Method for Producing Cathode Material Precursor

Abstract

A method for preparing cathode material precursors from metal carbonyl complexes is described.

Description

[Technical field]

[0001] [CROSS REFERENCE TO RELATED APPLICATIONS] Incorporation by reference of any priority application All applications in which a foreign or domestic priority claim is identified in the Application Data Sheet or application filed with this application, such as U.S. Provisional Application No. 63 / 195,545, filed June 1, 2021, are incorporated herein by reference under 37 CFR 1.57 and Rules 4.18 and 20.6. [Background technology]

[0002] Lithium-ion batteries are desirable due to their optimized cost, safety, life span and moderate energy density. Current methods of cathode manufacturing use multiple steps and can generate significant amounts of waste. For example, some conventional cathode material manufacturing processes (e.g., lithium iron phosphate) require the production of nanoparticles, which require spray drying or multiple chemical steps. Thus, new methods that reduce or eliminate processing steps in the production of battery raw materials could help lower the end-use cost of lithium-ion batteries. Summary of the Invention [Problem to be solved by the invention]

[0003] For the purpose of summarizing the present disclosure and the advantages achieved over the prior art, certain objects and advantages of the present disclosure are described herein. Not all such objects or advantages can be achieved in any particular embodiment. Thus, for example, a person skilled in the art will recognize that the present invention can be embodied or implemented to achieve or optimize one or a group of advantages as taught herein, without necessarily achieving other objects or advantages as may be taught or suggested herein. [Means for solving the problem]

[0004] All of these embodiments are intended to be within the scope of the invention disclosed herein. These and other embodiments will become readily apparent to those of ordinary skill in the art from the following detailed description of the preferred embodiments, taken in conjunction with the accompanying drawings, and the invention is not limited to any particular preferred embodiment disclosed.

[0005] In one aspect, a method of making a cathode material precursor is described, the method comprising reacting a metal carbonyl complex with an acid to form a cathode material precursor.

[0006] In some embodiments, the metal carbonyl complex may include a metal selected from Ni, Co, Fe, Mn, and combinations thereof. In some embodiments, the metal carbonyl complex may include Ni(CO)4, Co(CO)3(NO), H2Fe(CO)4, HCo(CO)4, Co2(CO)8, Fe(CO)5, Mn2(CO) 10 , Li[HFe(CO)4], metal carbonyl isocyanide complexes thereof, metal carbonyl phosphine complexes thereof, and combinations thereof. In some embodiments, the acid may include H3PO4, H3PO3, H2SO4, H2SO3, HNO3, HNO2, HI, HBr, HCl, HF, and combinations thereof. In some embodiments, the metal carbonyl complex may be heated to about 30-150°C. In some embodiments, the method of making the cathode material precursor further includes isolating the cathode material precursor. In some embodiments, the method of making the cathode material precursor further includes reacting the cathode material precursor with a lithium salt compound to form the cathode active material. In some embodiments, the lithium salt compound may include at least one of LiOH and LiCO3. In some embodiments, the iron ore includes a metal carbonyl complex. In some embodiments, the iron ore may be reacted with an acid to form the cathode material precursor. In some embodiments, the cathode material precursor may include a metal hydroxide, a metal oxide, a metal nitrate, a metal sulfate, or a metal phosphate.

[0007] In another aspect, a method of making a cathode material precursor is described that includes heating a metal carbonyl complex to form a metal powder and reacting the metal powder with an acid to form the cathode material precursor.

[0008] In some embodiments, the metal carbonyl complex is heated at a temperature between 25 and 200° C. In some embodiments, reacting the metal carbonyl complex with an acid decomposes the metal carbonyl complex into fine particle sized metal powder. In some embodiments, the fine particle sized metal powder is nano-sized. In some embodiments, the fine particle sized metal powder ranges from about 0.1 μm to about 50 μm. In some embodiments, one or more steps are performed in the gas phase.

[0009] In another aspect, a method of making a cathode active material is described that includes reacting a metal carbonyl complex with lithium hydroxide to form a lithium metal carbonyl hydride and reacting the lithium metal carbonyl hydride with an acid to form the cathode active material.

[0010] In some embodiments, the method of making a cathode active material further includes calcining the lithium metal hydride in the presence of an oxidizing agent.

