total mass of lithium in the non-aqueous electrolyte solution is at least 1633-LiEiectroiyte.

47. The lithium ion secondary battery of claim 37, wherein the positive-electrode active material is a cathode active material and comprises LixNiaMnbCocCMldO2 where CM1 represents one or more cations of a first coating modification compound thereon where preferably a + b + c = 1 and d < 2,300 parts per million (ppm) relative to the cathode active material on a mass basis, and satisfies the Formula of either:1) 0.95 < x < 1.2, 0.80 < a < 1, 0 < b < 0.1, 0 < c < 0.1; or2) x > 1.1, 0.1 < a < 0.2, 0.05 < b < 0.15, 0.5 < c < 0.6; wherein the graphite material having second coating modification compound thereon (CM2), where CM2 represents one or more cations of a second coating modification compound, wherein the cations of CM2 comprise less than 1,200 parts per million relative to the graphite material on a mass basis, and a silicon-comprising material and a third coating modification compound thereon (CM3), where CM3 represents one or more cations of a third coating modification compound, wherein the cations of CM3 comprise less than 1,600 parts per million relative to the silicon- comprising material on a mass basis.

48. The lithium ion secondary battery of any of the above claims, wherein the positive electrode active material, the graphite material and the silicon-comprising material have a measurable specific surface area using the BET technique and wherein the parts per million of the cations of CM1 on a mass basis as measured using ICP-OES satisfies the relationship 620 ppm <CMld / SA < 1 150 ppm, where SA is the specific surface area of the cathode active material in units of m2 / g.

49. The lithium ion secondary battery of any of the above claims, wherein the graphite material comprises natural graphite and CM2 ranges from 25 to 350 ppm, or 30 to 75 ppm, or 250 to 350 ppm; or wherein the graphite material comprises synthetic or artificial graphite, and CM2 ranges from 600 to 1200 ppm, or 700 to 1100 ppm, or 800 to 900 ppm.

50. The lithium ion secondary battery of any of the above claims, wherein CM1, CM2 and / or CM3 further comprise lithium within each coating modification compound, provided that the loading of lithium is not included in the satisfying criteria calculation provided herein for CM1, CM2 or CM3.

51. A lithium ion rechargeable battery comprising: a cathode plate having a first face and a second face, and a cathode active material capable of occluding and releasing lithium ions disposed on both the first face and second face of the cathode plate, an anode plate having a first face and a second face, and an anode active material capable of occluding and releasing lithium ions disposed on both the first face and the second face of the anode plate, a separator interposed between the cathode plate and the anode plate, and an electrolyte having lithium-ion conductivity; wherein the cathode active material comprises LixNiaMnbCocCMldO2 where CM1 represents one or more cations of a first coating modification compound thereon where preferably a + b + c = 1 and d < 2,300 parts per million (ppm) relative to the cathode active material on a mass basis, and satisfies the Formula of either:1) 0.95 < x < 1.2, 0.80 < a < 1, 0 < b < 0.1, 0 < c < 0.1; or2) x > 1.1, 0.1 < a < 0.2, 0.05 < b < 0.15, 0.5 < c < 0.6; wherein the anode comprises a first anode active material comprising a graphite material having second coating modification compound thereon (CM2), where CM2 represents one or more cations of a second coating modification compound, wherein the cations of CM2 comprise less than 1,200 parts per million relative to the first anode material on a mass basis, and a second anode active material comprising silicon and carbon and a third coating modification compound thereon (CM3),where CM3 represents one or more cations of a third coating modification compound, wherein the cations of CM3 comprise less than 1,600 parts per million relative to the second anode material on a mass basis; wherein the cathode active material, the first anode active material and the second anode active material have a measurable specific surface area using the BET technique and wherein the parts per million of the cations of CM1 on a mass basis as measured using ICP-OES satisfies the relationship 620 ppm < CMld / SA < 1150 ppm, where SA is the specific surface area of the cathode active material in units of m2 / g; and wherein the molar average Pauling electronegativity (known constants) of the one or more cations of CM1 is between 1.22 and 1.66, and / or range from 0.21 to 0.65 below the molar average electronegativity of the cations of the cathode active material (1.87 for Formula 1 wherein a = 0.8, b = 0.1 and c = 0.1).

