Methods to produce compositions including lithium and phosphorus

Abstract

The disclosure relates to methods that include combining a phosphorous-containing reactant and a lithium ion-containing ionic melt to produce a composition including lithium and phosphorous. The disclosure also relates to methods that include reacting a phosphorous- containing reactant with a lithium-containing species, such as a lithium ion-containing ionic melt, Li2O, and / or Li2O2, to form a composition including lithium and phosphorous, and related compositions and systems. The disclosure further relates to methods that include combining a phosphorous-containing reactant and a lithium ion-containing ionic melt to produce compositions including lithium and phosphorous, and related compositions and systems. In addition, the disclosure relates to methods that include combining a metal oxide of formula MvOw and a lithium ion-containing ionic melt to produce a composition of formula LixMyOz, and related compositions and systems. The disclosure also relates to compositions, including compositions produced by the methods of the disclosure, and to related systems. The disclosure also relates to various additional aspects, embodiments and features disclosed herein.

Description

[0001] METHODS TO PRODUCE COMPOSITIONS INCLUDING LITHIUM AND PHOSPHORUS

[0002] Cross-Reference to Related Applications

[0003] This application claims the benefit of U.S. patent application USSN 63 / 671,518, filed July 15, 2024, and entitled “METHODS TO PRODUCE COMPOSITIONS INCLUDING LITHIUM AND PHOSPHORUS.” The entire disclosure of this application is incorporated by reference herein.

[0004] Field

[0005] The disclosure relates to methods that include combining a phosphorous-containing reactant and a lithium ion-containing ionic melt to produce a composition including lithium and phosphorous. The disclosure also relates to methods that include reacting a phosphorous- containing reactant with a lithium-containing species, such as a lithium ion-containing ionic melt, LiiO, and / or LiiOi, to form a composition including lithium and phosphorous, and related compositions and systems. The disclosure further relates to methods that include combining a phosphorous-containing reactant and a lithium ion-containing ionic melt to produce compositions including lithium and phosphorous, and related compositions and systems. In addition, the disclosure relates to methods that include combining a metal oxide of formula MVOWand a lithium ion-containing ionic melt to produce a composition of formula LixMyOz, and related compositions and systems. The disclosure also relates to compositions, including compositions produced by the methods of the disclosure, and to related systems. The disclosure also relates to various additional aspects, embodiments and features disclosed herein.

[0006] Background

[0007] Phosphorus is used across various industries and application, such as in energy storage devices and agricultural fertilizers. Phosphorous can be obtained from various minerals, such as apatite. Phosphorus can be produced from phosphate-containing minerals using an acid, such as sulfuric acid (H2SO4).

[0008] Summary The disclosure relates to methods that include combining a phosphorous-containing reactant and a lithium ion-containing ionic melt to produce a composition including lithium and phosphorous. The disclosure also relates to methods that include reacting a phosphorous- containing reactant with a lithium-containing species, such as a lithium ion-containing ionic melt, L12O, and / or LiiOi, to form a composition including lithium and phosphorous, and related compositions and systems. The disclosure further relates to methods that include combining a phosphorous-containing reactant and a lithium ion-containing ionic melt to produce compositions including lithium and phosphorous, and related compositions and systems. In addition, the disclosure relates to methods that include combining a metal oxide of formula MVOWand a lithium ion-containing ionic melt to produce a composition of formula LixMyOz, and related compositions and systems. The disclosure also relates to compositions, including compositions produced by the methods of the disclosure, and to related systems. The disclosure also relates to various additional aspects, embodiments and features disclosed herein.

[0009] In some embodiments, the methods of the disclosure can be relatively safe, environmentally friendly, relatively fast, relatively simple, and / or relatively inexpensive relative to certain other methods for processing phosphorus-containing reactants and generating compositions including lithium and phosphorous (e.g., L PO-i), such as methods that include a use of an acid, such as sulfuric acid (H2SO4), and / or methods that generate phosphoric acid (H3PO4) and / or a related ion (e.g., NH4H2PO4, NasPO4). In some embodiments, the methods of the disclosure can be used, for example, to process phosphorus-containing reactants without producing undesired by-products, such as hydrogen fluoride, fluorosilicic acid, silicon tetrafluoride and / or phosphogypsum, which can be generated as a by-product in the reaction of phosphorus-containing reactants and acids, thereby reducing the use of subsequent purification steps. In some embodiments, the methods of the disclosure also can allow for the use of less solvent relative to other techniques for the processing of water-insoluble phosphorous-containing minerals. In some embodiments, the methods of the disclosure can generate relatively pure compositions including lithium and phosphorous (e.g., L PCh) from phosphorous-containing reactants with a radioactive element and / or rare-earth element. In some embodiments, the methods of the disclosure can be used with water-insoluble phosphorus-containing reactants which can be relatively abundant but relatively challenging to process using other methods. In some embodiments, the methods of the disclosure can be faster and / or more efficient relatively to certain other methods for processing phosphorus-containing reactants and generating compositions including lithium and phosphorous (e.g., LisPCL), such as bioleaching using the metabolic activity of microorganisms (e.g., T. thioparus).

[0010] In some embodiments, the methods of the disclosure can be used to produce compositions including lithium and phosphorous (e.g., L PO-i), which can be used directly and / or as precursors for various applications, such as in energy storage devices, hydrogen electrolysers, fuel cells, the production of metals and / or alloys, and / or fertilizers. In some embodiments, the methods of the disclosure can be used to generate compositions including lithium and phosphorous (e.g., L PO-i) and / or LiMPCh where M is a metal such as Fe and / or Mn for use as a cathode material in batteries (e.g., lithium-ion batteries), ceramic materials (e.g., glasses, enamels, glazes, bioactive lithia-silica glass-ceramic designed for bone tissue engineering applications), and / or as a precursor or catalyst in a chemical synthesis process.

[0011] In a first aspect, the disclosure provides a method, including combining a phosphorous- containing reactant and a lithium ion-containing ionic melt to produce a composition including lithium and phosphorous.

[0012] In some embodiments, the lithium ion-containing ionic melt includes at least one member selected from the group consisting of LiCl, LiF, LiBr, Lil, LiNCh, LiiCCh, LiOH, LiCICL, L1C2H3O2, L1BO2, L1B4O7, LIPF6, LiTFSl, and LiFSl.

[0013] In some embodiments, during the combining, a temperature of the lithium ion-containing ionic melt is from 20 °C to 1700 °C. In some embodiments, during the combining, a temperature of the lithium ion-containing ionic melt is from 20 °C to 1200 °C. In some embodiments, during the combining, a temperature of the lithium ion-containing ionic melt is from 100 °C to 1100 °C. In some embodiments, during the combining, a temperature of the lithium ion-containing ionic melt is from 200 °C to 1000 °C. In some embodiments, during the combining, a temperature of the lithium ion-containing ionic melt is from 300 °C to 900 °C.

[0014] In some embodiments, producing the composition includes reacting the lithium ion with the phosphorous-containing reactant.

[0015] In some embodiments, the lithium ion-containing ionic melt includes Li2O. In some embodiments, the Li2O is formed by hydrolysis of a lithium salt of the lithium ion-containing ionic melt. In some embodiments, producing the composition includes reacting the Li2O with the phosphorous-containing reactant. In some embodiments, the lithium ion-containing ionic melt includes LiiCh. In some embodiments, the LiiCh is formed by hydrolysis of a lithium salt of the lithium ion-containing ionic melt. In some embodiments, producing the composition includes reacting the LiiCh with the phosphorous-containing reactant.

[0016] In some embodiments, a concentration of water vapor present in an atmosphere around the lithium ion-containing ionic melt is from 0.1 % to 100 % relative humidity.

[0017] In some embodiments, the method further includes, after producing the composition including lithium and phosphorous, forming crystals of the composition in the lithium ioncontaining ionic melt.

[0018] In some embodiments, the method further comprises, after combining, exposing the combination to one or more forms of energy. The energy can be, for example, electromagnetic energy (e.g., micro wave energy) or ultrasound. In some cases, exposing to energy results in crystallites of the composition having particle sizes of from one nanometer to one micrometer.

[0019] In a second aspect, the disclosure provides a method which comprises combining a phosphorous-containing reactant and a lithium ion-containing salt to form a combination, and heating the combination above a melting point of the lithium ion-containing salt to melt the salt, thereby producing a composition comprising lithium and phosphorous. In some embodiments, the lithium ion-containing ionic salt comprises at least one member selected from the group consisting of LiCl, LiF, LiBr, Lil, LiNCh, LiiCCh, LiOH, LiCICL, LiCiHsOi, LiBCh, LiB-jO?, LiPFe, LiTFSl, and LiFSl. In some embodiments, producing the composition comprises reacting the lithium ion with the phosphorous-containing reactant. In some embodiments, the lithium ion-containing ionic melt comprises L12O, optionally wherein the LiiO is formed by hydrolysis of a lithium salt of the lithium ion-containing ionic melt. In some embodiments, producing the composition comprises reacting the L12O with the phosphorous-containing reactant. In some embodiments, the lithium ion-containing ionic salt comprises LiiCh and / or LiiOi. In some embodiments, the method further comprises, after producing the composition comprising lithium and phosphorous, forming crystals of the composition in the lithium ion-containing ionic melt. In some embodiments, combining comprises exposing to an external influence, such as, for example, grinding or ball milling. In some embodiments, the method further comprises, after heating the combination, exposing the combination to one or more forms of energy. The energy can be, for example, electromagnetic energy (e.g., micro wave energy) or ultrasound. In some cases, exposing to energy results in crystallites of the composition having particle sizes of from one nanometer to one micrometer.

[0020] In a third aspect, the disclosure provides a method, including combining a phosphorous- containing reactant and a lithium ion-containing ionic melt including a lithium salt dissolved in a solvent to produce a composition including lithium and phosphorous, where the solvent includes a member selected from the group consisting of water, ethanol, methanol, acetonitrile, DMSO, and DMF. In some embodiments, the solvent includes water. In some embodiments, the lithium salt includes at least one member selected from the group consisting of LiCl, LiF, LiBr, Lil, L1NO3, L12CO3, LiOH, L1CIO4, L1C2H3O2, L1BO2, L1B4O7, LIPF6, LiTFSl, and LiFSl. In some embodiments, the combining is performed at a temperature of 0 °C to 100 °C.

[0021] The following embodiments can be relevant to, for example, one or more of the first, second and third aspects.

[0022] In some embodiments, the combining is performed for 1 second to 4 weeks. In some embodiments, the combining is performed for 1 second to 1 week. In some embodiments, the combining is performed for 1 second to 1 day. In some embodiments, the combining is performed for 1 second to 5 hours.

[0023] In some embodiments, the composition includes at least one member selected from the group consisting of LixPyand LixPyOzwhere x = 1-7, y = 1-7, and z = 1-10.

[0024] In some embodiments, the composition includes at least one member selected from the group consisting of LisPCL, Li4P2O?, LiPCh, Li2PO3, LisPsOio, LiP?, LisP?, LiP, and LnP.

[0025] In some embodiments, the composition includes at least one member selected from the group consisting of LisPCL, Li4P2O?, LiPCh, Li2PC>3, and LisPsOio.

[0026] In some embodiments, the composition includes LisPCL. In some embodiments, the LisPCL is crystalline. In some embodiments, the LisPCL includes a gamma-orthorhombic crystalline structure.

[0027] In some embodiments, the composition is crystalline. In some embodiments, the composition includes a gamma-orthorhombic crystalline structure.

[0028] In some embodiments, the phosphorous-containing reactant includes an element selected from the group consisting of Ca, Fe, Al, Si, K, Mg, Ce, Nd, Na, Sr, Ba, La, Gd, and Pr and the element is doped into the crystalline composition. In some embodiments, the composition has a purity of at least 98 %. In some embodiments, the composition has a purity of at least 99 %. In some embodiments, the composition has a purity of at least 99.9 %.

[0029] In some embodiments, the phosphorous-containing reactant includes a phosphorus oxide.

[0030] In some embodiments, the phosphorous-containing reactant includes a compound of formula PxOy.

[0031] In some embodiments, the phosphorous-containing reactant includes at least one member selected from the group consisting of phosphate (PO4)3', (PiO?)4', (PCL)2', (PCL)', and (PsOio)5'.

[0032] In some embodiments, the phosphorous-containing reactant includes phosphate (PO4)3'.

[0033] In some embodiments, the phosphorous-containing reactant has a solubility of less than 1 g / L in water. In some embodiments, the phosphorous-containing reactant has a solubility of less than 0.1 g / L in water.

[0034] In some embodiments, the phosphorous-containing reactant includes at least one member selected from the group consisting of apatite, fluorapatite, chlorapatite, hydroxylapatite, carbonate apatite, pyromorphite, turquoise, variscite, monocalcium phosphate monohydrate, monocalcium phosphate anhydrous, dicalcium phosphate dihydrate, dicalcium phosphate anhydrous, octacalcium phosphate, tetracalcium phosphate, a-tricalcium phosphate, P-tricalcium phosphate, whitlockite, struvite, brushite, amblygonite, and phosphorite.

[0035] In some embodiments, the phosphorous-containing reactant includes apatite.

[0036] In some embodiments, the phosphorous-containing reactant includes a member selected from the group consisting of animal meat and animal bone.

[0037] In some embodiments, the phosphorous-containing reactant includes a battery cathode material. In some embodiments, the battery cathode material includes AMPO4, where A includes at least one member selected from the group consisting of Li and Na, and M includes at least one member selected from the group consisting of Fe, Mn, Ni and Co. In some embodiments, the battery cathode material includes at least one member selected from the group consisting of LiFePCL, LiMnPCL, LiCoPCL, LiFeMnPCL, and LiFeCoPCL.

[0038] In some embodiments, the phosphorous-containing reactant includes an element selected from the group consisting of Fe, Cd, Ca, Al, Sr, Ba, Si, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, U, Th, and Ra. In some embodiments, at least a portion of the element forms a chloride. In some embodiments, at least a portion of the chloride dissolves in the lithium ion-containing ionic melt. In some embodiments, at least a portion of the chloride evaporates.

[0039] In some embodiments, the method further includes, after forming the composition, separating a byproduct selected from the group consisting of the element, a chloride of the element, and an oxide of the element from the lithium ion-containing ionic melt. In some embodiments, the byproduct is separated by gravimetric separation. In some embodiments, the byproduct has a particle size of less than 5 pm. In some embodiments, the byproduct has a particle size of less than 1 pm. In some embodiments, the byproduct has a particle size of 100 nm to 5 pm. In some embodiments, the byproduct has a particle size of 10 nm to 1 pm.

[0040] In some embodiments, polarization is applied to the phosphorous-containing reactant. In some embodiments, the polarization is a cathodic polarization. In some embodiments, the polarization applied to the phosphorous-containing reactant is from -3.0 V to -0.1 V relative to a reference electrode immersed in the lithium ion-containing ionic melt.

[0041] In some embodiments, the method further includes converting the composition into LiMPO4, where M includes one or more metals. In some embodiments, M includes at least one member selected from the group consisting of Fe, Mn, Ni, Co, Al, W, Na, Ti, Mg, Ca, Si, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. In some embodiments, the method further includes making a component of an energy storage device using the LiMPO-i.

[0042] In some embodiments, the method further includes making a component of an energy storage device using the composition. In some embodiments, the component includes a member selected from the group consisting of an electrode, such as a cathode, and a solid-state electrolyte. In some embodiments, the energy storage device includes a lithium-ion battery.

[0043] In some embodiments, the method further includes converting the composition into a product selected from the group consisting of phosphoric acid, MH2PO4, where M is an alkali metal or ammonium, M2HPO4, where M is an alkali metal, or CoHPO4. In some embodiments, the product includes a member selected from the group consisting of phosphoric acid, LiH2PO4, NaH2PC>4, KH2PO4, NH4H2PO4, Na2HPO4, K2HPO4, Li2HPO4, and CoHPO4. In some embodiments, the product has a purity of at least 98 %. In some embodiments, the product has a purity of at least 99 %. In some embodiments, the product has a purity of at least 99.9 %.

[0044] In some embodiments, none of phosphogypsum, hydrofluoric acid, fluorosilicic acid and silicon tetrafluoride are generated in the converting. In some embodiments, the combining is acid-free.

[0045] In some embodiments, sulfuric acid is not consumed in the converting.

[0046] In some embodiments, the method is performed continuously. In some embodiments, reactant is added continuously.

[0047] In some embodiments, the method is performed in batches.

[0048] In a fourth aspect, the disclosure provides a composition, including crystals of Li^POr, where at least a portion of the crystals have a particle size of at least 1 pm, such as at least 2 pm, at least 5 pm, at least 10 pm, or at least 50 pm; at least a portion of the crystals have a crystalline domain size of at least 100 nm; and / or at least a portion of the crystals have an XRD peak at 34.5° (20) has a FWHM of less than 0.1° (20).

[0049] In some embodiments, the composition includes particles including crystals of LisPO4. In some embodiment, the composition includes single crystal particles of U3PO4.

[0050] In some embodiments, at least a portion of the crystals have a particle size of at most 200 pm.

[0051] In some embodiments, at least a portion of the crystals are in the form of at least one shape selected from the group consisting of rods, sheets, and irregularly shaped crystals.

[0052] In some embodiments, at least a portion of the crystals are in the form of sheets having a width of from 5 pm to 200 pm and a length of from 5 pm to 200 pm.

[0053] In some embodiments, at least a portion of the crystals are in the form of rods having a width of from 100 nm to 1 pm and a length of from 10 pm to 200 pm.

[0054] In some embodiments, at least a portion of the crystals have an orthorhombic crystalline structure.

[0055] In some embodiments, the crystals of U3PO4 have a purity of at least 98 %. In some embodiments, the crystals of Li3PO4 have a purity of at least 99 %. In some embodiments, the crystals of Li3PO4 have a purity of at least 99.9 %.

[0056] In a fifth aspect, the disclosure provides a system including a lithium ion-containing ionic melt and a composition including lithium and phosphorous dispersed in the lithium ioncontaining ionic melt.

[0057] In some embodiments, the composition includes at least one member selected from the group consisting of LixPyand LixPyOz. In some embodiments, the composition includes at least one member selected from the group consisting of Li3PO4, Li4P2O7, LiPCh, LiP?, U3P7, LiP, and U3P

[0058] In some embodiments, the composition includes at least one member selected from the group consisting of LisPCL, Li4P2O7, and LiPCL.