[0011] In another aspect, a method of making a cathode active material is described that includes reacting a first metal carbonyl complex with a base to form a metal hydroxide.

[0012] In some embodiments, the method of making a cathode active material further includes reacting the first metal carbonyl complex with a second metal carbonyl complex, the second metal carbonyl complex being selected from the group consisting of Ni(CO)4, Co(CO)3(NO), H2Fe(CO)4, HCo(CO)4, Co2(CO)8, Fe(CO)5, Mn2(CO) 10, Li[HFe(CO)4], their metal carbonyl isocyanide complexes, their metal carbonyl phosphine complexes, and combinations thereof. In some embodiments, the first metal carbonyl complex is exposed to ultraviolet light. In some embodiments, the first metal carbonyl complex is exposed to manganese sulfate, sodium aluminate, or combinations thereof.

[0013] In another embodiment, a method of making a cathode material precursor is described, the method comprising mixing a first gas stream comprising an inert carrier gas and a metal carbonyl complex with a second gas stream comprising an oxidant, and heating the mixed first and second gas streams to form a cathode material precursor.

[0014] The disclosed method provides a direct route to cathode production by eliminating the need for metal powders or metal sulfates during the manufacturing process. The disclosed method may include reacting metal carbonyl complexes to produce cathode material precursors and cathode materials for use in energy storage devices. In some embodiments, the disclosed method may include an acid method, a base method, a hydrogenation method, or an oxidant method, or a combination thereof. For example, in some embodiments, producing the cathode material precursor and / or the cathode material can be performed by an acid method in combination with a hydrogenation method. In other embodiments, producing the cathode material precursor and / or the cathode material can be performed by a base method in combination with an oxidant method.

[0015] Metal carbonyl complexes Metal carbonyl complexes are a large class of low-valent, low-coordinated transition metal compounds. They are unique because they function as molecular sources of reduced metal and are characterized by their tendency to undergo redox reactions with small molecules to obtain oxidized metal species and reduced products. Classical examples of metal carbonyls are Ni(CO)4, Co2(CO)8, and Fe(CO)5. Metal carbonyls are produced on a large scale and are readily available at low cost. Metal carbonyls may be used in catalysis and in the production of high-purity metal powders. For example, many carbonyls (e.g., nickel and iron carbonyls) are known intermediates in steam metallurgical refining (e.g., the Mond process). The Mond process is widely utilized to purify nickel and iron from sulfide deposits, laterite deposits, or other material sources. While industry typically processes these carbonyl intermediates as intermediates that are cracked to obtain high-purity metal powders or pellets, the present disclosure achieves the direct use of the carbonyl intermediates to produce high-value cathode active materials and / or intermediates.

[0016] In some embodiments, the metal of the metal carbonyl complex may include Ni, Co, Fe, Mn, or a combination thereof. In some embodiments, the metal carbonyl complex may be a binary metal carbonyl (e.g., Ni(CO)4, Co2(CO)8, Fe(CO)5, and Mn2(CO) 10 and the like), metal carbonyl hydrides (such as, for example, HFe(CO) and HCo(CO)), metal carbonyl nitrosyls (such as, for example, Co(CO)(NO)), metal carbonyl hydride salts (such as, for example, lithium metal carbonyl hydride (Li[HFe(CO)])), other metal carbonyl complexes containing alternative ligands (such as, for example, isocyanides and phosphines), and combinations thereof.

[0017] In some embodiments, the iron ore comprises a metal carbonyl complex. In some embodiments, the iron ore can be utilized in the methods disclosed herein, whereby the metal carbonyl complex reacts to produce a cathode material precursor (e.g., without purifying the iron ore and / or without extracting the metal carbonyl complex from the iron ore). In some embodiments, the iron ore can be reacted by an acid method, a base method, a hydrogenation method, an oxidant method, or a combination thereof.