52. The lithium ion rechargeable battery of claim 51, wherein the cations of CM1 comprise one or more of Y (1.22), Hf (1.30), Mg (1.31), Zr (1.33), Sc (1.36), Ta (1.50), Ti (1.54), Nb (1.60), Al (1.61), Tl (1.62), V (1.63), Zn (1.65) and Cr (1.66), wherein the Pauling Electronegativity of each cation is listed in parentheses.

53. The lithium ion rechargeable battery of claim 51, wherein the cations of CM1 satisfy the relationship 100 < CMlppm / PE < 900, preferably 150 < CMlppm / PE < 780, and sometimes 200 < CMlppm / PE < 560.

54. The lithium ion rechargeable battery of claim 51, wherein the first anode material comprises natural graphite and CM2 ranges from 25 to 350 ppm, or 30 to 75 ppm, or 250 to 350 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.60 to 1.66; or wherein the first anode material comprises synthetic or artificial graphite, and CM2 ranges from 600 to 1200 ppm, or 700 to 1100 ppm, or 800 to 900 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.60 to 1.66.

55. The lithium ion rechargeable battery of claim 51, wherein CM2 ranges from 450 to 1 ,600 ppm, or 500 to 1,500 ppm, or 600 to 1,400 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.22 to 1.60.

56. The lithium ion rechargeable battery of claim 51, wherein CM3 ranges from 25 to 350 ppm, or 80 to 275 ppm, or 150 to 240 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.60 to 1.66.

57. The lithium ion rechargeable battery of claim 51, wherein CM3 ranges from 450 to 1,600 ppm, or 500 to 1,500 ppm, or 600 to 1,400 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.22 to 1.60.

58. The lithium ion rechargeable battery of claim 51, wherein CM1, CM2 and / or CM3 further comprise lithium within each coating modification compound, provided that the loading and electronegativity of lithium is not included in the satisfying criteria calculation provided herein for CM1, CM2 or CM3.

59. A lithium ion rechargeable battery comprising: a cathode plate having a first face and a second face, and a cathode active material capable of occluding and releasing lithium ions disposed on both the first face and second face of the cathode plate, an anode plate having a first face and a second face, and an anode active material capable of occluding and releasing lithium ions disposed on both the first face and the second face of the anode plate, a separator interposed between the cathode plate and the anode plate, and an electrolyte having lithium-ion conductivity; wherein the cathode active material comprises LixNiaMnbCocCMldCh where CMl represents one or more cations of a first coating modification compound thereon where preferably a + b + c = 1 and d < 2,300 parts per million (ppm) relative to the cathode active material on a mass basis, and satisfies the Formula of either:1) 0.95 < x < 1.2, 0.80 < a < 1, 0 < b < 0.1, 0 < c < 0.1; or2) x > 1.1, 0.1 < a < 0.2, 0.05 < b < 0.15, 0.5 < c < 0.6;wherein the anode comprises a first anode active material comprising a graphite material having second coating modification compound thereon (CM2), wherein the cations of CM2 comprise less than 1,200 parts per million relative to the first anode material on a mass basis, and a second anode active material comprising silicon and carbon and a third coating modification compound thereon (CM3), wherein the cations of CM3 comprise less than 1,600 parts per million relative to the second anode material on a mass basis; wherein the cathode active material, the first anode active material and the second anode active material have a measurable specific surface area using the BET technique and wherein the parts per million of the cations of CM1 on a mass basis as measured using ICP-OES satisfies the relationship 620 ppm < CMla / SA < 1150 ppm, where SA is the specific surface area of the cathode active material in units of m2 / g; and wherein the first ionization of each of the one or more cations of CM1 is 745 kJ / mol or lower, which is the approximate threshold that will allow the first ionization energy of the one or more cations of CM1 to remain below that of Ni, Mn and Co cations of the Ni-rich cathode active material (approximately 750 kJ / mol or higher).

60. The lithium ion rechargeable battery of claim 59, wherein the cations of CM1 having a first ionization energy of 745 kJ / mol or lower, are selected from one or more of Y, Hf, Mg, Zr, Sc, Ti, Nb, Al, V and Cr.