[0059] In some embodiments, the composition includes LisPCL.

[0060] In some embodiments, the composition is crystalline.

[0061] In some embodiments, the crystals are rod-shaped. In some embodiments, the crystals are sheetlike. In some embodiments, the crystals include a single crystalline structure. In some embodiments, the crystals include an orthorhombic crystalline structure.

[0062] In some embodiments, the composition has a purity of at least 98 %. In some embodiments, the composition has a purity of at least 99 %. In some embodiments, the composition has a purity of at least 99.9 %.

[0063] In a sixth aspect, the disclosure provides a method including combining a metal oxide of formula MVOWand a lithium ion-containing ionic melt to produce a composition of formula LlxMyOz.

[0064] In some embodiments, the metal oxide includes at least one member selected from the group consisting of Mn, Co, Ni, Ti, Zr, Fe, Mo, W, Nb, Si, Al, V, and Cr.

[0065] In some embodiments, the lithium ion-containing ionic melt includes at least one member selected from the group consisting of LiCl, LiF, LiBr, Lil, LiNCh, LiiCCh, LiOH, LiCICL, L1C2H3O2, L1BO2, L1B4O7, LIPF6, LiTFSl, and LiFSl.

[0066] In some embodiments, the composition includes the formula LixMnyOz, where x ranges from 0.02 to 5.5, y ranges from 0.20 to 6.80, and z ranges from 2 to 16.

[0067] In some embodiments, the composition includes at least one member selected from the group consisting of LiCoCh, LiMnCh, LiMmCL, LiNiMnCoCh, LiNiCoAlCh, Li4Ti50i2.

[0068] In some embodiments, the composition includes a cubic, orthorhombic, rhombohedral, or hexagonal crystalline structure.

[0069] In some embodiments, a polarization is applied to the metal oxide. In some embodiments, the polarization applied to the metal oxide is from -3.5 V to -0.1 V relative to a reference electrode immersed in the lithium ion-containing ionic melt. In some embodiments, the polarization applied to the metal oxide is from -3 V to -0.1 V relative to a reference electrode immersed in the lithium ion-containing ionic melt. In a seventh aspect, the disclosure provides a system including a container including a lithium ion-containing ionic melt, a movable shaft, and a phosphorous-containing reactant attached to the movable shaft, where the movable shaft is configured to immerse and remove the phosphorous-containing reactant from the lithium ion-containing ionic melt.

[0070] In some embodiments, the container, the phosphorous-containing reactant, and at least a portion of the movable shaft are disposed in a reactor, and the reactor includes a gas port.

[0071] The present disclosure encompasses combining various features of one or more different embodiments as appropriate.

[0072] Brief Description of the Figures

[0073] Figure 1 shows the chemical structure of fluorapatite.

[0074] Figures 2a and 2b show a schematic for a system before and after, respectively, immersing a phosphorous-containing reactant into a lithium ion-containing ionic melt.

[0075] Figure 3 shows an X-ray diffraction (XRD) pattern of a fluorapatite sample.

[0076] Figures 4a-c show SEM micrographs and EDS analysis of a fluorapatite sample.

[0077] Figure 5a shows an XRD pattern of fluorapatite before (top) and after (bottom) sintering.

[0078] Figure 5b shows an XRD pattern of fluorapatite before (top) and after (bottom) sintering.

[0079] Figure 6a shows an XRD pattern of a porous compacted apatite mass (pellet).

[0080] Figure 6b shows an XRD pattern of a powder retrieved from the bulk of LiCl salt after freezing, washing, and vacuum filtration.

[0081] Figure 6c shows an XRD pattern of a powder retrieved from the bottom of an alumina crucible after treatment with an ionic melt.

[0082] Figure 6d shows an XRD pattern of a remaining pellet after treatment with an ionic melt.

[0083] Figure 7 shows an XRD pattern of a product obtained from the bulk of a salt after extraction of the remaining pellet, cooling, washing, and filtration.

[0084] Figures 8a-8c show SEM micrographs of a product obtained from the bulk of a salt after extraction of the remaining pellet, cooling, washing, and filtration.

[0085] Figure 8d shows the EDS spectrum recorded on the area identified as (1) in micrograph of Figure 8c.

[0086] Figure 9a shows a SEM micrograph of a product obtained from the bulk of a salt after extraction of the remaining pellet, cooling, washing, filtration, and ball-milling. Figure 9b shows an EDS spectrum recorded on the area identified as (1) in micrograph of Figure 9a.

[0087] Figure 10 shows a Raman spectrum of a product obtained from the bulk of salt after extraction of the remaining pellet, cooling, washing, and filtration.

[0088] Figure 11 shows an XRD pattern of particles retrieved from the bottom of a solidified salt (top), in comparison to those retrieved from the bulk of the salt (bottom).

[0089] Figure 12 shows SEM micrographs recorded on particles retrieved from the bottom of a solidified salt and EDS analysis recorded on the rectangle shown in the micrograph.

[0090] Figure 13 shows X-ray diffraction patterns of the remaining mass retrieved from the ionic melt and the patterns associated with standard cards.

[0091] Figure 14 shows an SEM micrograph and EDS analysis recorded on a remaining pellet after being extracted from ionic melt and pulverized.

[0092] Figure 15 shows an XRD pattern of a lithium manganese ferric phosphate (LMFP) compound fabricated using L PO-i.

[0093] Figure 16a shows a SEM micrograph of an LMFP compound fabricated using LnPO-i.

[0094] Figure 16b shows an EDS map spectrum of an LMFP compound fabricated using L PO-i.

[0095] Figure 17a shows an SEM micrograph of an LMFP particle fabricated using L PO-i.

[0096] Figure 17b shows an EDS spectrum recorded on an LMFP particle fabricated using LisPCL.

[0097] Figure 18 shows an SEM micrograph of ball-milled fluorapatite.

[0098] Figure 19 shown an XRD pattern of ball-milled fluorapatite.

[0099] Figure 20 shows an XRD pattern of ball-milled fluorapatite powder treated in an ionic melt.

[0100] Figures 21a-21c show SEM micrographs of ball-milled fluorapatite powder treated in an ionic melt.

[0101] Figure 22a shows an XRD pattern of a mixture containing fluorapatite and hematite.

[0102] Figure 22b shows an SEM micrograph of a mixture containing fluorapatite and hematite and EDS analysis recorded on the area identified by the rectangle.

[0103] Figure 23a shows an XRD pattern of ball-milled FeiCh' fluorapatite mixture exposed to an ionic melt. Figure 23b shows an SEM micrograph of ball-milled FeiCh' fluorapatite mixture exposed to an ionic melt.

[0104] Figure 24 shows an XRD pattern of product obtained by treatment of a mixture containing fluorapatite, FeiCh, and carbon.

[0105] Figure 25a shows an XRD pattern of a used LiFePCE (LFP) cathode.

[0106] Figure 25b shows an XRD pattern of a calcined LFP cathode.

[0107] Figure 25c shows an SEM micrograph of the calcined LFP, and the EDS analysis recorded on the area highlighted in the micrograph.

[0108] Figures 26a-26c show X-ray diffraction patterns of L PCh obtained from the bulk of solidified salt at various two-theta ranges.

[0109] Figures 26d and 26e show an SEM and EDS spectrum, respectively, recorded on L PCh crystals.

[0110] Figures 27a and 27b shows XRD patterns of material obtained from the bottom part of solidified salt produced using calcined LFP cathode material at various two-theta ranges.

[0111] Figures 28a and 28b shows SEM micrographs of the material obtained from the bottom part of solidified salt produced using calcined LFP cathode material.

[0112] Figure 28c shows an EDS analysis of the material from Figure 28b.

[0113] Figure 29a shows photographs of fluorapatite and products obtained by the thermal treatment of the fluorapatite in KC1 under flow of various gases.

[0114] Figure 29b shows XRD diffraction patterns of treated fluorapatite after washing and filtering.

[0115] Figures 30a and 30b show SEM micrographs of product obtained after thermal treatment of fluorapatite with KC1 under air.

[0116] Figure 30c shows an SEM micrograph of the product obtained after thermal treatment of fluorapatite with KC1 under moist Ar.

[0117] Figure 30d shows an EDS analysis of the product of Figure 30c.

[0118] Figure 31 shows an XRD pattern of L PCh produced using used LFP employing LiCl under nominally dry Ar.

[0119] Figures 32a and 32b show an XRD pattern and photograph, respectively, of an initial pellet. Figures 32c and 32d show an XRD pattern and photograph, respectively, of a pellet after cathodic polarization.

[0120] Figure 32e shows a graph of potential difference between a pellet and Mo reference electrode (negative voltage), and the potential difference between a graphite crucible and the Mo reference electrode (positive voltage) during the polarization.

[0121] Figure 33a shows a SEM micrograph of a recovered cathode material.

[0122] Figure 33b shows a SEM micrograph of regenerated LFP.

[0123] Figure 33c shows a graph of Li-ion storage performance.

[0124] Detailed Description

[0125] General Introduction

[0126] In general, the disclosure provides methods to produce compositions including lithium and phosphorous from a phosphorous-containing reactant, as well as related compositions and systems.

[0127] A method of the disclosure can include combining a phosphorous-containing reactant and a lithium ion-containing ionic melt to produce a composition including lithium and phosphorous.

[0128] A method of the disclosure can include reacting a phosphorous-containing reactant with a lithium-containing species to form a composition including lithium and phosphorous, where the lithium-containing species is a lithium ion-containing ionic melt, LiiO, and / or LiiCh. An ionic melt is a salt in the liquid state above the melting point of the salt. In some embodiments, the method further includes preparing the L12O and / or LiiOi prior to the reacting.

[0129] Alternatively or additionally, a method of the disclosure can include combining a phosphorous-containing reactant and a lithium ion-containing ionic melt to produce a composition including lithium and phosphorous. In some embodiments, the lithium ioncontaining ionic melt includes L12O and / or LiiOi.

[0130] In general, the reacting and / or combining is acid-free, that is no acid is added or consumed. For example, the reacting and / or combining is performed without the use or addition of H2SO4. For example, in some embodiments, the reacting and / or combining is performed with less than 0.01 wt. % acid (e.g., H2SO4) relative to the amount of the phosphorous-containing reactant. Without wishing to be bound by theory, it is believed that a possible reaction between a phosphorous-containing reactant (e.g., Ca3(PO4)2) and a lithium ion-containing ionic melt (e.g., LiCl), to generate a composition including lithium and phosphorous (e.g., LisPO^ is:

[0131] Ca3(PO4)2+ 6 LiCl 2 L13PO4 + 3 CaCl2AG° = 99.8 kJ (750 °C) (1)

[0132] It is also believed that, although the change in Gibbs free energy of this reaction is positive, the dissolution of CaCb in the ionic melt can provide the driving force for the reaction to proceed.

[0133] Without wishing to be bound by theory, it is believed that Li2O and / or Li2O2 can react with a phosphorous-containing reactant to generate a composition including lithium and phosphorous. It is further believed that a possible reaction between a phosphorous-containing reactant (e.g., Ca3(PO4)2) and Li2O and / or U2O2 to generate a composition including lithium and phosphorous (e.g., Li3PO4) is:

[0134] Ca3(PO4)2+ 3LI2O 2L13PO4 + 3CaO AG°= -174 to -115 kJ (0-1000 °C) (2a)

[0135] Ca3(PO4)2+ 3LI2O22L13PO4 + 3CaO + 1.5O2(g) AG°= -320 to -138 kJ (0-1000 °C) (2b)

[0136] It is also believed that the reactions are thermodynamically favourable and can proceed to completion. It is further believed that Li2O and / or Li2O2 have a relatively high solubility in a lithium ion-containing ionic melt, for example, greater than 1 g / L. Under such conditions, the Li2O and / or Li2O2 dissolved in the ionic melt at temperatures greater than the melting point of the salt can readily react with the (PO4) ' containing compound.

[0137] In some embodiments, Li2O is reacted with a phosphorous-containing reactant to generate a composition including lithium and phosphorous in a lithium ion-containing ionic melt with a relatively high solubility for both Li2O and CaO, and relatively good stability for the composition (e.g., Li3PO4). For example, the ionic melt can be an ionic melt containing LiCl and CaCh, allowing the dissolution of Li2O and CaO. An appropriate salt and temperature can be selected to provide relatively good solubility of Li2O and CaO (see discussion below). For instance, molten LiCl-CaCh can be obtained at temperatures greater than around 475 °C by selecting an appropriate chemical composition of the ionic melt.

[0138] In some embodiments, the Li2O can be prepared by reacting lithium metal and oxygen gas:

[0139] 4 Li + 02- 2 L12O (3) Without wishing to be bound by theory, it is believed that the above reaction is highly exothermic. Li2O can also be produced using lithium peroxide and metallic lithium or by thermal decomposition of lithium peroxide at temperatures greater than 400 °C. In some embodiments, the Li2O is prepared and used in situ, for example by contacting a lithium ion-containing ionic melt with moisture:

[0140] 2 LiCl + H2O L12O + 2HC1 (4)

[0141] Without wishing to be bound by theory, it is believed that moisture can be introduced into the ionic melt from the air. It is further believed that the dissolution of both Li2O and HC1 into the ionic melt can provide the driving force for the reaction. It is also believed that in the presence of a phosphorous-containing reactant, the generated Li2O can relatively instantaneously react with the phosphorous-containing reactant to produce the composition (e.g., LisPCL). In some embodiments, the composition (e.g., LisPCL) is dispersed in the ionic melt at room temperature. In some embodiments, other components present in the precursor become partially or completely separated from the generated composition (e.g., L PO-i), for example, by sinking in the ionic melt and / or removal from the ionic melt after the generation of the composition (e.g., L PO-i crystals) (see discussion below).

[0142] Phosphorous-containing reactants

[0143] In general, any suitable phosphorous-containing reactant can be employed in a method of the disclosure, including both water soluble and water insoluble phosphorous-containing reactants. In some embodiments, the phosphorous-containing reactant has relatively low (e.g., minimal or no) solubility in water. For example, in some embodiments, the phosphorous- containing reactant has a solubility of less than 1 g / L (e.g., less than 0.9 g / L, less than 0.8 g / L, less than 0.7 g / L, less than 0.6 g / L, less than 0.5 g / L, less than 0.4 g / L, less than 0.3 g / L, less than 0.2 g / L, less than 0.1 g / L) in water.

[0144] In some embodiments, the phosphorous-containing reactant is a phosphorous-containing mineral. Without wishing to be bound by theory, it is believed that any phosphorous-containing mineral containing phosphate anions (PO4 ' ) can be used. In some embodiments, the phosphorous-containing reactant is an amorphous calcium phosphate, of general formula Ca5(PO4)3(OH,F,Cl). In some embodiments, the phosphorous-containing reactant includes apatite, fluorapatite, chlorapatite, hydroxylapatite, carbonate apatite, pyromorphite, turquoise, variscite, monocalcium phosphate monohydrate, monocalcium phosphate anhydrous, dicalcium phosphate dihydrate, dicalcium phosphate anhydrous, octacalcium phosphate, tetracalcium phosphate, a-tricalcium phosphate, P-tricalcium phosphate, whitlockite, struvite, brushite, amblygonite, and / or phosphorite. In some embodiments, the phosphorous-containing reactant includes apatite. In some embodiments, the phosphorous-containing reactant includes fluorapatite. Figure 1 shows the chemical structure of fluorapatite.

[0145] In some embodiments, the phosphorous-containing reactant includes a hexagonal crystalline structure.

[0146] In some embodiments, the phosphorous-containing reactant includes a phosphorus oxide. In some embodiments, the phosphorous-containing reactant includes a compound of formula PxOy. In some embodiments, the phosphorous-containing reactant includes phosphate (PO-i) ', (PiO?)4', (PCh)2', (PCh)', and / or (P3O10)5'. In some embodiments, the phosphorous-containing reactant includes phosphate (PO4)3'.

[0147] In some embodiments, the phosphorous-containing reactant includes animal meat and / or bone, such as fish bone.

[0148] In some embodiments, the phosphorous-containing reactant includes one or more battery cathode materials (e.g., one or more used or spent battery cathode materials), such as from a lithium-ion battery and / or a sodium-ion battery. In some embodiments, the battery cathode materials include AMPO4, where A includes Li and / or Na, and M includes Fe, Mn, Ni and / or Co. In some embodiments, the battery cathode materials include LiFePCL, LiMnPCfl, LiCoPCL, LiFeMnPCL, and / or LiFeCoPCL.

[0149] Without wishing to be bound by theory, it is believed that a possible reaction to convert LiMPCfl into LisPCL is:

[0150] L1MPO4 + 2L1C1 MCh + L13PO4 (5)

[0151] Without wishing to be bound by theory, it is believed that a possible reaction to convert LiFePCL into LisPCL is:

[0152] LiFePO4+ 2L1C1 FeCh + L13PO4 (6)

[0153] It is believed that the reaction between LiFePCL and LiCl leads to the formation of L PCL and FeCh (with nominal melting point of 677 °C), which can dissolve in the molten LiCl. It is further believed that the dissolution of the products in the ionic melt can provide the driving force for the reaction.

[0154] Without wishing to be bound by theory, it is believed that a possible reaction to convert LiFePO4 into LisPO4 using U2O present in the ionic melt is:

[0155] LiFePCh + L12O — FeO + LisPO4 (7)

[0156] It is believed that the reaction generates an iron oxide and L PCh, where the iron oxide phase sinks in the melt, while the LisPO4 is dispersed. Thus, it is further believed that the methods of the disclosure can selectively lithiate (PO4)3' from a phosphorous-containing reactant that further includes elements such as iron and / or calcium (e.g., a mineral, a battery cathode material) to generate the composition (e.g., LisPO4) with relatively high purity and free from iron and / or calcium. For example, the composition (e.g., L PCh) can have no iron and / or calcium as detected by EDS.

