Lithium nickel oxide synthesis from mixed nickel sources

Abstract

The present disclosure is directed to systems and methods of producing lithium nickel oxide (Li2NiO2) and cation and / or anion doped counterparts thereof. The lithium nickel oxide (Li2NiO2) can be produced by mixing a lithium source with a first nickel source and a second nickel source different from the first nickel source; and heating the mixture, thereby producing a product powder comprising Li2NiO2 from the reaction between the lithium source with the first and second nickel sources.

Description

LITHIUM NICKEL OXIDE SYNTHESIS FROM MIXED NICKEL SOURCESFIELD

[0001] This disclosure relates to systems and methods for producing over-lithiated lithium nickel oxide (Li2NiO2). More specifically, this disclosure relates to systems and methods for producing Li2NiO2 and cation and / or anion doped counterparts thereof from at least two different nickel sources.BACKGROUND

[0002] Lithium-ion batteries have become indispensable in various fields due to their high energy density, rechargeability, and lightweight nature. At the heart of lithium-ion batteries lies the cathode material, pivotal for the reversible storage and release of lithium ions during charge and discharge cycles. Among the materials being explored for cathodes, over- lithiated lithium nickel oxide (Li2NiO2) has emerged as a promising candidate.SUMMARY

[0003] Described herein are systems and methods of producing over-lithiated lithium nickel oxide (Li2NiO2) and cation and / or anion doped counterparts thereof. Applicant discovered that high purity Li2NiCh can be synthesized from the reaction of a lithium source with at least two different nickel sources. For example, high purity Li2NiCh can be synthesized from the reaction of Li2O + xNi(0H)2 + (l-x)NiO.

[0004] The Li2NiCh (sometimes referred to as 212) produced herein can offer a unique set of properties essential for high-performance cathode applications. The Li2NiCh can act as a host for lithium ions, enabling their intercalation and deintercalation, thereby facilitating energy storage and release. This property can contribute to the energy density of lithium- ion batteries, key for maximizing capacity while minimizing size and weight. Using the high purity Li2NiO2 disclosed herein in a cathode can increase the delithiation capacity of a battery' that includes such a cathode. For example, the addition of Li2NiO2 to cathode active materials can deliver an extra >400 mAh / g of Li2NiO2in the first cycle, capable of offsetting losses at the anode without sacrificing valuable real estate in the cathode formulation.

[0005] In some embodiments, a method of producing lithium nickel oxide (Li NiCh) and cation and / or anion doped counterparts thereof comprising: mixing a lithium source with a first nickel source and a second nickel source different from the first nickel source; and heating the mixture, thereby producing a product powder comprising Li2NiO2 from theAttyDktNo.: ESS-L3-8142 WO reaction between the lithium source with the first and second nickel sources. In some embodiments, the lithium source comprises lithium oxide. In some embodiments, the lithium oxide has a Brunauer-Emmett-Teller (BET) specific surface area greater than 0.2 m2 / g. In some embodiments, the mixture comprises a mole ratio of lithium to nickel of 1.8- 2.2: 1 In some embodiments, the first nickel source comprises nickel oxide and the second nickel source comprises nickel hydroxide. In some embodiments, the mixture comprises a mole ratio of nickel oxide to lithium oxide of 0.5-0.9: 1. In some embodiments, the mixture comprises a mole ratio of nickel hydroxide to lithium oxide of 0.1-0.5: 1. In some embodiments, the mixture comprises a mole ratio of nickel oxide to nickel hydroxide of 0.5- 0.9:0. 1-0.5. In some embodiments, the mixture comprises more nickel oxide than nickel hydroxide. In some embodiments, the product powder comprises at least 80 wt.% Li2NiO2. In some embodiments, the mixture is heated to a temperature between 600-900°C for a period of at least 1 hour. In some embodiments, the mixture is heated in an inert environment. In some embodiments, the inert environment comprises nitrogen or argon. In some embodiments, the method includes using the product powder to form a cathode active material. In some embodiments, the cathode active matenal comprises at least about 0.5 wt.% product powder. In some embodiments, the cathode active material comprises 0.5-50 wt.% product powder. In some embodiments, the cathode active material comprises 5-15 wt.% product powder. In some embodiments, a battery includes any of the cathode active materials disclosed herein. In some embodiments, the battery is a lithium-ion battery.

[0006] It will be appreciated that any of the variations, aspects, features and options described in view of the systems, methods, and / or powders apply equally to the systems, methods, powders, other devices / configurations, and vice versa. It will also be clear that any one or more of the above variations, aspects, features and options can be combined.

[0007] Additional advantages will be readily apparent to those skilled in the art from the following detailed description. The aspects and descriptions herein are to be regarded as illustrative in nature and not restrictive.

[0008] All publications, including patent documents, scientific articles and databases, referred to in this application are incorporated by reference in their entirety for all purposes to the same extent as if each individual publication were individually incorporated by reference. If a definition set forth herein is contrary to or otherwise inconsistent with a definition set forth in the patents, applications, published applications and other publications that are herein incorporated by reference, the definition set forth herein prevails over the definition that is incorporated herein by reference.AttyDktNo.: ESS-L3-8142 WOBRIEF DESCRIPTION OF THE FIGURES

[0009] The disclosure will now be described, by way of example only, with reference to the accompanying drawings, in which:

[0010] FIG. 1 A illustrates an image of the segregated product powder formed from the reaction of lithium oxide (Li2O) with only nickel hydroxide (Ni(OH)2) at 600°C in accordance with some embodiments disclosed herein.

