Synthesis of lithium transition metal orthoborates

Abstract

The present technology provides methods for the aqueous synthesis of lithium transition metal orthoborates wherein chemical precursors are added to an aqueous solution and milled together (e.g. with grinding media) as one step in the synthesis process. In one aspect, the Li-containing orthoborate material has the formula Lil+xMl-xBO3, wherein M is a transition metal, and wherein 0 =< x < 0.3.

Description

Docket No. 113544-856283PCT APPLICATIONSYNTHESIS OF LITHIUM TRANSITION METAL ORTHOBORATESCROSS REFERENCE

[0001] The present patent application claims the benefit of priority to a Provisional Patent Application Serial No. 63 / 688,575, entitled “Synthesis of Lithium Transition Metal Orthoborates,” filed on August 29, 2024, which is incorporated herein by reference in its entirety.TECHNICAL FIELD

[0002] Embodiments of the present invention relate to a method of using an aqueous solution to mill precursor materials for lithium-ion batteries. More specifically, embodiments of the present invention include methods for the aqueous synthesis of lithium transition metal orthoborates wherein chemical precursors are added to an aqueous solution and milled together (e.g. with grinding media) to avoid the use of organic solvents.BACKGROUND

[0003] Batteries are an essential part of many devices from power tools to home power systems to electric and hybrid cars, among many other applications. Lithium-ion batteries have been widely adopted as the most promising portable energy source in electronic devices because of their high working voltage, high energy density, and good cyclic performance. Lithium-ion batteries are used in electric vehicles and hybrid electric vehicles.

[0004] Lithium Transition Metal Orthoborates (e.g. L1MBO3, where M is typically a transition metal such as Mn, Fe, Mg, V, Co, Ni, Zn, Ca, Na, Al, Cr, or Cu) are attractive cathode materials for lithium-ion batteries for two main reasons. First, their covalently bonded anions contribute to operational stability by effectively suppressing oxygen loss. Second, they exhibit high theoretical gravimetric capacities of approximately 220 mAh / g. In comparison, the theoretical gravimetric capacity of conventional lithium iron phosphate (LFP) is approximately 170 mAh Zg.

[0005] Currently, lithium transition metal orthoborates are synthesized by milling precursors in organic solution followed by evaporating the organic solvent. These methodologies are costly and difficult to scale. Accordingly, there remains a need in the art for a solution to at least one of the aforementioned problems.1105690361.2Docket No. 113544-856283PCT APPLICATIONBRIEF SUMMARY

[0006] Provided herein, inter alia, is a method for the aqueous synthesis of Li-containing orthoborate materials utilizing the (BOf-) anion includes: calculating amounts of precursor materials, wherein the precursor materials include: a lithium source, one or more transition metal sources, a boron source, and a carbon source; mixing the precursor materials in an aqueous solution to form a slurry; performing aqueous milling of the slurry to form a milled slurry; drying the milled slurry to form a dried powder; and, calcining the dried powder to form a Li-containing orthoborate material. In one aspect, the Li-containing orthoborate material has the formula Lii+xMi-xBCh, wherein M is a transition metal, and wherein 0 <x < 0.3.

[0007] In one aspect, a method of using aqueous milling to produce a Li-containing orthoborate material having the (BOj-) anion consists of the following steps: calculating amounts of precursor materials, wherein the precursor materials comprise a lithium source, one or more transition metal sources, a boron source, and a carbon source; mixing the precursor materials in an aqueous solution to form a slurry; performing aqueous milling of the slurry to form a milled slurry; drying the milled slurry to form a dried powder; and calcining the dried powder to form a Li-containing orthoborate material. In one aspect, the Li-containing orthoborate material has the formula Lii+xMi-xBCh, wherein M is a transition metal, and wherein 0 <x < 0.3.

[0008] In one aspect, an intermediate slurry in an aqueous synthesis process for synthesizing Li-containing orthoborate materials includes: water, precursors, and ceramic beads.