[0157] In embodiments where the phosphorous-containing reactant includes one or more battery cathode materials (e.g., one or more used or spent battery cathode materials), the methods of the disclosure can further include the separation of cathode material from batteries, such as pouch cells. For example, the cells can first be fully discharged, such as by immersion in an aqueous solution containing a salt (e.g., NaCl), the cells can be disassembled, and the aluminium current collector coated with the cathode material can be extracted. Optionally, the extracted electrodes are segmented and soaked in dimethyl carbonate (DMC) for a sufficient duration (e.g., 30 minutes to 15 hours) to remove residual electrolyte. After drying, the electrodes can be subjected to freeze-drying in a vacuum chamber (e.g., at -60 °C to -20°C), resulting in the effective separation of the cathode material from the aluminium foil.

[0158] In some embodiments, the separated cathode materials include a carbon coating. These cathode materials can optionally be thermally treated at a sufficiently high temperature (e.g., 300-700 °C) under an appropriate atmosphere, such as air, to remove impurities and, optionally, the carbon phase. The sample obtained after freeze-drying or after the additional thermal treatment can be used to produce LisPCE as discussed above.

[0159] In some embodiments, such as when the phosphorous-containing reactant includes a mineral, the phosphorous-containing reactant can include an at least one additional element. In some embodiments, the at least one additional element, a chloride of the at least one additional element, and / or an oxide of the at least one additional element is separated from the lithium ioncontaining ionic melt, for example, by gravimetric separation.

[0160] The phosphorous-containing reactant can include at least on additional element such as iron (Fe), cadmium (Cd), calcium (Ca), aluminum (Al), strontium (Sr), barium (Ba), silicon (Si), a rare earth metal such as scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and / or lutetium (Lu) and / or a radioactive element such as uranium (U), thorium (Th), and / or radium (Ra).

[0161] Without wishing to be bound by theory, it is believed that elements such as uranium, thorium, and radium have relatively poor solubility in a lithium ion-containing ionic melt, thus these elements can be separated from the composition including lithium and phosphorous (e.g., L PO-i) relatively easily.

[0162] In some embodiments, at least a portion of the at least one additional element forms a chloride (see reactions (5) and (6)). In some embodiments, at least a portion of the chloride dissolves in the lithium ion-containing ionic melt. In some embodiments, at least a portion of the chloride evaporates. In general, the dissolution and / or evaporation occurs at a temperature sufficiently high for the lithium salt to form an ionic melt.

[0163] In some embodiments, the at least one additional element, a chloride of the at least one additional element, and / or an oxide of the at least one additional element has a particle size of less than 5 pm (e.g., less than 4 pm, less than 3 pm, less than 2 pm, less than 1 pm, less than 900 nm, less than 800 nm, less than 700 nm, less than 600 nm, less than 500 nm, less than 400 nm, less than 300 nm, less than 200 nm, less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, less than 40 nm, less than 30 nm, less than 20 nm, less than 10 nm). In some embodiments, the at least one additional element, a chloride of the at least one additional element, and / or an oxide of the at least one additional element has a particle size of at least 100 nm (e.g., at least 200 nm, at least 300 nm, at least 400 nm, at least 500 nm, at least 600 nm, at least 700 nm, at least 800 nm, at least 900 nm, at least 1 pm, at least 2 pm, at least 3 pm, at least 4 pm) and / or at most 5 pm (e.g., at most 4 pm, at most 3 pm, at most 2 pm, at most 1 pm, at most 900 nm, at most 800 nm, at most 700 nm, at most 600 nm, at most 500 nm, at most 400 nm, at most 300 nm, at most 200 nm). In some embodiments, the at least one additional element, a chloride of the at least one additional element, and / or an oxide of the at least one additional element has a particle size of at least 10 nm (e.g., at least 20 nm, at least 30 nm, at least 40 nm, at least 50 nm, at least 60 nm, at least 70 nm, at least 80 nm, at least 90 nm, at least 100 nm, at least 200 nm, at least 300 nm, at least 400 nm, at least 500 nm, at least 600 nm, at least 700 nm, at least 800 nm, at least 900 nm and / or at most 1 pm (e.g., at most 900 nm, at most 800 nm, at most 700 nm, at most 600 nm, at most 500 nm, at most 400 nm, at most 300 nm, at most 200 nm, at most 100 nm, at most 90 nm, at most 80 nm, at most 70 nm, at most 60 nm, at most 50 nm, at most 40 nm, at most 30 nm, at most 20 nm).

[0164] In some embodiments, the phosphorous-containing reactant (e.g., apatite) is present with another mineral, such as iron oxide-apatite (IOA or Kiruna-type) deposit which can include a magnetite-apatite-actinolite / diopside.

[0165] In some embodiments, the phosphorous-containing reactant is directly be exposed to the lithium ion-containing ionic melt, with minimal or no pre-treatment. In some embodiments, the phosphorous-containing reactant is formed into a pellet (see Figure 2).

[0166] In some embodiments, the phosphorous-containing reactant includes an organic phosphorus compound, such as a compound with hydrophobic chains (e.g., phospholipids), elemental phosphorus, and / or phosphorus allotropes.

[0167] Compositions

[0168] In some embodiments, a composition prepared by a method of the disclosure includes LixPy and / or LixPyOzwhere x = 1-7, y = 1-7, and z = 1-10. In some embodiments, the composition includes Li3PO4, Li4P2O7, LiPO3, LiiPCh, LisP3Oio, LiP?, Li3P?, LiP, and / or Li3P. In some embodiments, the composition disclosure includes Li3PO4, I^PiO?, LiPO3, LiiPCh, and / or LI5P3O 10. In some embodiments, the composition includes lithium and (PCL)3', (PiO?)4', (PO3)2', (PO3)', and / or (P30io)5'. In some embodiments, the composition includes Li3PO4. In some embodiments, the composition includes y-Li3PO4.

[0169] In some embodiments, crystals of the composition forms in the lithium ion-containing ionic melt. In some embodiments, crystals of the composition are dispersed in the lithium ioncontaining ionic melt. In some embodiments, the composition includes an orthorhombic crystalline structure. In some embodiments, the composition includes Li3PO4 and the Li3PO4 is crystalline. In some embodiments, the crystalline LisPO4 includes a gamma-orthorhombic crystalline structure.

[0170] In general, the composition (e.g., crystalline LisPO-t) can be relatively pure. In some embodiments, the composition (e.g., crystalline LisPO^ has a purity of at least 98 % (e.g., at least 98.5 %, at least 99 %, at least 99.5 %, at least 99.8 %, at least 99.9 %) and / or at most 100% (e.g., at most 99.9 %, at most 99.8 %, at most 99.5 %, at most 99 %, at most 98.5 %), for example, as determined by EDS analysis.

[0171] In some embodiments, an element can be doped into the composition. Without wishing to be bound by theory, it is believed that doping of the composition is determined by the processing conditions and chemical composition of the phosphorous-containing reactant. In some embodiments the composition (e.g., crystalline LisPCE) is doped with Ca, Fe, Al, Si, K, Mg, Ce, Nd, Na, Sr, Ba, La, Gd, and / or Pr. In some embodiments the composition (e.g., crystalline L PO-i) is doped with Ca. In some embodiments, the phosphorous-containing reactant includes Ca, Mg, Al, Sr, Ba, Si, and / or a rare earth element and the element is doped into the composition (e.g., crystalline LisPCL).

[0172] The methods of the disclosure can be used to prepare crystals of L PO-i. In some embodiments, the crystals have a particle size of at least 1 pm (e.g., at least 2 pm, at least 3 pm, at least 4 pm, at least 5 pm, at least 6 pm, at least 7 pm, at least 8 pm, at least 9 pm, at least 10 pm, at least 20 pm, at least 30 pm, at least 40 pm, at least 50 pm, at least 60 pm, at least 70 pm, at least 80 pm, at least 90 pm, at least 100 pm, at least 110 pm, at least 120 pm, at least 130 pm, at least 140 pm) and / or at most 150 pm (e.g., at most 140 pm, at most 130 pm, at most 120 pm, at most 110 pm, at most 100 pm, at most 90 pm, at most 80 pm, at most 70 pm, at most 60 pm, at most 50 pm, at most 40 pm, at most 30 pm, at most 20 pm, at most 10 pm, at most 9 pm, at most 8 pm, at most 7 pm, at most 6 pm, at most 5 pm, at most 4 pm, at most 3 pm, at most 2 pm). In some embodiments, the crystals have a crystalline domain size of at least 100 nm (e.g., at least 150 nm, at least 200 nm, at least 250 nm, at least 300 nm, at least 350 nm, at least 400 nm, at least 450 nm) and / or at most 500 nm (e.g., at least 450 nm, at least 400 nm, at least 350 nm, at least 300 nm, at least 250 nm, at least 200 nm, at least 150 nm). In some embodiments, the crystals include an XRD peak at 34.5° (20) that has a FWHM of less than 0.1° (20).

[0173] In some embodiments, the methods of the disclosure provide particles including crystals of L13PO4. In some embodiments, the methods of the disclosure provide single crystal particles. In such embodiments, the crystal has a particle size of at least 2 pm (e.g., at least 3 pm, at least 4 pm, at least 5 pm, at least 6 pm, at least 7 pm, at least 8 pm, at least 9 pm, at least 10 pm, at least 15 pm, at least 20 pm, at least 25 pm, at least 30 pm, at least 35 pm, at least 40 pm, at least 45 pm, at least 50 pm, at least 55 pm, at least 60 pm, at least 65 pm, at least 70 pm, at least 75 pm, at least 80 pm, at least 85 pm, at least 90 pm, at least 95 pm, at least 100 pm, at least 110 pm, at least 120 pm, at least 130 pm, at least 140 pm, at least 150 pm, at least 160 pm, at least 170 pm, at least 180 pm, at least 190 pm) and / or at most 200 pm (e.g., at most 190 pm, at most 180 pm, at most 170 pm, at most 160 pm, at most 150 pm, at most 140 pm, at most 130 pm, at most 120 pm, at most 110 pm, at most 100 pm, at most 95 pm, at most 90 pm, at most 85 pm, at most 80 pm, at most 75 pm, at most 70 pm, at most 65 pm, at most 60 pm, at most 55 pm, at most 50 pm, at most 45 pm, at most 40 pm, at most 35 pm, at most 30 pm, at most 25 pm, at most 20 pm, at most 15 pm, at most 10 pm, at most 9 pm, at most 8 pm, at most 7 pm, at most 6 pm, at most 5 pm, most 4 pm, at most 3 pm).

[0174] In some embodiments, the crystals are in the form of rods, sheets, and / or irregularly shaped crystals.

[0175] In some embodiments, at least a portion of the crystals are in the form of sheets. In some embodiments, the sheets have a width of at least 5 pm (e.g., at least 6 pm, at least 7 pm, at least 8 pm, at least 9 pm, at least 10 pm, at least 15 pm, at least 20 pm, at least 25 pm, at least 30 pm, at least 35 pm, at least 40 pm, at least 45 pm, at least 50 pm, at least 55 pm, at least 60 pm, at least 65 pm, at least 70 pm, at least 75 pm, at least 80 pm, at least 85 pm, at least 90 pm, at least 95 pm, at least 100 pm, at least 110 pm, at least 120 pm, at least 130 pm, at least 140 pm, at least 150 pm, at least 160 pm, at least 170 pm, at least 180 pm, at least 190 pm) and / or at most 200 pm (e.g., at most 190 pm, at most 180 pm, at most 170 pm, at most 160 pm, at most 150 pm, at most 140 pm, at most 130 pm, at most 120 pm, at most 110 pm, at most 100 pm, at most 95 pm, at most 90 pm, at most 85 pm, at most 80 pm, at most 75 pm, at most 70 pm, at most 65 pm, at most 60 pm, at most 55 pm, at most 50 pm, at most 45 pm, at most 40 pm, at most 35 pm, at most 30 pm, at most 25 pm, at most 20 pm, at most 15 pm, at most 10 pm, at most 9 pm, at most 8 pm, at most 7 pm, at most 6 pm). In some embodiments, the sheets have a length of at least 5 pm (e.g., at least 6 pm, at least 7 pm, at least 8 pm, at least 9 pm, at least 10 pm, at least 15 pm, at least 20 pm, at least 25 pm, at least 30 pm, at least 35 pm, at least 40 pm, at least 45 pm, at least 50 pm, at least 55 pm, at least 60 pm, at least 65 pm, at least 70 pm, at least 75 pm, at least 80 pm, at least 85 pm, at least 90 pm, at least 95 pm, at least 100 pm, at least 110 pm, at least 120 pm, at least 130 pm, at least 140 pm, at least 150 pm, at least 160 pm, at least 170 pm, at least 180 pm, at least 190 pm) and / or at most 200 pm (e.g., at most 190 gm, at most 180 gm, at most 170 gm, at most 160 gm, at most 150 gm, at most 140 gm, at most 130 gm, at most 120 gm, at most 110 gm, at most 100 gm, at most 95 gm, at most 90 gm, at most 85 gm, at most 80 gm, at most 75 gm, at most 70 gm, at most 65 gm, at most 60 gm, at most 55 gm, at most 50 gm, at most 45 gm, at most 40 gm, at most 35 gm, at most 30 gm, at most 25 gm, at most 20 gm, at most 15 gm, at most 10 gm, at most 9 gm, at most 8 gm, at most 7 gm, at most 6 pm).

[0176] In some embodiments, at least a portion of the crystals are in the form of rods. In some embodiments, the rods have a width at least 100 nm (e.g., at least 150 nm, at least 200 nm, at least 250 nm, at least 300 nm, at least 350 nm, at least 400 nm, at least 450 nm, at least 500 nm, at least 550 nm, at least 600 nm, at least 650 nm, at least 700 nm, at least 750 nm, at least 800 nm, at least 850 nm, at least 900 nm, at least 950 nm) and / or at most 1 pm (e.g., at most 950 nm, at most 900 nm, at most 850 nm, at most 800 nm, at most 750 nm, at most 700 nm, at most 650 nm, at most 600 nm, at most 550 nm, at most 500 nm, at most 450 nm, at most 400 nm, at most 350 nm, at most 300 nm, at most 250 nm, at most 200 nm, at most 150 nm). In some embodiments, the rod have a length of at least 10 pm (e.g., at least 15 pm, at least 20 pm, at least 25 pm, at least 30 pm, at least 35 pm, at least 40 pm, at least 45 pm, at least 50 pm, at least 55 pm, at least 60 pm, at least 65 pm, at least 70 pm, at least 75 pm, at least 80 pm, at least 85 pm, at least 90 pm, at least 95 pm, at least 100 pm, at least 110 pm, at least 120 pm, at least 130 pm, at least 140 pm, at least 150 pm, at least 160 pm, at least 170 pm, at least 180 pm, at least 190 pm) and / or at most 200 pm (e.g., at most 190 pm, at most 180 pm, at most 170 pm, at most 160 pm, at most 150 pm, at most 140 pm, at most 130 pm, at most 120 pm, at most 110 pm, at most 100 pm, at most 95 pm, at most 90 pm, at most 85 pm, at most 80 pm, at most 75 pm, at most 70 pm, at most 65 pm, at most 60 pm, at most 55 pm, at most 50 pm, at most 45 pm, at most 40 pm, at most 35 pm, at most 30 pm, at most 25 pm, at most 20 pm, at most 15 pm).

[0177] In some embodiments, at least a portion of the crystals have an orthorhombic crystalline structure.

[0178] Without wishing to be bound by theory, it is believed that the temperature of the ionic melt and duration of exposure of the phosphorous-containing reactant to the ionic melt can influence the shape and size of the LisPO4 crystals and crystal sizes in the range of 1 nm to hundreds of micrometres can be produced by controlling these parameters.

[0179] Without wishing to be bound by theory, it is believed that in some embodiments, upon addition to the phosphorous-containing reactant to into the ionic melt, (PO4)3' anions form in the ionic melt and upon saturation of the ionic melt with dissolved (PO4)3', LisPO4 crystals grow from the ionic melt.

[0180] In some embodiments, L PCh is recovered from the lithium ion-containing ionic melt by cooling and dissolving the solidified salt matrix, for example in deionized water. The particle and crystalline sizes of LisPO4 can be altered using post-possessing. For example, in some embodiments, the extracted LisPO4 is ball-milled (e.g., in a vibrational ball mill or a planetary ball mill) to reduce its particle size. Without wishing to be bound by theory, it is believed that finer particles are more reactive than larger particles, which facilitates the production of other products from the L PCh, such as LFP It is also believed that the formation of finer particles is possible by controlling the parameters of the ball milling process. In some embodiments, the particle size after ball milling is at least 5 nm (e.g., at least 10 nm, at least 20 nm, at least 50 nm, at least 100 nm, at least 200 nm, at least 500 nm) and / or at most 1 pm (e.g., at most 500 nm, at most 200 nm, at most 100 nm, at most 50 nm, at most 20 nm, at most 10 nm) after ball milling.

[0181] Reaction conditions

[0182] In general, any appropriate lithium ion-containing ionic melt can be used. In some embodiments, the lithium ion-containing ionic melt includes LiCl, LiF, LiBr, Lil, LiNCF, L12CO3, LiOH, L1CIO4, L1C2H3O2, L1BO2, L1B4O7, LIPF6, LiTFSl, and / or LiFSl. In some embodiments the lithium ion-containing ionic melt includes Li2O and / or Li2C>2. In some embodiments, the lithium ion-containing ionic melt is prepared by melting of a lithium salt, which can be done with or without a solvent. Without wishing to be bound by theory, it is believed that the melting temperature of the lithium ion-containing ionic melt can be adjusted by varying the chemical composition and / or the pressure.

[0183] In some embodiments, the lithium ion-containing ionic melt further includes a potassium salt. Examples of suitable potassium salts include KC1, KF, and K2CO3. In some embodiments, the lithium ion-containing ionic melt further includes a calcium salt. Examples of suitable calcium salts include CaCCh, CaCh, CaSO4, Ca(NOs)2, Cas(PO4)2, Ca(C2HsO2)2, Ca(OH)2, CaC2O4, Ca(OH)2and CaF.

