DOPED NICKEL-RICH CATHODE ACTIVE MATERIALS AND COATED NICKEL-RICH CATHODE ACTIVE MATERIALS AND METHODS THEREOF

Abstract

Doped and coated nickel-rich cathode active materials and methods of manufacture are described that enable energy storage devices with improved performance, including but not limited to improved energy density and capacity retention.

Description

[Technical field]

[0001] [CROSS REFERENCE TO RELATED APPLICATIONS] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 266,506, entitled “DOPED AND COATED NICKEL-RICH CATHODE ACTIVE MATERIALS AND METHODS THEREOF,” filed January 6, 2022, the entire contents of which are incorporated herein by reference. [Background technology]

[0002] The present disclosure relates generally to energy storage devices, and more particularly to cathode active materials for lithium ion batteries and processes for forming the same.

[0003] Electrochemical energy storage systems are widely used to power electronic devices, electromechanical devices, electrochemical devices, and other useful devices. Lithium-ion batteries are one of the most common examples of electrochemical energy storage systems, and the popularity of lithium-ion batteries is due to their higher energy density compared to other electrochemical energy storage systems. Over the past decade, the use of lithium-ion batteries has expanded from home appliances to other areas, including the automotive industry. Lithium-ion batteries consist of four main components: a cathode electrode, an anode electrode, an electrolyte, and a separator, and the success of lithium-ion batteries can be at least partially attributed to the development of high-energy-density electrodes.

[0004] Currently, there are only a few cathode active materials known or under consideration for use in cathode electrodes for lithium ion batteries, for example in the automotive industry. Examples of cathode active materials include LiNiO2 (LNO), LiNi 1-x-y Co x Al y O2(NCA) or LiNi 1-x-y Co x Mny These nickel-rich cathode active materials can provide high energy density in part due to their high nickel content. Although these nickel-rich cathode active materials show great promise, they also have drawbacks, including a significant loss of charge capacity over repeated charge / discharge cycles. Thus, there is a need for the development of improved nickel-rich cathode active materials. Summary of the Invention [Means for solving the problem]

[0005] For purposes of summarizing the advantages achieved over the disclosure and the prior art, certain objects and advantages of the disclosure are described herein. Not all such objects or advantages may be achieved in any particular embodiment. Thus, for example, one skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught herein, without necessarily achieving other objects or advantages as may be taught or suggested herein.

[0006] In a first aspect, a doped nickel-rich cathode active material is provided. The doped nickel-rich cathode active material has the formula LiNi a Tm b M c O2 (wherein Tm is a transition metal element, M is a dopant element, a is a value of at least 0.9, b is a value of 0.01 to 0.0995, and c is a value of 0.005 to 0.02).

[0007] In some embodiments, the dopant element is selected from the group consisting of Ca, Mg, Zr, and combinations thereof. In some embodiments, the dopant element is Zr and another element selected from the group consisting of Ca, Mg, and combinations thereof. In some embodiments, the compound comprises an atomic weight of Zr of at least about 0.003. In some embodiments, the transition metal element is selected from the group consisting of Al, Zr, Mn, Ti, Co, and combinations thereof. In some embodiments, the transition metal element is Al. x (wherein x is a value between 0.01 and 0.03). In some embodiments, the transition metal element is Mn y Co z (wherein y is a value between 0 and 0.05 and z is a value between 0 and 0.05). In some embodiments, the transition metal element is Al x Mn y Co z where x is a value between 0.01 and 0.03, y is a value between 0.01 and 0.05, and z is a value between 0.01 and 0.05. In some embodiments, the nickel-rich cathode active material further comprises a coating material disposed on the nickel-rich cathode active material. In some embodiments, the coating material is selected from the group consisting of a sulfur compound, a metal compound, and combinations thereof.

[0008] In some embodiments, the electrode film comprises the provided doped nickel-rich cathode active material. In some embodiments, the electrode film is disposed on a current collector forming a nickel-rich cathode electrode. In some embodiments, the energy storage device comprises a nickel-rich cathode electrode, a separator, an anode electrode, an electrolyte, and a housing, the nickel-rich cathode electrode, the separator, and the anode electrode disposed within the housing. In some embodiments, the energy storage device is a battery.

[0009] In a second aspect, a coated nickel-rich cathode active material is provided, the coated nickel-rich cathode active material further comprising a nickel-rich cathode active material and a sulfur coating disposed on the nickel-rich cathode active material.

[0010] In some embodiments, the coated nickel-rich cathode active material further comprises a metal coating. In some embodiments, the sulfur coating comprises a compound selected from the group consisting of dimethyl sulfone, dimethyl sulfoxide, sulfur nanoparticles, sodium dodecyl sulfate, sodium sulfate, lithium sulfate, and combinations thereof. In some embodiments, the metal coating comprises an element selected from the group consisting of Al, W, Mo, and combinations thereof. In some embodiments, the coating comprises multiple coating layers. In some embodiments, the nickel-rich cathode active material further comprises a dopant element.

[0011] In a third aspect, a method for preparing a doped nickel-rich cathode active material is provided, the method comprising mixing a nickel-rich precursor with a dopant material and a lithium source to form a lithiated nickel-rich precursor mixture, and heating the lithiated nickel-rich precursor mixture to form the doped nickel-rich cathode active material.

[0012] In some embodiments, the method further includes disposing a sulfur coating material on the doped nickel-rich cathode active material.

[0013] In a fourth aspect, a method for preparing a coated nickel-rich cathode active material is provided, the method including mixing a nickel-rich cathode active material with a sulfur coating material to form a nickel-rich cathode active material mixture, where the sulfur coating material is disposed on the nickel-rich cathode active material, and heating the nickel-rich cathode active material mixture to form the coated nickel-rich cathode active material.

[0014] In some embodiments, the nickel-rich cathode active material further comprises a dopant element.

[0015] All of these embodiments are intended to be within the scope of the invention disclosed herein. These and other embodiments will become readily apparent to those of ordinary skill in the art from the following detailed description of the preferred embodiments, taken in conjunction with the accompanying drawings, and the invention is not limited to any particular preferred embodiment disclosed. [Brief description of the drawings]

[0016] [Figure 1] FIG. 2 is a schematic diagram illustrating a process for forming a doped nickel-rich cathode active material according to some embodiments.

[0017] [Diagram 2] FIG. 2 is a schematic diagram illustrating a process for forming a coated nickel-rich cathode active material according to some embodiments.