[0011] FIG. IB illustrates an SEM image of the product powder formed from the reaction of lithium oxide (Li2O) with only nickel hydroxide (Ni(0H)2) at 600°C in accordance with some embodiments disclosed herein.

[0012] FIG. 2 A illustrates an image of the Li2NiO2 powder produced from the reaction of Li2O + 0.3Ni(OH)2 + 0.7NiO at 715°C in accordance with some embodiments disclosed herein.

[0013] FIG. 2B illustrates an SEM image of the Li2NiCh powder produced from the reaction of Li2O + 0.3Ni(OH)2 + 0.7NiO at 715°C in accordance with some embodiments disclosed herein.DETAILED DESCRIPTION

[0014] Reference will now be made in detail to implementations and embodiments of various aspects and variations of devices, powders, systems, and methods described herein. Although several exemplary variations of the devices, powders, systems, and methods are described herein, other variations of the devices, powders, systems, and methods may include aspects of the devices, powders, systems, and methods described herein combined in any suitable manner having combinations of all or some of the aspects described.

[0015] Described herein are systems and methods of producing over-lithiated nickel oxide (LizNiCh) powder or particles and cation and / or anion doped counterparts thereof. Specifically, disclosed herein are systems and methods of synthesizing Li2NiCh by reacting a lithium source with at least two different nickel sources. The Li2NiO2 produced herein can be used for producing electrode (e.g., cathode) materials in lithium-ion batteries.

[0016] To form the Li2NiO2 disclosed herein, at least one lithium source can be mixed with at least a first nickel source and at least a second nickel source different from the first nickel source.

[0017] In some embodiments, the lithium source can be lithium metal-containing compounds such as inorganic lithium salts, organic lithium salts, non-salt lithiumAttyDktNo.: ESS-L3-8142 WO compounds that include lithium metals, lithium alloys, lithium oxides, lithium hydroxides, or combinations thereof. Mixtures of any two or more lithium compounds, or mixtures from different types of lithium sources (e.g., a lithium alloy and an inorganic lithium salt) can be used as the lithium source. In some embodiments, the lithium metals and / or lithium alloys (e.g., with silicon, magnesium, and / or aluminum) can be the one or more lithium sources, alone or in combinations with one or more organic and / or inorganic lithium salts. In some embodiments, the lithium source can be lithium oxide (Li2O). In some embodiments, the one or more lithium sources can be in the form of a powder.

[0018] In some embodiments, the lithium source can be milled prior to mixing with the nickel sources. In some embodiments, the lithium source can be milled via a ball mill, jet mill, attrition mill, hammer mill, cryogenic mill, colloid mill, fluid energy mill, and / or ultrasonic mill to the desired particle size. In some embodiments, the lithium source can have an average particle size of about 50 nanometer to 100 microns.

[0019] In some embodiments, the lithium source has a Brunauer-Emmett-Teller (BET) specific surface area of about 0. 1-30 m2 / g. In some embodiments, the lithium source has a specific surface area of at least about 0.1 m2 / g, at least about 0.2 m2 / g, at least about 0.5 m2 / g, at least about 1 m2 / g, at least about 2 m2 / g, at least about 3 m2 / g, at least about 4 m2 / g, at least about 5, at least about 6 m2 / g, at least about 7 m2 / g, at least about 8 m2 / g, at least about 9 m2 / g, at least about 10 m2 / g, at least about 11 m2 / g, at least about 12 m2 / g, or at least about 15 m2 / g. In some embodiments, the lithium source has a specific surface area of at most about 30 m2 / g, at most about 20 m2 / g, at most about 15 m2 / g, at most about 14 m2 / g, at most about 13 m2 / g, at most about 12 m2 / g, at most about 11 m2 / g, at most about 10 m2 / g, at most about 8 m2 / g, or at most about 5 m2 / g. Specific surface area can be measured by techniques known to those of ordinary skill in the art, including for example, a Micromeritics ASAP 2020 Plus.

[0020] In some embodiments, a nickel source can be nickel metal-containing compounds such as inorganic nickel salts, organic nickel salts, non-salt nickel compounds that include nickel metals, nickel alloys, nickel oxides, nickel hydroxides, or combinations thereof. Mixtures of any two or more nickel compounds, or mixtures from different types of nickel sources (e.g., a nickel alloy and an inorganic nickel salt) can be used as the nickel sources. In some embodiments, the nickel metals and / or nickel alloys (e.g., with silicon, magnesium, and / or aluminum) can be the one or more nickel sources, alone or in combinations with one or more organic and / or inorganic nickel salts. In some embodiments, a first nickel source can be nickel oxide (NiO). In some embodiments, a second nickel source can be nickelAttyDktNo.: ESS-L3-8142 WO hydroxide (Ni(0H)2). In some embodiments, the nickel sources can be in the form of a powder.

[0021] In some embodiments, the mixture can be formed in a vessel or mixer. In some embodiments, the at least two nickel sources can be mixed together (in the vessel / mixer) prior to mixing with the lithium source. In some embodiments, one of the nickel sources can be mixed together with the lithium source before the other nickel source is mixed in. In some embodiments, the lithium source and the nickel sources are simultaneously mixed together (in the mixer / vessel). In some embodiments, the mixing can include a magnetic stirrer, an overhead stirrer, and / or a shaker, among others. In some embodiments, the mixture of the lithium source(s) and nickel sources can be a homogenous mixture.