[0009] These and other objects, features, and advantages of the present invention will become more readily apparent from the attached drawings and the detailed description of the preferred embodiments which follow and may be attained by means of the instrumentalities and combinations particularly pointed out in the appended claim(s).BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

[0010] The preferred embodiments of the invention will hereinafter be described in conjunction with the appended drawings, which are incorporated into and form a part of the specification and together with the description, are provided to illustrate and not to limit the invention, where like designations denote like elements, and in which:2105690361.2Docket No. 113544-856283PCT APPLICATION

[0011] FIG. 1 illustrates a method for the aqueous synthesis of lithium transition metal orthoborates; and

[0012] FIG. 2 shows an X-ray diffraction pattern with a fitting from an X-ray diffraction refinement model also shown. The refinement model includes two phases, those being the well- known C2 / c monoclinic space group #15 phase for LiMnBCh (the majority phase) and the well- known P6 hexagonal space group #174 phase for LiMnBCh (the majority phase). We note than in Fig. 2, the majority phase (> 95%) is the well-known C2 / c monoclinic space group #15. See Table 1 below for details. Information on the P6 hexagonal space group #174 can be found in DOI: 10.1016 / SO 167-2738(00)00813-4.DETAILED DESCRIPTION

[0013] Embodiments of the invention describe new synthesis methods for lithium transition metal orthoborates, wherein chemical precursors are added to an aqueous solution and milled together (e.g. with grinding media) as one step in the synthesis process to avoid the use of organic solvents. The detailed description set forth below is intended as a description of various configurations of the subject technology and is not intended to represent the only configurations in which the subject technology can be practiced. The appended drawings are incorporated herein and constitute a part of the detailed description. The detailed description includes specific details to provide a more thorough understanding of the subject technology. However, it will be clear and apparent that the subject technology is not limited to the specific details set forth herein and may be practiced without these details. In some instances, structures and components are shown in block diagram form to avoid obscuring the concepts of the subject technology.

[0014] Accordingly, it should be understood that, although steps of various processes or methods may be shown and described as being in a sequence or temporal order, the steps of any such processes or methods are not limited to being carried out in any particular sequence or order, absent an indication otherwise. Indeed, the steps in such processes or methods generally may be carried out in various different sequences and orders while still falling within the scope of the present disclosure. Accordingly, it is intended that the scope of patent protection is to be defined by the issued claim(s) rather than the description set forth herein.

[0015] The following detailed description refers to the accompanying drawings. Wherever possible, the same reference numbers are used in the drawings and the following description to3105690361.2Docket No. 113544-856283PCT APPLICATION refer to the same or similar elements. While many embodiments of the disclosure may be described, modifications, adaptations, and other implementations are possible. For example, substitutions, additions, or modifications may be made to the elements illustrated in the drawings, and the methods described herein may be modified by substituting, reordering, or adding stages to the disclosed methods.

[0016] Embodiments of the invention describe new synthesis methods for lithium transition metal orthoborates, wherein chemical precursors are added to an aqueous solution and milled together (e.g. with grinding media) as one step in the synthesis process to avoid the use of organic solvents. The disclosed method advantageously uses aqueous milling instead of milling precursors in organic solution followed by evaporating the organic solvent of the conventional methodologies in the art. Additionally, the method may utilize an organic carbon source in the slurry which may be subjected to a spray drying step. This aqueous milling step can avoid the use of organic solvents and any subsequent step needed to evaporate such organic solvent, which would otherwise turn the process costly and difficult to scale. In addition, the use of an organic carbon source during spray drying affords better electrochemical performance than using an inorganic carbon source, due to an improved conductive carbon coating on the orthoborate particle surfaces.

[0017] In particular, the Li-containing orthoborate material comprises a chemical composition written as Lii+xMi-xBO3. Specifically, the lithium source is lithium carbonate. In the formula, x is < 1.0, x is < 0.9, x is < 0.8, x is < 0.7, x is < 0.6, x is < 0.5, x is < 0.4, or x is < 0.3 or x is < 0.2, or x is < 0.1, or x is < 0.05. In addition, x is > 0, x is > 0.01, x is > 0.05, x is > 0.1, x is > 0.3, or x is > 0.5 or x is > 0.8. In an embodiment, in the formula Lii+xMi-xBO3, x is 0 < x < 0.3.

