Lithiated precursor for cathode active materials field

Abstract

Provided are methods of making a lithium peroxide-coated transition metal precursor comprising: mixing lithium hydroxide and hydrogen peroxide to form a suspension; adding a precipitant to the suspension to accelerate precipitation of lithium peroxide; and adding a transition metal precursor into the suspension to form a lithium peroxide-coated transition metal precursor.

Description

[0001]LITHIATED PRECURSOR FOR CATHODE ACTIVE MATERIALS FIELD The present disclosure relates to a precursor for cathode active materials, and more particularly, to a lithiated precursor for cathode active materials for lithium-ion batteries. BACKGROUND Cathode materials (such as lithium nickel-cobalt-aluminum oxide (NCA) or lithium nickel manganese cobalt (NMC)) for rechargeable lithium-ion batteries are typically formed from transition metal precursors and lithium compounds. The transition metal precursors for cathode active materials specifically used for rechargeable lithium- ion batteries often include one or more metals such as nickel, cobalt, and manganese, and are typically synthesized through co-precipitation including nucleation, primary particle growth, and agglomeration to form secondary particles. In particular, cathode materials are typically formed by calcining the transition metal precursors and the lithium salts. Before calcination, the lithium salts are often milled, dehydrated, and mixed with the transition metal precursor at a targeted stoichiometric ratio, which requires extra equipment under environmental control to achieve. SUMMARY Provided are methods of making composite precursors for cathode active materials comprising transition metal precursors (comprising a compound or a mixture of compounds each having the formula 1 and / or 2 or an oxide counterpart thereof) coated by lithium peroxide. qMn(OH)2^(1-q)NiaMnbCocMyX1+k(1) wherein 0≤ q ≤0.8, c = 1-a-b, 0≤ a≤1, 0<b≤1, 0≤ y≤ 0.05 and M includes one or moreselected from the group consisting of Al, Mg, Ti, Mo, Nb, Zr, Hf, Ta, W, B,P and F;wherein X is selected from the group consisting of OH-, CO32-, NO3-, SO42-, C2O42-,C2H3O2-, CHO2-, stearate, oleate, tartrate and lactate, and-0.025≤ k≤ 1.25.(NixCoyMnz)Ab(2) AttyDktNo.: ESS-L3-8135 WO in which x + y + z = 1; A = OH-, OOH-, O2-, CO32-, and / or C2O42-; b = 2 when A = OH- and / or OOH-, otherwise b = 1. The composite precursor can be formed by synthesizing lithium peroxide in situ from the reaction between lithium hydroxide and hydrogen peroxide (in a basic water solution) in the presence of a transition metal precursor. These methods of making composite precursors for cathode active materials can simplify the cathode active material production process as explained below. Conventional processes by which transition metal precursors for cathode active materials (e.g., ternary nickel-manganese-cobalt (NMC) cathode materials) are typically produced from a co-precipitation process, in which a water solution of the transition metal salt, such as nickel sulfate, cobalt sulfate and manganese sulfate at designated stoichiometric ratio is mixed with precipitating solution such as sodium hydroxide, sodium oxalate, or sodium carbonate to form the transition metal precursor. To make the cathode active materials, the transition metal precursor is blended with lithium salts (e.g. lithium hydroxide, lithium carbonate, and / or lithium oxide). Once blended, the lithium salt and transition metal precursor mixture are loaded into a saggar and placed in a high- temperature furnace for calcination. The lithium salt requires pre-processing (e.g., milling, mixing) before blending. However, using a composite precursor containing both transition metal and lithium described herein can eliminate the pre-processing step(s). Additional benefits of the materials and processes / methods described herein can include a reduction of carbon dioxide uptake. The processes described herein combine lithium hydroxide (LiOH) and hydrogen peroxide (H2O2) to form lithium peroxide (Li2O2), which is then combined with a transition metal to form a precursor cathode active material (i.e., lithium peroxide-coated transition metal precursor). Specifically, lithium peroxide can be formed in situ from lithium hydroxide and hydrogen peroxide. The lithium peroxide can then coat a transition metal precursor to form the lithium peroxide-coated transition metal precursor (or lithiated precursor cathode active material). This process / method can minimize or eliminate any pretreatment processes that would otherwise be required (e.g., milling or mixing of lithium salts) before calcination (i.e., cathode active material synthesis). By making a composite precursor that includes both lithium (lithium peroxide) and a transition metal for a cathode AttyDktNo.: ESS-L3-8135 WO active material (CAM) from a solution-based reaction, there may be no need to mill and mix the lithium salt in with the transition metal as typically done in CAM precursor synthesis. In some embodiments, a method of making a lithium peroxide-coated transition metal precursor comprising: mixing lithium hydroxide and hydrogen peroxide to form a suspension; adding a precipitant to the suspension; and adding a transition metal precursor into the suspension to form a lithium peroxide-coated transition metal precursor. In some embodiments, adding the precipitant to the suspension accelerates precipitation of lithium peroxide. In some embodiments, the precipitant comprises a saturated solution of lithium salt having a lithium peroxide solubility between 0.1 and 10 mg / g at room temperature. In some embodiments, the