[0184] Examples of a lithium ion-containing ionic melt, which may not include a solvent, include LiCl at a temperature of from 600 °C to 1380 °C, LiCl-KCl at a temperature of from 300 °C to 800 °C, Li2CC>3 at a temperature of from 720 °C to 1310 °C, Li2CO3-K2CO3 at a temperature of from 490 °C to 900 °C, LiF at a temperature of from 840 °C to 1676 °C, LiF-KF at a temperature of from 500 °C to 850 °C, LiBr at a temperature of from 550 °C to 1300 °C, Lil at a temperature of from 470 °C to 1170 °C, LiNCF at a temperature of from 250 °C to 600 °C, Li OH at a temperature of from 460 °C to 920 °C, LiF at a temperature of from 840 °C to 1676 °C, LiClO4 at a temperature of from 230 °C to 400 °C, lithium bis(trifluoromethane)sulfonimide (LiTFSI, LiC2FeNO4S2) at a temperature of from 230 °C to 360 °C, and lithium bis(fhiorosulfonyl)imide (LiFSI, LiN(SO2F)2) at a temperature of from 120 °C to 200 °C.

[0185] In general, the reacting and / or combining can be performed for any appropriate duration. In some embodiments, the reacting and / or combining occurs for at least 1 second (e.g., at least 2 seconds, at least 3 seconds, at least 4 seconds, at least 5 seconds, at least 6 seconds, at least 7 seconds, at least 8 seconds, at least 9 seconds, at least 10 seconds, at least 30 seconds, at least 1 minute, at least 2 minutes, at least 3 minutes, at least 4 minutes, at least 5 minutes, at least 6 minutes, at least 7 minutes, at least 8 minutes, at least 9 minutes, at least 10 minutes, at least 30 minutes, at least 1 hour, at least 2 hours, at least 3 hours, at least 4 hours, at least 5 hours, at least

[0186] 6 hours, at least 7 hours, at least 8 hours, at least 9 hours, at least 10 hours, at least 12 hours, at least 1 day, at least 2 days, at least 3 days, at least 4 days, at least 5 days, at least 6 days, at least 1 week, at least 2 weeks, at least 3 weeks) and / or at most 4 weeks (e.g., at most 3 weeks, at most 2 weeks, most 1 week, at most 6 days, at most 5 days, at most 4 days, at most 3 days, and most 2 days, at most 1 day, at most 12 hours, at most 10 hours, at most 9 hours, at most 8 hours, at most

[0187] 7 hours, at most 6 hours, at most 5 hours, at most 4 hours, at most 3 hours, at most 2 hours, and most 1 hour, at most 30 minutes, at most 10 minutes, at most 9 minutes, and most 8 minutes, at most 7 minutes, at most 6 minutes, at most 5 minutes, at most 4 minutes, at most 3 minutes, at most 2 minutes, at most 1 minute, and most 30 seconds, at most 10 seconds, at most 9 seconds, at most 8 seconds, at most 7 seconds, at most 6 seconds, at most 5 seconds, at most 4 seconds, at most 3 seconds, at most 2 seconds). In general, the reacting and / or combining can be performed at any appropriate temperature. In some embodiments, the reacting and / or combining is performed at a temperature of at least 0 °C (e.g., at least 100 °C, at least 200 °C, at least 300 °C, at least 400 °C, at least 500 °C, at least 600 °C, at least 700 °C, at least 800 °C, at least 900 °C, at least 1000 °C, at least 1100 °C, at least 1200 °C, at least 1300 °C, at least 1400 °C, at least 1500 °C, at least 1600 °C) and / or at most 1700 °C (e.g., at most 1600 °C, at most 1500 °C, at most 1400 °C, at most 1300 °C, at most 1200 °C, at most 1100 °C, at most 1000 °C, at most 900 °C, at most 800 °C, at most 700 °C, at most 600 °C, at most 500 °C, at most 400 °C, at most 300 °C, at most 200 °C, at most 100 °C).

[0188] In general, the reacting and / or combining can be performed under any appropriate atmosphere. In some embodiments, the atmosphere includes air, nitrogen, and / or argon. In some embodiments, a flow of carrier gas (such as argon, nitrogen, and / or air) can be humidified. Humidification can be achieved by passing the gas through a water bath maintained at a temperature ranging from 0 °C to 100 °C. This humidified gas can either enter the atmosphere above the ionic melt or be bubbled directly into the ionic melt. In some embodiments, a concentration of water vapor present in an atmosphere around the lithium ion-containing ionic melt is at least 0.1 % (e.g., at least 0.2 %, at least 0.3 %, at least 0.4 %, at least 0.5 %, at least 0.6 %, at least 0.7 %, at least 0.8 %, at least 0.9 %, at least 1 %, at least 2 %, at least 3 %, at least 4 % at least 5 %, at least 6 %, at least 7 %, at least 8 %, at least 9 %, at least 10 %, at least 15 %, at least 20 %, at least 25 %, at least 30 %, at least 35 %, at least 40 %, at least 45 %, at least 50 %, at least 55 %, at least 60 %, at least 65 %, at least 70 %, at least 75 %, at least 80 %, at least 85 %, at least 90 %, at least 95 %) and / or at most 100 % (e.g., at most 95 %, at most 90 %, at most 85 %, at most 80 %, at most 75 %, most 70 %, at most 65 %, at most 60 %, at most 55%, at most 50 %, at most 45 %, at most 40 %, at most 35 %, at most 30 %, at most 25 %, at most 20 %, at most 15 %, at most 10 %, at most 9 %, at most 8 %, at most 7 %, at most 6 %, at most 5 %, at most 4 %, most 3 %, at most 2 %, at most 1 %, at most 0.9 %, at most 0.8 %, at most 0.7 %, at most 0.6 %, at most 0.5 %, at most 0.4 %, at most 0.3 %, at most 0.2 %) relative humidity. Without wishing to be bound by theory, it is believed that the presence of moisture increases the rate of the LisPO4 crystalline formation and growth.

[0189] In some embodiments, a polarization is applied to the phosphorous-containing reactant. In some embodiments, the polarization is a cathodic polarization. In some embodiments, the polarization between the phosphorous-containing reactant and a reference electrode immersed in the lithium ion-containing ionic melt is at least -3.0 V (e.g., at least -2.9 V, at least -2.8 V, at least -2.7 V, at least -2.6 V, at least -2.5 V, at least -2.4 V, at least -2.3 V, at least -2.2 V, at least -2.1 V, at least -2 V, at least -1.9 V, at least -1.8 V, at least -1.7 V, at least -1.6 V, at least -1.5 V, at least - 1.4 V, at least -1.3 V, at least -1.2 V, at least -1.1 V, at least -1 V, at least -0.9 V, at least -0.8 V, at least -0.7 V, at least -0.6 V, at least -0.5 V, at least -0.4 V, at least -0.3 V, at least -0.2 V) and / or at most -0.1 V (e.g., at most -0.2 V, at most -0.3 V, at most -0.4 V, at most -0.5 V, at most -0.6 V, at most -0.7 V, most -0.8 V, at most -0.9 V, and most -I V, and most -1.1 V, at most -1.2 V, and most -1.3 V, at most -1.4 V, and most -1.5 V, at most -1.6 V, at most -1.7 V, at most -1.8 V, and most - 1.9 V, and most -2 V, and most -2.1 V, and most -2.2 V, and most -2.3 V, and most -2.4 V, at most -2.5 V, at most -2.6 V, at most -2.7 V, most -2.8 V). Without wishing to be bound by theory, it is believed that a polarization (e.g., cathodic polarization) can reduce the stability of the phosphorous-containing reactant to make it more reactive.

[0190] In some embodiments, the reacting and / or combining is performed continuously. In some embodiments, reactant is added continuously.

[0191] In some embodiments, the reacting and / or combining is performed in batches.

[0192] In some tend to embodiments, the composition containing lithium and phosphorus forms crystals which are dispersed into the ionic melt, while other components from the phosphorous- containing reactant sink in the ionic melt. Without wishing to be bound by theory, it is believed that this separation is facilitated by the similarity in the densities between the ionic melt and the crystals of the composition (e.g., LisPO4 crystals), and the difference of density between the other components and the ionic melt. For example, the density of LisPO4 is relatively close to the density of molten LiCl (around 2 g / cm3), while the densities of components such as F 036)4 (> 5 g / cm3) and hydroxylapatite (> 3 g / cm3) are considerably greater, facilitating their gravimetric separation in the ionic melt.

[0193] Reaction systems

[0194] Figure 2a depicts a system 1000 which can be used to perform a method of the disclosure. The system 1000 includes a gas-controlled reactor 1100 equipped with a gas entry port 1200 and a gas exit port 1300. The gas-controlled reactor 1100 also includes an ionic melt container 1400, which holds an ionic melt 1500 (see discussion above). The gas-controlled reactor 1100 further includes a movable shaft 1600 which can be moved vertically in the gas- controlled reactor 1100. Attached to the movable shaft 1600 is a compacted porous mass 1700, which includes a phosphorous-containing reactant (see discussion above). The movable shaft can be used to immerse the compacted porous mass 1700 into the ionic melt 1500. Figure 2b shows the set-up after exposing of the compacted porous mass 1700 to the ionic melt 1500. After the exposure, the ionic melt 1800 contains a composition that includes lithium and phosphorous, such as LisPO4 (see discussion above). The compacted porous mass 1700 is converted into an extracted mass 1900, which includes elements present in the compacted porous mass 1700 that do not contribute to the formation of LnPO-i. For example, if the compacted porous mass 1700 includes calcium phosphate, the extracted mass will contain Ca. Thus, the system 1000 can be used to convert a phosphorous-containing reactant, such as a (PO4)3' containing compound, into LisPO4, and simultaneously separate other elements of the resource present in the phosphorous- containing reactant from the ionic meltl800.

[0195] Methods of producing compositions with lithium, phosphorus, and a metal

[0196] The methods of the disclosure can include combining a metal oxide of formula MVOWand a lithium ion-containing ionic melt to produce a composition of formula LixMyOz. In some embodiments, the metal oxide includes Mn, Co, Ni, Ti, Zr, Fe, Mo, W, Nb, Si, Al, V, and / or Cr. In some embodiments, the composition includes LiCoCh, LiMnCh, LiMniCh, LiNiMnCoCh, LiNiCoAlCh, and / or I^TisO 12. In some embodiments, the composition includes a cubic, orthorhombic, rhombohedral, and / or hexagonal crystalline structure.

[0197] In some embodiments, the composition includes Mn. In some embodiments, the composition includes the formula LixMnyOz, where x ranges from 0.02 to 5.5, y ranges from 0.20 to 6.80, and z ranges from 2 to 16. In some embodiments, the composition includes a cubic, orthorhombic, rhombohedral, and / or hexagonal crystalline structure. Examples of LixMnyOzwith a cubic crystalline structure include Lio.nsMnCh, Lio tuMmCE, Lii.353Mm.626O4, Li1.36Mn1.63O4, Lil.24Mni.72O4, Lil.i2Mni.7O4, Lil.27Mni.73O4, Lil.198Mni.802O3.972, Li5.28Mn6.72016, Li1.2ssMn1.7i6O3.732, Li1.nMn1.74O4, Li1.32Mn1.6sO4, Li1.34Mm.66O4, Lio.89Mn1.7sO4, Lio.o5Mn204, Li4MmOi2, Lio.o3Mn204, Lio.2Mn204, Li1.6Mm.6O4, Lii.237Mm.763O4, Lio.8sMn204, Li1.08Mm.9sO4, Lio.97iMm.94504, Lio.98iMm.94904, Lio.982Mn2.ois04, Li1.12Mm.88O4, and Lii.05MmO4. Examples of LixMnyOzwith an orthorhombic crystalline structure include LiMnO4, Li3MnO4, Lio 5MnO2, Lii.i3MmO4, Lio.3Mn02, and Lio.9Mn02. Examples of LixMnyOzwith a monoclinic crystalline structure include LiiMnCh, Lio.sMnCh, and Li1.99Mn1.01O3. Examples of LixMnyOz with a with tetragonal crystalline structure include LiMmO-i, Lio.s9Mn2O3.84, Li2Mn2O4, Lio.eMn02.3, Li1.5Mno.97O2, and LiMn3O4. The LixMnyOz product can also exhibit a hexagonal structure, such as Li2MnO2.

[0198] In some embodiments, the composition includes Co. In some embodiments, the composition includes the formula LixCoyOz, where x ranges from 0.10 to 6, y ranges from 0.70 to 31, and z ranges from 1 to 41. In some embodiments, the composition includes a cubic, orthorhombic, rhombohedral, and / or hexagonal crystalline structure. Examples of LixCoyOzwith a cubic crystalline structure include Lio.5C01.02O2, Li1.47Co3O3.72, Lii.47Co3O4, Lio.i85Coo.8i5O, Lio.125Coo.875O, Lio.uCoo.seO, Lio.115Coo.885O, and Lio.210Coo.790O. An example of LixCoyOzwith an orthorhombic crystalline structure includes LieCoO4. Examples of LixCoyOzwith a rhombohedral crystalline structure include LiCoO2, Lio.4Co02, and Lio.9sC01.04O2. Examples of LixCoyOz with a hexagonal crystalline structure include Lio.73Co02.

[0199] In some embodiments, the composition includes Ti. In some embodiments, the composition includes the formula LixTiyOz, where x ranges from 0.10 to 4, y ranges from 0.80 to 11.0, and z ranges from 2 to 16. In some embodiments, the composition includes an orthorhombic, monoclinic, cubic, and / or hexagonal crystalline structure. Examples of LixTiyOzwith an orthorhombic crystalline structure include Lio.94Ti204, LitusTiCh, Lio.4iTi02, Lio.57Tio.86O2, Li2.03Ti3.43Os, Li4TiO4, LisTisO?, LiTi2O4, Li2Ti3O?, Lio.i4Ti02, Li4TiO4, Lio.ieTi02, and Lio.5Ti02. Examples of LixTiyOzwith a monoclinic crystalline structure include Lio.74Ti30e, Li2TieO 13, Li2Ti4O9, and Li2TiO3. Examples of LixTiyOzwith a cubic crystalline structure include Lil.26Til.66O4, Lil.334Til.666O4, Lil.333Til.667O4, Li4Ti7O16, Lil.2Til.sO4, Li4Ti5O12, Lio.89Ti204, LiTi2O4, L12T10.667O3, Li1.14Ti1.sO4, Lio.93Ti204, Lio.75Ti204, Li2.66eTii .333O3.999, Lio.sTi2.2O4, Li2TiO3, Li1.03Ti1.9O4, Lio.92Ti204, and LiTiO2. An example of LixTiyOzwith a hexagonal crystalline structure includes Li2MnO2.

[0200] In some embodiments, the composition includes Ni. In some embodiments, the composition includes the formula LixNiyOz, where x ranges from 0.05 to 2, y ranges from 0.5 to 8, and z ranges from 1 to 10. In some embodiments, the composition includes an orthorhombic, monoclinic, cubic, and / or hexagonal crystalline structure. Examples of LixNiyOzwith a hexagonal crystalline structure include Li2NiC>2 and Li2NisOio. Examples of LixNiyOzwith a rhombohedral crystalline structure include Li0.89Ni1.01O2, Li0.99Ni1.01O2, Li0.79Ni1.01O2, LiNiO2, Lio.996Nil.00802, Li0.95Nil.05O2, Li0.85Nil.05O2, Lio.4sNio.52O, Lio.79Nil.2iO2, Lio.99Ni02, Li0.92Nil.0sO2, Lio.96?Nil.03302, Li0.09Nil.0iO2, Li0.75Nil.05O2, Lio.275Nio.725O, Lio.524Nil.47602, Lio.65Nil.0802, Lio.68Nil.3202, Lio.27Nio.730, Li0.19Nil.01o2, Li0.25Nil.05o2, Li0.29Nil.01o2, Li0.35Ni1.05O2, Li0.05Ni1.05O2, Li0.45Ni1.05O2, and Lio.30iNii.69902. Examples of LixNiyOzwith a monoclinic crystalline structure include Li0.69Ni1.01O2, Li2NiO2.ss, Li0.63Ni1.02O2, Li0.49Ni1.01O2, Li2NiO2.9i, Li0.39Ni1.01O2, and Li0.59Ni1.01O2. Examples of LixNiyOz with a cubic crystalline structure include Lio.4Ni1.eO2, Lio.2sNio.72O, Lio.3Nio.7O, and Lio.20sNii.79202. An example of LixNiyOz with an orthorhombic structure includes Li2NiO2.

[0201] The metal oxide MVOWis a mineral that includes M. In some embodiments, the metal oxide MVOWis a waste material, for example a waste material recovered from an electrochemical system such as a metal-ion battery (e.g., a lithium-ion battery). In some embodiments, the metal oxide MVOWis the cathode material from a metal-ion battery (e.g., a lithium-ion battery).

[0202] In general, any appropriate lithium ion-containing ionic melt can be used. In some embodiments, the lithium ion-containing ionic melt includes LiCl, LiF, LiBr, Lil, LiNOi, L12CO3, LiOH, L1CIO4, L1C2H3O2, L1BO2, L1B4O7, LIPF6, LiTFSl, and / or LiFSl.

[0203] In general, the combining can be performed at any appropriate temperature. In some embodiments, the combining is performed at a temperature of at least 20 °C (e.g., at least 25 °C, at least 50 °C, at least 100 °C, at least 200 °C, at least 300 °C, at least 400 °C, at least 500 °C, at least 600 °C, at least 700 °C, at least 800 °C, at least 900 °C, at least 1000 °C, at least 1100 °C, at least 1200 °C, at least 1300 °C, at least 1400 °C, at least 1500 °C, at least 1600 °C) and / or at most 1700 °C (e.g., at most 1600 °C, at most 1500 °C, at most 1400 °C, at most 1300 °C, at most 1200 °C, at most 1100 °C, at most 1000 °C, at most 900 °C, at most 800 °C, at most 700 °C, at most 600 °C, at most 500 °C, at most 400 °C, at most 300 °C, at most 200 °C, at most 100 °C, at most 50 °C, at most 25 °C).