[0018] In the formula, M is one or more elements selected from the group of elements comprising at least one of Mn, Fe, Mg, V, Co, Ni, Zn, Ca, Na, Al, Cr, or Cu. Alternatively, M is one or more metal species not limited to the transition metals.

[0019] In an embodiment, M is at least one of Mn, Fe, Mg and combinations thereof. Alternatively, M consists of the combination of Mn and Fe wherein the molar ratio of Mn:Fe ranges from about 1 :1 to about 9:1. For example, the molar ratio of Mn:Fe ranges from about 1.5:1 to about 8: 1, or the molar ratio of Mn:Fe ranges from about 2:1 to about 6:1, or the molar ratio of Mn:Fe ranges from about 2:1 to about 8: 1, or the molar ratio of Mn:Fe ranges from about 2.4:1 to about 5:1, or the molar ratio of Mn:Fe ranges from about 2.6:1 to about 4:1, or the molar ratio of Mn:Fe ranges from about 1.5:1 to about 4:1.4105690361.2Docket No. 113544-856283 PCT APPLICATION

[0020] In another embodiment, the molar ratio of Mn:Fe ranges from about 2.8:1 to about 3.8:1, or the molar ratio of Mn:Fe ranges from about 2.8:1 to about 3.6:1, or the molar ratio of Mn:Fe ranges from about 2.8:1 to about 3.4: 1, or the molar ratio of Mn:Fe ranges from about 2.8:1 to about 3.2:1. In an aspect, M consists of the combination of Mn and Fe wherein the molar ratio of Mn:Fe is about 3:1.

[0021] Specifically, the sum of metal elements other than Li is less than 0.75, less than 0.8, less than 0.9 or less than 1.0 when normalized to the stoichiometry of boron. Alternatively, the sum of metal elements other than Li is equal to one when normalized to the stoichiometry of boron. In an embodiment, the sum of metal elements other than Li is less than or equal to one but greater than 0.7 when normalized to the stoichiometry of boron.

[0022] FIG. 1 illustrates an example method 100 for a method for the synthesis of lithium transition metal orthoborates milled in an aqueous solution. The method 100 comprises step 102 for calculating amounts of precursor materials (e.g., Lithium carbonate, Manganese (II) carbonate, boric acid, and sucrose). The chemical composition of the orthoborate can be written as Lii+xMi-xBO3, wherein M can be one or more metal species not limited to the transition metals and 0 < x < 0.3. M can be one or more elements selected from the group of elements comprising at least one of Mn, Fe, Mg, V, Co, Ni, Zn, Ca, Na, Al, Cr, or Cu.

[0023] The precursor material further includes adding a carbon source, wherein the carbon source is added in an amount that does not alter the stoichiometry of the precursor material. In particular, the carbon source includes a carbon-containing compound selected from an aromatic hydrocarbon compound including an alcohol, an acid, or a ketone. The aromatic hydrocarbon compound may include toluene, p-xylene, asphalt, or paraffin oil. Finally, a gas containing carbon atom may be utilized as a carbon-containing compound. The gas containing compound may include ethylene, methane, acetylene, carbon monoxide or the like.

[0024] The carbon-containing compound may be ascorbic acid, malic acid, tartaric acid, succinic acid, fumaric acid, citric acid, oxalic acid, gluconic acid, or lauric acid. Further, the carbon-containing compound may include carbon nanotubes, graphene, graphite, or carbon black.

[0025] Another source of the carbon-containing compound includes sugars including but not limited to sucrose, glucose, dextrose, fructose, lactose, or maltodextrin. In an embodiment, the carbon-containing compound may include organic polymers comprising polyethylene,5105690361.2Docket No. 113544-856283PCT APPLICATION polypropylene, polystyrene, polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, polymethyl methacrylate, polyurethane, polyacrylamide, poly(acrylic acid), polyethylene oxide, poly(ethylene imine), carboxylmethyl cellulose, hydroxypropyl cellulose, polyethylene oxide, alkylated polyethylene oxide, crosslinked polyethylene oxide, polyvinyl ether, poly(methyl methacrylate), polyvinylidene fluoride, a copolymer of polyhexafluoropropylene and polyvinylidene fluoride, poly(ethyl acrylate), polytetrafluoro ethylene, polyvinyl chloride, polyacrylonitrile, derivatives, blends, or copolymers thereof.