precipitant comprises one or more of lithium chloride or lithium nitrate. In some embodiments, the transition metal precursor is a compound or a mixture of compounds each having the formula 1 or an oxide counterpart thereof: qMn(OH)2^(1-q)NiaMnbCocMyX1+k (1) wherein 0≤ q ≤0.8, c = 1-a-b, 0≤ a≤1, 0<b≤1, 0≤ y≤ 0.05 and M includes one or moreselected from the group consisting of Al, Mg, Ti, Mo, Nb, Zr, Hf, Ta, W, B,P and F;wherein X is selected from the group consisting of OH-, CO32-, NO3-, SO42-, C2O42-, C2H3O2-, CHO2-, stearate, oleate, tartrate and lactate, and -0.025≤ k≤ In some embodiments, the mixing lithium hydroxide and hydrogen peroxide comprises mixing at a temperature between 20 and 80 ℃ for 20-40 minutes. In some embodiments, a method of making cathode active material comprises calcinating any of the above lithium peroxide-coated transition metal precursors. In some embodiments, calcinating the lithium peroxide-coating transition metal precursor comprises calcinating at 800 ℃ for 1.5 hours. In some embodiments, a lithium peroxide-coated transition metal precursor prepared by a method comprising: mixing lithium hydroxide and hydrogen peroxide to form a suspension; adding a precipitant to the suspension; and adding a transition metal precursor into the suspension to form a lithium peroxide-coated transition metal precursor. AttyDktNo.: ESS-L3-8135 WO In some embodiments, a method of making a cathode active material comprising: mixing lithium hydroxide and hydrogen peroxide to form a suspension; adding a precipitant to the suspension; adding a transition metal precursor into the suspension to form a lithium peroxide-coated transition metal precursor; and calcinating a lithium peroxide-coated transition metal precursor. In some embodiments, a cathode active material prepared by a method comprising: mixing lithium hydroxide and hydrogen peroxide to form a suspension; adding a precipitant to the suspension; adding a transition metal precursor into the suspension to form a lithium peroxide-coated transition metal precursor; and calcinating a lithium peroxide-coated transition metal precursor. In some embodiments, the electrode further comprises 0.1-10 wt. % carbon black and / or carbon nanotubes and 0.1-10 wt. % polyvinylidene fluoride binder. In some embodiments, a rechargeable battery includes any of the electrodes described above and herein. In some embodiments, the rechargeable battery includes a lithium metal anode. In some embodiments, the rechargeable battery includes an electrolyte comprising 1.2 M of LiPF6 in ethylene carbonate / diethyl carbonate (vol: vol= 3:7) with 5 wt. % fluoroethylene carbonate. In some embodiments, the rechargeable battery has a first discharge capacity of 195-210 mAh / g at cycles carried out between 2.9V and 4.3V at a rate of C / 20. In some embodiments, the rechargeable battery has a first discharge capacity that is greater than a first discharge capacity of a rechargeable battery comprising an electrode comprising a cathode material synthesized with lithium hydroxide anhydrous at cycles carried out between 2.9V and 4.3V at a rate of C / 20. In some embodiments, the rechargeable battery has a first coulombic energy of 89- 92 % at cycles carried out between 2.9V and 4.3V at a rate of C / 20. In some embodiments, the rechargeable battery has a first coulombic energy that is greater than a first coulombic energy of a rechargeable battery comprising an electrode comprising a cathode material synthesized with lithium hydroxide anhydrous at cycles carried out between 2.9V and 4.3V at a rate of C / 20. In some embodiments, a precursor cathode active material comprising: lithium peroxide particles coating transition metal precursor particles, wherein the lithium peroxide particles coat at least 5% of a surface of the transition metal precursor particles. AttyDktNo.: ESS-L3-8135 WO In some embodiments, any one or more of the features, characteristics, or elements discussed above with respect to any of the embodiments may be incorporated into any of the other embodiments mentioned above or described elsewhere herein. BRIEF DESCRIPTION OF THE FIGURES FIG.1 shows a process for making lithium peroxide-coated transition metal precursor, according to some embodiments; FIG.2 shows an XRD of NMC(OH)2 with Li2O2 generated in situ from the reaction between a LiOH solution / suspension combined with 30 wt. % H2O2, according to some embodiments; FIG.3 shows an XRD of NMC(OH)2with Li2O2generated in-situ from reaction between LiOH solution / suspension with 30 wt. % H2O2 with the same weight of LiCl saturated solution, according to some embodiments; FIG.4A shows a scanning electron microscope (SEM) image confirming the integrity of the secondary structure of the precursor, according to some embodiments; FIG.4B shows the presence of a layer of coating and the characteristic hexagonal plates, according to some embodiments; FIG.5 shows an SEM image of a lithiated transition metal oxide (i.e., the single phase product after calcination), according to some embodiments; and FIG.6 discharge capacities and first coulombic energy values of cathode materials synthesized used LiOH anhydrous (LiOH ANH) and cathode materials synthesized using lithium-containing precursors as described herein at 3 hour and 1.5 hour calcination, according to some embodiments. DETAILED DESCRIPTION Provided are methods of making composite precursors for cathode active materials including lithium peroxide-coated transition metal precursor. Also provided are methods of making the composite precursor by forming lithium peroxide in situ from lithium hydroxide and hydrogen peroxide and coating a transition