[0204] In general, the reacting and / or combining can be performed under any appropriate atmosphere. In some embodiments, the atmosphere includes air, nitrogen, and / or argon. In some embodiments, a flow of carrier gas (such as argon, nitrogen, and / or air) can be humidified. Humidification can be achieved by passing the gas through a water bath maintained at a temperature ranging from 0 °C to 100 °C. This humidified gas can either enter the atmosphere above the ionic melt or be bubbled directly into the ionic melt. In some embodiments, a concentration of water vapor present in an atmosphere around the lithium ion-containing ionic melt is at least 0.1 % (e.g., at least 0.2 %, at least 0.3 %, at least 0.4 %, at least 0.5 %, at least 0.6 %, at least 0.7 %, at least 0.8 %, at least 0.9 %, at least 1 %, at least 2 %, at least 3 %, at least 4 % at least 5 %, at least 6 %, at least 7 %, at least 8 %, at least 9 %, at least 10 %, at least 15 %, at least 20 %, at least 25 %, at least 30 %, at least 35 %, at least 40 %, at least 45 %, at least 50 %, at least 55 %, at least 60 %, at least 65 %, at least 70 %, at least 75 %, at least 80 %, at least 85 %, at least 90 %, at least 95 %) and / or at most 100 % (e.g., at most 95 %, at most 90 %, at most 85 %, at most 80 %, at most 75 %, most 70 %, at most 65 %, at most 60 %, at most 55%, at most 50 %, at most 45 %, at most 40 %, at most 35 %, at most 30 %, at most 25 %, at most 20 %, at most 15 %, at most 10 %, at most 9 %, at most 8 %, at most 7 %, at most 6 %, at most 5 %, at most 4 %, most 3 %, at most 2 %, at most 1 %, at most 0.9 %, at most 0.8 %, at most 0.7 %, at most 0.6 %, at most 0.5 %, at most 0.4 %, at most 0.3 %, at most 0.2 %) relative humidity.

[0205] In some embodiments, the metal oxide MVOWis compacted into a pellet and the pellet is exposed to the ionic melt.

[0206] In some embodiments, a polarization is applied to the metal oxide. Without wishing to be bound by theory, it is believed that the cathodic polarization can facilitate the lithiation of the metal oxide. In some embodiments, the polarization between the metal oxide and a reference electrode immersed in the lithium ion-containing ionic melt is at least -3.5 V (e.g., at least -3.4 V, at least -3.3 V, at least -3.2 V, at least -3.1 V, at least -3 V, at least -2.9 V, at least -2.8 V, at least - 2.7 V, at least -2.6 V, at least -2.5 V, at least -2.4 V, at least -2.3 V, at least -2.2 V, at least -2.1 V, at least -2 V, at least -1.9 V, at least -1.8 V, at least -1.7 V, at least -1.6 V, at least -1.5 V, at least - 1.4 V, at least -1.3 V, at least -1.2 V, at least -1.1 V, at least -1 V, at least -0.9 V, at least -0.8 V, at least -0.7 V, at least -0.6 V, at least -0.5 V, at least -0.4 V, at least -0.3 V, at least -0.2 V) and / or at most -0.1 V (e.g., at most -0.2 V, at most -0.3 V, at most -0.4 V, at most -0.5 V, at most -0.6 V, at most -0.7 V, most -0.8 V, at most -0.9 V, and most -I V, and most -1.1 V, at most -1.2 V, and most -1.3 V, at most -1.4 V, and most -1.5 V, at most -1.6 V, at most -1.7 V, at most -1.8 V, and most - 1.9 V, and most -2 V, and most -2.1 V, and most -2.2 V, and most -2.3 V, and most -2.4 V, at most -2.5 V, at most -2.6 V, at most -2.7 V, at most -2.8 V, at most -2.9 V, at most -3 V, at most -3.1 V, at most -3.2 V, at most -3.3 V, at most -3.4 V) measured relative to a quasi-reference electrode immersed in the melt. In some embodiments, the quasi-electrode is a molybdenum rod immersed in the ionic melt. Without wishing to be bound by theory, it is believed that by controlling the polarization parameters, including the polarization voltage, the atmosphere of the polarization cell, and the polarization temperature and chemical composition of the atmosphere above the ionic melt the product can be controlled and various lithiated phases can be produced. In some embodiments, the formation of the lithiated phase can be controlled by the variation of the cathodic voltage (the voltage between the pellet and the reference electrode). In some embodiments, lithiated phases of the metal oxides can be formed by disposing the metal oxide into the melt without applying a polarization, while the polarization may still facilitate the formation of the lithiated phase.

[0207] Applications in energy storage devices

[0208] A composition including lithium and phosphorous (e.g., LisPCL) produced using a method of the disclosure can be converted into LiMPO-i, where M includes one or more metals. In some embodiments, M includes iron (Fe), manganese (Mn), nickel (Ni), cobalt (Co), aluminum (Al), tungsten (W), sodium (Na), titanium (Ti), magnesium (Mg), calcium (Ca), silicon (Si), scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and / or lutetium (Lu). In some embodiments, M includes iron (Fe), manganese (Mn), nickel (Ni), and / or cobalt (Co). In some embodiments, M includes iron (Fe) and / or manganese (Mn). In some embodiments, the LiMPOr is olivine structured.

[0209] In some embodiments, the LMPO4 has no detectable impurities, for example, as measured by EDS. In some embodiments, the LMPO4 is doped with Ca, Fe, Al, Si, K, Mg, Ce, Nd, Na, Sr, Ba, La, Gd, and / or Pr.

[0210] In some embodiments, a composition including lithium and phosphorous (e.g., LisPCL) produced using a method of the disclosure can be converted into LiFePCL (LFP) and / or lithium manganese iron phosphate, LiMnxFei-xPO4 (LMFP, where x = 0.05-0.9, e.g., 0.05-0.5).

[0211] In general, a composition including lithium and phosphorous (e.g., LisPCL) can be converted into LFP using any appropriate methods and reagents. For example, the composition including lithium and phosphorous (e.g., L PCL) can be mixed with an iron source, such as hydrated ferrous sulfate (FeSCL xEEO) and / or non-hydrated ferrous sulfate (FeSCh). In some embodiments, a reducing agent, such as 20 wt. % ascorbic acid is included. In some embodiments, a carbon precursor such as glucose is added to the mixture at a mass percentage of approximately 1 to 20 %. The pH of the reaction mixture can adjusted to an appropriate range, such as 5.5 to 9.5, or 6 to 8.5, and the mixture can be introduced into a hydrothermal reactor. Other possible iron precursors include ferrous chloride (FeCb), ferrous nitrate (Fe(NO3)2), ferrous acetate (Fe(C2H3O2)2), ferrous gluconate, and ferrous fumarate, in either hydrated or anhydrous forms.

[0212] The resulting mixture can be transferred to a polymeric container and subjected to hydrothermal treatment at a temperature between 150 and 250 °C, or around 200 °C, for a duration ranging from 30 minutes to 48 hours, or around 24 hours. In some embodiments, the thermal treatment is conducted in an inert atmosphere such as argon or nitrogen.

[0213] In general, a composition including lithium and phosphorous (e.g., LisPCL) can be converted into LFMP using any appropriate methods and reagents. For example, the methods discussed above to produce LFP can further include a manganese source such as MnSCL (hydrated or anhydrous), MnCb, Mn(NO3)2, Mn(CH3COO)2, MnBn, Mnh, Mn(C104)2, and / or KMnO4 incorporated into the mixture. Without wishing to be bound by theory, it is believed that the relative quantities of Fe and Mn can be varied to achieve a desired composition of the LMFP phase.

[0214] In some embodiments, a crystalline structure of LFP or LMFP can be further modified through thermal treatments to stabilize the crystal structure, for example by varying the temperature between 150 °C and 700 °C and the duration between 30 minutes and 10 hours, depending on the desired product characteristics.

[0215] In some embodiments, LFP, LMFP, and related phases can have a particle size of at least 10 nm (e.g., at least 20 nm, at least 30 nm, at least 40 nm, at least 50 nm, at least 60 nm, at least 70 nm, at least 80 nm, at least 90 nm, at least 100 nm, at least 150 nm, at least 200 nm, at least 250 nm, at least 300 nm, at least 350 nm, at least 400 nm, at least 450 nm) and / or at most 500 nm (e.g., at most 450 nm, at most 400 nm, at most 350 nm, at most 300 nm, at most 250 nm, at most 200 nm, at most 150 nm, at most 100 nm, at most 90 nm, at most 80 nm, at most 70 nm, at most 60 nm, at most 50 nm, at most 40 nm, at most 30 nm, at most 20 nm).

[0216] In some embodiments, a composition including lithium and phosphorous (e.g., LisPCL) produced using a method of the disclosure and / or LiMPCL prepared from the composition is used to make a component of an energy storage device using the composition. In some embodiments, the energy storage device includes a lithium-ion battery.

[0217] In some embodiments, a composition including lithium and phosphorous (e.g., LisPCL) produced using a method of the disclosure and / or LiMPCh prepared from the composition is used to make an electrode, such as a cathode (e.g., a battery cathode). In some embodiments, the battery cathode is a lithium-ion battery cathode. In some embodiments, the lithium-ion battery cathode is of formula LiMPCh where M includes one or more metals. In some embodiments, M includes iron (Fe), manganese (Mn), nickel (Ni), cobalt (Co), aluminum (Al), tungsten (W), sodium (Na), titanium (Ti), magnesium (Mg), calcium (Ca), silicon (Si), scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and / or lutetium (Lu). In some embodiments, M includes iron (Fe), manganese (Mn), nickel (Ni), and / or cobalt (Co). In some embodiments, M includes iron (Fe) and / or manganese (Mn).

[0218] In some embodiments, a composition including lithium and phosphorous (e.g., LisPCL) produced using a method of the disclosure and / or LiMPCh prepared from the composition is used to manufacture a solid-state electrolyte for a lithium-ion battery.

[0219] Without wishing to be bound by theory, it is believed that lithium ion batteries prepared using a composition including lithium and phosphorous (e.g., LisPCL) produced using a method of the disclosure and / or LiMPO-i prepared from the composition can be relatively low cost, have relatively good resource availability, be relatively non-toxic, have relatively fast charging / discharging capabilities, have relatively good thermal stability, have relatively good tuneable working voltage / energy density, and / or relatively long cycle life for, in comparison to certain other alternatives such as lithium cobalt oxide (LCO) and nickel-manganese-cobalt (NMC). Without wishing to be bound by theory, it is believed that the electrochemical performance of LFP and LMFP prepared using the methods of the disclosure can be equal to or greater than the original cathode material when the phosphorous-containing reactant includes cathode materials.

[0220] Conversion to phosphoric acid, MH2PO4, and M2HPO4 A composition including lithium and phosphorous (e.g., Li3PO4) produced using a method of the disclosure can be converted into phosphoric acid, MH2PO4 (where M is an alkali metal or ammonium), such as LiHiPCh, and / or M2HPO4 (where M is an alkali metal). Examples of MH2PO4 include LiPEPCE, NaPEPCE, KH2PO4, and NH4H2PO4. Examples of M2HPO4 include Na2HPO4, K2HPO4, and Li2HPO4. Additionally, composition including lithium and phosphorous (e.g., LisPCE) produced using a method of the disclosure can be converted into CoHPO4.

[0221] In general, the composition including lithium and phosphorous (e.g., LisPCE) can be converted into phosphoric acid, MH2PO4 (e.g., LiPEPCE) and / or M2HPO4 using any appropriate method. Without wishing to be bound by theory, it is believed that possible reactions are:

[0222] L13PO4 + 2HC1 2L1C1 + L1H2PO4 AG° = -47.0 kJ (25°C) (8a)

[0223] L13PO4 + 3HC1 3L1C1 + H3PO4 (8b) where the E PCE is produced using the methods of the disclosure. The phosphoric acid and / or a salt thereof can be produced without the generation of phosphogypsum, hydrofluoric acid, fluorosilicic acid, and / or silicon tetrafluoride. Without wishing to be bound by theory, it is believed that the product of the above reactions can be selected by controlling the reactant concentration, temperature, and / or reactant time.

[0224] The phosphoric acid, MH2PO4 (e.g., LiPEPCE), and / or M2HPO4 can obtained without the inclusion of impurities present in the phosphorous-containing reactant, such as rare earth metals and / or radioactive elements. In some embodiments, the phosphoric acid, MH2PO4 (e.g., LiPEPCE), and / or M2HPO4 has a purity of at least 98 % (e.g., at least 98.5 %, at least 99 %, at least 99.5 %, at least 99.8 %, at least 99.9 %). In some embodiments, the phosphoric acid, MH2PO4 (e.g., LiPEPCE), and / or M2HPO4 has a level of radioactive elements between 0 and 1 ppm, or no radioactive elements, as detected by inductively coupled plasma (ICP) techniques, such as ICP-OES (optical emission spectroscopy) or ICP -MS (mass spectrometry), even if the phosphorous-containing reactant includes radioactive elements.

[0225] Without wishing to be bound by theory, it is believed that LiPbPCE produced using methods of the disclosure can be used as a coating material to improve the performance of cathode materials in lithium-ion batteries (LIBs) as LiPEPCE has relatively good ionic conductivity, which enhances the electrochemical performance of cathode materials when applied as a coating layer on their outer surfaces, such as in NCA (nickel cobalt aluminium oxide) cathodes. It is further believed that LiH2PO4 has beneficial properties, such as a relatively high oxidation potential (>4.5 V), relatively good chemical stability against the electrolyte and the cathode, relatively high ionic conductivity, and relatively wide bandgaps. The coated cathodes can be used in batteries employing a liquid electrolyte or in solid-state Li-ion batteries.

[0226] Without wishing to be bound by theory, it is believed that compounds with the general formula MH2PO4, where M is an alkali metal, include hydrogen-bonded tetrahedral oxyanions (PO4) and monovalent cations. These compounds can form solid acid materials with an ordered arrangement of hydrogen bonds at room temperature, which can undergo a structural transition to a disordered state with relatively high proton mobility upon heating. In particular, LilLPCL exhibits an exceptionally high protonic conductivity (10-3— 10-5S / cm), and therefore, may be used as electrolyte for hydrogen fuel cells.

[0227] LilLPCL produced using methods of the disclosure can be used to make solid polymer electrolytes for use in rechargeable batteries, advanced electrochemical displays, sensors, and fuel cells. These polymer electrolytes, in addition to LilLPCL, can include a polymer matrix such as poly(vinyl alcohol) and a ceramic filler to reduce the glass transition temperature and the crystallinity of the polymer, thereby increasing the ionic conductivity as well as thermal and mechanical properties of the electrolyte. In some embodiments, fillers include TiCh, ZrCh, and / or AI2O3. In some embodiments, the filler is a phosphorous-containing compound and / or an aluminosilicate compound. In some embodiments, the aluminosilicate compound is MAlxSiyOz, where M is absent or represents one or more metal cations such as potassium, sodium, and / or calcium; and x, y, and z are numbers between 0.1 and 10. In some embodiments MAlxSiyOzis KAlSisOs, KAlSiCL, and / or AhSi2O5. In some embodiments, x is 0 and MAlxSiyOzis Ca2(SiO4). Without wishing to be bound by theory, it is believed that the presence of these aluminosilicates can provide relatively good structural and thermal stability to the electrolyte. In some embodiments, the solid electrolyte described above includes a composition including lithium and phosphate (e.g., LisPCL) produced using methods of the disclosure.

[0228] Without wishing to be bound by theory, it is believed that the pure or high purity compositions including lithium and phosphate and / or the pure or high-purity LilLPCL prepared using methods of the disclosure have applications in fuel cells and hydrogen generation technologies and can therefore be employed in applications involving hydrogen, such as transportation, energy, and the production of metals and alloys. Without wishing to be bound by theory, it is believed that LiH2PO4 generated using the methods of the disclosure can be converted into alternative MH2PO4 compounds, where M is an alkali meta. As an example, LiH2PO4 can be converted into KH2PO4 using K2CO3 at a temperature in the range of 0-1000°C:

[0229] 2L1H2PO4 + K2CO3 L12CO3 + 2KH2PO4 AG° = -26.7 kJ (9)

[0230] The above reaction has a negative Gibbs Free Energy value in the temperature range of 0-1000 °C, indicating that the formation of KH2PO4 is thermodynamically favourable. In some embodiments, the reaction (9) can proceed in an aqueous environment, where the relatively high solubility of KH2PO4 (-226-835 g / L at 25-90 °C) and the relatively low solubility of Li2CC>3 (-13-7.0 g / L at 25-90 °C) allow for the separation of the products.

[0231] Without wishing to be bound by theory, it is believed that pure or high-purity KH2PO4 produced using methods of the disclosure can be used as a fertilizer due to its relatively high phosphorus and potassium content and appropriate solubility. It is also believed that KH2PO4 produced using the methods of the disclosure can provide important nutrients for plant growth and to crops without introducing other elements present in the phosphorous-containing reactant (e.g., apatite).

[0232] Applications in hydrogen production

[0233] Compositions including lithium and phosphate prepared using methods of the disclosure can be used as the electrolyte component or the electrolyte for the electroproduction of hydrogen, for example at temperatures from 100 °C to 400 °C. A metal oxide can be placed into a molten electrolyte including Li bPCh (see discussion above) and / or LnPCE, followed by the application of a cathodic polarization on the metal oxide to prepare hydrogen on the surfaces of the metal oxide, causing the reduction of the metal oxide into its corresponding metal and alloy. In some embodiments, the metal oxide includes Fe, Ni, Co, Mn, Mo, W, Ti, Si, Al, Ca, K, Mg, and / or Cr. In some embodiments, the cathodic polarization is applied to a metal oxide immersed in an electrolyte containing LiFLPCL and / or LnPCL with a graphite electrode, a glassy carbon electrode, or a metallic electrode, which acts as the anode. In some embodiments, hydrogen can be generated at cell voltages of 0.8-2.0 V, and the generated hydrogen can reduce the metal oxide to generate the corresponding metal. LiFEPCL produced using the methods of the disclosure can be used as the electrolyte or part of an electrolyte composition for generating hydrogen gas by electrolysis of the electrolyte. Without wishing to be bound by theory, it is believed that pure or high-purity LiFbPCh is an ionic salt with a melting point of around 220 °C and a melt stability up to 370 °C in the presence of humidity. Thus, the LiFbPCh can be used as an electrolyte for water splitting to generate hydrogen at relatively high temperatures, for example between 200 °C to 300 °C or 200 °C to 370 °C, without the use of noble metals as electrodes and with relatively low potential relatively to certain other systems and methods for water splitting.

[0234] Without wishing to be bound by theory, it is believed that LiFbPCh and / or L PCh have relatively good stability and relatively low vapour pressure at temperatures in the range 200-400 °C in which water can be dissolved and dissociate during the electrolysis of such electrolytes, making them desirable electrolytes.