[0026] In another aspect of the invention, the carbon-containing compound can be selected from the group consisting of organic carbon sources, including sucrose, glucose, lactose, maltodextrin, soluble starch, polymers (e.g. poly(ethylene glycol), poly(vinyl alcohol), poly(acrylic acid), polyvinyl pyrrolidone), vinyl alcohol, acrylic acid, citric acid, oxalic acid, and lauric acid; inorganic carbons; urea; and combinations thereof.

[0027] In an aspect the carbon source is an organic carbon source added in an amount equal to 0.00 wt% to 0.01 wt%, 0.01 wt% to 0.02 wt%, 0.02 wt% to 0.03 wt%, 0.02 wt% to 0.04 wt%, 0.03 wt% to 0.04 wt%, 0.04 wt% to 0.2 wt%, 0.05 wt% to 0.2 wt%, 0.05 wt% to 0.1 wt%, 0.08 wt% to 0.15 wt%, or 0.1 wt% to 0.2 wt%.

[0028] In an embodiment, an organic carbon source is sucrose. The amount of sucrose for the precursor materials may be chosen such that there are about 1.0 to about 1.5 carbon atoms per transition metal atom in an initial slurry. In another embodiment, the amount of sucrose for the precursor materials may be chosen such that there are about 1.2 to about 1.5 carbon atoms per transition metal atom in an initial slurry. In another embodiment, the amount of sucrose for the precursor materials may be chosen such that there are 1.5 carbon atoms per transition metal atom in an initial slurry.

[0029] The method 100 further comprises step 104 for mixing precursors materials in water for aqueous milling. The precursors may be mixed together in distilled water, with a weight percentage of solids of, for example, about 20%. Zirconia beads (e.g., 0.5 mm beads) may be added to the slurry, where the mass of beads may be twice the mass of the entire slurry (including water). In an embodiment, the precursor materials are mixed together in the distilled water with a final solids content of about 20 wt. %.6105690361.2Docket No. 113544-856283PCT APPLICATION

[0030] The method 100 further comprises step 106 for aqueous milling. The aqueous milling may be carried about 300 rpm to about 1000 rpm, or about 400 rpm to about 800 rpm, or 500 rpm to about 700 rpm, or about 600 rpm to about 800 rpm. Further, the aqueous milling may be carried out for about 40 minutes and about 220 minutes of active milling, or 50 minutes and about 150 minutes of active milling, or 60 minutes and about 120 minutes of active milling. In an embodiment, the aqueous milling may be carried out for about 70 minutes and about 110 minutes of active milling. In an embodiment, the aqueous milling may be carried out in, for example, a planetary ball mill at about 600 rpm for about 96 minutes of active milling. The milling may be carried out with intermittent rest steps.

[0031] The method 100 further comprises step 108 for drying the slurry. The slurry may be dried by, for example, spray drying, but other methods may be used. The spray drying step may be carried out with a spray dryer, for example, a Yamato GB210. The desired spray drying outlet temperature is about 50 °C to about 500 °C, about 50 °C to about 300 °C, about 50 °C to about 250 °C, about 50 °C to about 200 °C, about 80 °C to about 250 °C, about 80 °C to about 150 °C, about 90 °C to about 125 °C, or about 95 °C to about 150 °C, about 80 °C to about 120 °C, about 90 °C to about 110 °C, or about 100 °C to about 110 °C. The preferable spray drying outlet temperature is about 90 °C, about 95 °C, about 100 °C or about 105 °C. In an embodiment, the spray drying may be carried out with, for example, an outlet temperature of about 100 °C.