[0022] In some embodiments, the nickel sources can be milled prior to mixing with the lithium source. In some embodiments, the nickel sources can be milled via a ball mill, jet mill, attrition mill, hammer mill, cryogenic mill, colloid mill, fluid energy7mill, and / or ultrasonic mill to the desired particle size. In some embodiments, the nickel sources can have an average particle size of about 50 nanometers to 50 microns.

[0023] In some embodiments, the mole ratio of the lithium source(s) to the nickel sources (i.e., all nickel sources) in the mixture of lithium source(s) and nickel sources is about 0.5- 1.5:0.5-! .5, about 0.75-1.25:0.75-1.25, or about 1 :1. For example, a mole ratio of lithium source(s) to the nickel sources in the mixture of 1 : 1 means there is one mole of lithium source(s) to or per one mole of all nickel sources. In addition, a mole ratio of lithium source(s) to the nickel sources in the mixture of 0.75-1.25:0.75-1.25 means there is 0.75- 1.25 moles of lithium source(s) to or per 0.75-1.25 moles of all nickel sources. In some embodiments, the mole ratio of lithium to nickel in the mixture is about 1.8-2.2:1.

[0024] In some embodiments, a mole ratio of a first nickel source (e.g., nickel oxide) to the lithium source(s) in the mixture of lithium source(s) and nickel sources can be about 0.1- 0.99: 1, about 0.3-0.95: 1, about 0.5-0.9: 1, about 0.6-0.8: l, about 0.65-0.75: 1 or about 0.7: 1. For example, a mole ratio of a first nickel source to the lithium source in the mixture of 0.7: 1 means there is one mole of lithium source(s) to or per 0.7 moles of a first nickel source. In some embodiments, the lithium source is lithium oxide and the first nickel source is nickel oxide.

[0025] In some embodiments, a mole ratio of a second nickel source (e.g., nickel hydroxide) to the lithium source(s) in the mixture of lithium source(s) and nickel sources can be about 0.01-0.9: 1, about 0.05-0.75: 1, about 0. 1-0.5: 1. about 0.2-0.4: 1, about 0.25-0.35: 1 or about 0.3: 1. For example, a mole ratio of a second nickel source to the lithium source in theAttyDktNo.: ESS-L3-8142 WO mixture of 0.3: 1 means there is one mole of lithium source(s) to or per 0.3 moles of a second nickel source. In some embodiments, the lithium source is lithium oxide and the second nickel source is nickel hydroxide.

[0026] In some embodiments, a mole ratio of a first nickel source to a second nickel source in the mixture of lithium source(s) and nickel sources can be X: l-X, wherein X is less than 1. In some embodiments, a mole ratio of a first nickel source to a second nickel source in the mixture of lithium source(s) and nickel sources can be about 0. 1-0.9: 0.9-0. 1, about 0.5- 0.9:0. 1-0.5, about 0.6-0.8:0.2-0.4, about 0.65-0.75:0.25-0.35, or about 0.7:0.3. In some embodiments, the first nickel source is nickel oxide and the second nickel source is nickel hydroxide.

[0027] In some embodiments, the mixture of lithium source(s) and nickel sources can be heated in a reaction step such that a product that includes Li2NiCh is produced. In some embodiments, the lithium source(s) and the nickel sources can react to form a product that includes Li2NiCh. In some embodiments, the Li2NiCh product is in powder form. In some embodiments, this heating can initiate solid-state reactions between the lithium source(s) and the nickel sources to form Li2NiC>2

[0028] For example, in some embodiments, Li2NiCh can be synthesized from the reaction of Li2O + xNi(0H)2 + (l-x)NiO. Applicant has discovered that at least two factors can impact the synthesis of Li2NiCh. The first factor is the surface area of the lithium source. The second factor is the selective replacement of one nickel source with another (e.g.. the selective replacement of some NiO with Ni(0H)2). For example, the introduction of nickel hydroxide can allow for the generation of transient water upon the decomposition of the hydroxide to nickel oxide. This can accelerate the reaction with the lithium source (e.g., lithium oxide) to form high purity Li2NiO2. Using exclusively one nickel source such as nickel hydroxide can allow the reaction to occur at lower temperatures (~600°C), but yields a phase separated product with visible lithium source (e.g., lithium oxide) segregation. For example, FIG. 1A illustrates an image of the segregated product powder formed from the reaction of lithium oxide (U2O) with nickel hydroxide (Ni(0H)2) at 600°C. As shown in FIG. 1 A, the crust or extenor of the product is lithium oxide, whereas the interior or core of the product is Li2NiO2. FIG. IB is an SEM image of the product powder produced from the reaction of lithium oxide (Li2O) with nickel hydroxide (Ni(OH)2) at 600°C. As you can see, the particles generated from exclusively using nickel hydroxide are large with sharp edges and surface impurities mirroring those seen in the bulk.AttyDktNo.: ESS-L3-8142 WO

[0029] Applicant discovered that by replacing a percentage of the first nickel source (e.g., (Ni(0H)2) with a second nickel source (e.g., NiO) and increasing the temperature, a decrease in the segregation of the lithium source upon reaction can occur, thereby creating a high purity Li2NiCh powder. FIG. 2A illustrates an image of the Li2NiCh powder produced from the reaction of Li2O + 0.3Ni(OH)2 + 0.7NiO at 715°C. As show n in FIG. 2A, replacing 70% of the nickel hydroxide with nickel oxide and increasing the temperature yields a bright green solid, indicating far less segregation of the lithium oxide upon reaction. Without being bound by any theory, it is believed that the decreased phase segregation can be due to the limited generation of gaseous water upon reaction as the source (i.e., nickel hydroxide) is decreased. As such, using two different nickel sources can result in a more uniform Li2NiCh product.