[0018] Cathode material precursors and cathode materials In some embodiments, the cathode material precursor is a metal hydroxide (Ni x Co y Mn z Al a (OH)2;x+y+z+a=1), metal oxide (LiNi x Co y Mn z Al a (O)2), metal nitrates, metal sulfates, or metal phosphates. In some embodiments, the cathode active material may include metal oxides, metal sulfides, lithium metal oxides and / or phosphates, such as lithium nickel manganese cobalt oxide (NMC), nickel manganese aluminum oxide (NMA), lithium iron phosphate (LFP), lithium nickel manganese spinel (LNMO), lithium nickel cobalt aluminum oxide (NCA), lithium manganese oxide (LMO), and lithium cobalt oxide (LCO). In some embodiments, the cathode active material may include, for example, layered transition metal oxides (e.g., LiCoO2 (LCO), Li(NiMnCo)O2 (NMC) and / or LiNi 0.8 Co 0.15 Al 0.05 O2(NCA)), spinel manganese oxide (LiMn2O4(LMO) and / or LiMn 1.5 Ni 0.5 O4(LMNO)), olivine (LiFePO4(LFP) or LiMn 1-x Fe x PO4 (LMFP), etc.

[0019] Method for preparing cathode material precursor and cathode material In some embodiments, one or more steps can be carried out in the gas phase. In other embodiments, one or more steps of the methods of the present disclosure can be carried out in the aqueous phase.

[0020] In some embodiments, producing the cathode material precursor may include direct oxidation of a metal carbonyl complex. In some embodiments, producing the cathode material precursor may include reacting a metal carbonyl complex (e.g., a metal carbonyl) with an acid, a base, a lithium salt, an oxidizing agent, or a combination thereof.

[0021] In some embodiments, producing the cathode material precursor and / or cathode material can be performed using heat and / or light. In some embodiments, producing the cathode material precursor and / or cathode material can be performed at about, at least, or at least about 25°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 300°C, 350°C, 400°C, 450°C, or 500°C, or any range of values ​​therebetween. In some embodiments, producing the cathode material precursor and / or cathode active material can be performed in the presence of low intensity, medium intensity, or high intensity light, or a combination thereof. In some embodiments, the metal carbonyl complex may be exposed to ultraviolet light. In some embodiments, the light is short wavelength visible light, long wavelength UV light, mid wavelength UV light or short wavelength UV light, or a combination thereof. In some embodiments, the metal carbonyl complex may be heated and exposed to ultraviolet light simultaneously and / or sequentially, or vice versa.

[0022] In some embodiments, the cathode material precursor may be isolated from the reaction mixture. In some embodiments, the cathode material may be isolated from the reaction mixture. In some embodiments, the isolation may include filtration, crystallization, and combinations thereof.

[0023] In some embodiments, the cathode material precursor can be reacted with a lithium salt to produce the cathode material or cathode active material. For example, in some embodiments, the lithium salt can be selected from LiOH, LiCO3, hydrates thereof, and combinations thereof.

[0024] In some embodiments, the metal carbonyl can be reacted to form a fine particle sized metal powder. In some embodiments, the fine particle sized metal powder is nano-sized. In some embodiments, the metal carbonyl can be reacted to form a fine particle sized metal powder of about, at most, or up to about 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, 35 μm, 36 μm, 37 μm, 38 μm, 39 μm, 40 μm, 41 μm, 42 μm, 43 μm, 44 μm, 45 μm, 46 μm, 47 μm, 48 μm, 49 μm, 50 μm, 51 μm, 52 μm, 53 μm, 54 μm, 55 μm, 56 μm, 57 μm, 58 μm, 59 μm, 60 μm, 61 μm, 62 μm, 63 μm, 64 μm, 65 μ The size of the particulate sized metal powder can be in the range of 100 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, or 100 μm, or any value therebetween. In some embodiments, the size of the particulate sized metal powder can be determined by the average particle size or particle size distribution (e.g., D 50 particle size distribution).

[0025] In some embodiments, preparing the cathode material precursor and / or cathode active material can be performed in the presence of an additive. In some embodiments, the additive can function as an oxidizer and / or a stabilizer. In some embodiments, for example, the additive can include a Lewis base, a surfactant, a chelating agent, manganese sulfate, sodium aluminate, or an oxygen atom transfer reagent (e.g., an oxidizer), or a combination thereof.

[0026] ·Acid method In some of the methods disclosed herein, producing the cathode material precursor and / or the cathode material can be performed by reacting a metal carbonyl complex or an intermediate thereof with an acid. In some embodiments, the acid can include a strong acid and / or a weak acid. In some embodiments, the acid can be selected from H3PO4, H3PO3, H2SO4, H2SO3, HNO3, HNO2, HI, HBr, HCl, HF, or a combination thereof.