[0032] The desired spray drying atomizing pressure is about 0.005 MPa, 0.01 MPa, 0.05 MPa, 0.08 MPa, 0.1 MPa, 0.15 MPa. In an embodiment, the spray drying atomizing pressure is about 0.2 MPa. Furthermore, the desired blower rate for spray drying is about 0.1 m3 / min, about 0.2 m3 / min, about 0.3 m3 / min, about 0.4 m3 / min or about 0.5 m3 / min.

[0033] The method 100 further comprises step 110 for calcining. Calcination is a method known to one skilled in the art. Calcination involves exposing the dried mixture to temperatures of about 700 to about 900 °C to remove any remaining water or solvent ftom the drying process, and to fuse the metals tightly together. Precise temperature control throughout the process is critical, as it influences the electrochemical performance, optimizes the crystal structure, and particle size of the materials.

[0034] As known to a person skilled in the art, calcination involves a flow of inert gas, usually nitrogen or argon, is used to remove traces of oxygen as well as gaseous byproducts. If desired,7105690361.2Docket No. 113544-856283PCT APPLICATION the atmosphere can be made mildly reductive by inclusion of traces of reducing gases such as hydrogen, methane, or ammonia in the incoming gas flow. In some embodiments, the furnace interior containing the material can be evacuated and placed under vacuum to remove ambient gases before refilling with inert, oxygen-free gases.

[0035] During the calcination process an internal temperature of the furnace may be raised from room temperature at 0.5 to 15 °C / min continuously or with one or more intermediate hold temperature periods. In an embodiment, calcining may be carried out at a temperature greater than about 1000 °C, or at a temperature greater than about 800 °C, or at a temperature greater than about 600 °C or at a temperature greater than about 400 °C.

[0036] According to the aspects of the invention, the final temperature may be held for about 2 to about 12 hours before cooling to a safe handling temperature, usually below 100 °C. The final temperature may be held for about 5 to about 10 hours. In an embodiment, the final temperature is held for about 8 to about 10 hours.

[0037] In an embodiment, the calcining may be carried out at a temperature greater than about 400 °C. The calcining may be carried out at a temperature of about 600 °C for about 10 hours with a ramping rate of about 5°C per minute. For materials where M = Mn, the dried powder may be calcined under flowing nitrogen (N2) gas. For materials where M = Mn (75 %), Fe (25 %), the dried powder may be calcined under a flowing gas mixture of N2 and CO2.

[0038] In an embodiment, the calcining is carried out at a temperature of about 600 °C for about 10 hours with a ramping rate of about 5°C per minute under flowing nitrogen (N2) gas where M = Mn. In another embodiment, the calcining is carried out at a temperature of about 600 °C for about 10 hours with a ramping rate of about 5 °C per minute under flowing gas mixture comprising CO2 and N2 where M = Mn, Fe (i.e. containing both Mn and Fe).

[0039] Optionally, the method 100 may comprise electrochemical testing 112 of the synthesized lithium transition metal orthoborate.EXAMPLE;

[0040] The embodiments of the invention are further illustrated by the following non-limiting example.Example LiMnBOs Synthesis Process8105690361.2Docket No. 113544-856283PCT APPLICATION

[0041] Experiments were performed based on the above example method 100. Lithium carbonate, Manganese (II) carbonate, boric acid, and sucrose were dispersed in water, with a final solids content of 20 wt. %. The amount of sucrose was chosen to give a 1.5:1 ratio of carbon atoms from sucrose to manganese atoms from manganese (II) carbonate in the initial mixture. Relative to the nominal compositions, the Li amount was increased by a factor of 1.04 A typical quantity of solids is about 30g. 300g of 0.5 mm zirconia beads were added, and the slurry was milled in a planetary ball mill at 600 rpm for a total of 96 minutes of active milling with some intermittent rest steps.

[0042] The slurry was removed from the mill and the zirconia beads were removed via filtration. The slurry was then spray dried in air to dry the slurry. This process was carried out on a Yamato GB210 spray dryer with an inlet temperature of 156 °C and an outlet temperature of about 105 °C.