[0018] [Diagram 3] 1 is an XRD pattern plot of a nickel-rich cathode active material according to some embodiments.

[0019] [Figure 4] 1 is a plot showing the effect of doping a nickel-rich cathode active material with calcium on normalized half-cell discharge capacity according to some embodiments.

[0020] [Diagram 5] 1 is a plot showing the effect of doping a nickel-rich cathode active material with calcium on normalized full cell discharge energy according to some embodiments.

[0021] [Figure 6]1 is a plot showing the effect of coating a nickel-rich cathode active material with sulfur on normalized half-cell discharge capacity according to some embodiments.

[0022] [Figure 7] 1 is a plot showing the effect of coating a nickel-rich cathode active material with sulfur on normalized full cell cathode discharge energy according to some embodiments.

[0023] [Figure 8A] 1 is a plot showing the effect of coating a nickel-rich cathode active material with a metal on normalized half-cell discharge capacity according to some embodiments.

[0024] [Figure 8B] 1 is a plot showing the effect of coating a nickel-rich cathode active material with a metal on the average charge voltage-average discharge voltage of a half-cell according to some embodiments.

[0025] [Figure 9] 1 is a plot showing the effect of coating a calcium-doped nickel-rich cathode active material with sulfur on normalized half-cell discharge capacity according to some embodiments.

[0026] [Figure 10] 1 is a plot showing the effect of coating a calcium-doped nickel-rich cathode active material with sulfur on normalized full cell cathode discharge energy according to some embodiments.

[0027] [Figure 11A] 1 is a plot showing the effect of including various transition metals in a nickel-rich cathode active material on normalized half-cell discharge capacity, according to some embodiments.

[0028] [Figure 11B]1 is a plot showing the effect of including various transition metals in a nickel-rich cathode active material on the charge voltage-discharge voltage of a half-cell according to some embodiments.

[0029] [Figure 12] 1 is a plot showing the effect of including various transition metals in a nickel-rich cathode active material on normalized full cell cathode energy, according to some embodiments. Detailed Description of the Invention

[0030] Various embodiments of nickel-rich cathode active materials with improved discharge capacity and capacity retention, as well as methods for preparing nickel-rich cathode active materials, are provided herein. Such nickel-rich cathode active materials may be doped and / or coated to 1) reduce the intermixing of lithium and nickel atoms within the crystal lattice, and 2) reduce oxygen mobility or evolution at the cathode electrode surface during cycling. Thus, the improved nickel-rich cathode active materials described herein may be used to reduce electrical resistance and improve cycle life in energy storage devices.

[0031] In certain embodiments, the nickel-rich cathode active material has the general formula LiNi a O2 or LiNi a Tm b O2 (wherein "a" is at least 0.8, or at least about 0.8, and "Tm" is at least one transition metal element). For example, such nickel-rich cathode active materials include LiNi 1-x-y Co x Al y O2 ("NCA") and LiNi 1-x-y Co x Mn y O2 ("NCM").

[0032] In certain embodiments, the nickel-rich cathode active material can include a dopant material. In some embodiments, the dopant material can be a metal (M), a metal oxide (M y Oz ), metal hydroxide (M y (OH) z ), and combinations thereof, where "M" represents a metal and "y" and "z" are values ​​that produce a neutrally charged dopant material. In some embodiments, the dopant material comprises a metal ("M") selected from calcium (Ca), magnesium (Mg), zirconium (Zr), and combinations thereof. In some embodiments, the dopant material comprises Zr and a metal selected from calcium (Ca), magnesium (Mg), and combinations thereof.

[0033] In certain embodiments, the nickel-rich cathode active material may include a coating material. In some embodiments, the coating material includes a sulfur compound, a metal compound, and combinations thereof. In some embodiments, the sulfur compound is selected from dimethyl sulfone (DMS), dimethyl sulfoxide (DMSO), and combinations thereof. In some embodiments, the metal compound includes a metal selected from tungsten (W), molybdenum (Mo), aluminum (Al), and combinations thereof.

[0034] In some embodiments, the nickel-rich cathode active material can include a dopant material and a coating material. Such doped and coated nickel-rich cathode active materials are described and can be prepared by the processes described herein. DOPED NICKEL-RICH CATHODE ACTIVE MATERIAL AND PROCESS THEREOF - Patent application