61. The lithium ion rechargeable battery of claim 59, wherein the first anode material comprises natural graphite and CM2 ranges from 25 to 350 ppm, or 30 to 75 ppm, or 250 to 350 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.60 to 1.66; or wherein the first anode material comprises synthetic or artificial graphite, and CM2 ranges from 400 to 1200 ppm, or 500 to 1100 ppm, or 600 to 900 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.60 to 1.66.

62. The lithium ion rechargeable battery of claim 59, wherein CM2 ranges from 450 to 1,600 ppm, or 500 to 1,500 ppm, or 600 to 1,400 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.22 to 1.60.

63. The lithium ion rechargeable battery of claim 59, wherein CM3 ranges from 25 to 350 ppm, or 80 to 275 ppm, or 150 to 240 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.60 to 1.66.

64. The lithium ion rechargeable battery of claim 59, wherein CM3 ranges from 450 to 1,600 ppm, or 500 to 1,500 ppm, or 600 to 1,400 ppm, for cations having a stoichiometric average Pauling Electronegativity (PE) ranging from 1.22 to 1.60.

65. The lithium ion rechargeable battery of claim 59, wherein CM1, CM2 and / or CM3 further comprise lithium within each coating modification compound, provided that the loading and electronegativity of lithium is not included in the satisfying criteria calculation provided herein for CM1, CM2 or CM3.

66. The lithium ion rechargeable battery of any of the above claims, wherein the ratio of the first anode active material to the second anode active material is 1.68 to 2.79, or 1.81 to 2.75, or 1.96 to 2.74, or 2.13 to 2.72, or 2.50 to 2.71.

67. The lithium ion rechargeable battery of any of the above claims, wherein the weight loading of the cathode active material and CM1 comprises at least 97.5% of the material disposed on each of the first face and second face of the cathode plate.

68. The lithium ion rechargeable battery of any of the above claims, wherein the ratio of the first anode active material to the second anode active material is 1.68 to 2.79, or 1.81 to 2.75, or 1.96 to 2.74, or 2.13 to 2.72, or 2.50 to 2.71.

69. The lithium ion rechargeable battery of any of the above claims, wherein the weight loading of the cathode active material and CM1 comprises at least 97.5% of the material disposed on each of the first face and second face of the cathode plate.

70. A lithium ion rechargeable battery comprising:a cathode plate having a first face and a second face, and a cathode active material capable of occluding and releasing lithium ions disposed on both the first face and second face of the cathode plate, an anode plate having a first face and a second face, and an anode active material capable of occluding and releasing lithium ions disposed on both the first face and the second face of the anode plate, a separator interposed between the cathode plate and the anode plate, and an electrolyte having lithium-ion conductivity; wherein the electrolyte comprises at least one oxygenated lithium salt selected from “LiFSI” (Lithium bisfluoro-sulfonylimide, LiF2S2NO4), “LiBETI” (lithium bisperfluoro-ethane- sulfonimide, LiN(C2FsSO2)2), “LiTFSI” (lithium (bis)trifluoro-methane-sulfonimide, LiN(CF3SO2)2, LiCF3SO3, LiC(CF3SO2)3, “LiDFOB” (LiC2BO4F2), “LiTFOP” (LiC2PO4F4), “LiDFBOP” (LiC4PO4F2), “LiDFP” (LiPO2F2), LiN(C2F5SO2)2, “LiBOB” (LiC4BO8) and mixtures thereof; wherein the cathode active material comprises a first coating modification compound (CM1) comprising one or more cations at a total cation loading of less than or equal to 2,300 parts per million (ppm) relative to the cathode active material on a mass basis (CMlppm) and converted to moles by multiplying mass of CM1 by the molecular weight of the one or more cations of CM1 (CMlmoi), and wherein CM1 has a weighted average oxidation state (CMlos) of the one or more cations of CM1 as measured using X-ray photoelectron spectroscopy; wherein the anode active material comprises a second coating modification compound (CM2) comprising one or more cations at a total cation loading of less than or equal to 1,600 parts per million (ppm) relative to the anode active material on a mass basis (CM2ppm) and converted to moles by multiplying the mass of CM2 by the molecular weight(s) of the one or more cations of CM2 (CM2moi), and wherein CM2 has a weighted average oxidation state (CM2os) of the one or more cations of CM2 as measured using X-ray photoelectron spectroscopy; and wherein the total moles of the at least one oxygenated lithium salt(s) is within ± 50% of: [CMlmoi • CMlos / 2 + CM2moi • CM2os / 2],71. The lithium ion rechargeable battery of claim 70, wherein the cathode active material comprises LixNiaMnbCocO2 where preferably a + b + c = 1, and satisfies the Formula of either:1) 0.95 < x < 1.2, 0.80 < a < 1, 0 < b < 0.1, 0 < c < 0.1; or2) x > 1.1, 0.1 < a < 0.2, 0.05 < b < 0.15, 0.5 < c < 0.6.