[0043] After spray drying, the dry powder was subjected to a heat treatment of 600 °C for 10 hrs in a flowing nitrogen atmosphere with a ramp rate of 5 °C per minute to form the carbon- coated Li transition metal orthoborate material.Example Li transition metal Orthoborate Analysis

[0044] FIG. 2 shows the X-ray diffraction pattern for LiMnBCL. The refinement model included two phases, those being the well-known C2 / c monoclinic space group #15 phase for LiMnBOs (the majority phase) and the well-known P6 hexagonal space group #174 phase for LiMnBCh (the minority phase). The agreement between the experimental and fitted patterns confirmed the successful synthesis of LiMnBCh. See paragraph

[0012] and Table 1 for more details on the fitting of the diffraction pattern.Table 1.9105690361.2Docket No. 113544-856283PCT APPLICATION

[0045] Details of the C2 / c monoclinic space group (#15) used in the X-ray diffraction refinement model. The space group used was C2 / c (#15). Initial lattice parameters were set to a = 5.204375 A, b = 8.976579 A, c = 10.380446 A, = 91.8464°. Parameters that could be varied include, but are not limited to, lattice parameters, crystallite size, isotropic strain, anisotropic strain, atomic displacement parameters, site occupancies, instrumental parameters, background, and atomic positions. See reference paper with DOI: 10.1002 / adma.201001039.Example Electrochemical Testing

[0046] The samples were immediately brought into a dry room after unloading from the furnace. They were then dried in a vacuum oven at 80 - 200 °C for at least 12 hours in order to remove residual moistures in the produced powder. All other cell components or chemicals were also vacuum dried in advance.

[0047] A FlackTek Speedmixer was used for slurry preparation. The material was mixed with PVDF, Carbon Black, and NMP such that the ratio of active material : PVDF : Carbon Black was 80 : 10 : 10. The amount of NMP to add was chosen to achieve a suitable viscosity for coating the electrode sheet. PVDF was added via a premixed 10% PVDF / NMP solution.

[0048] Once the slurry was made, it was taken to a doctor blade coater. A carbon-coated aluminum sheet was vacuum mounted onto the coater chuck as the substrate. The chuck was heated to 60°C. For these samples, the doctor blade gap was set to 200 micrometers. The slurry was then cast onto the substrate by the doctor blade. After coating, the electrode was transferred into a forced air oven at 80°C to be dried for at least 4 hrs. Then, a Hohsen puncher was used to punch out coin disks (13.8mm in diameter) out of the electrode. Each disk was weighed in the dry room in order to know the precise active material amount for each cell. These disks were then vacuum dried under 80-110°C for at least 12 hrs in the antechamber attached to the glovebox. After drying, the disks are transferred into an Ar-filled glovebox without exposure to atmosphere.

[0049] In the glovebox, the disks are made into 2032 coin cells with a PP / PE / PP separator, Li metal as the anode and LP58 electrolyte. The cells are then loaded into temperature-controlled chambers connected to battery testers (Arbin) and are cycled. For the testing mentioned here, the cells are cycled at 22 mA g1to an upper cutoff voltage of 4.6 V. They are then held at that10105690361.2Docket No. 113544-856283PCT APPLICATION voltage until the current decays to 4.4 mA g1. Following this, they are discharged again at 22 mA g1, corresponding to an approximately C / 10 cycling rate, to a lower cutoff voltage of 2 V. This testing is done at 45°C.

[0050] Coin cells made via this protocol with a composition of LiMnBCh achieved a first discharge capacity of 87 mAh g1, with 73 mAh g'1of this coming above 2.5 V vs. Li / Li+. In contrast, previous use of an inorganic carbon source during spray drying with a composition of LiMnBCh led to a capacity of about 62 mAh g1, with just 18 mAh g1of this coming above 2.5 V vs. Li / Li+. See DOI: 10.1016 / j.cap.2013.04.027.

[0051] The use of an organic carbon source during spray drying allowed for better electrochemical performance than the use of an inorganic carbon source.