metal precursor with the lithium AttyDktNo.: ESS-L3-8135 WO peroxide. In some embodiments, the transition metal precursor can be a compound or a mixture of compounds each having the formula 1 or an oxide counterpart thereof: qMn(OH)2^(1-q)NiaMnbCocMyX1+k(1) wherein 0≤ q ≤0.8, c = 1-a-b, 0≤ a≤1, 0<b≤1, 0≤ y≤ 0.05 and M includes one or moreselected from the group consisting of Al, Mg, Ti, Mo, Nb, Zr, Hf, Ta, W, B,P and F;wherein X is selected from the group consisting of OH-, CO32-, NO3-, SO42-, C2O42-,C2H3O2-, CHO2-, stearate, oleate, tartrate and lactate, and-0.025≤ k≤ 1.25.In some embodiments, the transition metal precursor can be a compound or a mixture of compounds each having the formula 2 or an oxide counterpart thereof: (NixCoyMnz)Ab(2) in which x + y + z = 1; A = OH-,OOH-,CO32-,and / or C2O42-; b = 2 when A = OH- and / or OOH-, otherwise b = 1. These methods of making precursor cathode active materials can simplify the cathode active material production process and / or reduce carbon dioxide uptake. Further, the lithium peroxide-coated transition metal precursor formed from these processes can provide better contact between the transition metal precursor and the lithium salt than from the physical mixing processes in the conventional cathode manufacturing operation. Specifically, making cathode active material from the composite precursor, in particular a lithium peroxide-coated transition metal precursor, described herein can increase the simplicity and reduce the amount of time required to produce the cathode active materials via calcination, since the preprocessing step for lithium salt is no longer required. Additional benefits of the materials and processes / methods described herein can include a reduction of carbon dioxide uptake and enhancement of the contact between the transition metal precursor and the lithium salts. Therefore, the processes of producing precursor cathode active materials, and more specifically, lithium peroxide-coated transition metal precursor materials as described herein, can be more efficient and less costly than conventional processes. AttyDktNo.: ESS-L3-8135 WO Also described herein are cathode active materials that are made from lithium peroxide-coated transition metal precursor materials and lithium peroxide-coated transition metal precursors. Further, electrodes comprising the cathode active materials described and methods of making thereof, and rechargeable batteries comprising said electrodes and methods of making thereof are also provided herein. Described below are (1) Methods for Producing Lithium Peroxide-Coated Transition Metal Precursor; (2) Processes for Producing Cathode Active Materials from Lithium Peroxide-Coated Transition Metal Precursor; (3) Characterization of Cathode Active Materials Formed from the Processes Described Herein; (4) Preparing Electrodes and Batteries from Lithiated Transition Metal Precursor Materials; (5) Lithium Peroxide- Coated Transition Metal Precursor, Cathode Active Materials, Electrodes Comprising Cathode Active Materials, and Rechargeable Batteries Comprising Said Electrodes; and (6) Electrochemical Performance. 1. Methods for Producing Lithium Peroxide-Coated Transition Metal Precursor As described above, conventional processes for producing cathode active materials require obtaining lithium, a transition metal, and oxygen separately, and then combining all three materials to form the cathode active material. However, the processes provided herein form lithium peroxide in situ and then coat a transition metal precursor with the lithium peroxide. This process is described in further detail below. FIG.1 shows a process for making lithium peroxide-coated transition metal precursor, according to some embodiments. At step 102, lithium peroxide can be formed in situ by mixing lithium hydroxide with hydrogen peroxide to form a suspension. The lithium hydroxide and hydrogen peroxide can be mixed to form a solution with LiOH suspension. In some embodiments, this suspension or solution can then be stirred in a carbon dioxide-free and / or in an inert gas environment. In some embodiments, a carbon dioxide-free environment can be an environment comprising 0.001 wt.% or less carbon dioxide. In some embodiments, the inert gas can be nitrogen or argon. Because lithium hydroxide can react with carbon AttyDktNo.: ESS-L3-8135 WO dioxide, the reaction may be more successful in a carbon dioxide-free (or inert gas) environment. In some embodiments, the reaction of step 102 can occur in an oxygen-rich or in an oxygen-depleted environment. In some embodiments, using a molar ratio of amount of hydrogen peroxide greater than that of lithium hydroxide may help drive the reaction more closely to completion. In some embodiments, the lithium hydroxide and hydrogen peroxide are mixed at a temperature of between 20 ℃ and 80 ℃ or between 50 and 70 ℃. In some embodiments, the lithium hydroxide and hydrogen peroxide are mixed at a temperature of less than or equal to 80 ℃, less than or equal to 70 ℃, less than or equal to 60 ℃, less than or equal to 50 ℃, less than or equal to 40 ℃, or less than or equal to 30 ℃. In some embodiments, the lithium hydroxide and hydrogen peroxide are mixed at a temperature of greater than or equal to 20 ℃, greater than or equal to 30 ℃, greater than or equal to 40 ℃, greater than or equal to 50 ℃, greater than or equal to 60 ℃, or greater than or equal to 70 ℃. In some embodiments, the lithium hydroxide and hydrogen peroxide are mixed for 5 to 60 minutes or 20 to 40 minutes. In some embodiments, the lithium hydroxide and hydrogen peroxide are mixed for less than or equal to 60 minutes, less than or