[0027] In some embodiments, the method of making a cathode material precursor may include in situ dissolution of a metal powder. In some embodiments, the method of making a cathode material precursor may include heating a metal carbonyl complex to form a metal powder and reacting the metal powder with an acid. In some embodiments, the method is carried out in the presence of an oxidizing agent (e.g., oxygen) and / or at elevated temperatures.

[0028] In some embodiments, a cathode for a lithium-ion battery is prepared by reacting iron pentacarbonyl with an acid, such as H3PO4, to form an iron(III) phosphate precursor. The precursor is then contacted with a lithium salt compound (e.g., LiOH and / or LiCO3, etc.) to form a lithium iron(III) phosphate cathode material.

[0029] Base method In some of the methods disclosed herein, producing the cathode material precursor and / or cathode material can be performed by reacting a metal carbonyl complex or an intermediate thereof with a base. In some embodiments, the base can include a strong base and / or a weak base. In some embodiments, producing the cathode material precursor and / or cathode active material can be performed in the presence of aqueous ammonia or an alternative Lewis base. In some embodiments, the Lewis base can include aqueous ammonia, NaOH, LiOH, CaOH2, MgOH2, triethylamine, pyridine, or combinations thereof.

[0030] In other embodiments, preparing the cathode material precursor and / or cathode active material can be performed in the presence of a second metal carbonyl complex. For example, in some embodiments, the second metal carbonyl complex can be Ni(CO)4, Co(CO)3(NO), H2Fe(CO)4, HCo(CO)4, Co2(CO)8, Fe(CO)5, Mn2(CO) 10 , or a combination thereof.

[0031] Hydrogenation method In some of the methods disclosed herein, producing the cathode material precursor and / or cathode material can be by hydride formation. In some embodiments, the method of producing the cathode material precursor and / or cathode material can include reacting a metal carbonyl complex to form a metal carbonyl hydride salt (e.g., lithium metal carbonyl hydride (Li[HFe(CO)4], etc.). In some embodiments, the method of producing the cathode material precursor and / or cathode material can include reacting a metal carbonyl complex with a lithium salt (e.g., lithium hydroxide) to form a lithium metal carbonyl hydride (i.e., the cathode material precursor). In some embodiments, the lithium metal carbonyl hydride is further reacted with an acid to form the cathode material.

[0032] In some embodiments, a metal carbonyl complex is vapor-deposited onto lithium salt (e.g., LiOH·HO) particles to form a metal-coated lithium salt (i.e., a cathode material precursor). In some embodiments, the metal-coated lithium salt is calcined to form the cathode material. In some embodiments, the calcination is performed in the presence of an oxidizing agent. In some embodiments, the oxidizing agent may include a gas containing oxygen (e.g., oxygen gas, oxygen-enriched gas, or ordinary air), an oxidizing agent, or a combination thereof.

[0033] Oxidizing agent method In some embodiments, producing the cathode material precursor may include reacting a metal carbonyl complex or an intermediate thereof with an oxidizing agent. In some embodiments, producing the cathode material precursor and / or cathode active material may be performed in the presence of one or more oxidizing agents. In some embodiments, the metal carbonyl complex is mixed with the oxidizing agent. In some embodiments, the metal carbonyl complex is in gaseous form. In some embodiments, the first gas stream includes the metal carbonyl complex and a carrier gas. In some embodiments, the carrier gas is an inert gas (e.g., nitrogen, carbon dioxide, helium, neon, argon, krypton, xenon). In some embodiments, the second gas stream includes the oxidizing agent. In some embodiments, the first and second gas streams are mixed and / or reacted. In some embodiments, the oxidizing agent may include O2, O3, N2O, NO2, N2O4, HNO3, KNO3, NH4NO3, H2O2, H2SO4, NaClO, KMnO4, PbO2, or combinations thereof. In some embodiments, the oxidizing agent may be a gas, a liquid, or a combination thereof. In some embodiments, the reaction between the metal carbonyl complex and the oxidizing agent may be carried out in the presence of heat and / or light.