72. The lithium ion rechargeable battery of claim 70, wherein the electrolyte further comprises at least one non-oxygenated lithium salt, at least one oxygenated lithium salt, at least one carbonate solvent, and optionally at least one non-carbonate solvent, wherein the non-oxygenated lithium salt is present at a concentration of 1.3 M or above and 5.0 M or less in the electrolyte.

73. The lithium ion rechargeable battery of claim 70, wherein the weight loading of the cathode active material and CM1 comprises at least 97.5% of the material disposed on each of the first face and second face of the cathode plate.

74. The lithium ion rechargeable battery of claim 71, wherein the cathode active material has a measurable specific surface area using the BET technique (“SA”) and wherein CMlppmon a mass basis as measured using ICP-OES satisfies the relationship 620 ppm < CMlppm / SA < 1150 ppm, where SA is the specific surface area of the cathode active material in units of m2 / g.

75. The lithium ion rechargeable battery of claim 70, wherein the sum of all Coating Modification Compounds (CMlppm+ CM2ppm) as measured using ICP-OES ranges from 500 to 3,000 parts per million (ppm), or ranges from 650 to 2,600 ppm, or ranges from 800 to 2,400 ppm.

76. A lithium ion rechargeable battery comprising: a cathode plate having a first face and a second face, and a cathode active material capable of occluding and releasing lithium ions disposed on both the first face and second face of the cathode plate, an anode plate having a first face and a second face, and a first anode active material and second anode active material capable of occluding and releasing lithium ions disposed on both the first face and the second face of the anode plate, a separator interposed between the cathode plate and the anode plate, and an electrolyte having lithium-ion conductivity; wherein the electrolyte comprises at least one oxygenated lithium salt selected from “LiFSI” (Lithium bisfluoro-sulfonylimide, LiF2S2NO4), “LiBETI” (lithium bisperfluoro-ethane- sulfonimide, LiN^FsSCh^), “LiTFSI” (lithium (bis)trifluoro-methane-sulfonimide, LiN(CF3SO2)2, LiCF3SO3, LiC(CF3SO2)3, “LiDFOB” (LiC2BO4F2), “LiTFOP” (LiC2PO4F4),“LiDFBOP” (LiC4PO4F2), “LiDFP” (LiPO2F2), LiN(C2F5SO2)2, “LiBOB” (LiC4BO8) and mixtures thereof; wherein the cathode active material comprises a first coating modification compound (CM1) comprising one or more cations at a total cation loading of less than or equal to 2,300 parts per million (ppm) relative to the cathode active material on a mass basis (CMlppm) and converted to moles by multiplying mass of CM1 by the molecular weight of the one or more cations of CM1 (CMlmoi), and wherein CM1 has a weighted average oxidation state (CMlos) of the one or more cations of CM1 as measured using X-ray photoelectron spectroscopy; wherein the first anode active material comprises a graphite material having a second coating modification compound (CM2) comprising one or more cations at a total cation loading of less than or equal to 1,200 parts per million (ppm) relative to the first anode active material on a mass basis (CM2ppm) and converted to moles by multiplying the mass of CM2 by the molecular weight(s) of the one or more cations of CM2 (CM2moi), and wherein CM2 has a weighted average oxidation state (CM2os) of the one or more cations of CM2 as measured using X-ray photoelectron spectroscopy; and wherein the second anode active material comprises a silicon-comprising material having a third coating modification compound (CM3) comprising one or more cations at a total cation loading of less than or equal to 1,600 parts per million (ppm) relative to the second anode active material on a mass basis (CM3ppm) and converted to moles by multiplying the mass of CM3 by the molecular weight(s) of the one or more cations of CM3 (CM3moi), and wherein CM3 has a weighted average oxidation state (CM3os) of the one or more cations of CM3 as measured using X-ray photoelectron spectroscopy; and wherein the total moles of the at least one oxygenated lithium salt(s) is within -50% to 200% (or within ± 50%) of: [CMlmoi■ CMlos / 2 + CM2moi• CM2os / 2 + CM3moi• CM3os / 2],77. The lithium ion rechargeable battery of claim 76, wherein the cathode active material comprises LixNiaMnbCocO2where preferably a + b + c = 1, and satisfies the Formula of either:1) 0.95 < x < 1.2, 0.80 < a < 1, 0 < b < 0.1, 0 < c < 0.1; or2) x > 1.1, 0.1 < a < 0.2, 0.05 < b < 0.15, 0.5 < c < 0.6.