equal to 50 minutes, less than or equal to 40 minutes, less than or equal to 30 minutes, or less than or equal to 20 minutes. In some embodiments, the lithium hydroxide and hydrogen peroxide are mixed for greater than or equal to 5 minutes, greater than or equal to 10 minutes, greater than or equal to 20 minutes, greater than or equal to 30 minutes, greater than or equal to 40 minutes, or greater than or equal to 50 minutes. In some embodiments, the lithium hydroxide and hydrogen peroxide are mixed at about 60℃ for about 30 minutes. At step 104, a precipitant (such as a highly soluble lithium salt and / or an antisolvent) can be added to the suspension to promote acceleration of precipitation of lithium peroxide. In some embodiments, a suitable precipitant can suppress lithium peroxide dissolution. Table 1, below, shows the lithium peroxide solubility for several different precipitants. In some embodiments, a suitable precipitant has a lithium peroxide solubility of equal to or less than 31 mg / g solvent. In some embodiments, a suitable precipitant has a lithium peroxide solubility of equal to or less than 10 mg / g solvent. In some embodiments, a suitable precipitant has a lithium peroxide solubility of equal to or AttyDktNo.: ESS-L3-8135 WO less than 1 mg / g solvent. In some embodiments, a suitable precipitant has a lithium peroxide solubility of equal to or greater than 0.1 mg / g solvent. In some embodiments, a suitable precipitant has a lithium peroxide solubility of equal to or greater than 1 mg / g solvent. In some embodiments, a suitable precipitant has a lithium peroxide solubility of equal to or greater than 10 mg / g solvent. In some embodiments, a suitable precipitant has a lithium peroxide solubility between 0.1 and 10 mg / g solvent. As used herein, the solvent of the solubility units “mg / g solvent” is a saturated solution of the precipitant to which it refers. For example, the Li2O2solubility at room temperature of a LiOH saturated solution is 31 mg / g LiOH saturated solution. In some embodiments, the precipitant is lithium chloride and / or lithium nitrate. Solvent / Solution Li2O2solubility at room temperature (mg / g solvent) Di H2O 70 LiOH saturated solution 31 Li2SO4 saturated solution 41.63 LiCl saturated solution 0.74 LiNO3 saturated solution 2.97 Table 1. The solubility of Li2O2in different solvent or solutions In some embodiments, once the lithium peroxide is formed in situ, as described above, the transition metal precursor can added to the suspension to form a lithium peroxide-coated transition metal precursor in step 106. In some embodiments, the mixture is stirred to allow the continuous reaction for between 5 and 60 minutes. In some embodiments, the mixture is stirred for less than or equal to 60 minutes, less than or equal to 50 minutes, less than or equal to 40 minutes, less than or equal to 30 minutes, less than or equal to 20 minutes, or less than or equal to 10 minutes. In some embodiments, the mixture is stirred for greater than or equal to 5 minutes, greater than or equal to 10 minutes, greater than or equal to 20 minutes, greater than or equal to 30 minutes, greater than or equal to 40 minutes, or greater than or equal to 50 minutes. In some embodiments, the transition metal precursor can be a compound or a mixture of compounds each having the formula 1 or an oxide counterpart thereof: AttyDktNo.: ESS-L3-8135 WO qMn(OH)2^(1-q)NiaMnbCocMyX1+k (1) wherein 0≤ q ≤0.8, c = 1-a-b, 0≤ a≤1, 0<b≤1, 0≤ y≤ 0.05 and M includes one or moreselected from the group consisting of Al, Mg, Ti, Mo, Nb, Zr, Hf, Ta, W, B,P and F;wherein X is selected from the group consisting of OH-, CO32-, NO3-, SO42-, C2O42-,C2H3O2-, CHO2-, stearate, oleate, tartrate and lactate, and-0.025≤ k≤ 1.25.In some embodiments, the transition metal precursor can be a compound or a mixture of compounds each having the formula 2 or an oxide counterpart thereof: (NixCoyMnz)Ab(2) in which x + y + z = 1; A = OH-, OOH-, CO32-, and / or C2O42-; b = 2 when A = OH- and / or OOH-, otherwise b = 1. In some embodiments, suitable transition metal precursors can include, but are not limited to, NixCoyMnz(OH)2, NixCoyMnz(OOH)2, NixCoyMnzO2, and / or NixCoyMnz(OOH)3. Non-limiting examples of suitable transition metal precursorsinclude,Ni0.82Mn0.06Co0.12(OH)2, Ni0.88Co0.06Mn0.03Al0.03(OH)2, and the like. Non-limitingexamples of suitable oxide counterparts of the transition metal precursors includeNi0.82Mn0.06Co0.12O, Ni0.88Co0.06Mn0.03Al0.03O, and the like.In some embodiments, othersuitable metal compounds can include a metal hydroxide, hydroperoxide, peroxide, or oxide hydroxide containing one or more of lithium, nickel, manganese, cobalt, aluminum, magnesium, zirconium, titanium, and / or phosphorus. In some embodiments, the order of the steps in FIG.1 can be mixed and matched (e.g., 106 ^ 102 ^ 104; 102 ^ 106 ^ 104; 104 ^ 106 ^ 102; 104 ^ 102 ^ 106). For the lithium hydrogen can be added to a suspension that includes the transition metal precursor. Then, the precipitant can be added to the suspension to accelerate the precipitation of lithium peroxide. 