[0034] Combination of methods Some of the methods disclosed herein may combine two or more of the aforementioned methods. For example, in some embodiments, producing the cathode material precursor and / or the cathode material can be performed by an acid method combined with a hydrogenation method. In other embodiments, producing the cathode material precursor and / or the cathode material can be performed by a base method combined with an oxidant method.

[0035] Energy storage element Once the cathode active material is prepared, it may be utilized in an electrode for an energy storage device. In some embodiments, an electrode film comprises the cathode active material described herein. In some embodiments, the cathode active material is incorporated into the electrode film. In some embodiments, the electrode film further comprises a binder. In some embodiments, an electrode comprises a current collector and an electrode film described herein. In some embodiments, the electrode film is disposed on the current collector to form a cathode electrode.

[0036] In some embodiments, the energy storage device utilizes the cathode active material described herein. In some embodiments, the energy storage device includes a separator, an anode electrode, a cathode electrode described herein, and a housing, where the separator, the anode electrode, and the cathode electrode are disposed within the housing, and the separator is disposed between the anode electrode and the cathode electrode. In some embodiments, the energy storage device is formed by disposing the separator, the anode electrode, and the cathode electrode described herein within the housing, and the separator is disposed between the anode electrode and the cathode electrode. In some embodiments, the energy storage device is a battery. In some embodiments, the energy storage device is a lithium ion battery. EXAMPLES

[0037] The cathode material precursors and cathode active materials of the present disclosure can be prepared utilizing the methods disclosed herein.

[0038] Example 1 The cathode material precursor is prepared by direct oxidation as shown in Scheme 1. Under an inert atmosphere, water (e.g., deoxygenated and / or deionized water) is added to a pressure vessel (e.g., a round-bottom flask) equipped with an agitator (e.g., a magnetic stir bar). The vessel is then heated to the desired temperature (e.g., 30-150 °C). Iron pentacarbonyl is then added dropwise by syringe over a period of 5 minutes with vigorous stirring to ensure effective dispersion of the resulting two-phase mixture. Phosphoric acid (65-85%) is then introduced via syringe or other suitable transfer device. The liquid phase is gradually oxygenated via an air stone or other suitable gas dispersion device. This results in H2 / CO2 / CO2 evolution and the concomitant formation (e.g., precipitation) of iron(III) phosphate. The stirring speed, temperature and reagent addition rate are used to control the morphology of the product. Once gas evolution has ceased, the reaction mixture is cooled to room temperature and the product is isolated by filtration. Scheme 1 TIFF2024521997000001.tif47129

[0039] Examples 2 and 3 The cathode material precursor is prepared by a two-step oxidation as shown in Scheme 2. Iron pentacarbonyl is introduced into a distillation flask along with a magnetic stir bar. The flask is heated to generate Fe(CO)5 vapor, which is passed through a heated glass tube by nitrogen carrier gas. The tube is heated to a temperature sufficient to induce rapid decomposition of iron pentacarbonyl into nano-sized iron powder. Iron metal is placed into a stirred flask of dilute phosphoric acid. As the iron metal enters the phosphoric acid solution, it is converted to iron(III) phosphate with the concomitant evolution of H2. The iron(III) phosphate is then filtered and dried.

[0040] Additionally, cathode material precursors are prepared by an in situ two-step decomposition / oxidation, also shown in Scheme 2. Using nitrogen as a carrier gas, iron pentacarbonyl vapor (15-40 v / v%) is introduced into the headspace of a stirred pressure vessel (e.g., a distillation flask) containing phosphoric acid (65-85%) and water. The vessel is sealed and heated to induce thermal decomposition of Fe(CO)5. As Fe(CO)5 is decomposed, iron metal is formed in situ and reacts with H3PO4 to yield iron(III) phosphate. Scheme 2 TIFF2024521997000002.tif33123

[0041] Example 4 The cathode material is prepared as shown in Scheme 3. Iron pentacarbonyl is introduced via syringe into a stirred aqueous solution of lithium hydroxide to form lithium iron tetracarbonyl hydride. The stirring speed, temperature, and Fe(CO)5 addition rate can be used to control the intermediate particle size and morphology. Once Fe(CO)5 is completely consumed, the aqueous solution is quenched with phosphoric acid to form lithium iron phosphate, where the stirring speed and phosphoric acid addition rate are again used to control the product morphology. The lithium iron phosphate is isolated by filtration. Scheme 3 TIFF2024521997000003.tif30118