[0030] FIG. 2B is an SEM image of the lithium nickel oxide powder produced from the reaction of Li2O + 0.3Ni(OH)2 + 0.7NiO at 715°C. FIGS. IB and 2B illustrate the difference in particle morphology' upon partial replacement of nickel hydroxide with nickel oxide. The particles generated from exclusively nickel hydroxide shown in FIG. IB are visibly larger than those in FIG. 2B. When using predominantly nickel oxide (FIG. 2B), the particles are more uniformly sized with rounded edges and no visible impurities when compared with those of FIG. IB. These differences can have downstream impact on the inclusion into electrode formulations. For example, the Li2NiO2 product generated with mixed nickel sources can have much closer particle size distribution as the cathode active material allowing for more synergistic electrochemical performance.

[0031] In some embodiments, this heating / reaction step can take place in a reactor(s) such as a stationary' or rotary' kiln or roller hearth kiln. In some embodiments, the mixture of lithium source(s) and nickel sources is heated to at least about 400°C, at least about 500 °C, at least about 550 °C, at least about 600 °C, at least about 650 °C, at least about 700 °C, at least about 750 °C, at least about 800 °C, or at least about 850 °C. In some embodiments, the mixture of lithium source(s) and nickel sources is heated to at most about 1100 °C, at most about 1050 °C, at most about 1000 °C, at most about 950 °C, at most about 900 °C, at most about 850 °C, at most about 800 °C. at most about 750 °C, or at most about 700 °C. In some embodiments, the mixture of lithium source(s) and nickel sources is heated to about 400-1100 °C, about 500-1000 °C, about 600-900 °C, 600-800 °C, or about 650-750 °C. In some embodiments, the mixture of lithium source(s) and nickel sources is heated for at least about 30 minutes, at least about 1 hour, at least about 2 hours, at least about 5 hours, at least about 6 hours, at least about 8 hours, at least about 10 hours, at least about 11 hours, or atAttyDktNo.: ESS-L3-8142 WO least about 12 hours. In some embodiments, the mixture of lithium source(s) and nickel sources is heated for at most about 24 hours, at most about 20 hours, at most about 18 hours, at most about 16 hours, at most about 14 hours, at most about 13 hours, at most about 12 hours, at most about 11 hours, at most about 10 hours, at most about 8 hours, or at most about 5 hours. In some embodiments, the mixture of lithium source(s) and nickel sources is heated for about 1-24 hours, about 5-17 hours, about 10-14 hours, or about 11-13 hours. In some embodiments, these times refer to the combined total time if multiple reactors are used for the heating / reaction step or if multiple reaction segments are used.

[0032] In some embodiments, the heating / reacting of the mixture of lithium source(s) and nickel sources is performed in an inert environment to form the product powder. In some embodiments, the inert environment can be static or a flow of the inert gas or gases in the inert environment. In some embodiments, the inert environment can include argon, nitrogen, helium, or combinations thereof.

[0033] In some embodiments, the yield (or purity of the Li2NiCh product) of the reaction between the lithium source(s) and the nickel sources can be 75-100%. about 75-99.99%, about 80-99%, about 85-99%, or about 90-99%. In some embodiments, the yield (or purity of the LizNiCh product) of the reaction between the lithium source(s) and the nickel sources can be at least about 75%, at least about 80%, at least about 85%, at least about 87%, at least about 90%, at least about 92%, at least about 95%, or at least about 98%. In some embodiments, the yield (or purity of the Li2NiO2 product) of the reaction between the lithium source(s) and the nickel sources can be at most 100%, at most 99.9%, at most 99%, at most 98%, at most 95%, at most 93%, or at most 90%. In some embodiments, the yield (or purity of the Li2NiCh product) of the reaction between the lithium source(s) and the nickel sources can be measured by techniques known to those of ordinary skill in the art, including for example using XRD techniques.

[0034] In some embodiments, the Li2NiCh product and cation and / or anion doped counterparts thereof can have a certain particle size distribution. For example, in some embodiments, the Li2NiO2 product can be sieved at a 325 mesh (40 pm) before the particle size distribution is measured. The particle size and particle size distributions can be measured by techniques known to those of ordinary skill in the art, including for example, a Malvern Mastersizer 300. In some embodiments, the Li2NiCh product (after sieving with a 325 mesh (40 pm)) has a particle size distribution with a D10 (i.e., size below which 10% of all particles are found) of about 0. 1-10 microns, about 0.2-9 microns, about 1-7 microns, about 1-6 microns, or about 2-5 microns. In some embodiments, the Li2NiC>2 product (afterAttyDktNo.: ESS-L3-8142 WO sieving with a 325 mesh (40 gm)) has a particle size distribution with a DIO of greater than about 0. 1, greater than about 0.5 microns, greater than about 1 micron, greater than about 2 microns, greater than about 3 microns, greater than about 4 microns, greater than about 5 microns, greater than about 6 microns, greater than about 7 microns, greater than about 8 microns, greater than about 9 microns, or greater than about 10 microns. In some embodiments, the Li2NiCh product (after sieving with a 325 mesh (40 pm)) has a particle size distribution with a D10 of less than about 10 microns, less than about 8 microns, less than about 7 microns, less than about 6 microns, less than about 5 microns, less than about 4 microns, less than about 3 microns, or less than about 2 microns.