2. Processes for Producing Cathode Active Materials from Lithium Peroxide- Coated Transition Metal Precursor After the lithium peroxide-coated transition metal precursor (composite precursor for cathode active material) is formed using the methods described above, a single phase cathode active material product (a lithiated transition metal oxide) can be formed by a AttyDktNo.: ESS-L3-8135 WO calcination process. During the calcination process, the transition metal precursor can be oxidized at high temperature and the lithium from lithium peroxide can diffuse into the layered transition metal oxide framework to form the cathode active material. In some embodiments, the lithium peroxide-coated transition metal precursor may be calcinated at a temperature between 600 and 1200 ℃ or between 700 ℃ and 900 ℃. In some embodiments, the lithium peroxide-coated transition metal precursor may be calcinated at a temperature less than or equal to 1200 ℃, less than or equal to 1100 ℃, less than or equal to 1000 ℃, less than or equal to 900 ℃, less than or equal to 800 ℃, or less than or equal to 700 ℃. In some embodiments, the lithium peroxide-coated transition metal precursor may be calcinated at a temperature greater than or equal to 600 ℃, greater than or equal to 700 ℃, greater than or equal to 800 ℃, greater than or equal to 900 ℃, greater than or equal to 1000 ℃, or greater than or equal to 1100 ℃. In some embodiments, the lithium peroxide-coated transition metal precursor may be calcinated between 30 minutes and 6 hours, between 1 hour and 2 hours, or between 2 hours and 4 hours. In some embodiments, the lithium peroxide-coated transition metal precursor may be calcinated for less than or equal to 6 hours, 5 hours, 4 hours, 3 hours, 2 hours, or 1 hour. In some embodiments, the lithium peroxide-coated transition metal precursor may be calcinated for greater than or equal to 30 minutes, 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours. In some embodiments, the length of the calcination process may be less than that which is required for conventionally produced precursor cathode active materials. In some embodiments, the length of the calcination process may be between 20 and 90 % or between 70 and 90 % shorter than the calcination process required for conventionally produced precursor cathode active materials. In some embodiments, the length of the calcination process may be less than or equal to 90 %, less than or equal to 80 %, less than or equal to 70 %, less than or equal to 60 %, less than or equal to 50 %, less than or equal to 40 %, or less than or equal to 30 % shorter than the calcination process required for conventionally produced precursor cathode active materials. In some embodiments, the length of the calcination process may be greater than or equal to 20 %, greater than or equal to 30 %, greater than or equal to 40 %, greater than or equal to 50 %, greater than or equal to 60 %, greater than or equal to 70 %, or greater than or equal to 80 % shorter than AttyDktNo.: ESS-L3-8135 WO the calcination process required for conventionally produced precursor cathode active materials. The processes provided herein can be used to prepare nickel-containing cathode active materials, and in particular, ternary nickel-manganese-cobalt (NMC) and / or nickel- cobalt-aluminum (MCA) cathode active materials. In some embodiments, the processes provided herein may be used to prepare high nickel cathode materials, comprising 60 wt. % nickel or greater (i.e., NMC 80 series and above). In some embodiments, the cathode active materials described herein may comprise greater than or equal to 60 wt. %, greater than or equal to 65 wt. %, greater than or equal to 70 wt. %, greater than or equal to 75 wt. %, greater than or equal to 80 wt. %, greater than or equal to 85 wt. %, greater than or equal to 90 wt. %, or greater than or equal to 95 wt. % nickel. In some embodiments, the cathode active materials described herein may comprise less than or equal to 99 wt. %, less than or equal to 95 wt. %, less than or equal to 90 wt. %, less than or equal to 85 wt. %, less than or equal to 80 wt. %, less than or equal to 75 wt. %, less than or equal to 70 wt. %, or less than or equal to 75 wt. % nickel. In some embodiments, the cathode active material product (i.e., the lithiated transition metal oxide) can be a compound having the formula (3): qLi2MnO3^(1-q)LiNiaMnbCocMyO2+z (3) wherein 0≤ q ≤0.8, c = 1-a-b, 0≤ a≤1, 0<b≤1, 0≤ y≤ 0.05, -0.025≤ z≤0.125, and M is selected from the group consisting of Al, Mg, Ti, Mo, Nb, Zr, Hf, Ta, W, B, P, F and a combination of any two or more of the foregoing. 3. Characterization of Cathode Active Materials and Formed from the Processes Described Herein X-ray powder diffraction (XRD) on a D8 ADVANCE powder diffractometer (Bruker Inc.) using a CuKα anode as the X-ray source (λ=1.54060 Å) was used to identify the speciation of the reaction products between the acids / oxides with LiOH. FIG.2 shows an XRD of NMC(OH)2with Li2O2generated in situ from the reaction between a LiOH solution / suspension combined with 30 wt. % H2O2. Specifically, this XRD shows synthesis of the Li2O2-containing precursor without precipitant. As confirmed by the XRD, the Li speciation is dominated by LiOH (16.0%) instead of Li2O2 AttyDktNo.: ESS-L3-8135 WO (9.4%). This suggests Li loss and a potential decomposition reaction as the precipitated Li2O2converts to LiOH. FIG.3 shows an XRD of NMC(OH)2with Li2O2generated in-situ from reaction between LiOH solution / suspension with 30 wt. % H2O2 with the same weight of LiCl saturated solution. Specifically, this XRD shows synthesis of Li2O2-containing precursor with LiCl saturation solution as a precipitant. As confirmed by the XRD of the precursor, the Li speciation is dominated by Li2O2(32.4%), and close to the stoichiometric ratio of the LiOH added to the reaction. FIGS.4A and 4B show a scanning electron microscope (SEM) image confirming the integrity of the secondary structure of the precursor (FIG.4A) and the presence of a layer of coating and the characteristic hexagonal plates in between (FIG.4B). Specifically, both FIGs.4A and 4B show the lithium peroxide 304 coating the transition metal 302. In