[0235] As an example, FeiCh can be used to prepare a pellet which can be exposed to an ionic melt containing 1.0-99.9 mass% LiFLPCL and / or 1.0-99.9% LisPCL at a temperature of 100-400 °C. Cathodic polarization in the range 0.8-2.5 V would lead to the production of hydrogen at the cathode, and the reduction of the FeiCh into Fe.

[0236] Other applications

[0237] Without wishing to be bound by theory, it is believed that a composition including lithium and phosphorous (e.g., LisPO^ produced using a method of the disclosure can be used for the fabrication of specific ceramic materials and / or as a component in glasses, enamels, and glazes, where it can contribute to the chemical and thermal stability of these materials. Examples of such applications include the preparation of bioactive lithia-silica glass-ceramic designed for bone tissue engineering applications.

[0238] Without wishing to be bound by theory, it is believed that a composition including lithium and phosphorous (e.g., LisPCL) produced using a method of the disclosure can be used as a precursor or catalyst in various chemical synthesis processes, for example as catalyst for the rearrangement of epoxides to carbonyl compounds or allyl alcohols.

[0239] EXAMPLES Powder X-ray diffraction (XRD) characterization was conducted using a D8 ADVANCE difractometer using Cu-Karadiation (1.5405 A). Scanning electron microscopy (SEM) was conducted using a ZEISS EVO 18 electron microscope at an acceleration voltage of 20 kV. For SEM characterization, carbon tape was placed onto aluminium sample holders, and samples in powder form was placed on the carbon substrate.

[0240] Example 1 : Characterization of fluorapatite containing (PO-i) ~

[0241] Fluorapatite containing (PO-i) '- is largely available in nature. X-ray diffraction pattern of this sample (Figure 3) can be indexed to calcium fluoride phosphate with chemical formula of Cas(PO4)3F (Inorganic Crystal Structure Database (ICSD: 01-077-0120) with hexagonal crystalline structure. Alternatively, the XRD pattern of this resource can be indexed to similar hexagonal compounds including (Ca9.11Nao.39Ceo.34Dyo.i6) (P5.ssSio.12) O24F2.25 with ICSD code of 01-087-2027; Ca6Eu2Na2 (PO4)6F2with ICSD code of 01-076-2268; (Ca9.25Nao.33Pro.35Ero.12) (P5.8iSio.13) O24 (F, OH)2with ICSD code of 01-087-2028; (Ca3.544Na0.304Gd0.152) (Ca5.496Na0.042Gd0.462) ((P5.72Sio.2s) O24)F2 with ICSD code of 01-083-1011; Ca9.2s3Ceo.6i7Nao.1o (SIO.44P5.56024)F2 with ICSD code of 01-080-2233; (Ca, Na, La, Gd)io (P, S)6O24 (F, OH)2with ICSD code of 01-087-2026; Ca9.42Sro.i8Ho.4 (P04)6 (OH)I.6O with ICSD code of 01-082-1429; (Ca9.37Sro.63) (PO4)eF2 with ICSD code of 01-079-1459; (Ca9.42Nao.26Euo.35Luo.o5) (P5.7sSio.14)024 (F, OH)2with ICSD code of 01-087-2029; and Cas.i84Ndo.4s (PO4)6Fi.8i2 with ICSD code of 01- 076-0560. The XRD pattern of the apatite sample can also be indexed to alternative calcium fluoride phosphate compounds with hexagonal structures including those identified by ICSD codes of 01-087-0480, 01-083-1010, 01-082-1109, 01-083-1012, 01-079-1573, 01-080-2234, 01- 083-0556, 01-083-0557, 01-079-1574, 01-079-1572, 01-073-1727, 01-071-0881, 01-075-0915, 01-076-0558, 01-076-0559, 00-034-0011, 01-087-2462, 01-071-0880, 01-080-2231, 01-083- 1009, 01-089-6437, 01-084-1997, 01-080-2232, 01-086-0740, and 00-015-0876. These phosphate compounds have similar hexagonal crystalline structure and are generally considered insoluble in pure water.

[0242] SEM micrographs of a fluorapatite sample and EDS analysis were recorded on specific locations in the micrographs are shown in Figures 4a-c. As can be seen, the fluorapatite sample is inhomogeneous in terms of both particle sizes and chemical composition, while the presence of P in addition to other elements including F, Na, Ca, Nd, Sr, Ba, La, and Ce is evident. Example 2: Conversion of Apatite Mineral into Porous Compacted Mass

[0243] The apatite sample of Example 1 was mixed with 20 wt. % NH4HCO3 and the mixture was pressed into cylindrical pellets with a diameter of 20 mm at a uniaxial pressure of 20 MPa. Such a pellet (1.650 g) was heated to 800 °C with a heating rate of 50 °C / min, and a dwell time at maximum temperature of 3 hours to provide sufficient strength for handing. NH4HCO3 decomposed into gas species at temperatures below 200 °C, providing porosity to the compacted pellet. Figures 5a and 5b shows the X-ray diffraction patterns of the initial fluorapatite powder (top) and the sintered pellet (bottom) at different two-theta domains. As can be observed, the processed apatite does not experience any phase transition during the process of making the pellet. For example, as shown in Figure 5b, the peak with two-theta positions of 25.890, 31.919, 32.253, 33.086 and 40.006° can be related to diffraction peaks arising from (002), (121), (112), (300), and (310) of fluorapatite (ICSD: 01-079-1459) with nominal formulation of (Ca9.37Sro.63) (PO4))eF2 with hexagonal structure. Since the X-ray diffraction peaks of alternative fluorapatite compounds are very close to each other, alternative compounds can be considered as (Ca9.11Nao.39Ceo.34Dyo.i6) (P5.88S10.12)024F2.25 (ICSD: 01-087-2027), Ca6Eu2Na2(PO4)6F2 (ICSD: 01-076-2268), Ca9.25Ero.12F2Nao.33O24P5.8iPro.35Sio.13 (ICSD: 01-087-2028), (Ca3.544N.304Gd0.152)(Ca5.496N.042Gd0.462) ((P5.72S10.28)°24)F2 (ICSD: 01-083-1011), Ca9.283Ceo.6i7Nao.io (Sio.44P5.56024)F2 (ICSD: 01-080-2233), (Ca, Na, La, Gd)io (P, S)6O24 (F, OH)2(ICSD: 01-087-2026), and (Ca9 42Na026Eu0 35Lu0 05) (P5 78Si0 14)O24(F, OH)2(ICSD: 1- 087-2029). These compounds have hexagonal crystalline structures containing calcium, phosphorous, oxygen and other elements.

[0244] According to Figure 5b, in the sintered pellet, the diffraction peaks arising from (002), (121), (112), (300), and (310) of fluorapatite can be observed at 25.873, 31.909, 32.239, 33.078, and 40.003°, respectively, demonstrating the structural stability of the apatite compound during fabrication of the pellet.

[0245] Example 3 : Exposing the Porous Compacted Mass

[0246] The apatite mineral discussed in the previous example was exposed to an ionic melt to form lithium phosphate, predominantly dispersed in the ionic melt, as shown in Figure 2. The sintered porous compacted mass (1.586 g), reported in Example 2 was fixed on the end of an alumina tube using steel wire, and processed in the ionic melt. About 143 g LiCl was added into an alumina crucible (internal diameter = 51 mm; height = 100 mm). The crucible was placed into a steel retort, with gas inlet / outlet ports. The alumina tube was inserted into the retort, located approximately 5 cm above the alumina crucible. The retort was then gas-sealed, and the temperature of the retort was increased under a flow of Ar gas to 750 °C, where molten LiCl could be formed in the alumina crucible with an approximate depth of 5 cm. When the temperature reached 750 °C, the Ar gas flow was humidified by insertion of a U-shaped quartz tube in the path of the gas before entering the retort. Under this condition, gas flow can be humidified bringing moisture to the atmosphere of the melt.

[0247] After 10 min of water injection, the pellet was immersed into the ionic melt, and exposed for 30 min. After this period, the alumina tube was pulled above the ionic melt, the water containing U-shaped tube was removed from the path of the Ar gas, and the retort was allowed to cool down to the room temperature. The water injected into the retort during the process was measured to be 1.55 g.

[0248] A light colour pellet with smaller thickness relative to the initial pellet remained in the same position as the original pellet, while the majority of the pellet mass had been transferred into the melt. Two samples were retrieved from the ionic melt by washing with distilled water and vacuum filtration. The first sample was obtained from the bulk of the electrolyte and the second sample was obtained from the bottom of the alumina crucible used as the melt container.

[0249] As shown in Figures 6a-6d, the XRD patterns of the porous compacted mass of the apatite (Figure 6a) is different from the powder retrieved from the bulk of electrolyte (Figure 6b), the powder retrieved from the bottom of the crucible (Figure 6c), and the remaining mass of the pellet (Figure 6d) after exposing and extracting of the compacted mass to the ionic melt. The higher resolution XRD of the product obtained from the bulk of the salt, after washing and filtration is shown in Figure 7, where the reflections identified in the pattern are indexed to those of lithium phosphate (ICSD: 01-083-0339) with the chemical composition LisPCL and orthorhombic crystalline structure. In particular, the peaks at the two-theta values of 17.22°, 22.63°, 34.50°, and 61.31° correspond to (020), (120), (040), and (260) reflections of gamma- LisPCL (ICSD: 01-083-0339. Space group pmnb), with an average right shift of 0.20° (two- theta). Without wishing to be bound by theory, it is believed that this small right shift may be due to the dissolution of doping elements originating from the apatite into the crystalline structure of L PO_i. Table 1 shows the information extracted from the XRD pattern of Figure 7.

[0250] Three forms of LisPO4 can exist in the solid state, namely the low-temperature orthorhombic form (beta) stable until around 400 °C (Pmn2i); medium temperature allotrope (gamma) with orthorhombic crystalline structure (Pmnb) which can be obtained by heating of the alpha allotrope. Once formed, gamma-Li3PO4 can be kinetically stable at room temperature. The third solid state allotrope is alpha phase which is stable at only a short temperature window before melting of the compound. The transition temperatures of these three polymorphs 0, y, and a-Li3PO4 are reported to be around 500, 1170, and 1220 °C, respectively. Figure 6 demonstrates that the method is capable of converting apatite into gamma-L PCh, which remains stable at room temperature.

[0251] Table 1. Data extracted from the XRD pattern of Figure 7.

[0252] Figures 8a-8c show SEM micrographs of the LnPO-i product obtained from the bulk of salt, after extraction of the remaining pellet, cooling, washing, and filtration. As seen in the micrographs, the L PCh crystals had various shapes and sizes, including rod-shaped crystals with various lengths and widths, such as 44.0 pm and 1.2 pm, respectively. Rods with spiky- shaped heads were also observed in the SEM micrographs. The L PCE crystals also included irregularly shaped flat crystals with dimensions of typically 5-90 pm. Particles with dimensions of less than 15 pm were also observed. The EDS spectrum shown in Figure 8d confirms the presence of P and O in the flat L PCh crystal shown in the figure, confirming the purity of the sample.

[0253] The product obtained from the bulk of salt, after extraction of the remaining pellet, cooling, washing, and filtration (Figure 8a-8c) was ball milled in a vertical ball-milling equipment using a polymeric container and AI2O3 balls with a ball: powder ratio of 20: 1 for 1 h. The SEM morphology of the ball-milled sample is shown in Figure 9a. LisPCE particles with sizes of 110 and 190 nm are highlighted. The EDS spectrum recorded in the L PCh particles is shown in Figure 9b, confirming the purity of the product.

[0254] The Raman spectrum of the product obtained from the bulk of salt, after extraction of the remaining pellet, cooling, washing, and filtration is shown in Figure 10, in which the peaks observed at the Raman shift values of 1059.6, 1021.6, 949.8, 619.4, 601.4, 505.9, 481.2, 417.5, 377.6, 359.1, 323.9, and 213.0 cm’1are highlighted. The peak at 949.8 cm’1is related to vi (PO4)3vibration, and the peaks at 619.4 and 610.4 cm’1to asymmetric bending vibration V4 (PO4)3'. The symmetric bending vibration V4 (PCE)3' provides a peak at 505.9 cm’1. Moreover, Li(2)-0 stretching vibrations can be seen at 478 and 444 cm’1. The Raman spectrum confirms the formation of L PO4.

[0255] After washing and filtration of the bulk of solidified salt, a small quantity of powder (darker in appearance) was retrieved from bottom of the solidified salt by washing and filtration. The powder retrieved from the bottom of the solidified salt was darker in appearance relative to the material retrieved from the bulk of the salt (pure L PCh) X-ray diffraction pattern recorded on the powder is shown in Figure 11 (top). In this figure, the XRD pattern recorded on the powder retrieved from the bulk of solidified salt is also shown for comparison (bottom), providing evidence that both samples contain L PO-i. However, while the XRD peaks in the pattern of the sample obtained from the bulk of electrolyte can entirely be assigned to those of Li3P4O, additional small peaks were also detected in the sample obtained from bottom part of the crucible.

[0256] SEM micrographs of the particles retrieved from the bottom of the solidified salt are shown Figure 12, confirming the presence of clusters of fine particles. As can be observed, the sample includes large L PCh crystals, typically larger than 10 pm, and clusters of much smaller particles, typically less than 1 pm. The EDS analysis recorded on these fine particles is also shown in Figure 12, providing evidence that these particles are rich in elements present in the raw apatite such as Ce, Si, Al, Ca, and Mg. Thus, the LnPOr crystals produced are readily and largely separable in the ionic melt in which they form.

[0257] Without wishing to be bound by theory, it is believed that one possible reason that two portions of LisPO4 are present in the bulk and at the bottom of the solidified salt is based on their crystalline sizes, and therefore, their apparent density. While finer particles with more sheet-like morphology tend to be suspended in the bulk of the ionic melt, LisPO4 crystals that have grown to larger sizes tend to sink to the lower part of the ionic melt. Therefore, to LisPO4 crystals can be separated based on their crystalline sizes and morphology, with the latter affected by the temperature and during of the processing.

[0258] The crystalline sizes of LisPO4 particles formed in the bulk of the salt were calculated from the Scherrer equation, using the data provided in Table 1, in the direction perpendicular to the (040) crystalline planes observed at two-theta value of 34.4997° with the full width at half maximum (FWHM) value of 0.0738° (0.00128805 radian). The value with the Scherrer constant=0.9, and wavelength of Cu-Karadiation used as the X-ray source (0.154 nm), was obtained to be 112.7 nm. The crystalline sizes measured on the LisPO4 powder collected from the bottom of the solidified salt was obtained to be 140.9 nm (two-theta=34.4401° and FWHM=0.0590°). This observation provides confirmation that L PCh with larger crystalline sizes can preferentially be collected from bottom of the ionic melt, while the finer particles can be collected from the bulk of the ionic melt. Without wishing to be bound by theory, it is believed that by accurate controlling of processing parameters, including the chemical composition and temperature of the ionic melt and duration of exposure of the compacted porous pellet to the ionic melt, LisPO4 can be produced with specific particle and crystalline sizes, while the crystals that grow larger tend to sink to the bottom the ionic melt.

[0259] LisPO4 can be produced using phosphorus containing precursors, such as, natural minerals based on (PO4)3' containing compounds without the use of acids, and undesired elements can be separated from the product. This example shows that the compacted mass of natural fluorapatite was exposed to molten LiCl at 750 °C for a duration of 30 min, and then the remaining mass was removed from the melt. The X-ray diffraction pattern of the retrieved mass is shown in Figure 6d, and the higher resolution pattern in Figure 13. As can be observed, the remaining compacted mass includes calcium phosphate fluoride chloride, Ca5(P04)3Fo.i7Clo.s3, with hexagonal crystalline structure, as the major phase, and Li3PO4 as the minor phase. In particular, the most intense diffraction pattern observed in the pattern at the two-theta value of 32.246° (FEHM=0.1777120°) is related to the (112) reflection of Cas PO^Fo.nClo.ss which is located at two-theta value of 32.293° in the standard card (ICSD: 01-070-2066).

[0260] The remaining pellet, after being extracted from the ionic melt, was pulverized and subjected to SEM characterization (Figure 14). The SEM micrograph shows that the remaining pellet is made of semi-spherical particles with dimensions typically in the range of 3-30 pm. The EDS spectra recorded on these particles, such as that shown in Figure 14, demonstrates the presence of a high quantity of calcium and chlorine, confirming the XRD result of Figure 13.

[0261] Based on these observations, the phosphorus-containing resources with low to zero solubility in pure water can be converted into to L PCh crystals, without the use of acidic or basic solutions. This conversion can be implemented by exposing the P-containing resource to an ionic melt containing Li+, such as LiCl. In some embodiments, the resource is mixed with LiCl or a mixture containing LiCl, and the mixture is heated above the melting point of LiCl and / or above melting point of the mixture. For example, in the case of LiCl, the mixture is heated to above 605 °C. If the resource is treated with LiCl-KCl, the mixture can be heated to an appropriate temperature above 350 °C, where LiCl-KCl is in molten state.

[0262] Example 4: Conversion of Li3PO4 into cathode materials

[0263] Cathode materials for Li-ion batteries can be prepared using water-insoluble phosphorus- containing resources and / or phosphorus-containing resources with low solubility in pure water, such as less than 1 g / L or less than 100 mg / L, without the use of acids or alkali chemicals. Among various types of cathode materials, intercalation-type cathodes can be highly attractive due to their tuneable operating voltage, relatively large capacity, and relatively minor volume change during Li+ion insertion / de-insertion, which provides good structural stability and allows the original crystal structure to be maintained under the relatively harsh conditions of high current operation. There are four well-known types of intercalation cathodes categorized based on their crystal structure, such as olivine structures like LiMPO-i. In these structures, M represents trivalent transition metal ions such as Fe3+, Mn3+, Co3+, and / or Ni3+in combination with (PO4)3polyoxyanions. Owing to the robust P-0 covalent bonding, the (PO4)3' polyoxyanions are important in maintaining the thermal and structural stability of the cathode, which is important for high-power density applications, while also providing additional advantages in terms of economic viability, safety, and abundance of resources for LiMPO4 compared to those in NCA. Examples of olivine cathode materials include LiFePCE (LFP) and lithium manganese ferric phosphate (LMFP). LMFP can be synthesized by replacing a portion of the iron cations with manganese in the tetragonal structure, at a mole ratio ranging from 0.1 to 0.9. Without wishing to be bound by theory, it is believed that LMFP can have several advantages over traditional LFP, such as increased energy density and enhanced thermal stability, resulting in improved cycle life. The L PCh produced from phosphorous containing resources using the methods of the disclosure can be used for the preparation of olivine LiMPCL cathode materials, where M is one or more of trivalent transition metal ions, including Fe3+, Ni3+, Co3+and / or Mn3+, such as LFP and LMFP with orthorhombic crystalline structures.