78. The lithium ion rechargeable battery of claim 76, wherein the electrolyte further comprises at least one non-oxygenated lithium salt, at least one oxygenated lithium salt, at least one carbonate solvent, and optionally at least one non-carbonate solvent, wherein the non-oxygenated lithium salt is present at a concentration of 1.3 M or above and 5.0 M or less in the electrolyte.

79. The lithium ion rechargeable battery of claim 76, wherein the ratio of the first anode active material to the second anode active material is 1.68 to 2.79, or 1.81 to 2.75, or 1.96 to 2.74, or 2.13 to 2.72, or 2.50 to 2.71.

80. The lithium ion rechargeable battery of claim 76, wherein the weight loading of the cathode active material and CM1 comprises at least 97.5% of the material disposed on each of the first face and second face of the cathode plate.

81. The lithium ion rechargeable battery of claim 77, wherein the cathode active material has a measurable specific surface area using the BET technique (“SA”) and wherein CMlppmon a mass basis as measured using ICP-OES satisfies the relationship 620 ppm < CMlppm / SA < 1150 ppm, where SA is the specific surface area of the cathode active material in units of m2 / g.

82. The lithium ion rechargeable battery of claim 76, wherein the sum of all Coating Modification Compounds (CMlppm+ CM2ppm+ CM3ppm) as measured using ICP-OES ranges from 500 to 3,000 ppm, or ranges from 650 to 2,600 ppm, or ranges from 800 to 2,400 ppm.

83. The lithium ion secondary battery of any of the above claims, wherein the positiveelectrode active material comprises at least one of: Nickel-rich Lithium Nickel Cobalt Manganese Oxide and a doping and / or coating modified compound thereof (LixNiaCobMncO2, 0.95<x<1.2, 0.8<a<l, 0<b<0.1, 0<c<0.1) or Lithium-rich Lithium Nickel Cobalt Manganese Oxide and a doping and / or coating modified compound thereof (LiwNixCoyMnzO2, where w>l .l, 0.1<x<0.2, 0.05<y<0.15, 0.5<z<0.6); the negative-electrode active material contains a mixture containing a graphite material and a silicon-comprising material, wherein the ratio of the graphite material to the silicon-comprising material is 1.68 to 2.79, or 1.81 to 2.75, or 1.96 to 2.74, or 2.13 to 2.72, or 2.50 to 2.71.

84. The lithium ion secondary battery of any of the above claims, wherein the ratio of Li in the electrolyte to total Li in the cell is in the range of 0.13 to 0.54 and non-oxygenated Li salt concentration is in the range of 1 to 5 mol / L.

85. The lithium ion secondary battery of any of the above claims, wherein non-oxygenated Li salt concentration (defined as x) is in the range of 1 to 5 mol / L; and the ratio of Li in the electrolyte to total Li in the cell (defined as y) is in the range of y = O.2Ox0 63to O.12x063.