[0042] Example 5 As shown in Scheme 4, a cathode material precursor (e.g., nickel hydroxide) is prepared by direct oxidation. In a batch, semi-batch or continuous pressure reactor, an oxygen-free suspension of nickel tetracarbonyl (Ni(CO)4) in water is gently heated (e.g., 0-150 °C) and / or exposed to UV light. The system is actively mixed to ensure effective dispersion of the biphasic mixture. This is done in the presence of aqueous ammonia or an alternative Lewis base. The pH of the reaction mixture is optionally controlled by varying the concentration of ammonia or other hydroxide sources (e.g., NaOH, LiOH, CaOH2, MgOH2). One or more oxidants are gradually introduced into the reactor either as a gas (e.g., O2, N2O), a salt (e.g., NH4NO3) or a solution. Under these conditions, the CO molecules dissociate to yield low-coordinated nickel carbonyls (e.g., Ni(CO)3, Ni(CO)2 or Ni(CO)) and / or submicron nickel powder. These intermediates undergo redox reactions with oxidants and / or water to produce nickel hydroxide. The concentration of ammonia (or other Lewis base) and the pH of the solution are used to control the morphology of the crystalline nickel hydroxide product. This allows for the production of material of a predetermined particle size and morphology. The precipitated crystalline nickel hydroxide is then filtered from the reaction mixture to yield the desired product. Scheme 4 TIFF2024521997000004.tif52138

[0043] Example 6 Prepare the cathode material precursor. In a batch, semi-batch or continuous pressure reactor, an oxygen-free suspension of (Ni(CO)4) in water is vigorously stirred at about room temperature. Mn2(CO) 10and Co2(CO)8 are added as a solid or solution. The resulting mixture is gently heated (e.g., 0-150 °C) and / or exposed to UV light to remove carbon monoxide. This is done in the presence of ammonia or an alternative Lewis base. The pH of the reaction mixture is optionally controlled by varying the concentration of ammonia or other hydroxide sources (e.g., NaOH, LiOH, CaOH2, MgOH2). One or more oxidants are gradually introduced into the reactor either as gases (e.g., O2, N2O), salts (e.g., NH4NO3) or solutions. Under these conditions, the metal carbonyl complexes react to give an aqueous solution of metal ions. A battery precursor product can then be obtained by controlled precipitation, which can then be reacted with a lithium material to form lithium nickel manganese cobalt oxide (NMC).

[0044] Example 7 Prepare the cathode material precursor. In a batch, semi-batch or continuous pressure reactor, an oxygen-free suspension of nickel tetracarbonyl (Ni(CO)4) in water is gently heated (e.g., 0-150 °C) and / or exposed to UV light. This is done in the presence of aqueous ammonia or an alternative Lewis base. The pH of the reaction mixture is optionally controlled by varying the concentration of ammonia or other hydroxide source (e.g., NaOH, LiOH, CaOH2, MgOH2). One or more oxidants are gradually introduced into the reactor either as a gas (e.g., O2, N2O), salt (e.g., NH4NO3) or solution.

[0045] Nickel is oxidized to Ni 2+Once the ions are obtained, an oxygen-free solution of manganese sulfate and sodium aluminate is gradually introduced in a volumetric amount sufficient to achieve the desired cathode stoichiometry. The mixed metal hydroxide product is then precipitated. The concentration of ammonia (or other Lewis base) and the pH of the solution are used to control the morphology of the crystalline hydroxide product. This allows for the production of material of a predetermined particle size and morphology. The precipitated crystalline metal hydroxide is then filtered from the reaction mixture to obtain the desired product, which can then be reacted with a lithium material to form lithium nickel manganese aluminum oxide (NMA).