[0264] 0.3 g ball milled LisPCL produced according to the Example 3 (Figure 9), 0.144 g FeSCh 7H2O, and 0.350 g MnSCL H2O together with 15 mL distilled water were added into a polymeric container with a capacity of 50 mL. The container was heated in a hydrothermal reactor at 180°C for 5 h. Then, the material obtained was filtered, washed with deionised water, and dried to produce 0.33 g LFMP. The XRD pattern of the prepared compound is shown in Figure 15. The diffraction peaks highlighted in the pattern are related to the reflections arising from the orthorhombic structure of LMFP (Space group: Pmnb, ICSD: 01-074-0375).

[0265] The SEM micrographs of the obtained sample and the EDS analysis recorded on the SEM micrographs are shown in Figures 16 and 17. As observed, the LMFP compound fabricated predominantly included submicrometer-sized particles containing oxygen, phosphorus, manganese, and iron. A small amount of calcium could also be detected in the EDS analysis recorded on the SEM micrograph of Figure 16a. Such Ca can be introduced from the original apatite. Some other SEM-EDS examinations show the preparation of pure LMFP particles without any detectable impurity, as shown in the SEM-EDS map analysis of Figure 16a and SEM-EDS examination of Figure 17a.

[0266] Example 5: Direct Fabrication

[0267] Phosphorous present in a mixture of various compounds can be selectively converted into LnPCh. The initial P-containing resource can have a high solubility in water, for instance > 1 g / L. The P-containing resource can also have a low to zero solubility in pure water, for instance less than 1 g / L or less than 0.5 g / L or less than 0.1 g / L, for example, as measured by ICP-OES or ICP-MS.

[0268] A fluorapatite sample (Example 1, Figures 4a-c) was ball milled for 10 h to reduce its particle and crystalline sizes. The SEM micrograph of the ball-milled sample (Figure 18) confirmed the formation of agglomerated particles, generally less than 10 pm, often between 1-3 pm. Typical EDS analysis recorded on the agglomerated particles revealed the presence of Al (0.4 wt%) and Fe (0.56 wt%) in addition to P (17.30 wt%), Ca (36.27 wt%), and O (45.46 wt%).

[0269] The XRD pattern of the ball-milled sample can be observed in Figure 19, representing the nanocrystalline fluorapatite (Cas(PO4)3F) demonstrated by the presence of broad diffraction peaks.

[0270] The ball-milled sample (2 g) was mixed with LiCl (50 g) and the mixture was placed in an alumina crucible and heated to 700 °C under Ar flow. Then, a humid Ar flow was conducted for 2h, after which the humid Ar was replaced by Ar flow, and the temperature was reduced to room temperature. Then, the solidified salt was entirely washed with distilled water by the application of a mechanical stirrer, and the suspension was filtered to obtain a filtrate, which was dried at 100 °C for 2 h. The XRD pattern of the dried filtrate is shown in Figure 20. The pattern can be indexed to the reflections arising from lithium phosphate (L PCh) with orthorhombic crystalline structure and hydroxylapatite (Ca5(PO4)3(OH)) with hexagonal crystalline structure.

[0271] SEM micrographs recorded on the product (Figures 21a-c) provide evidence that L PCE crystals had various sizes and shapes including rods of several tens of micrometres, for instance around 10, 20, 50, or 100 pm, with a cross section few micrometres. Such crystals were also grown into octahedral crystals with sizes of 1 to 50 pm. Without wishing to be bound by theory, it is believed that the size of the L PCE crystals depends on the temperature of the ionic melt, its chemical composition, and the processing time. By controlling these parameters, L13PO4 with various sizes, such as less than 100 nm, for instance in the range 1-100 nm, greater than 100 nm, for instance in the range 100 nm-1 pm, or larger crystals, for instance in the range 1-100 pm or 10-300 pm, can be prepared by treating a phosphate-containing compound, such apatite, in an ionic melt containing Li, such as LiCl, at a temperature in which the ionic melt is in molten state, for instance 300-1000 °C, for a period of time from 1 second to 5 hours.

[0272] Example 6: Extraction of Li3PO4 from Mixtures of Various Minerals Phosphate minerals such as apatite can often be present with other minerals. One example is the iron oxide-apatite (IOA or Kiruna-type) deposits which typically consist of a magnetite- apatite-actinolite / di opside. Phosphorus can be recovered out of such resources in the form of LisPO4.

[0273] To represent a resource containing a P-containing mineral combined with other minerals, fluorapatite (14 g), as presented in Figures 3 and 4, was mixed with FeiOs (6.0 g), and the mixture was ball milled for 10 h. The XRD and SEM analysis of the ball-milled sample, shown in Figure 22a and 22b respectively, revealed the presence of agglomerated Ca4(PO4)sF + FeiCh with particle sizes of typically less than 5 pm, with a typical iron content of around 23 wt%.

[0274] The ball milled sample was exposed to the treatment explained in Example 5. The XRD pattern of the product obtained is shown in Figure 23a. As can be observed, the product contains orthorhombic LnPCh as the major phase, hexagonal hydroxylapatite Cas(PO4)3(OH) and a small amount of cubic magnetite (FesCE). The hexagonal Ca5(PO4)3(OH) originates from the initial fluorapatite with the same crystalline structure. It can be observed that that only (PCh) ' polyanions selectively underwent lithiation during the process to form LnPOr crystals, as no compound containing lithium and iron or lithium and calcium was detected. As can be seen from the SEM of Figure 23b, the LnPCh crystals could grow into large size crystals with various shapes and sizes including rods with a length of several tens of micrometres and a cross-section with dimensions in the scale of sub-micrometre or few micrometres. The LnPCh crystals also included irregular sheet-like crystals with sizes of several micrometres or several hundreds of micrometres.

[0275] Based on the results, the methods of the disclosure allow for the selective lithiation of (PO4)3anions present in a mixture of various minerals including (PCh) ' anions. This lithiation is achieved through an efficient and single-step method that does not necessarily include the use of acids. The methods are particularly efficient for minerals with a relatively low solubility in water, for instance less than 1 g / L or less than 0.1 g / L.

[0276] Without wishing to be bound by theory, it is believed that (PO4) ' from various resources can be readily dissolved in an ionic melt containing Li cations, for instance, an ionic melt containing LiCl. This is also suggests that crystals of LnPCL are formed upon saturation of the ionic melt with (PCL)3'. Since the density of LisPCL is close to the density of ionic melt containing LiCl (around 2 g / cm3), the resulting LnPCh crystals formed from the supersaturated ionic melt can be relatively well dispersed in the melt, while other compounds, such as FesO4 (density > 5 g / cm3) and hydroxylapatite (density > 3 g / cm3) tend to sink to the bottom of the container holding the ionic melt. Some other components may also be dissolved into the ionic melt (see reaction (6)). Thus, the methods of the disclosure allow for the selective preparation of LisPO4 from mixtures of various minerals containing a phosphorus oxide, and the separation of the LisPO4 product from other components.

[0277] Example 7 : Extraction of Li3PO4 from mixtures of minerals in the presence of carbon

[0278] LnPCh crystals can be selectively produced in an ionic melt using minerals containing phosphorous, while other minerals can be removed relatively quickly and / or easily, such as by dissolution in the ionic melt or evaporation from the ionic melt.

[0279] 14.0 g fluorapatite, 8.7g FeiOs, and 1.5 g activated carbon were ball milled for 10 h to make a mixture of minerals, and then the mixture was exposed to the ionic melt according to the procedure explained in the Example 5. The obtained powder, after washing, filtration, and drying, was characterized to contain L POr as the major phase and hydroxylapatite, while no phase related to iron could be detected (Figure 24), showing the effective removal of iron from the system. Carbon was also not detected, though activated carbon does not exhibit sharp XRD peaks.

[0280] Example 8: Extraction of Li3PO4 from spent LFP

[0281] LnPCh can extracted from spend LFP using the methods of the disclosure, without the use of an acid. The process described in Example 2 except that a spent LFP cathode material was used as the phosphorous containing compound. To obtain this raw material, a spent lithium-ion battery with a LFP cathode was fully discharged in a saturated NaCl solution for 24 h to avoid short-circuiting and self-ignition, followed by drying in a vacuum drying oven at 70 °C for 8 h. Then, the spent battery was manually disassembled and separated in a fume cupboard. The XRD pattern of the spent electrode is shown in Figure 25a, where the diffraction patterns of LiFePCE can be observed together with additional peaks from other components of the electrode. Then, the cathode was calcined in a muffle furnace under air atmosphere at 600 °C for 3 h to remove the polyvinylidene fluoride (PVDF) binder and the conductive agent. After calcination, the spent LFP could be separated from the Al current collector. An XRD pattern of the spent cathode material after calcination is shown in Figure 25b, where the diffraction peaks associated with Li3Fe2(PO4)3 and FeiOs in addition to other diffraction peaks can be distinguished. Tables 2a and 2b provide the peaks of Figures 25a and 25b, respectively. SEM micrograph and EDS analysis of the calcined spent LFP, shown in Figure 25 c, suggest that the calcined spent LFP contained agglomerated particles. The size of these agglomerated clusters are on the scale of several tens of micrometres, containing submicrometric phosphate particles. The sample has a relatively high proportion of Fe in addition to phosphorous and a minimal amount of Al coming from the current collector. The calcined spent LFP powder was treated according to the same process explained in the Example 2, including preparing a pellet and exposing the pellet to molten LiCl for a duration of 30 min. It was observed that the calcined spent LFP pellet completely disintegrated in the ionic melt, such that no residual pellet could be obtained after pulling up the rod. After the high temperature treatment, the temperature was reduced to room temperature and the solidified salt was washed with water and filtered. XRD patterns of the product obtained from the bulk of the solidified salt is shown in the Figures 26a-26c, where the diffraction peaks can be assigned to lithium phosphate LnPOr (ICSD: 01-083-0339) with an orthorhombic crystalline structure.

[0282] Table 3 provides the peaks of Figures 26a-26c. No diffraction pattern corresponding to Fe and Al could be detected, suggesting the ionic melt method employed had a purification effect. An SEM micrograph of the L PCh crystals is shown in Figure 26d, showing that the crystals have various morphologies such as sheet- and rod-like morphologies with dimensions from a submicrometer range to several tens of micrometers. The EDS spectrum recorded on a sheet-like LnPOr particle is shown in Figure 26e, from which the relatively high purity of the L PCh is evident. These results confirm that the method is relatively fast and efficient in the extraction of phosphorus from phosphorus-containing compounds and conversion into L PCh with relatively high purity. Notably, there are no elements such as Fe and Al in the L PCh product.

[0283] Apart from the LisPCL crystals obtained from the bulk of salt (Figures 26a-26e), a quantity of materials was obtained by washing of the solidified salt at the bottom of the salt container (corresponding to the ionic melt container 1400 in the system 1000 of Figures 2a and 2b). The X-ray diffraction pattern of this product is shown in Figures 27a and 27b. Apart from diffraction peaks related to L PO-i, the peaks associated with hematite (FeiOs) with rhombohedral structure (ICSD: 01-089-0599) and magnesium aluminum iron oxide Alo.74Fei.26MgC>4 (ICSD: 01-088-0867) with tetragonal structure were present. The SEM micrograph of the material obtained is shown in Figures 28a and 28b, where the presence of LisPO4 crystals with dimension of several tens of micrometer is evident, demonstrating the dispersion of LisPO4 within the salt. In addition to LisPO4, submicrometer particles could also be observed. EDS analysis recorded on these particles (Figure 28c) confirms the presence of elements such as Fe, Cr and Al. The result shows that calcined LFP can be converted into pure LnPOr dispersed in the ionic melt, while other elements present in the LFP material can be efficiently separated from the LnPCE product.

[0284] Table 2a: Data extracted from the XRD pattern of Figure 25a.

[0285]

[0286] Table 2b: Data extracted from the XRD pattern of Figure 25b.

[0287]

[0288] Table 3: Data extracted from the XRD pattern of Figures 26a-26c.

[0289]

[0290] Example 9: Purification of Apatite

[0291] The methods of the disclosure provide green approaches for the purification of natural phosphorous containing resources. As shown in Example 1, the natural fluorapatite mineral is inhomogeneous in terms of chemical composition, containing various elements such as rare earth metals (like Nd, La, and Ce) in addition to phosphorous. The phosphorous containing material may also contain radioactive elements such as uranium. In such cases, the separation of rare earth metals and / or radioactive elements from the mineral containing phosphorus is of economic and safety importance. The natural fluorapatite of Example 1 (2 g) was mixed with potassium chloride (KC1, 10 g), and the mixture was placed in a quartz boat and the boat was placed into a tube furnace. Then, the furnace was heated under various atmospheres of air, Ar, Ar-4% H2, and moist Ar with a heating rate of 4 °C / min to the target temperature of 820 °C with a dwell time at the maximum temperature of 1 h. For the case of moist Ar, the gas flow was moisturized only at the maximum temperature for 1 h, before and after which Ar flow was maintained. After cooling down to room temperature, the solidified salt containing the products were collected. The solidified salts containing the treated apatite exhibited a different appearance relative to the original apatite (Figure 29a). The samples were washed, and the filtrates were dried and examined by XRD, shown in Figure 29b. As can be observed, all samples exhibited diffraction peaks similar to those of the initial fluorapatite, confirming that the thermal treatment in the presence of KC1 does not cause a structural change to the fluorapatite sample. However, without wishing to be bound by theory, it is believed that the treatment can purify the fluorapatite sample by removing components such as rare earth and / or radioactive elements that can exist in natural phosphate deposits such apatite materials. Figures 30a-30c show the SEM micrographs recorded on the products, the products of 30a and 30b were treated under air and the product of 30c was treated under moist Ar. As can be observed, the fluorapatite particles were well defined crystals with sizes in the range of few micrometres, which is different from the original fluorapatite sample (Figures 4a-c). The EDS recorded on a fluorapatite crystal of Figure 30c is shown in Figure 30d, based on which the crystal contains O, P, Ca, and minor amounts of K. This result suggests that the thermal treatment led to the formation of pure fluorapatite, with possible minor amounts of K, while the rare earth elements present in the original fluorapatite (see Figures 4a-c) had been extracted from the fluorapatite crystal.

[0292] Example 10. Preparation of Li , PO4 under nominally dry Ar

[0293] A spent LFP cathode (Figure 25a) was freeze dried under vacuum for 2 h to separate the cathode material from the Al current collector. The cathode material obtained (2 g) was mixed with LiCl (50 g) and the mixture was placed in an alumina boat. The boat was placed inside a tube furnace, and heated to 750 °C with the dwell time at the maximum temperature of 20 min under nominally dry Ar. Then, the temperature was reduced under the same gas follow, and the freezed salt was washed with water to separate the product. X-ray diffraction pattern of this product is shown in Figure 31, confirming the formation of LnPO-i. Without wishing to be bound by theory, it is believed that the presence of moisture increases the rate of the LisPO4 crystalline formation and growth.

[0294] Example 11. Lithiation of Metal Oxides

[0295] MnO powder was compacted to form a pellet according to the Example 2. The the X-ray diffraction pattern of the compacted pellet obtained and appearance are shown in Figure 32a and 32b, respectively, the former showing the pellet has MiyOi. The diffraction peaks obtained can be assigned to those of Manganese Oxide (MmOy Reference code: 00-024-0508) with orthorhombic crystalline structure. This pellet was assembled on an alumina covered copper rod using steel wire as shown in Figure 32b. Then the pellet was introduced into a graphite crucible containing molten LiCl at 700 °C, so that the pellet was exposed to the melt. The graphite crucible was attached to a second copper rod so that it could be polarized against the copper rod attached to the pellet. A Mo wire was also exposed to the ionic melt to act as the reference electrode. Then, a voltage of 1 V was applied between the pellet and crucible through the copper rods, in a way that the pellet underwent cathodic (negative) polarization. The potential difference between the pellet and the crucible was also measured with respect to the Mo reference electrode, as shown in Figure 32e. The polarization at the cell potential of 1 V was conducted for 6 h, and then, the pellet was extracted from the melt and allowed to cool down to the room temperature. Then the residual salt on the pellet was washed with water, and the washed pellet was dried at 100 °C for 2 h. The X-ray diffraction pattern recorded and appearance of the pellet obtained after the cathodic polarization on the sample are shown in Figures 32c and 32d, respectively, where the presence of lithiated phase LiMnCh is evident. The diffraction peaks of the LiMnCh phase can be assigned to those of Lithium Manganese Oxide (Reference code: 01- 072-0411) with orthorhombic crystalline structure. Thus, LiMnOi can be produced using the methods described above.

[0296] Example 12, Fabrication of regenerated LFP

[0297] A partially spent LFP pouch cell was fully discharged by immersion in a 10 wt% NaCl solution. After discharge, the cell was manually disassembled to retrieve the aluminium current collector coated with the positive electrode. The electrode was cut into ~3 x 3 cm pieces and soaked in dimethyl carbonate (DMC) for 12 hours to remove residual electrolyte. Subsequently, the electrode was dried at 60 °C for 12 hours and then freeze-dried in a vacuum chamber at - 47 °C, which facilitated the separation of the aluminium foil from the cathode material.

[0298] The SEM micrograph of the recovered cathode material is shown in Figure 33a, revealing particles with a non-uniform size distribution. This recovered cathode material was used to fabricate a Li-ion half-cell using a composition of active material :PVDF: conductive carbon (C45) in the mass ratio of 70: 10:20. The half-cell, assembled in coin-cell format with Li foil as the counter electrode, was subjected to cycling tests. The Li-ion storage performance, shown in Figure 33 c, indicates a capacity of 101.1 mAh / g after 49 cycles at a current density of 100 mA / g, demonstrating that the recovered cathode material remains functionally viable.