[0035] In some embodiments, the Li2NiCh product (after sieving with a 325 mesh (40 pm)) and cation and / or anion doped counterparts thereof has a particle size distribution with a D50 (i.e., size below which 50% of all particles are found) of about 5-25 microns, about 5- 20 microns, about 8-15 microns, or about 10-15 microns. In some embodiments, the Li2NiCh product (after sieving with a 325 mesh (40 pm)) has a particle size distribution with a D50 of greater than about 5 microns, greater than about 6 microns, greater than about 7 microns, greater than about 8 microns, greater than about 9 microns, greater than about 10 microns, greater than 1 1 microns, greater than 12 microns, or greater than 15 microns. In some embodiments, the Li2NiCh product (after sieving with a 325 mesh (40 pm)) has a particle size distribution with a D50 of less than about 25 microns, less than about 20 microns, less than about 15 microns, less than about 14 microns, less than about 13 microns, less than about 12 microns, less than about 1 1 microns, or less than about 10 microns, less than about 9 microns, less than about 8 microns, less than about 7 microns, less than about 6 microns, less than about 5 microns, or less than about 4 microns.

[0036] In some embodiments, the Li2NiCh product (after sieving with a 325 mesh (40 pm)) and cation and / or anion doped counterparts thereof has a particle size distribution with a D90 (i.e., size below which 90% of all particles are found) of about 15-45 microns, about 15-35 microns, about 20-30 microns, or about 22-27 microns. In some embodiments, the Li2NiO2 product (after sieving with a 325 mesh (40 pm)) has a particle size distribution with a D90 of greater than about 10 microns, greater than 12 microns, greater than 15 microns, greater than about 18 microns, greater than about 20 microns, greater than about 22 microns, greater than about 23 microns, greater than about 24 microns, or greater than about 25 microns. In some embodiments, the Li2NiCh product (after sieving with a 325 mesh (40 pm)) has a particle size distribution with a D90 of less than about 45 microns, less than about 35 microns, less than about 30 microns, less than about 29 microns, less than aboutAttyDktNo.: ESS-L3-8142 WO28 microns, less than about 27 microns, less than about 26 microns, or less than about 25 microns.

[0037] In some embodiments, the Li2NiCh product (after sieving with a 325 mesh (40 pm)) and cation and / or anion doped counterparts thereof has a particle size distribution with a D100 (i.e., size below which 100% of all particles are found) of about 25-75 microns, about 35-65 microns, about 40-60 microns, or about 45-55 microns. In some embodiments, the Li2NiO2 product (after sieving with a 325 mesh (40 pm)) has a particle size distribution with a D100 of greater than about 25 microns, greater than about 30 microns, greater than about 35 microns, greater than about 40 microns, greater than about 45 microns, greater than about 46 microns, greater than about 47 microns, greater than about 48 microns, greater than about 49 microns, or greater than about 50 microns. In some embodiments, the LizNiCh product (after sieving with a 325 mesh (40 pm)) has a particle size distribution with a DI 00 of less than about 100 microns, less than about 75 microns, less than about 70 microns, less than about 65 microns, less than about 60 microns, less than about 55 microns, less than about 54 microns, less than about 53 microns, less than about 52 microns, less than about 51 microns, or less than about 50 microns.

[0038] As explained above, using a balanced ratio of a first nickel source (e.g., nickel oxide) and a second nickel source (e.g., nickel hydroxide) to react with a high surface area lithium source (e.g., lithium oxide) to form a Li2NiCh can be more beneficial than using a single nickel source (e.g., nickel hydroxide). Without being bound by any theory, it is believed that the reactivity can be enhanced by the formation of gaseous water upon decomposition of the second nickel source (e.g., nickel hydroxide) at elevated temperatures.

[0039] In some embodiments, after the reaction step, the Li2NiCh product can be posttreated in a post-treatment step such as doping, surface coating, washing, etc.Electrode Active Material

[0040] In some embodiments, the Li2NiCh product powder and cation and / or anion doped counterparts thereof can be an electrode (e.g., cathode) active material. In some embodiments, the Li2NiO2 product powder and cation and / or anion doped counterparts thereof can be used as an additive to an electrode (e.g., cathode) active material. In some embodiments, the cathode active material can include about 0. 1-100 wt.% Li2NiO2 product powder, about 0.5-50 wt.% Li2NiCh product powder, about 1-20 wt.% Li2NiCh product powder, or about 5-15 wt.% Li2NiCh product. In some embodiments, the cathode active material can include at least about 0. 1 wt.% Li2NiO2 product powder, at least about 0.5 wt.% Li2NiO2 product powder, at least about 1 wt.% Li2NiCh product powder, at least about 5AttyDktNo.: ESS-L3-8142 WO wt.% LizNiOz product powder, at least about 10 wt.% LizNiOz product powder, at least about 15 wt.% Li2NiO2 product powder, at least about 20 wt.% Li2NiO2 product powder, at least about 25 wt.% LizNiOz product powder, or at least about 30 wt.% LizNiOz product powder. In some embodiments, the cathode active material can include at most about 100 wt.% LizNiOz product powder, at most about 90 wt.% LizNiOz product powder, at most about 80 wt.% Li2NiO2 product powder, at most about 75 wt.% Li2NiO2 product powder, at most about 50 wt.% Li2NiO2 product powder, at most about 30 wt.% Li2NiO2 product powder, at most about 25 wt.% Li2NiO2 product powder, or at most about 15 wt.% LizNiOz product powder.