[0046] Example 8 Lithium nickel oxide and / or lithium metal oxide are prepared by vapor deposition of the metal onto lithium salt (e.g., Li2CO3 or LiOH·H2O) particles followed by calcination, as shown in Scheme 5. Scheme 5 TIFF2024521997000005.tif71146

[0047] A stream of metal carbonyl vapor or mixed metal carbonyl vapor contained in a carrier gas (e.g., N2 and / or Ar) is fed into a stirred heated pressure vessel containing a lithium salt (e.g., LiOH·H2O or Li2CO3). The vessel temperature is then raised to above 150°C to induce thermal decomposition of the metal carbonyl and deposition of a metal film onto the lithium salt substrate. Residence time and temperature are used to control the deposition rate of the metal film and the thickness of the film. Thus, the metal carbonyl or metal carbonyl mixture is reacted in the presence of lithium salt (e.g., Li2CO3 or LiOH·H2O) particles to obtain metal-coated lithium salt (e.g., lithium hydroxide) particles. In some embodiments, with the aid of a carrier gas and / or additives, the particle size and morphology of the lithium salt (e.g., Li2CO3 or LiOH·H2O) can function to template the metal carbonyl decomposition, allowing for products of well-defined size and morphology to be obtained.

[0048] The metal-coated lithium salt is then transferred to a calcination furnace (600-900° C.) where it is reacted with the cathode active material.

[0049] Example 9 High value salts are prepared by controlled oxidation of Fe(CO)5 or other metal carbonyls in the presence of acid. An aqueous dispersion of Fe(CO)5 is gradually heated (e.g., 30-150°C) in the absence of oxygen, whereupon dilute mineral acid is introduced along with optional additives that may function as oxidizing agents or stabilizers. These additives may include Lewis bases, surfactants, chelating agents, and oxygen atom transfer reagents (e.g., oxidizing agents). Without wishing to be bound by theory, the role of these reagents is to facilitate the controlled decarbonylation and oxidation to produce the ferric or ferrous salts of the inorganic acid conjugate base.

[0050] Example 10 Two vapor streams are fed simultaneously to the top of a vertical heated tube with a powder collection trap at the bottom. One stream contains iron pentacarbonyl in an inert carrier gas (e.g., Ar or N2) and the other gas stream contains nitrogen and oxygen (<5 v / v%). The vertical column is heated to induce thermal decomposition of the iron carbonyl. As the iron carbonyl thermally decomposes, it reacts with oxygen to form high purity iron oxide suitable for use as a precursor in the production of lithium iron phosphate.

[0051] Although certain specific embodiments have been described, these embodiments are presented as examples and are not intended to limit the scope of the present disclosure. Indeed, the novel methods and systems described herein may be embodied in various other forms. Furthermore, various omissions, substitutions, and modifications of the systems and methods described herein may be made without departing from the spirit of the present disclosure. The appended claims and their equivalents are intended to cover such forms or modifications as fall within the scope and spirit of the present disclosure.

[0052] It should be understood that features, materials, properties, or groups described in connection with a particular aspect, embodiment, or example are applicable to any other aspect, embodiment, or example described in this section or elsewhere in this specification, unless incompatible therewith. All of the features disclosed in this specification (including the accompanying claims, abstract, and drawings), and / or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations in which at least some of such features and / or steps are mutually exclusive. Protection is not limited to the details of any of the foregoing embodiments. Protection extends to any novel, or any novel combination of features disclosed in this specification (including the accompanying claims, abstract, and drawings), or any novel, or any novel combination of steps of any method or process so disclosed.

[0053] Moreover, certain features described in this disclosure in the context of separate embodiments can also be implemented in combination in a single embodiment. Conversely, various features described in the context of a single embodiment can also be implemented in multiple embodiments separately or in any suitable subcombination. Furthermore, although features may be described above as acting in a certain combination, one or more features from the claimed combination may, in some cases, be deleted from the combination, and the combination may be claimed as a subcombination or a variation of the subcombination.

[0054] For the purpose of this disclosure, certain aspects, advantages, and novel features are described herein.Not all such advantages can be achieved according to any particular embodiment.Thus, for example, a person skilled in the art will recognize that the present disclosure can be embodied or implemented to achieve one advantage or group of advantages as taught herein, without necessarily achieving other advantages as taught or suggested herein.

[0055] The scope of the present disclosure is not intended to be limited by the specific disclosure of preferred embodiments in this section or elsewhere herein, but may be defined by the claims, as presented in this section or elsewhere herein, or as presented in the future. The language of the claims should be interpreted broadly based on the language used in the claims, and not limited to the examples described herein or during the prosecution of this application, and the examples should be interpreted as non-exclusive.

[0056] The headings provided herein, if any, are for convenience only and do not necessarily affect the scope or meaning of the devices and methods disclosed herein.