[0035] High nickel content ("nickel-rich") cathode active materials may include dopants to improve the performance of the cathode electrode. In some embodiments, the nickel-rich cathode active material includes lithium (Li), nickel (Ni), a dopant element (M), and oxygen (O). In some embodiments, the nickel-rich cathode active material further includes a transition metal element (Tm). In some embodiments, the nickel-rich cathode active material includes LiNia Z c O2, LiNi a Tm b Z c O2 or a combination thereof. In some embodiments, the nickel-rich cathode active material may include LiNi a M c O2, LiNi a Tm b M c O2 or combinations thereof. In some embodiments, "a" is 0.7, 0.75, 0.8, 0.85, 0.9, 0.92, 0.95, 0.98, or 0.99, or any range of values ​​therebetween; about 0.7, about 0.75, about 0.8, about 0.85, about 0.9, about 0.92, about 0.95, about 0.98, or about 0.99, or any range of values ​​therebetween; at least 0.7, at least 0.75, at least 0.8, at least 0.85, at least 0.9, at least 0.92, at least 0.95, at least 0.98, or at least 0.99, or any range of values ​​therebetween; or at least about 0.7, at least 0.75, at least about 0.8, at least about 0.85, at least about 0.9, at least about 0.92, at least about 0.95, at least about 0.98, or at least about 0.99, or any range of values ​​therebetween. For example, in some embodiments, "a" is a number between 0.7 and 0.99, between 0.85 and 0.95, or between 0.9 and 0.99. In some embodiments, the transition metal element ("Tm") is selected from aluminum (Al), manganese (Mn), titanium (Ti), cobalt (Co), zirconium (Zr), and combinations thereof. In some embodiments, the transition metal element ("Tm") is selected from aluminum (Al), manganese (Mn), titanium (Ti), cobalt (Co), and combinations thereof. In some embodiments, the transition metal element is selected from Mn y Co z(wherein y is a value between 0.01 and 0.05, or between 0 and 0.05, and / or z is a value between 0.01 and 0.05, or between 0 and 0.05). In some embodiments, when y is 0, z is greater than 0 (e.g., 0.01). In some embodiments, when z is 0, y is greater than 0 (e.g., 0.01). In some embodiments, the transition metal element is Al x Mn y Co zwhere x is a value between 0.01 and 0.03, y is a value between 0.01 and 0.05, and z is a value between 0.01 and 0.05. In some embodiments, "b" is 0, 0.001, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.0995, 0.1, or any range of values ​​therebetween, or is about 0, about 0.001, about 0.005, about 0.01, about 0.02, about 0.03, about 0.04, about 0.05, about 0.06, about 0.07, about 0.08, about 0.09, about 0.0995, about 0.1, or any range of values ​​therebetween. For example, in some embodiments, "b" is a number between 0.001 and 0.1, a number between 0.001 and 0.05, or a number between 0.001 and 0.03. In some embodiments, each element of Tm is 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.0995, or 0.1 mol % or any range of values ​​therebetween, or about 0, about 0.01, about 0.02, about 0.03, about 0.04, about 0.05, about 0.06, about 0.07, about 0.08, about 0.09, about 0.0995, or about 0.1 mol % or any range of values ​​therebetween in the nickel-rich cathode active material. In some embodiments, the dopant element ("Z") comprises a metal ("M"). In some embodiments, the metal ("M") is selected from calcium (Ca), magnesium (Mg), zirconium (Zr), and combinations thereof. In some embodiments, the dopant element (e.g., metal) comprises Zr and a metal selected from calcium (Ca), magnesium (Mg), zirconium (Zr), and combinations thereof. In some embodiments, "c" is 0.005, 0.01, 0.015, 0.02, 0.025, 0.04, 0.06, 0.08, 0.1, or any range of values ​​therebetween, or about 0.005, about 0.01, about 0.015, about 0.02, about 0.025, about 0.04, about 0.06, about 0.08, about 0.1, or any range of values ​​therebetween. For example, in some embodiments, "c" is a number between 0.005 and 0.1, a number between 0.005 and 0.025, or a number between 0.005 and 0.01.In some embodiments, the nickel-rich cathode active material can include an atomic weight of Zr of 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, or any range of values ​​therebetween, about 0.002, about 0.003, about 0.004, about 0.005, about 0.006, about 0.007, about 0.008, or any range of values ​​therebetween, at least 0.002, at least 0.003, at least 0.004, at least 0.005, at least 0.006, at least 0.007, at least 0.008, or any range of values ​​therebetween, or at least about 0.002, at least about 0.003, at least about 0.004, at least about 0.005, at least about 0.006, at least about 0.007, at least about 0.008, or any range of values ​​therebetween.

[0036] In some embodiments, the nickel-rich cathode active material is Li a Ni b Al c Ca d Zr eIn some embodiments, "a" is 0.97, 0.975, 0.98, 0.99, 0.995, 1, or any range of values ​​therebetween, or about 0.97, about 0.975, about 0.98, about 0.99, about 0.995, about 1, or any range of values ​​therebetween. For example, in some embodiments, "a" is a number between 0.97 and 1, a number between 0.98 and 1, or a number between 0.99 and 1. In some embodiments, "b" is 0.95, 0.955, 0.96, 0.965, 0.97, 0.975, 0.98, or any range of values ​​therebetween, or about 0.95, about 0.955, about 0.96, about 0.965, about 0.97, about 0.975, about 0.98, or any range of values ​​therebetween. For example, in some embodiments, "b" is a number between 0.95 and 0.98, a number between 0.96 and 0.97, or a number between 0.96 and 0.98. In some embodiments, "c" is 0.001, 0.0015, 0.002, 0.0025, 0.003, or any range of values ​​therebetween, or about 0.001, about 0.0015, about 0.002, about 0.0025, about 0.003, or any range of values ​​therebetween. For example, in some embodiments, "c" is a number between 0.001 and 0.003, a number between 0.0015 and 0.0025, or a number between 0.0015 and 0.003. In some embodiments, "d" is 0.001, 0.0015, 0.002, 0.0025, 0.003, 0.0035, 0.004, or any range of values ​​therebetween, or about 0.001, about 0.0015, about 0.002, about 0.0025, about 0.003, about 0.0035, about 0.004, or any range of values ​​therebetween. For example, in some embodiments, "d" is a number between 0.001 and 0.004, a number between 0.0015 and 0.004, or a number between 0.0015 and 0.0035.In some embodiments, "e" is 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, or any range of values ​​therebetween, or about 0.002, about 0.003, about 0.004, about 0.005, about 0.006, about 0.007, about 0.008, or any range of values ​​therebetween, or at least 0.002, at least 0.003, at least 0.004, at least 0.005, at least 0.006, at least 0.007, at least 0.008, or any range of values ​​therebetween, or at least about 0.002, at least about 0.003, at least about 0.004, at least about 0.005, at least about 0.006, at least about 0.007, at least about 0.008, or any range of values ​​therebetween. For example, in some embodiments, "e" is a number between 0.002 and 0.008, a number between 0.003 and 0.008, or a number between 0.003 and 0.007. In some embodiments, the nickel-rich cathode active material is Li. a Ni b Al c Ca d Zr e O2, where a is from about 0.99 to about 1, b is from about 0.96 to about 0.97, c is from about 0.015 to about 0.025, d is from about 0.0015 to about 0.0035, and e is from about 0.003 to about 0.007. In some embodiments, the nickel-rich cathode active material is LiNi 0.965 Al 0.02 Ca 0.0025 Zr 0.005 The formula for O2, or approximately LiNi 0.965 Al 0.02 Ca 0.0025 Zr 0.005 It has the formula O2.

[0037] The nickel-rich precursor material, the nickel-rich precursor mixture, and the lithiated nickel-rich precursor mixture are processed to form a doped nickel-rich cathode active material. FIG. 1 is a flow chart 100 illustrating an example of a doped nickel-rich cathode active material formation process, according to some of the embodiments. A nickel-rich precursor 102 and a dopant material 104 are provided and combined (e.g., mixed) in a processing step 106 to form a nickel-rich precursor mixture 108. The nickel-rich precursor mixture 108 is combined (e.g., mixed) with a lithium source 110 in a processing step 112 to form a lithiated nickel-rich precursor mixture 114. The lithiated nickel-rich precursor mixture 114 is heated (e.g., high temperature calcined) in a processing step 116 to form a doped nickel-rich cathode active material 118. Although FIG. 1 illustrates the processing step 106 occurring before the processing step 108, it should be understood that the processing steps may be performed simultaneously or that the processing step 106 may occur after the processing step 108.