[0041] In some embodiments, the addition of the LizNiOz product disclosed herein to a cathode active materials can deliver an extra delithiation capacity of at least about 200 mAh / g of Li2NiO2 product, at least about 250 mAh / g of LizNiOz product, at least about 300 mAh / g of LizNiOz product, at least about 350 mAh / g of LizNiOz product, or at least about 400 mAh / g of LizNiOz product in first cycle. This addition of LizNiOz product and cation and / or anion doped counterparts thereof to cathode active materials can be capable of offsetting losses at the anode without sacrificing valuable real estate in the cathode formulation.Electrode Manufacturing

[0042] In some embodiments, the electrode (e.g.. cathode) active material (including LizNiOz product powder and cation and / or anion doped counterparts thereof) can be used to make an electrode. In some embodiments, the electrode can be formed by mixing the electrode active material, conductive additive(s), binder(s), and / or solvent to form a slurry. In some embodiments, the conductive additives can include carbon black, vapor grown carbon fiber (VGCF). graphite, graphene, and / or carbon nanotubes. In some embodiments, the binder can include polyvinylidene fluoride (PVDF), carboxymethoxy cellulose (CMC), lithium substituted polyacrylic acid (LiPAA). In some embodiments, the solvent can include N-Methyl-2-pyrrolidone (NMP), water, another aqueous solution, or combinations thereof.

[0043] In some embodiments, the slurry includes about 80-95 wt. % electrode active material described herein. In some embodiments, the slurry may include less than or equal to 98 wt. %, less than or equal to 97 wt. %, less than or equal to 95 wt. %, less than or equal to 90 - t. %, or less than or equal to 85 wt. % electrode active material described herein. In some embodiments, the slurry’ includes about greater than or equal to 80 wt. %, greater than or equal to 85 wt. %, greater than or equal to 90 wt. %, greater than or equal to 95 wt. %,AttyDktNo.: ESS-L3-8142 WO greater than or equal to 96 wt %, greater than or equal to 97 wt. %, greater than or equal to 98 wt. % electrode active described herein.

[0044] In some embodiments, the slurry' includes 0.1-10 wt. % conductive additives. In some embodiments, the slurry may include less than or equal to 10 wt. %, less than or equal to 9 wt. %, less than or equal to 8 wt. %, less than or equal to 7 wt. %, less than or equal to 6 wt. %, less than or equal to 5 wt. %, less than or equal to 4 wt. %. less than or equal to 3 wt. %, less than or equal to 2 wt. %, or less than or equal to 1 wt. % conductive additives. In some embodiments, the slurry may include greater than or equal to 0. 1 wt. %, greater than or equal to 1 wt. %, greater than or equal to 2 wt. %, greater than or equal to 3 wt. %, greater than or equal to 4 wt. %, greater than or equal to 5 wt. %, greater than or equal to 6 wt. %, greater than or equal to 7 wt. %, greater than or equal to 8 wt. %, or greater than or equal to 9 wt. % conductive additives.

[0045] In some embodiments, the slurry’ includes 0.1-10 wt. % binder(s). In some embodiments, the slurry' may include less than or equal to 10 wt. %, less than or equal to 9 wt. %. less than or equal to 8 wt. %, less than or equal to 7 wt. %, less than or equal to 6 wt. %, less than or equal to 5 wt. %, less than or equal to 4 wt. %, less than or equal to 3 wt. %, less than or equal to 2 wt. %, or less than or equal to 1 wt. % binder(s). In some embodiments, the slurry' may include greater than or equal to 0. 1 wt. %, greater than or equal to 1 wt. %, greater than or equal to 2 wt. %, greater than or equal to 3 wt. %, greater than or equal to 4 wt. %, greater than or equal to 5 wt. %, greater than or equal to 6 wt. %. greater than or equal to 7 wt. %, greater than or equal to 8 wt. %, or greater than or equal to 9 wt. % binder(s).

[0046] In some embodiments, the slurry can include solvent such that the solids content is about 5-85 wt.% of the slurry.

[0047] In some embodiments, the slurry can be coated onto a current collector by any method typically used in the art. In some embodiments, the current collector can be a metal foil. In some embodiments, the current collector can be an aluminum current collector. In some embodiments, the aluminum current collector can include aluminum metal, etched aluminum, carbon coated aluminum, or combinations thereof. The coating can then be dried and the coated current collector can be pressed or calendared to form the electrode (e.g., cathode).

[0048] In some embodiments, the electrode may comprise 0.1-10 wt. % conductive additive(s). In some embodiments, the electrode may comprise less than or equal to 10 wt. %, less than or equal to 9 wt. %, less than or equal to 8 wt. %, less than or equal to 7 wt. %,AttyDktNo.: ESS-L3-8142 WO less than or equal to 6 wt. %, less than or equal to 5 wt. %, less than or equal to 4 wt. %, less than or equal to 3 wt. %, less than or equal to 2 wt. %, or less than or equal to 1 wt. % conductive additive(s). In some embodiments, the electrode may comprise greater than or equal to 0. 1 wt. %, greater than or equal to 1 wt. %, greater than or equal to 2 wt. %, greater than or equal to 3 wt. %, greater than or equal to 4 wt. %, greater than or equal to 5 wt. %, greater than or equal to 6 wt. %, greater than or equal to 7 wt. %, greater than or equal to 8 wt. %. or greater than or equal to 9 wt. % conductive additive(s).