some embodiments, the lithium peroxide may only penetrate the transition metal. In some embodiments, the lithium peroxide may partially penetrate and partially coat the transition metal. In some embodiments, the lithium peroxide may only coat the transition metal. FIG.5 shows an SEM image of a lithiated transition metal oxide (i.e., the single phase product after calcination). Specifically, FIG.5 shows NMC811 materials synthesized from the lithium containing precursor at 800oC with 1.5-hour calcination and under oxygen atmosphere. In some embodiments, at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 50%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, or at least about 95% of the surface of a transition metal precursor can be coated with lithium peroxide. In some embodiments, the lithium peroxide-coated transition metal precursor can have a core-shell structure, wherein the transition metal precursor can form the core and the shell is a layer or coating that includes lithium peroxide 4. Preparing Electrodes and Batteries from Lithiated Transition Metal Precursor Materials AttyDktNo.: ESS-L3-8135 WO In some embodiments, an electrode (i.e., cathode) in the form of a laminate may be prepared by combining the lithiated transition metal materials (i.e., the calcinated lithium peroxide-coated transition metal precursor) with carbon black and / or carbon nanotubes and a binder. In some embodiments, the electrode may comprise 0.1-10 wt. % carbon black and / or carbon nanotubes. 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. % carbon black and / or carbon nanotubes. 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. % carbon black and / or carbon nanotubes. In some embodiments, the electrode may comprise 0.1-10 wt. % binder. 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. 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. In some embodiments, the electrode may comprise 80-99.8 wt. % the lithiated transition metal materials (i.e., the calcinated lithium peroxide-coated transition metal precursor) 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 lithiated transition metal materials (i.e., the calcinated lithium peroxide-coated transition metal precursor) described herein. In some embodiments, the electrode may comprise greater than or equal AttyDktNo.: ESS-L3-8135 WO 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 lithiated transition metal materials (i.e., the calcinated lithium peroxide-coated transition metal precursor) described herein. In some embodiments, the cathode laminates may be used in coin cells (e.g., 2032 coin cell) with lithium metal as a counter electrode. In some embodiments, the electrolyte may be liquid. For example, the electrolyte may comprise LiPF6. In some embodiments, the electrolyte may comprise 1.2 M of LiPF6in ethylene carbonate / diethyl carbonate (vol: vol= 3:7) with 5 wt. % fluoroethylene carbonate. 5. Lithium Peroxide-Coated Transition Metal Precursor, Lithiated Cathode Active Materials, Electrodes Comprising Lithiated Cathode Active Materials, and Rechargeable Batteries Comprising Said Electrodes Also provided herein are lithium peroxide-coated transition metal precursors, lithiated cathode active materials, electrodes comprising lithiated cathode active materials, and rechargeable batteries comprising said electrodes comprising lithiated cathode active materials. In some embodiments, lithium peroxide-coated transition metal precursor provided herein may be produced by the processes and methods described herein. In some embodiments, at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 50%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, or at least about 95% of the surface are of the transition metal precursor particles of the lithium peroxide-coated transition metal precursor is coated by the lithium peroxide particles. The lithiated cathode active materials provided herein may be produced using the methods described above. Specifically, the lithiated cathode active materials may be prepared by calcinating the lithium peroxide-coated transition metal precursor provided herein. In some embodiments, calcinating the lithium peroxide-coated transition metal precursor is a faster and simpler process than a process calcinating precursor cathode active materials prepared using conventional methods. AttyDktNo.: ESS-L3-8135 WO 6. Electrochemical Performance In some embodiments, a half-cell prepared from the lithium peroxide-coated transition metal precursor as described herein may require a lower calcination time than that of a half-cell prepared using other types of precursor cathode active materials. In some embodiments, the calcination step may be 20-90 % less than that required of other precursor cathode active materials. Some specific electrochemical performance data is shown in FIG.6 and described below. In some embodiments, the first discharge capacity of a half-cell prepared from the calcined lithium peroxide-coated transition metal precursor is 195-210 mAh / g at cycles carried out between 2.9V and 4.3V at a rate of C / 20. In some embodiments, the first discharge capacity of a half-cell prepared from the calcined lithium peroxide-coated transition metal precursor is greater than a first discharge capacity of half-cell comprising a cathode material synthesized with lithium hydroxide anhydrous at cycles carried out between 2.9V and 4.3V at a rate of C / 20. In some embodiments, a half-cell prepared from the calcined lithium peroxide-coated transition metal precursor has a first coulombic energy of 89-92 % at cycles carried out between 2.9V and 4.3V at a rate of C / 20. In some embodiments, a half-cell prepared