[0038] In some embodiments, the nickel-rich precursor is an oxide, a hydroxide, or a combination thereof. In some embodiments, the nickel-rich precursor comprises a transition metal element ("Tm") selected from aluminum (Al), manganese (Mn), titanium (Ti), cobalt (Co), zirconium (Zr), and combinations thereof. In some embodiments, the nickel-rich precursor is selected from NiAl(OH)2, NiMnAl(OH)2, NiMnCo(OH)2, NiCoAl(OH)2, NiZr(OH)2, and combinations thereof.

[0039] In some embodiments, the dopant material is a metal (M), a metal oxide (M y O z ), metal hydroxide (M y (OH) z), and combinations thereof, where "M" represents a metal and "y" and "z" are values ​​that produce a neutrally charged dopant material. In some embodiments, the dopant material comprises a metal ("M") selected from calcium (Ca), magnesium (Mg), zirconium (Zr), and combinations thereof. In some embodiments, the dopant material is a metal hydroxide selected from Ca(OH)2, Mg(OH)2, and combinations thereof. In some embodiments, the dopant material is a metal oxide, such as ZrO2. In some embodiments, the nickel-rich precursor mixture comprises 0.1 mol%, 0.125 mol%, 0.25 mol%, 0.5 mol%, 0.75 mol%, 1 mol%, or 1.5 mol%, or any range of values ​​therebetween, of the dopant material, or about 0.1 mol%, about 0.125 mol%, about 0.25 mol%, about 0.5 mol%, about 0.75 mol%, about 1 mol%, or about 1.5 mol%, or any range of values ​​therebetween. In some embodiments, the molar ratio of nickel to dopant material in the nickel-rich precursor mixture is 1:0.005, 1:0.01, 1:0.015, 1:0.02, 1:0.025, 1:0.03, 1:0.035, 1:0.04, 1:0.045, or 1:0.05, or any range of values ​​therebetween, or about 1:0.005, about 1:0.01, about 1:0.015, about 1:0.02, about 1:0.025, about 1:0.03, about 1:0.035, about 1:0.04, about 1:0.045, or about 1:0.05, or any range of values ​​therebetween.

[0040] The lithiated nickel-rich precursor mixture may include a nickel-rich precursor mixture and a lithium source. In some embodiments, the lithium source includes a lithium salt. In some embodiments, the lithium salt is selected from LiOH.H2O, Li2CO3, and combinations thereof. In some embodiments, the molar ratio of lithium to nickel in the lithiated nickel-rich precursor mixture is 0.9:1, 0.95:1, 0.99:1, 1:1, 1.01:1, 1.05:1, or 1.1:1, or any range of values ​​therebetween, or is about 0.9:1, about 0.95:1, about 0.99:1, about 1:1, about 1.01:1, about 1.05:1, or about 1.1:1, or any range of values ​​therebetween. In some embodiments, the nickel-rich active material mixture includes 10 wt%, 11 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, or 40 wt%, or any range of values ​​therebetween, or about 10 wt%, about 11 wt%, about 12 wt%, about 14 wt%, about 16 wt%, about 18 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, or about 40 wt%, or any range of values ​​therebetween, of a lithium source.

[0041] In some embodiments, the lithiated nickel-rich precursor mixture is heated after formation, in some embodiments, the heating is at 550° C., 600° C., 625° C., 650° C., 675° C., 700° C., 725° C., 750° C., 760° C., 780° C., 800° C., 820° C., 840° C., 850° C., 860° C., 880° C., 900° C., 950° C., or 1000° C., or any range of values ​​therebetween, about 550° C., about 600° C., about 625° C., about 650° C., about 675° C., about 700° C., about 725° C., about 750° C. , about 760°C, about 780°C, about 800°C, about 820°C, about 840°C, about 850°C, about 860°C, about 880°C, about 900°C, about 950°C, or about 1000°C, or any range of values ​​therebetween, at least 550°C, at least 600°C, at least 625°C, at least 650°C, at least 675°C, at least 700°C, at least 725°C, at least 750°C, at least 760°C, at least The heating is carried out at a temperature of at least 780° C., at least 800° C., at least 820° C., at least 840° C., at least 850° C., at least 860° C., at least 880° C., at least 900° C., at least 950° C., or at least 1000° C., or any range of values ​​therebetween, or at least about 550° C., at least about 600° C., at least about 625° C., at least about 650° C., at least about 675° C., at least about 700° C., at least about 725° C., at least about 750° C., at least about 760° C., at least about 780° C., at least about 800° C., at least about 820° C., at least about 840° C., at least about 850° C., at least about 860° C., at least about 880° C., at least about 900° C., at least about 950° C., or at least about 1000° C., or any range of values ​​therebetween. In some embodiments, the heating of the lithiated nickel-rich precursor mixture is carried out in an oxidizing, inert, or reducing atmosphere. In some embodiments, the oxidizing atmosphere is an atmosphere that includes oxygen, such as air or an oxygen-rich atmosphere, hi some embodiments, the oxygen-rich atmosphere includes at least 21% oxygen by volume, at least 23.5% oxygen by volume, or at least 25% oxygen by volume.In some embodiments, the inert atmosphere is an atmosphere comprising helium, neon, argon, krypton, xenon, radon, nitrogen, or combinations thereof, hi some embodiments, the reducing atmosphere is an atmosphere comprising hydrogen, carbon monoxide, hydrogen sulfide, or combinations thereof. In some embodiments, the heating is carried out for a duration of 0 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 7 hours, 10 hours, 20 hours, or 50 hours, or any range of values ​​therebetween, a duration of about 0 hours, about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 7 hours, about 10 hours, about 20 hours, or about 50 hours, or any range of values ​​therebetween, a duration of at least 0 hours, at least 1 hour, at least 2 hours, at least 3 hours, at least 4 hours, at least 5 hours, at least 7 hours, at least 10 hours, at least 20 hours, or at least 50 hours, or any range of values ​​therebetween, or a duration of at least about 0 hours, at least about 1 hour, at least about 2 hours, at least about 3 hours, at least about 4 hours, at least about 5 hours, at least about 7 hours, at least about 10 hours, at least about 20 hours, or at least about 50 hours, or any range of values ​​therebetween. In some embodiments, the lithiated nickel-rich precursor mixture is calcined upon heating.