[0049] In some embodiments, the electrode may comprise 0.1-10 wt. % binder(s). In some embodiments, the electrode may comprise less than or equal to 10 wt. %, less than or equal to 9 wt. %, less than or equal to 8 wt. %, less than or equal to 7 wt. %. less than or equal to 6 wt. %, less than or equal to 5 wt. %, less than or equal to 4 wt. %. less than or equal to 3 wt. %, less than or equal to 2 wt. %, or less than or equal to 1 wt. % binder(s). In some embodiments, the electrode may comprise greater than or equal to 0. 1 wt. %, greater than or equal to 1 wt. %, greater than or equal to 2 wt. %, greater than or equal to 3 wt. %, greater than or equal to 4 wt. %, greater than or equal to 5 wt. %, greater than or equal to 6 wt. %, greater than or equal to 7 wt. %, greater than or equal to 8 wt. %, or greater than or equal to 9 wt. % binder(s).

[0050] In some embodiments, the electrode may comprise 80-99.8 wt. % the electrode (e.g., cathode) active material (i.e., Li2NiCh product powder) described herein. In some embodiments, the electrode may comprise less than or equal to 99.8 wt. %, less than or equal to 99.5 wt. %, less than or equal to 99 wt. %, less than or equal to 98 wt. %, less than or equal to 97 wt. %, less than or equal to 95 wt. %, less than or equal to 90 wt. %, or less than or equal to 85 wt. % the electrode (e.g., cathode) active material described herein. In some embodiments, the electrode may comprise greater than or equal to 80 wt. %. greater than or equal to 85 wt. %, greater than or equal to 90 wt. %, greater than or equal to 95 wt. %, greater than or equal to 96 wt. %, greater than or equal to 97 wt. %, greater than or equal to 98 wt. %, greater than or equal to 99 wt. %, or greater than or equal to 99.5 wt. % the electrode (e g., cathode) active material described herein.

[0051] In some embodiments, the electrode (e.g., cathode) can be used in a battery (e.g.. a lithium-ion battery). In some embodiments, the Li2NiCh product powder disclosed herein can be used to make an electrolyte. In some embodiments, the battery can include an anode, a cathode, a separator, and / or an electrolyte. In some embodiments, the battery can be a solid-state battery.AttyDktNo.: ESS-L3-8142 WO

[0052] For the purpose of clarity and a concise description, features are described herein as part of the same or separate embodiments; however, it will be appreciated that the scope of the disclosure includes embodiments having combinations of all or some of the features described.EXAMPLES

[0053] The following examples are presented for purposes of illustration, and are not intended to impose limitations on the scope of this disclosure.

[0054] Li2NiO2 products were produced to illustrate the more synergistic electrochemical performance of using the synthesis methods disclosed herein that utilize at least two different nickel sources. A first Li2NiO2 product was produced using only one nickel source (i.e., 100% nickel hydroxide) reacted with lithium oxide. A second Li2NiCh product was produced using 70% nickel oxide and 30% nickel hydroxide as the nickel sources to be reacted with lithium oxide. For each of the Li2NiCh products, a particle size distribution was measured as well as its delithiation capacity. Before particle size distribution measurement and electrochemical testing for delithation capacity, the L NiCh products were sieved at 325 mesh (40 pm).

[0055] E-Chem Testing: A portion (~1 g) of the Li2NiO2 product from the examples was made into a slurry with the following ingredients: 80 wt% product; 10 wt% PVDF; 10 wt% carbon black; and NMP. The amount of NMP was such that the solid content was about 40 wt% of the slurry. The slurry was coated onto an aluminum foil current collector and then the coating was dried and then calendared to 40% porosity, forming an electrode. The loading on the electrode was about 3 mg / cm2. Four coin cells were assembled from each calendared electrode, with lithium foil as the counter electrode and 1.2 M LiPF6 (ethylene carbonate: diethyl carbonate= 3:7) with 5% fluoroethylene carbonate as the electrolyte solution. The cells were cycled at C / 20 for 10 cycles.

[0056] As shown in Table 1 below; the Li2NiO2 product produced with 100% nickel hydroxide has bigger Li2NiC>2 powder particles in contrast to the Li2NiCh product produced with 0.7 NiO and 0.3 nickel hydroxide:AttyDktNo.: ESS-L3-8142 WOTABLE 1

[0057] As shown in the above table, the Li2NiCh product generated with mixed nickel sources has a much narrower particle size distribution as the cathode active material (NMC 622 cathode) allowing for more synergistic electrochemical performance. In addition, the delithiation capacity of the Li2NiC>2 product produced with mixed nickel sources has a greater delithiation capacity' compared to the Li2NiCh product produced from only nickel hydroxide.

[0058] As stated above, Applicant also discovered that using mixed nickel sources to react with the lithium source to produce the Li2NiCh product can be impacted by the surface area of the lithium source (e.g., lithium oxide). As shown in the below Table 2, the Li2NiCh yields were measured after reacting two lithium oxides having different specific surface areas (10.34 and 0.25 m2 / g) with: (1) only one nickel source (i.e., 100% nickel hydroxide); and (2) 70% nickel oxide and 30% nickel hydroxide.TABLE 2

[0059] As shown above, the use of mixed nickel sources in the reaction with the lithium source can be beneficial when the specific surface of the lithium source is high (i.e., Li2O- A), whereas using exclusively nickel hydroxide can provide a higher conversion / purity of the Li2NiCh product when the surface area of the lithium source reactant is loyv (i.e., Li2O-AttyDktNo.: ESS-L3-8142 WOB). Without being bound by any theory', it is believed that the combination of high surface area lithium source (e.g., lithium oxide) with excess gaseous water generation at the reaction temperature (for example, nickel hydroxide is exclusively used) can lead to excessive reactivity between the lithium source and the water vapor, thereby forming a transient Li(H20)x species and resulting in bulk mass transfer as the volatile species continues to evolve and are entropically driven from the reaction. This can lead to the separation of the lithium source (e.g., lithium oxide) from the reaction mixture as seen in FIG. 1 A and limits conversion to Li2NiCh. The reactivity between transient gaseous water and the lithium source (e.g., lithium oxide) with lower surface area (e.g., Li2O-B) can be low enough that the gaseous water leaves the reaction bed faster than it can react with the low surface lithium source, thereby allowing the lithium source to react with the nickel source to form Li2NiO2.