from the calcined lithium peroxide-coated transition metal precursor has a first coulombic energy that is greater than a first coulombic energy of a half-cell comprising a cathode material synthesized with lithium hydroxide anhydrous at cycles carried out between 2.9V and 4.3V at a rate of C / 20. EXAMPLES Example 1: The synthesis process was carried out in glass vessel under stirring, in which 20g of LiOH and 30g H2O2 solution (30 wt. %) or 18g H2O2 (50 wt. %) were mixed to generate a solution with LiOH suspension. The solution or suspension is then stirred in CO2-free air (or inert gas atmosphere) at 60oC for 30 min. A precipitant (LiCl saturated solution), such as a highly soluble lithium salt or an antisolvent is added to accelerate the reaction and precipitation of Li2O2.As the solution / suspension was stirred, the transition metal precursor (Ni0.83Mn0.06Co0.11(OH)2) is added to the reaction and allowed stirring and continuous reaction for 5-60 min. AttyDktNo.: ESS-L3-8135 WO Example 2: 1% of carbon black / carbon nanotube and 2% of polyvinylidene fluoride (PVDF) binder were mixed with the compounds of the disclosure to form the cathode laminates. The thereby obtained laminates were then tested in 2032-coin cells using lithium metal as counter electrodes. The electrolyte was 1.2 M of LiPF6in ethylene carbonate / diethyl carbonate (vol: vol= 3:7) with 5 wt. % fluoroethylene carbonate. The cycles were carried out between 2.9V and 4.3V at a rate of C / 20. The 1stdischarge capacity and the coulombic efficiency of the first cycle of the compound of disclosure and are illustrated, comparing the NMC 811 synthesized using the composite precursor composing lithium peroxide coated transition metal precursor at 3 hour and 1.5 hour calcination time, and using LiOH and transition metal precursor mixture at 3 hour calcination time. FIG.6 shows discharge capacities and first coulombic energy values of cathode materials synthesized used LiOH anhydrous (LiOH ANH) and cathode materials synthesized using lithium-containing precursors as described herein at 3 hour and 1.5 hour calcination. The electrochemical performance in the half-cell suggests that the lithium- containing precursor favors a lower calcination time of 1.5 hours, which corresponds to an 80% reduction of the calcination time. Advantages are also observed when compared to cathode material synthesized with LiOH anhydrous, which is known to be used by some cathode manufacturers to enhance cathode material synthesis throughput. In this disclosure, while compositions and / or processes or methods are often described in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of” or “consist of” the various components or steps, unless stated otherwise. For example, a process consistent with aspects of the disclosed subject matter can comprise; alternatively, can consist essentially of; or alternatively, can consist of; the process steps indicated. The terms “a,” “an,” and “the” are intended to include plural alternatives, e.g., at least one, one or more, and one or more than one, unless otherwise specified. The terms “room temperature” or “ambient temperature” are used herein to describe any temperature from 15° C to 35° C wherein no external heat or cooling source is directly applied to the reaction vessel. Accordingly, the terms “room temperature” and “ambient temperature” encompass the individual temperatures and any and all ranges, AttyDktNo.: ESS-L3-8135 WO subranges, and combinations of subranges of temperatures from 15° C to 35° C wherein no external heating or cooling source is directly applied to the reaction vessel. The term “atmospheric pressure” is used herein to describe an earth air pressure wherein no external pressure modifying means is utilized. Generally, unless practiced at extreme earth altitudes, “atmospheric pressure” is about 1 atmosphere (alternatively, about 14.7 psi or about 101 kPa). The term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate including being larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement errors, and the like, and other factors known to those of skill in the art. In general, an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such. The term “about” also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term “about,” the claims include equivalents to the stated quantities. When a numerical range of any type is disclosed or claimed herein (e.g., “ranging from…”, “in a range of from…”, “in the range of from…”, “in a range of from”, “in a range of”) the intent is to disclose or claim individually each possible number or ratio that such a range could reasonably encompass, including end points of the range as well as any sub-ranges and combinations of sub-ranges encompassed therein, unless otherwise specified. Embodiments disclosed herein can provide the materials listed as suitable for satisfying a particular feature of the embodiment delimited by the term “or.” For example, a particular feature of the disclosed subject matter can be disclosed as follows: Feature X can be A, B, or C. It is also contemplated that for each feature the statement can also be phrased as a listing of alternatives such that the statement “Feature X is A, alternatively B, or alternatively C” is also an embodiment of the present disclosure whether or not the statement is explicitly recited. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the subject matter described herein, the typical methods and materials are herein described. AttyDktNo.: ESS-L3-8135 WO All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications, which can be used in connection with the presently described subject matter.