[0042] In some embodiments, the process further comprises disrupting the structure of the doped nickel-rich cathode active material. In some embodiments, the disrupting comprises a step selected from crushing, grinding, and combinations thereof. In some embodiments, the process comprises treating the doped nickel-rich cathode active material. In some embodiments, the treating comprises a step selected from sieving, washing, filtering, drying, coating, and combinations thereof.

[0043] Coated nickel-rich cathode active material and its process The nickel-rich cathode active material may include a coating to improve the performance of the cathode electrode. In some embodiments, the coating includes a layer disposed on the outer surface of the cathode active material. In some embodiments, the coating includes multiple coating elements disposed on the outer surface of the cathode active material. In some embodiments, the coating (e.g., a layer and / or multiple coating elements) partially, substantially, or completely covers the outer surface of the cathode active material. In some embodiments, the coating includes multiple coating layers, such as one, two, three, four, five, or any range of values ​​therebetween. In some embodiments, the coating includes a sulfur compound, a metal compound, and combinations thereof. In some embodiments, the sulfur compound includes sulfur nanoparticles, sulfur gel, sulfur solution, or combinations thereof. In some embodiments, the sulfur compound includes (CH3)2SO2, (CH3)2SO2, NaC 12 H 25 In some embodiments, the metal compound comprises an element selected from the group consisting of Al, W, Mo, and combinations thereof. In some embodiments, the metal compound comprises the compound NH4W, NH4Mo, NaAlO2, or combinations thereof. In some embodiments, the nickel-rich cathode active material is a doped nickel-rich cathode active material prepared by the processes described and described herein.

[0044] The nickel-rich cathode active material and coating material are processed to form a coated nickel-rich cathode active material. Figure 2 is a flow chart 200 illustrating an example of a coated nickel-rich cathode active material formation process, according to some of the embodiments. A nickel-rich cathode active material 202 and a coating material 204 are provided and combined (e.g., mixed) in a processing step 206 to form a nickel-rich cathode active material mixture 208. The nickel-rich cathode active material mixture 208 is heated in a processing step 210 to form a coated nickel-rich cathode active material 212.

[0045] In some embodiments, the coating material includes a sulfur compound, a metal compound, and combinations thereof. In some embodiments, the metal compound includes a metal selected from tungsten (W), molybdenum (Mo), aluminum (Al), and combinations thereof. In some embodiments, the aluminum coating material is selected from Al2O3, NaAlO2, Al(OH)3, and combinations thereof. In some embodiments, the tungsten coating material is NH4W, (NH4) 10 H2(W2O7)6, Na2WO4, WO3, and combinations thereof. In some embodiments, the molybdenum compound is NH4Mo. In some embodiments, the sulfur compound comprises a compound selected from the group consisting of dimethyl sulfoxide (DMSO), dimethyl sulfone (DMS), sulfur nanoparticles, sodium dodecyl sulfate, sodium sulfate, lithium sulfate, and combinations thereof. In some embodiments, the coating material is added to the nickel-rich cathode active material at 0.01 mol%, 0.02 mol%, 0.04 mol%, 0.08 mol%, 0.1 mol%, 0.15 mol%, 0.20 mol%, 0.25 mol%, 0.30 mol%, 0.35 mol%, 0.40 mol%, 0.45 mol%, 0.50 mol%, or 0.60 mol%, or any range of values ​​therebetween.

[0046] In some embodiments, the nickel-rich cathode active material is washed with water prior to mixing with the coating material. In some embodiments, a solid-liquid separation is performed on the washed nickel-rich cathode active material prior to mixing with the coating material. In some embodiments, the nickel-rich cathode active material comprises 1 wt%, 2 wt%, 3 wt%, 5 wt%, 7 wt%, 9 wt%, or 12 wt% water, or any range of values ​​therebetween, of a lithium source, or comprises about 1 wt%, about 2 wt%, about 3 wt%, about 5 wt%, about 7 wt%, about 9 wt%, or about 12 wt% water, or any range of values ​​therebetween, of a lithium source.

[0047] In some embodiments, the nickel-rich cathode active material mixture is heated after formation. In some embodiments, the heating is carried out at a temperature of 100°C, 125°C, 150°C, 175°C, 200°C, 225°C, 250°C, 275°C, 300°C, 325°C, or 350°C, or any range of values ​​therebetween, about 100°C, about 125°C, about 150°C, about 175°C, about 200°C, about 225°C, about 250°C, about 275°C, about 300°C, about 325°C, or about 350°C, or any range of values ​​therebetween, at least about 100°C, at least about 125°C, at least about 150°C, at least about 175°C, at least about 200°C, at least about 225°C, at least about 250°C, at least about 275°C, at least about 300°C, at least about 325°C, or at least about 350°C, or any range of values ​​therebetween. In some embodiments, the heating of the nickel-rich cathode active material mixture is carried out in an oxidizing atmosphere, an inert atmosphere, or a reducing atmosphere. In some embodiments, the oxidizing atmosphere is an atmosphere containing oxygen, such as air or an oxygen-rich atmosphere. In some embodiments, the oxygen-rich atmosphere contains at least 21% oxygen by volume, at least 23.5% oxygen by volume, or at least 25% oxygen by volume. In some embodiments, the inert atmosphere is an atmosphere containing helium, neon, argon, krypton, xenon, radon, nitrogen, or a combination thereof. In some embodiments, the reducing atmosphere is an atmosphere containing hydrogen, carbon monoxide, hydrogen sulfide, or a combination thereof.In some embodiments, the heating is carried out for a duration of 0 hours, 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 20 hours, or 30 hours, or any range of values ​​therebetween; a duration of about 0 hours, about 1 hour, about 2 hours, about 4 hours, about 6 hours, about 8 hours, about 10 hours, about 20 hours, or about 30 hours, or any range of values ​​therebetween; a duration of at least 0 hours, at least 1 hour, at least 2 hours, at least 4 hours, at least 6 hours, at least 8 hours, at least 10 hours, at least 20 hours, or at least 30 hours, or any range of values ​​therebetween; or a duration of at least about 0 hours, at least about 1 hour, at least about 2 hours, at least about 4 hours, at least about 6 hours, at least about 8 hours, at least about 10 hours, at least about 20 hours, or at least about 30 hours, or any range of values ​​therebetween.