[0060] Additional Examples of ratio of nickel hydroxide and nickel oxide along with the yield and appearance are disclosed in the following Table 3:TABLE 3DEFINITIONS

[0061] Unless defined otherwise, all terms of art, notations and other technical and scientific terms or terminology used herein are intended to have the same meaning as is commonly understood by one of ordinary skill in the art to which the claimed subject matter pertains. In some cases, terms with commonly understood meanings are defined herein for clarity and / or for ready reference, and the inclusion of such definitions herein should not necessarily be construed to represent a substantial difference over what is generally understood in the art.AttyDktNo.: ESS-L3-8142 WO

[0062] The terms “powders” and “particles” used herein are equivalent, except that a single powder refers to a plurality of particles. This disclosure can apply to a wide range of particles and powders.

[0063] As used herein, the word “layer(s)” and “coating(s)” are equivalent. Specifically, each term “layer(s)” or “coating(s)” as used in relation to a particle(s) indicates that at least a portion of the surface of such particle, substantially all, or all of the surface of such particle(s) is covered by or in contact with the “layer(s)” or “coating(s).” Similarly, the term “coated” in relation to a particle(s) indicates that at least a portion of the surface of the particle, substantially all, or all of the surface of the particle(s) is covered by or in contact with the substance(s) with which the parti cle(s) is said to be “coated.”

[0064] Reference to “about” a value or parameter herein includes (and describes) variations that are directed to that value or parameter per se. For example, description referring to “about X” includes description of “X”. In addition, reference to phrases “less than”, “greater than”, “at most”, “at least”, “less than or equal to”, “greater than or equal to”, or other similar phrases followed by a string of values or parameters is meant to apply the phrase to each value or parameter in the string of values or parameters.

[0065] As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It is also to be understood that the term “and / or” as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items. It is further to be understood that the terms “includes, “including,” “comprises,” and / or “comprising,” when used herein, specify the presence of stated features, integers, steps, operations, elements, components, and / or units but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, units, and / or groups thereof.

[0066] This application discloses several numerical ranges in the text and figures. The numerical ranges disclosed inherently support any range or value within the disclosed numerical ranges, including the endpoints, even though a precise range limitation is not stated verbatim in the specification because this disclosure can be practiced throughout the disclosed numerical ranges.

[0067] The above description is presented to enable a person skilled in the art to make and use the disclosure, and is provided in the context of a particular application and its requirements. Various modifications to the preferred embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the disclosure.AttyDktNo.: ESS-L3-8142 WOThus, this disclosure is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein.

Claims

AttyDktNo.: ESS-L3-8142 US PROCLAIMS1. A method of producing lithium nickel oxide (Li2NiO2) and cation and / or anion doped counterparts thereof comprising: mixing a lithium source with a first nickel source and a second nickel source different from the first nickel source; and heating the mixture, thereby producing a product powder comprising Li2NiO2 and cation and / or anion doped counterparts thereof from the reaction between the lithium source with the first and second nickel sources.

2. The method of claim 1, wherein the lithium source comprises lithium oxide.

3. The method of claim 2, wherein the lithium oxide has a Brunauer-Emmett-Teller (BET) specific surface area greater than 0.2 m2 / g.

4. The method of any one of claims 2-3. wherein the mixture comprises a mole ratio of lithium to nickel of 1.8-2.2:

15. The method of any one of claims 2-4. wherein the first nickel source comprises nickel oxide and the second nickel source comprises nickel hydroxide.

6. The method of claim 5, wherein the mixture comprises a mole ratio of nickel oxide to lithium oxide of 0.5-0.9: 1.

7. The method of claim 6, wherein the mixture comprises a mole ratio of nickel hydroxide to lithium oxide of 0.1-0.5: 1.

8. The method of any one of claims 5-7. wherein the mixture comprises a mole ratio of nickel oxide to nickel hydroxide of 0.5-0.9:0.1-0.5.

9. The method of any one of claims 5-8. wherein the mixture comprises more nickel oxide than nickel hydroxide.

10. The method of any one of claims 1-9, wherein the product powder comprises at least 80 wt.% Li2NiO2.

11. The method of any one of claims 1-10, wherein the mixture is heated to a temperature between 600-900°C for a period of at least 1 hour.AttyDktNo.: ESS-L3-8142 US PRO12. The method of claim 11, wherein the mixture is heated in an inert environment.

13. The method of claim 12, wherein the inert environment comprises nitrogen or argon.

14. The method of any one of claims 1-13, further comprising using the product powder to form a cathode comprising active material.

15. The method of claim 14, wherein the cathode comprising active material comprises at least about 0.5 wt.% product powder.

16. The method of claim 15, wherein the cathode comprising active material comprises 0.5-50 wt.% product powder.

17. The method of claim 16, wherein the cathode comprising active material comprises5-15 wt.% product powder.

18. A battery comprising the cathode of any one of claims 14-17.

19. The battery of claim 18, wherein the battery is a lithium-ion battery.

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