Claims

AttyDktNo.: ESS-L3-8135 WO CLAIMS 1. A method of making a lithium peroxide-coated transition metal precursor comprising: mixing lithium hydroxide and hydrogen peroxide to form a suspension; adding a precipitant to the suspension; and adding a transition metal precursor into the suspension to form a lithium peroxide- coated transition metal precursor.

2. The method of claim 1, wherein adding the precipitant to the suspension accelerates precipitation of lithium peroxide.

3. The method of claim 1 or 2, wherein the precipitant comprises a saturated solution of lithium salt having a lithium peroxide solubility between 0.1 and 10 mg / g at room temperature.

4. The method of any one of claims 1-3, wherein the precipitant comprises one or more of lithium chloride or lithium nitrate.

5. The method of any one claims 1-4, wherein the transition metal precursor is a compound or a mixture of compounds each having the formula 1 or an oxide counterpart thereof: qMn(OH)2^(1-q)NiaMnbCocMyX1+k (1) wherein 0≤ q ≤0.8, c = 1-a-b, 0≤ a≤1, 0<b≤1, 0≤ y≤ 0.05 and M includes one or moreselected from the group consisting of Al, Mg, Ti, Mo, Nb, Zr, Hf, Ta, W, B,P and F;wherein X is selected from the group consisting of OH-, CO32-, NO3-, SO42-, C2O42-,C2H3O2-, CHO2-, stearate, oleate, tartrate and lactate, and-0.025≤ k≤ 1.25.

6. The method of any of claims 1-5, wherein the mixing lithium hydroxide and hydrogen peroxide comprises mixing at a temperature between 20 and 80 ℃ for 20-40 minutes.

7. A method of making a cathode active material comprising calcinating the lithium peroxide-coating transition metal precursor of claims 1-6.AttyDktNo.: ESS-L3-8135 WO 8. The method of claim 7, wherein calcinating the lithium peroxide-coating transition metal precursor comprises calcinating at 800 ℃ for 1.5 hours.

9. A lithium peroxide-coated transition metal precursor prepared by a method comprising: mixing lithium hydroxide and hydrogen peroxide to form a suspension; adding a precipitant to the suspension; and adding a transition metal precursor into the suspension to form a lithium peroxide-coated transition metal precursor.

10. A method of making a cathode active material comprising: mixing lithium hydroxide and hydrogen peroxide to form a suspension; adding a precipitant to the suspension; adding a transition metal precursor into the suspension to form a lithium peroxide- coated transition metal precursor; and calcinating a lithium peroxide-coated transition metal precursor.

11. A cathode active material prepared by a method comprising: mixing lithium hydroxide and hydrogen peroxide to form a suspension; adding a precipitant to the suspension; adding a transition metal precursor into the suspension to form a lithium peroxide- coated transition metal precursor; and calcinating a lithium peroxide-coated transition metal precursor.

12. An electrode comprising the cathode active material of claim 11.

13. The electrode of claim 12, wherein the electrode further comprises 0.1-10 wt. % carbon black and / or carbon nanotubes and 0.1-10 wt. % polyvinylidene fluoride binder.

14. A rechargeable battery comprising the electrode of claim 10 or 11.

15. The rechargeable battery of claim 14, comprising a lithium metal anode.

16. The rechargeable battery of claim 14 or 15, comprising an electrolyte comprising 1.2 M of LiPF6 in ethylene carbonate / diethyl carbonate (vol: vol= 3:7) with 5 wt. % fluoroethylene carbonate.AttyDktNo.: ESS-L3-8135 WO 17. The rechargeable battery of any one of claims 14-16, wherein the rechargeable battery has a first discharge capacity of 195-210 mAh / g at cycles carried out between 2.9V and 4.3V at a rate of C / 20.

18. The rechargeable battery of any one of claims 14-17, wherein the rechargeable battery has a first discharge capacity that is greater than a first discharge capacity of a rechargeable battery comprising an electrode comprising a cathode material synthesized with lithium hydroxide anhydrous at cycles carried out between 2.9V and 4.3V at a rate of C / 20.

19. The rechargeable battery of any one of claims 14-18, wherein the rechargeable battery has a first coulombic energy of 89-92 % at cycles carried out between 2.9V and 4.3V at a rate of C / 20.

20. The rechargeable battery of any one of claims 14-19, wherein the rechargeable battery has a first coulombic energy that is greater than a first coulombic energy of a rechargeable battery comprising an electrode comprising a cathode material synthesized with lithium hydroxide anhydrous at cycles carried out between 2.9V and 4.3V at a rate of C / 20.

21. A precursor cathode active material comprising: lithium peroxide particles coating transition metal precursor particles, wherein the lithium peroxide particles coat at least 5% of a surface of the transition metal precursor particles.

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