[0048] Energy Storage Devices The doped and / or coated nickel-rich cathode active material can be used to prepare an electrode for an energy storage device. In some embodiments, an electrode film (e.g., a doped and / or coated nickel-rich electrode film) comprises the doped and / or coated nickel-rich cathode active material. In some embodiments, an electrode comprises a current collector and an electrode film. In some embodiments, the electrode is a cathode electrode.

[0049] In some embodiments, the energy storage device includes an electrode as described herein. In some embodiments, the energy storage device includes a separator, an anode electrode, a cathode electrode, and a housing, where the separator, the anode electrode, and the cathode electrode are disposed within the housing, and the separator is disposed between the anode electrode and the cathode electrode. In some embodiments, the energy storage device is formed by disposing the separator, the anode electrode, and the cathode electrode within the housing, and the separator is disposed between the anode electrode and the cathode electrode. In some embodiments, the energy storage device is a battery. In some embodiments, the energy storage device is a lithium ion battery. EXAMPLES

[0050] Exemplary embodiments of the present disclosure, including processes, materials, and / or resulting products, are described in the following examples.

[0051] Example 1 - Calcium-doped nickel-rich cathode active material Calcium-doped nickel-rich cathode active materials and doped-controlled nickel-rich cathode active materials were prepared. 0.98 Al 0.02 The (OH)2 precursor material was mixed with 0.125-1.00 mol% ZrO2 and 0.25 mol% Ca(OH)2 dopant materials to form a calcium-doped nickel-rich precursor mixture. 0.98 Al 0.02A doped nickel-rich precursor mixture was prepared by mixing (OH)2 precursor material with 0.125-1.00 mol% ZrO2 dopant material. A lithium source, LiOH, was mixed with the calcium-doped nickel-rich precursor mixture and the doped nickel-rich precursor mixture in a molar ratio of 1.03:1 lithium:nickel to form a lithiated calcium-doped nickel-rich precursor mixture and a lithiated doped nickel-rich precursor mixture. The lithiated calcium-doped nickel-rich precursor mixture and the lithiated doped nickel-rich precursor mixture were heated in oxygen at 670-700°C for 3-8 hours. The heated lithiated calcium-doped nickel-rich precursor mixture and the heated lithiated doped nickel-rich precursor were ground and sieved to produce a calcium-doped nickel-rich cathode active material and a doped nickel-rich cathode active material.

[0052] The calcium-doped nickel-rich cathode active material produced was Li a Ni b Al c Ca d Zr e O2, where a was from about 0.99 to about 1, b was from about 0.96 to about 0.97, c was from about 0.015 to about 0.025, d was from about 0.0015 to about 0.0035, and e was from about 0.003 to about 0.007. The values ​​of a, b, c, d, and e produced a neutrally charged dopant material.

[0053] Example 2 - Sulfur-coated nickel-rich cathode active material Sulfur-coated nickel-rich cathode active material and coating-controlled nickel-rich cathode active material were prepared. The doped nickel-rich cathode active material was washed with water, followed by solid-liquid separation on the washed nickel-rich cathode active material. The washed nickel-rich cathode active material was mixed with NaAlO2 solution, followed by NH4W solution to form metal-coated nickel-rich cathode active material. A portion of the metal-coated nickel-rich cathode active material was removed and heated in oxygen at 200-250°C for 3-8 hours to form coating-controlled nickel-rich cathode active material.

[0054] The metal-coated nickel-rich cathode active material was mixed with 0.1-0.5 mol % of DMS dry powder and heated at 200-250° C. for 3-8 hours in oxygen to form a sulfur-coated nickel-rich cathode active material.

[0055] Example 3 - XRD peak width Figure 3 is an XRD pattern plot comparing the lattice structure of the calcium doped nickel-rich cathode active material with the doped controlled cathode active material. The data provided in Figure 3 is further summarized in Table 1 below. As can be seen in Figure 3 and Table 1, the calcium doped nickel-rich cathode active material (labeled "Ca") was found to have narrower X-ray diffraction peak widths than the doped controlled nickel-rich cathode active material (labeled "Non-Ca"). This indicates that there is less lithium and nickel mixed into the crystal lattice of the calcium doped nickel-rich cathode active material. [Table 1]

[0056] Example 4 - Preparation and testing of electrochemical cells Half-cells containing calcium-doped nickel-rich cathode active material and controlled doping, and / or sulfur-coated nickel-rich cathode active material and controlled coating were prepared and tested. The doped and / or coated cathode active materials were prepared using processes similar to those described in Examples 1 and 2. The cathode electrodes were prepared by providing the doped and coated cathode active materials. The materials were mixed in N-methyl-2-pyrrolidone (NMP) with polyvinylidene difluoride (PVDF) and Super-S carbon black in a ratio of 85:10:5 wt.% to form a slurry. The slurry was cast onto a piece of aluminum foil and dried in an oven at 120° C. for 3 hours. The dried mixture was then calendered at a pressure of 2000 atm to obtain a loading of 10.51 mg / cm 2 A 1.2 cm coin cell electrode was punched out of the bulk electrode material and the coin cell electrode was dried under vacuum at 120° C. for 14 hours. The coin cell was assembled in an argon-filled glove box by laminating the coin cell electrode, the first separator, the second separator, and the lithium foil cathode.

[0057] Whole cells (i.e., pouch-type cells) containing calcium-doped nickel-rich cathode active material and dope-controlled nickel-rich cathode active material, and / or sulfur-coated nickel-rich cathode active material and coating-controlled nickel-rich cathode active material were prepared and tested. The cathode electrodes for the whole cells were prepared similarly to the cathode electrodes prepared for the half cells. The whole cells were prepared by stacking the cathode electrode, separator, and anode electrode together to form an electrode stack. The electrode stack was placed in a pouch filled with lithium hexafluorophosphate electrolyte. As prepared, the capacity of the whole cell was approximately 200 mAh. Constant current charge-discharge cycles were performed using an Arbin battery test system. The whole cells were maintained at 40° C. during testing. The whole cells were first charged to 4.2 V at a constant rate of C / 20 and then discharged to 2.5 V at a rate of C / 20. All cells were then cycled between 2.85 and 4.20 V at a constant rate of C / 3. Example 5 - Electrochemical Cell with Calcium-Doped Nickel-Rich Cathode Active Material