[0052] Through modification of the chemical composition and / or electrode fabrication procedures in Lii+xMi.xBO3, but while using the same process involving aqueous milling and spray drying in the presence of an organic carbon source, a first discharge capacity of 158 mAh g'1was obtained, demonstrating the promise of this synthesis method.

[0053] The preceding example can be repeated with similar success by substituting the generically or specifically described parameters of this invention for those used in the preceding examples.

[0054] Although the invention has been described in detail with particular reference to these described embodiments, other embodiments can achieve the same results. Variations and modifications of the present invention will be obvious to those skilled in the art and it is intended to cover in the appended claims all such modifications and equivalents. The entire disclosures of all references, applications, patents, and publications cited above are hereby incorporated by reference.DEFINITIONS

[0055] All publications, patents and patent applications cited herein, whether supra or infra, are hereby incorporated by reference in their entirety to the same extent as if each individual publication, patent, or patent application were specifically and individually indicated to be incorporated by reference.

[0056] The terms “comprising,” “including,” “having” and their derivatives, are not intended to exclude the presence of any additional component, step, or procedure, whether or not the11105690361.2Docket No. 113544-856283PCT APPLICATION same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary.

[0057] The term “or” unless stated otherwise, refers to the listed members individually as well as in any combination. Use of the singular includes use of the plural and vice versa.

[0058] The terms “a,” “an,” “the” and similar referents used in the context of describing the inventive features (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Thus, for example, reference to a “starch” may include one, two or more starches.

[0059] The term “method” refers to a sequence of steps performed to complete a process.

[0060] The term “composition” refers to a mixture of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0061] The term “<” as used herein refers to a quantitative measure which is interpreted as “less than or equal to.”

[0062] The term “LMP” used in reference to cathode material refers to “lithium-transition metal-phosphate.” As used herein, “LFP” refers to “lithium iron phosphate.”

[0063] “Capacity” of a battery or battery cell is a measure of the charge stored by the battery and is determined by the active materials contained in the battery. The capacity represents the maximum amount of charge that can be extracted from the battery under certain specified conditions. The battery has a discharge current in amperes that can be delivered over time. The capacity of the battery is given in ampere-hours (Ah).

[0064] “Gravimetric capacity” is the capacity per unit mass (mAh / g). Gravimetric capacity is also referred to as specific discharge capacity.

[0065] Unless otherwise stated, all percentages, ratios, parts, and amounts used and described herein are by weight.

[0066] Numbers, percentages, ratios, or other values stated herein may include that value, and other values that are about or approximately the stated value, as would be appreciated by one of ordinary skill in the art. A stated value should therefore be interpreted broadly enough to encompass values that are at least close enough to the stated value to perform a desired12105690361.2Docket No. 113544-856283PCT APPLICATION function or achieve a desired result, and / or values that round to the stated value. The stated values include at least the variation to be expected in a typical manufacturing process, and may include values that are within 25%, 15%, 10%, within 5%, within 1%, etc. of a stated value.

[0067] “wt%” as used herein refers to the percent ratio of the mass of the non-fluid particles or dissolved solids relative to the total mass of said mixture. For example, mass of the particles of ions, additional compounds, and / or dopants in a given mixture relative to the total mass of the olivine-type LMP material.

[0068] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The initial definition provided for a group or term herein applies to that group or term throughout the present specification individually or as part of another group unless otherwise indicated.13105690361.2

Claims

Docket No. 113544-856283PCT APPLICATIONCLAIMSWhat is claimed is:

1. An aqueous synthesis method for synthesizing Li-containing orthoborate materials utilizing the (BOf-) anion, the method comprising: calculating amounts of precursor materials, wherein the precursor materials include: a lithium source, a transition metal source, a boron source, and a carbon source; mixing the precursor materials in an aqueous solution to form a slurry; performing aqueous milling of the slurry to form a milled slurry; drying the milled slurry to form a dried powder; and, calcining the dried powder to form a Li-containing orthoborate material wherein the Li-containing orthoborate material has the formula Lii+xMi-xBO3, wherein M is a transition metal, and wherein 0 < x < 0.3.