Claims

1. 1. A method of making a cathode material precursor, comprising the steps of: reacting a metal carbonyl complex with an acid under an inert atmosphere to form a cathode material precursor; The method, wherein the cathode material precursor is selected from the group consisting of a metal hydroxide, a metal oxide, a metal nitrate, a metal sulfate, or a metal phosphate.

2. 2. The method of claim 1, wherein the metal carbonyl complex comprises a metal selected from the group consisting of Ni, Co, Fe, Mn, and combinations thereof.

3. The metal carbonyl complex is Ni(CO) ４ , Co(CO) ３ (NO), H ２ Fe(CO) ４ , HCo(CO) ４ , Co ２ (CO) ８ , Fe(CO) ５ , Mn ２ (CO) １０ , Li[HFe(CO) ４ 3. The method of claim 1 or 2, wherein the metal carbonyl isocyanide complexes thereof, metal carbonyl phosphine complexes thereof, and combinations thereof are selected from the group consisting of:

4. The acid is H ３ P.O. ４ , H ３ P.O. ３ , H ２ SO ４ , H ２ SO ３ , HNO ３ , HNO ２ 3. The method of claim 1 or 2, wherein the alkoxy group is selected from the group consisting of HI, HBr, HCl, HF, and combinations thereof.

5. The method of claim 1 or 2, wherein the metal carbonyl complex is heated to 30 to 150° C.

6. 3. The method of claim 1 or 2, further comprising isolating the cathode material precursor.

7. 1. A method for making a cathode active material, comprising the steps of: Producing a cathode material precursor according to the method of claim 1; reacting the cathode material precursor with a lithium salt compound to form an active cathode material.

8. The lithium salt compound is LiOH and LiCO ３ The method of claim 7 , comprising at least one of:

9. 8. The method of claim 1, 2 or 7, wherein iron ore comprises said metal carbonyl complex.

10. 10. The method of claim 9, wherein the iron ore is reacted with the acid to form the cathode material precursor.

11. 1. A method of making a cathode material precursor, comprising the steps of: heating the metal carbonyl complex to form a metal powder; reacting the metal powder with an acid to form a cathode material precursor.

12. The method of claim 11, wherein the metal carbonyl complex is heated at a temperature of from 25 to 200° C.

13. 13. The method of claim 11 or 12, wherein reacting the metal carbonyl complex with an acid decomposes the metal carbonyl complex into fine particle sized metal powder.

14. The method of claim 13 , wherein the fine particle sized metal powder is nano-sized.

15. The method of claim 13, wherein the fine particle size metal powder ranges from 0.1 μm to 50 μm.

16. 13. The method of claim 11 or 12, wherein one or more steps are carried out in the gas phase.

17. 1. A method for making a cathode active material, comprising the steps of: reacting the metal carbonyl complex with lithium hydroxide to form a lithium metal carbonyl hydride; reacting the lithium metal carbonyl hydride with an acid to form a cathode active material.

18. 20. The method of claim 17, further comprising calcining the lithium metal carbonyl hydride in the presence of an oxidizing agent.

19. 1. A method for making a cathode active material, comprising the steps of: A method comprising reacting a first metal carbonyl complex with a base to form a metal hydroxide.

20. The method further comprises reacting the first metal carbonyl complex with a second metal carbonyl complex, the second metal carbonyl complex being Ni(CO) ４ , Co(CO) ３ (NO), H ２ Fe(CO) ４ , HCo(CO) ４ , Co ２ (CO) ８ , Fe(CO) ５ , Mn ２ (CO) １０ , Li[HFe(CO) ４ 20. The method of claim 19, wherein the metal is selected from the group consisting of: metal carbonyl isocyanide complexes thereof; metal carbonyl phosphine complexes thereof; and combinations thereof.

21. 21. The method of claim 19 or 20, wherein the first metal carbonyl complex is exposed to ultraviolet light.

22. 21. The method of claim 19 or 20, wherein the first metal carbonyl complex is exposed to manganese sulfate, sodium aluminate, or a combination thereof.

23. 1. A method of making a cathode material precursor, comprising the steps of: mixing a first gas stream comprising an inert carrier gas and a metal carbonyl complex with a second gas stream comprising an oxidant; and heating the mixed first and second gas streams to form a cathode material precursor.