[0058] Figures 4 and 5 are plots showing the performance of half-cells and full-cells, respectively, including calcium-doped nickel-rich cathode active material compared to electrochemical cells including controlled-doped nickel-rich cathode active material. As can be seen in Figures 4 and 5, the normalized discharge capacity of the electrochemical cells including calcium-doped nickel-rich cathode active material (labeled "with Ca") showed improved performance relative to the cells including controlled-doped nickel-rich cathode active material (labeled "without Ca"). Example 6 - Electrochemical Cell with Sulfur-Coated Nickel-Rich Cathode Active Material

[0059] 6 and 7 are plots showing the performance of a half-cell and a full cell, respectively, including a sulfur-coated nickel-rich cathode active material (labeled "coating+sulfur") compared to an electrochemical cell including a coated nickel-rich cathode active material (labeled "coating") with a controlled nickel-rich cathode active material. As can be seen in FIGs. 6 and 7, the normalized discharge capacity and normalized capacity retention, respectively, of the electrochemical cell including the sulfur-coated nickel-rich cathode active material showed improved performance relative to the cell including the doped controlled nickel-rich cathode active material. Example 7 - Electrochemical cells containing either tungsten-coated nickel-rich cathode active material or molybdenum-coated nickel-rich cathode active material

[0060] 8A and 8B are plots showing the performance of half-cells containing tungsten-coated nickel-rich cathode active material (labeled "W-treated") and molybdenum-coated nickel-rich cathode active material (labeled "Mo-treated") compared to cells containing uncleaned uncoated nickel-rich cathode active material (labeled "Uncleaned"), cleaned uncoated nickel-rich cathode active material (labeled "Cleaned"), and cleaned and reheated uncoated nickel-rich cathode active material (labeled "Cleaned + Reheated"). As can be seen in FIGS. 8A and 8B, the discharge capacity and dV growth of electrochemical cells containing tungsten-coated nickel-rich cathode active material or molybdenum-coated nickel-rich cathode active material showed improved performance relative to electrochemical cells containing uncleaned uncoated nickel-rich cathode active material, cleaned uncoated nickel-rich cathode active material, and cleaned and reheated uncoated nickel-rich cathode active material, respectively.

[0061] Example 8 - Electrochemical cell containing sulfur-coated nickel-rich cathode active material and / or calcium-doped active material 9 and 10 are plots showing the performance of half-cells and full-cells, respectively, including a DMS-coated (i.e., sulfur-coated) nickel-rich cathode active material (labeled "sulfur only") and a calcium-doped nickel-rich cathode active material ("Ca only"). As can be seen in FIGs. 9 and 10, the normalized discharge capacity and normalized capacity retention of the electrochemical cells including the sulfur-coated, calcium-doped nickel-rich cathode active material, respectively, showed improved performance relative to the electrochemical cells including the calcium-doped and sulfur-coated nickel-rich cathode active materials.

[0062] Example 9 - Electrochemical cells containing cathode active materials containing either aluminum or zirconium transition metals 11A and 11B are plots showing the performance of half-cells including cathode active materials with 2 mol%, 1 mol%, or 0.5 mol% aluminum transition metal (labeled "2%Al", "1%Al", "0.5%Al", respectively), or alternatively 0.5 mol% or 0.25 mol% zirconium transition metal (labeled "0.5%Zr", "0.25%Zr", respectively) within the active material. As can be seen in FIG. 11A and 11B, the discharge capacity and average charge voltage-average discharge voltage growth, respectively, of electrochemical cells including nickel-rich cathode active materials with aluminum transition metal showed improved performance as the mol% of the transition metal increased.

[0063] Figure 12 shows the LiNi 0.8 Co 0.1 Mn 0.112 is a plot showing the performance of full cells including cathode active materials including 2 mol%, 1 mol%, or 0.5 mol% aluminum transition metal (labeled "2%Al", "1%Al", "0.5%Al", respectively) within the active material, or alternatively 0.5 mol% or 0.25 mol% zirconium transition metal (labeled "0.5%Zr", "0.25%Zr", respectively) within the active material, when compared to electrochemical cells including NMC811 and LNO cathode active materials. As can be seen in FIG. 12, electrochemical cells including nickel-rich cathode active materials including zirconium transition metal exhibited improved lifetimes relative to electrochemical cells including NMC811 and LNO cathode active materials.

[0064] Although specific embodiments have been described, these embodiments are presented by way of example only and are not intended to limit the scope of the present disclosure. Indeed, the novel methods and systems described herein may be embodied in a variety of other forms. Furthermore, various omissions, substitutions, and modifications of the systems and methods described herein may be made without departing from the spirit of the present disclosure. The appended claims and their equivalents are intended to cover such forms or modifications as fall within the scope and spirit of the present disclosure.

[0065] It should be understood that features, materials, properties or groups described in connection with a particular aspect, embodiment or example are applicable to any other aspect, embodiment or example described in this section or elsewhere in this specification, unless they are inconsistent. All of the features disclosed herein (including any accompanying claims, abstract and drawings) and / or all of the steps of any method or process disclosed similarly may be combined in any combination, except combinations in which at least some of such features and / or steps are mutually exclusive. Protection is not limited to the details of any of the foregoing embodiments. Protection extends to any one or any novel combination of features disclosed herein (including any accompanying claims, abstract and drawings) or to any one or any novel combination of steps of any method or process disclosed similarly.

[0066] Moreover, certain features described in this disclosure in the context of separate implementations may also be implemented in combination in a single implementation. Conversely, various features described in the context of a single implementation may also be implemented separately in multiple implementations or as components of any suitable combination. In addition, although features may be described above as acting in a particular combination, one or more features of a claimed combination may in some cases be deleted from the combination. Also, a combination may be claimed as a component of the combination or a variation of the components of the combination.

[0067] In addition, although operations may be shown in the figures or described herein in a particular order, such operations need not be performed in the particular order shown or sequential order, and all operations may be performed to achieve a desired result. Other operations not shown or described may be incorporated into the exemplary methods and processes. For example, one or more additional operations may be performed before, after, simultaneously with, or between any of the described operations. Furthermore, operations may be re-ordered or rearranged in other implementations. Those skilled in the art will appreciate that in some embodiments, the actual steps performed in the illustrated and / or disclosed processes may differ from those shown in the figures. Depending on the embodiment, certain of the steps may be omitted and other steps may be added. Furthermore, the features and attributes of certain embodiments disclosed above may be combined in different ways to form additional embodiments, all of which are within the scope of the present disclosure. Additionally, the separation of various system components in the above implementations should not be understood as requiring such separation in all implementations, and it should be understood that the desired components and systems may generally be integrated together in a single product or packaged into multiple products. For example, any of the components for the energy storage system described herein may be used separately or integrated together (e.g., packaged together or mounted together) to form the energy storage system.