2. The method of claim 1, wherein the carbon source is an organic carbon source.

3. The method of claim 1 or claim 2, wherein drying the milled slurry is done by spray drying.

4. The method of claim 1, wherein M comprises one or more of Mn, Fe, Mg, V, Co, Ni, Zn,Ca, Na, Al, Cr, and Cu.

5. The method of claim 1 , wherein the calcining is carried out at a temperature of at least 400 °C.

6. The method of claim 5, wherein the calcining is carried out at a temperature of about 600 °C for about 10 hours with a ramping rate of about 5°C per minute.14105690361.2Docket No. 113544-856283 PCT APPLICATION7. The method of claim 6, further comprising calcining under flowing nitrogen (N2) gas where M = Mn.

8. The method of claim 6, further comprising calcining under a flowing gas mixture comprising CO2 and N2, and wherein M comprises the combination of Mn and Fe.

9. The method of claim 1, wherein the slurry is formed by adding ceramic beads to the aqueous solution.

10. The methods of claim 9, wherein the ceramic beads are 0.5 mm Zirconia beads.

11. The method of claim 1, wherein the precursor materials are mixed together in distilled water with a final solids content of about 20 wt. %.

12. The method of claim 9, wherein a mass of the ceramic beads is twice the mass of the entire slurry, including water.

13. The method of claim 1, wherein the milling is carried out at about 600 rpm for between about 70 and about 110 minutes of active milling.

14. A method of using aqueous milling to produce a Li-containing orthoborate material having the (BO^~) anion according to the following steps: calculating amounts of precursor materials, wherein the precursor materials comprise a lithium source, a transition metal source, a boron source, and a carbon source; mixing the precursor materials in an aqueous solution to form a slurry; performing aqueous milling of the slurry to form a milled slurry; drying the milled slurry to form a dried powder; and calcining the dried powder wherein the Li-containing orthoborate material has the formula Lii+xMi-xBO3,15105690361.2Docket No. 113544-856283PCT APPLICATION wherein M is a transition metal, and wherein 0 < x < 0.3.

15. The method of claim 14, wherein the milling is carried out at about 600 rpm for about 96 minutes of active milling.

16. The method of claim 14, wherein the milled slurry is dried by spray drying.

17. The method of claim 16, wherein the spray drying is carried out with an outlet temperature of about 100 °C, an atomizing pressure of about 0.2 MPa, and a blower rate of about 0.5 m3 / min.

18. The method of claim 16, wherein M comprises one or more of Mn, Fe, Mg, V, Co, Ni, Zn, Ca, Na, Al, Cr, and Cu.

19. The method of claim 16, wherein the calcining is carried out at a temperature of at least 400° C.

20. The method of claim 19, wherein the calcining is carried out at a temperature of about 600 °C for about 10 hours with a ramping rate of about 5°C per minute.

21. The method of claim 18, further comprising calcining under flowing nitrogen (N2) gas, and wherein M is Mn.

22. The method of claim 20, further comprising calcining under a flowing gas mixture of about 5% CO2 and about 95% N2, and wherein M is Mn and Fe.

23. The method of claim 14, wherein the lithium source is lithium carbonate.

24. An intermediate slurry in an aqueous synthesis process for synthesizing Li-containing orthoborate materials, the intermediate slurry comprising: water, precursors, and ceramic beads.

25. The intermediate slurry of claim 24, wherein the ceramic beads are 0.5 mm Zirconia beads.16105690361.2Docket No. 113544-856283PCT APPLICATION26. The intermediate slurry of claim 24, wherein the precursors are a lithium source, one or more transition metal sources, a boron source, and a carbon source.

27. The intermediate slurry of claim 24, wherein M comprises one or more of Mn, Fe, Mg, V, Co, Ni, Zn, Ca, Na, Al, Cr, and Cu.

28. The intermediate slurry of claim 24, wherein the amount of precursors is calculated for a resulting Li-containing orthoborate material having the formula Lii+xMi-xBO3, wherein M comprises a transition metal, and 0 < x < 0.3.17105690361.2

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