[0068] For purposes of this disclosure, certain aspects, advantages, and novel features are described herein. Not all such advantages may be achieved in accordance with any particular embodiment. Thus, for example, one skilled in the art will recognize that the disclosure may be embodied or carried out in a manner that achieves one advantage or group of advantages as taught herein, without necessarily achieving other advantages as may be taught or suggested herein.

[0069] Conditional language such as "can," "could," "might," or "may," unless otherwise specifically stated or understood within the context in which it is used, is generally intended to convey that a particular embodiment includes, while other embodiments do not include, certain features, elements, and / or steps that other embodiments do not include. Thus, such conditional language is generally not intended to imply that features, elements, and / or steps are required in any way by one or more embodiments, or that one or more embodiments necessarily include logic for determining whether those features, elements, and / or steps will be included in or performed in any particular embodiment, with or without user input or prompting.

[0070] Conjunctions such as phrases such as "at least one of X, Y, and Z," unless specifically stated otherwise, will be understood in the context as they are commonly used to convey that an item, term, etc. can be either X, Y, or Z. As such, such conjunctives are generally not intended to indicate that a particular embodiment requires the presence of at least one of X, at least one of Y, and at least one of Z.

[0071] Language of degree, such as "approximately," "about," "generally," and "substantially," as used herein, denotes a value, amount, or characteristic that approximates a stated value, amount, or characteristic that still performs a desired function or achieves a desired result.

[0072] The scope of the present disclosure is not intended to be limited by the specific disclosure of the embodiments in this section or elsewhere herein, but may be defined by the claims, as they appear in this section or elsewhere herein, or as they may appear in the future. Claim language should be interpreted broadly based on the language used in the claims, and not limited to the examples described herein or during prosecution of the application, which examples should be interpreted as non-exclusive.

[0073] Although specific embodiments have been described, these embodiments are presented by way of example only and are not intended to limit the scope of the present disclosure. Indeed, the novel methods and systems described herein may be embodied in a variety of other forms. Furthermore, various omissions, substitutions, and modifications in the systems and methods described herein may be made without departing from the spirit of the present disclosure. The appended claims and their equivalents are intended to cover such forms or modifications as fall within the scope and spirit of the present disclosure. Thus, the scope of the present invention is defined solely by reference to the appended claims.

Claims

1. A doped nickel-rich cathode active material having the formula Li++ ａ Tm ｂ M ｃ O ２ ; (In the formula, Tm is a transition metal element, M is a dopant element, said dopant element being Zr and another element selected from the group consisting of Ca, Mg and combinations thereof; a has a value of at least 0.9, b is a value between 0.01 and 0.0995; c is a value between 0.005 and 0.02) 1. A doped nickel-rich cathode active material comprising a compound having the formula:

2. 10. The material of claim 1, wherein the compound comprises an atomic weight of Zr of at least about 0.

003.

3. 2. The material of claim 1, wherein the transition metal element is selected from the group consisting of Al, Mn, Ti, Co, and combinations thereof.

4. The transition metal element is Al ｘ 3. The material of claim 1 or 2, comprising: wherein x is a value between 0.01 and 0.

03.

5. The transition metal element is Mn ｙ Co ｚ 3. The material of claim 1 or 2, comprising: wherein y is a value between 0 and 0.05 and z is a value between 0 and 0.

05.

6. The transition metal element is Al ｘ Mn ｙ Co ｚ 3. The material of claim 1 or 2, comprising: wherein x has a value of from 0.01 to 0.03, y has a value of from 0.01 to 0.05, and z has a value of from 0.01 to 0.

05.

7. 3. The material of claim 1 or 2, further comprising a coating material disposed on the doped nickel-rich cathode active material.

8. 8. The material of claim 7, wherein the coating material is selected from the group consisting of sulfur compounds, metal compounds, and combinations thereof.

9. 3. An electrode film comprising the material of claim 1 or 2.

10. A nickel-rich cathode electrode comprising the electrode film of claim 9 disposed on a current collector.

11. 1. An energy storage device, comprising: The nickel-rich cathode electrode according to claim 10. separator, anode electrode, electrolytes, and An energy storage device comprising a housing, the nickel-rich cathode electrode, the separator, and the anode electrode disposed within the housing.

12. The energy storage device of claim 11 , wherein the energy storage device is a battery.

13. 1. A coated nickel-rich cathode active material comprising: a nickel-rich cathode active material, and a sulfur coating disposed on the nickel-rich cathode active material.

14. 14. The material of claim 13, wherein the sulfur coating comprises a compound selected from the group consisting of dimethyl sulfone, dimethyl sulfoxide, sulfur nanoparticles, sodium dodecyl sulfate, sodium sulfate, lithium sulfate, and combinations thereof.

15. 15. The material of claim 13 or 14, further comprising a metal coating.

16. 16. The material of claim 15, wherein the metallic coating comprises an element selected from the group consisting of Al, W, Mo, and combinations thereof.

17. The material of claim 15 , wherein the metal coating comprises multiple coating layers.

18. 15. The material of claim 13 or 14, wherein the nickel-rich cathode active material comprises a dopant element.

19. A process for preparing a substance according to claim 1 or 2, comprising: mixing a nickel-rich precursor, a dopant material, and a lithium source to form a lithiated nickel-rich precursor mixture; and heating the lithiated nickel-rich precursor mixture to form a doped nickel-rich cathode active material.

20. 20. The process of claim 19, further comprising disposing a sulfur coating material on the doped nickel-rich cathode active material.

21. 15. A process for preparing a substance according to claim 13 or 14, comprising the steps of: mixing a nickel-rich cathode active material with a sulfur coating material to form a nickel-rich cathode active material mixture, wherein the sulfur coating material is disposed on the nickel-rich cathode active material; and heating the nickel-rich cathode active material mixture to form a coated nickel-rich cathode active material.

22. 22. The process of claim 21, wherein the nickel-rich cathode active material further comprises a dopant element.

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