[0299] This recovered cathode material contained a carbon coating, which was removed by thermal treatment in air at 600 °C for 3 hours. For the regeneration process, the material was subsequently exposed to molten LiCl at 700 °C for 2 hours under an Ar atmosphere to form LisPC After cooling, the solidified salt was dissolved in deionized water to extract the LisPCL dispersed within the bulk salt. The extracted LisPCL was then ball-milled at 3000 rpm for 30 minutes using vibrational milling equipment to reduce particle size.

[0300] A portion of the resulting LisPCL sample (0.3714 g, 3.0 mmol), FeSCL^FEO (0.8347 g, 3.0 mmol), and 20% ascorbic acid solution (adjusted to pH 8.48) were placed in a hydrothermal polymeric reactor. The mixture underwent hydrothermal treatment at 200 °C for 24 hours. The resulting product was thermally treated under argon flow at 200 °C for 2 hours to yield regenerated LFP

[0301] An SEM micrograph of the regenerated LFP is shown in Figure 33b, revealing more uniform LFP crystals compared to the original sample, with particle sizes ranging from 20 to 200 nm. The electrode prepared from this regenerated LFP, under the same conditions as the original cathode material (Figure 33c), demonstrated superior electrochemical performance at 100 mAh / g, achieving a reversible Li-ion storage capacity of 128.6 mAh / g after 49 charge / discharge cycles.

[0302] Other Embodiments

[0303] While certain embodiments have been disclosed above, the disclosure is not limited to such embodiments. As an example, in some embodiments, rather than including a lithium ion-containing ionic melt, the methods of the disclosure include a lithium salt dissolved in a suitable polar solvent such as water, ethanol, methanol, acetonitrile, DMSO, and / or DMF. In such embodiments, a phosphorous-containing reactant is combined with the lithium salt dissolved in the solvent to produce a composition including lithium and phosphorous. The lithium salt, phosphorous-containing reactant, and composition including lithium and phosphate can be a lithium salt, a phosphorous-containing reactant, and a composition including lithium and phosphorous, respectively, as described herein. In some embodiments, the solvent includes water. In some embodiments, the temperature is at least 0 °C (e.g., at least 10 °C, at least 20 °C, at least 30 °C, at least 40 °C, at least 50 °C, at least 60 °C, at least 70 °C, at least 80 °C, at least 90 °C) and / or at most 100 °C (e.g., at most 90 °C, at most 80 °C, at most 70 °C, at most 60 °C, at most 50 °C, at most 40 °C, at most 30 °C, at most 20 °C, at most 10 °C).

[0304] As another example, in some embodiments, rather than combining a phosphorus- containing reactant with a lithium ion-containing ionic melt, the phosphorus-containing material can be combined with a lithium ion-containing salt that is in the solid state, thereby forming a combination. Thus, such embodiments can include combining two different solid components. In such embodiments, the method can further include heating the combination above the melting point of the lithium ion-containing salt to melt the salt, thereby producing a composition comprising lithium and phosphorus. In such embodiments combining can further include exposing the phosphorus-containing material and the lithium ion-containing salt to an external force, such as grinding or ball milling.

[0305] As still another example, in some embodiments, a method includes combining a phosphorus- containing with a lithium-ion-containing ionic melt, and subjecting the resulting mixture to one or more forms of energy. Examples of such energy include electromagnetic radiation (e.g., microwave irradiation) and, ultrasound. Without wishing to be bound by theory, it is believed that under these conditions, the growth of LisPO4 crystallites can be inhibited and / or that existing crystallites can be broken down, resulting in U3PO4 crystals with reduced particle sizes ranging from, for example, 1 nm to 1 pm.

[0306] As yet another example, in some embodiments, a method includes: combining a phosphorus-containing material with a lithium-ion-containing ionic salt; heating the combination to a temperature sufficient to melt the ionic salt; and subjecting the melt to to one or more forms of energy. Examples of such energy include electromagnetic radiation (e.g., microwave irradiation) and, ultrasound. Without wishing to be bound by theory, it is believed that under these conditions, the growth of LnPCh crystallites can be inhibited and / or that existing crystallites can be broken down, resulting in LnPCh crystals with reduced particle sizes ranging from, for example, 1 nm to 1 pm.

Claims

WHAT IS CLAIMED:

1. A method, comprising: combining a phosphorous-containing reactant and a lithium ion-containing ionic melt to produce a composition comprising lithium and phosphorous.

2. The method of claim 1 , wherein the lithium ion-containing ionic melt comprises at least one member selected from the group consisting of LiCl, LiF, LiBr, Lil, LiNCh, LiiCOs, LiOH, L1CIO4, L1C2H3O2, L1BO2, L1B4O7, LIPF6, LiTFSl, and LiFSl.

3. The method of claim 1 or 2, wherein, during the combining, a temperature of the lithium ion-containing ionic melt is from 20 °C to 1700 °C, optionally from 20 °C to 1200 °C, optionally from 100 °C to 1100 °C, optionally from 200 °C to 1000 °C, or optionally from 300 °C to 900 °C.

4. The method of claim 1 or 2, further comprising, after combining, exposing the combination to one or more forms of energy.

5. The method of claim 4, wherein the energy is selected from the group consisting of electromagnetic energy and ultrasound.

6. The method of claim 4, wherein the energy comprises microwave electromagnetic radiation.

7. The method of any one of claims 4-6, wherein exposing to energy results in crystallites of the composition having particle sizes of from one nanometer to one micrometer.

8. The method of any one of the preceding claims, wherein producing the composition comprises reacting the lithium ion with the phosphorous-containing reactant.

9. The method of any one of the preceding claims, wherein the lithium ioncontaining ionic melt comprises L12O, optionally wherein the LiiO is formed by hydrolysis of a lithium salt of the lithium ion-containing ionic melt.

10. The method of claim 9, wherein producing the composition comprises reacting the L12O with the phosphorous-containing reactant.

11. The method of any one of the preceding claims, wherein the lithium ioncontaining ionic melt comprises LiiCh, optionally wherein the LiiOi is formed by hydrolysis of a lithium salt of the lithium ion-containing ionic melt.

12. The method of claim 11, wherein producing the composition comprises reacting the LiiCh with the phosphorous-containing reactant.

13. The method of any one of the preceding claims, wherein a concentration of water vapor present in an atmosphere around the lithium ion-containing ionic melt is from 0.1 % to 100 % relative humidity.

14. The method of any one of the preceding claims, further comprising, after producing the composition comprising lithium and phosphorous, forming crystals of the composition in the lithium ion-containing ionic melt.

15. A method, comprising: combining a phosphorous-containing reactant and a lithium ion-containing salt to form a combination; and heating the combination above a melting point of the lithium ion-containing salt to melt the salt, thereby producing a composition comprising lithium and phosphorous.

16. The method of claim 15, wherein the lithium ion-containing ionic salt comprises at least one member selected from the group consisting of LiCl, LiF, LiBr, Lil, LiNCh, LiiCOs, LiOH, L1CIO4, L1C2H3O2, L1BO2, L1B4O7, LIPF6, LiTFSl, and LiFSl.

17. The method of claim 15 or claim 16, wherein producing the composition comprises reacting the lithium ion with the phosphorous-containing reactant.

18. The method of any one of claims 15-17, wherein the lithium ion-containing ionic melt comprises L12O, optionally wherein the LiiO is formed by hydrolysis of a lithium salt of the lithium ion-containing ionic melt.

19. The method of claim 18, wherein producing the composition comprises reacting the L12O with the phosphorous-containing reactant.

20. The method of any one of claims 15-19, wherein the lithium ion-containing ionic salt comprises LiiCh and / or LiiCh.

21. The method of any one of claims 15-20, further comprising, after producing the composition comprising lithium and phosphorous, forming crystals of the composition in the lithium ion-containing ionic melt.

22. The method of any one of claims 15-21, wherein combining comprises exposing to an external influence.

23. The method of claim 22, wherein the external influence comprises grinding or ball milling.

24. The method of any one of claims 15-23, further comprising, after heating the combination, exposing the combination to one or more forms of energy.

25. The method of any one of claims 15-24, wherein heating the combination comprises exposing the combination to one or more forms of energy.

26. The method of claim 25, wherein the energy is selected from the group consisting of electromagnetic energy and ultrasound.

27. The method of claim 25, wherein the energy comprises microwave electromagnetic radiation.

28. The method of any one of claims 25-27, wherein exposing to energy results in crystallites of the composition having particle sizes of from one nanometer to one micrometer.

29. A method, comprising: combining a phosphorous-containing reactant and a lithium salt dissolved in a solvent to produce a composition comprising lithium and phosphorous, wherein the solvent comprises a member selected from the group consisting of water, ethanol, methanol, acetonitrile, DMSO, and DMF, optionally wherein the solvent comprises water.

30. The method of claim 29, wherein the lithium salt comprises at least one member selected from the group consisting of LiCl, LiF, LiBr, Lil, LiNCh, LiiCCh, LiOH, LiCICL, L1C2H3O2, L1BO2, L1B4O7, LIPF6, LiTFSl, and LiFSl.

31. The method of claim 29 or 30, wherein the combining is performed at a temperature of 0 °C to 100 °C.

32. The method of any one of the preceding claims, wherein the combining is performed for 1 second to 4 weeks, optionally for 1 second to 1 week, optionally for 1 second to 1 day, or optionally for 1 second to 5 hours.

33. The method of any one of the preceding claims, wherein the composition comprises at least one member selected from the group consisting of LixPyand LixPyOzwhere x = 1-7, y = 1-7, and z = 1-10.

34. The method of any one of claims 1-32, wherein the composition comprises at least one member selected from the group consisting of Li3PC>4, Li4P2O?, LiPO3, LiiPCh, LisP3Oio, LiP?, Li3P?, LiP, and Li3P.

35. The method of any one of claims 1-32, wherein the composition comprises at least one member selected from the group consisting of Li3PO4, Li4P2O?, LiPO3, Li2PO3, and LisP3Oio.

36. The method of any one of claims 1-32, wherein the composition comprises Li3PO4.

37. The method of any one of the preceding claims, wherein the composition is crystalline, optionally wherein the composition comprises a gamma-orthorhombic crystalline structure.

38. The method of claim 37, wherein the phosphorous-containing reactant comprises an element selected from the group consisting of Ca, Fe, Al, Si, K, Mg, Ce, Nd, Na, Sr, Ba, La, Gd, and Pr and the element is doped into the crystalline composition.

39. The method of any one of the preceding claims, wherein the composition has a purity of at least 98 %, optionally of at least 99 %, or optionally of at least 99.9 %.

40. The method of any one of the preceding claims, wherein the phosphorous- containing reactant comprises a phosphorus oxide.

41. The method of any one of claims 1-39, wherein the phosphorous-containing reactant comprises a compound of formula PxOy.

42. The method of any one of claims 1-39, wherein the phosphorous-containing reactant comprises at least one member selected from the group consisting of phosphate (PCL)3', (P2O7)4; (PO3)2’, (PO3); and (P30io)5-.

43. The method of any one of claims 1-39, wherein the phosphorous-containing reactant comprises phosphate (PO4)3'.

44. The method of any one of the preceding claims, wherein the phosphorous- containing reactant has a solubility of less than 1 g / L in water, such as less than 0.1 g / L in water.

45. The method of any one of the preceding claims, wherein the phosphorous- containing reactant comprises at least one member selected from the group consisting of apatite, fluorapatite, chlorapatite, hydroxylapatite, carbonate apatite, pyromorphite, turquoise, variscite, monocalcium phosphate monohydrate, monocalcium phosphate anhydrous, dicalcium phosphate dihydrate, dicalcium phosphate anhydrous, octacalcium phosphate, tetracalcium phosphate, a- tricalcium phosphate, P-tricalcium phosphate, whitlockite, struvite, brushite, amblygonite, and phosphorite.

46. The method of any one of claims 1 -44, wherein the phosphorous-containing reactant comprises apatite.

47. The method of any one of claims 1-44, wherein the phosphorous-containing reactant comprises a member selected from the group consisting of animal meat and animal bone.

48. The method of any one of claims 1-44, wherein the phosphorous-containing reactant comprises a battery cathode material.

49. The method of claim 48, wherein the battery cathode material comprises AMPO4, where A comprises at least one member selected from the group consisting of Li and Na, and M comprises at least one member selected from the group consisting of Fe, Mn, Ni and Co.

50. The method of claim 48 or 49, wherein the battery cathode material comprises at least one member selected from the group consisting of LiFePO4, LiMnPO4, LiCoPO4, LiFeMnPO4, and LiFeCoPC51. The method of any one of the preceding claims, wherein the phosphorous- containing reactant comprises an element selected from the group consisting of Fe, Cd, Ca, Al, Sr, Ba, Si, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, U, Th, and Ra.

52. The method of claim 51, wherein at least a portion of the element forms a chloride.

53. The method of claim 52, wherein: at least a portion of the chloride dissolves in the lithium ion-containing ionic melt; or at least a portion of the chloride evaporates.

54. The method of claim 52 or 53, wherein the method further comprises, after forming the composition, separating a byproduct selected from the group consisting of the element, a chloride of the element, and an oxide of the element from the lithium ion-containing ionic melt.

55. The method of claim 54, wherein the byproduct is separated by gravimetric separation.

56. The method of claim 54 or 55, wherein the byproduct has a particle size of less than 5 pm, optionally less than 1 pm, optionally 100 nm to 5 pm, or optionally 10 nm to 1 pm.

57. The method of any one of the preceding claims, wherein polarization is applied to the phosphorous-containing reactant.

58. The method of claim 57, wherein the polarization is a cathodic polarization.

59. The method of claim 57 or 58, wherein the polarization applied to the phosphorous-containing reactant is from -3.0 V to -0.1 V relative to a reference electrode immersed in the lithium ion-containing ionic melt.

60. The method of any one of the preceding claims, further comprising converting the composition into LiMPO4, where M comprises one or more metals.

61. The method of claim 60, wherein M comprises at least one member selected from the group consisting of Fe, Mn, Ni, Co, Al, W, Na, Ti, Mg, Ca, Si, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

62. The method of claim 60 or 61, further comprising making a component of an energy storage device using the LiMPO-i.

63. The method of any one of claims 1-59, further comprising making a component of an energy storage device using the composition.

64. The method of claim 62 or 63, wherein at least one of the following holds: the component comprises a member selected from the group consisting of an electrode, such as a cathode, and a solid-state electrolyte; and / or the energy storage device comprises a lithium-ion battery.

65. The method of any one of claims 1-59, further comprising converting the composition into a product selected from the group consisting of phosphoric acid, MH2PO4, where M is an alkali metal or ammonium, M2HPO4, where M is an alkali metal, or CoHPO4.

66. The method of claim 65, wherein the product comprises a member selected from the group consisting of phosphoric acid, LiH2PO4, NaH2PO4, KH2PO4, NH4H2PO4, Na2HPO4, K2HPO4, Li2HPO4, and CoHPO4.

67. The method of claim 65 or 66, wherein the product has a purity of at least 98 %, optionally of at least 99 %, or optionally of at least 99.9 %.

68. The method of any one of claims 60-67, wherein none of phosphogypsum, hydrofluoric acid, fluorosilicic acid and silicon tetrafluoride are generated in the converting.

69. The method of any one of the preceding claims, wherein the combining is acid- free.

70. The method of any one of claims 60-69, wherein sulfuric acid is not consumed in the converting.

71. The method of any one of the preceding claims, wherein the method is performed continuously, optionally wherein reactant is added continuously.

72. The method of any one of the preceding claims, wherein the method is performed in batches.

73. A composition, comprising: crystals of LisPO4, wherein at least one of the following holds: at least a portion of the crystals have a particle size of at least 1 pm, such as at least 2 pm, at least 5 pm, at least 10 pm, or at least 50 pm; at least a portion of the crystals have a crystalline domain size of at least 100 nm; or at least a portion of the crystals have an XRD peak at 34.5° (20) has a FWHM of less than 0.1° (20).

74. The composition of claim 73, wherein: the composition comprises particles comprising crystals of L PO_i; or the composition comprises single crystal particles of U3PO4.

75. The composition of claim 73 or 74, wherein at least a portion of the crystals have a particle size of at most 200 pm.

76. The composition of any one of claims 73-75, wherein at least a portion of the crystals are in the form of at least one shape selected from the group consisting of rods, sheets, and irregularly shaped crystals.

77. The composition of any one of claims 73-75, wherein at least a portion of the crystals are in the form of sheets having a width of from 5 pm to 200 pm and a length of from 5 pm to 200 pm.

78. The composition of any one of claims 73-77, wherein at least a portion of the crystals are in the form of rods having a width of from 100 nm to 1 pm and a length of from 10 pm to 200 pm.

79. The composition of any one of claims 73-78, wherein at least a portion of the crystals have an orthorhombic crystalline structure.

80. The composition of any one of claims 73-79, wherein the crystals of LisPO4 have a purity of at least 98 %, optionally of at least 99 %, or optionally of at least 99.9 %.

81. A system comprising: a lithium ion-containing ionic melt; and a composition comprising lithium and phosphorous dispersed in the lithium ioncontaining ionic melt.

82. The system of claim 81, wherein the composition comprises at least one member selected from the group consisting of LixPyand LixPyOz.

83. The system of claim 81, wherein the composition comprises at least one member selected from the group consisting of Li3PO4, ITjPiO?, LiPCh, LiP?, LisP?, LiP, and L P.

84. The system of claim 81, wherein the composition comprises at least one member selected from the group consisting of LisPCL, ITiPiO?, and LiPCh.

85. The system of claim 81, wherein the composition comprises LisPCL.

86. The system of any one of claims 81-85, wherein the composition is crystalline.

87. The system of claim 86, wherein at least one of the following holds: the crystals are rod-shaped; the crystals are sheetlike; the crystals comprise a single crystalline structure; or the crystals comprise an orthorhombic crystalline structure.

88. The system of any one of claims 81-87, wherein the composition has a purity of at least 98 %, optionally of at least 99 %, or optionally of at least 99.9 %.

89. A method, comprising: combining a metal oxide of formula MVOWand a lithium ion-containing ionic melt to produce a composition of formula LixMyOz.

90. The method of claim 89, wherein the metal oxide comprises at least one member selected from the group consisting of Mn, Co, Ni, Ti, Zr, Fe, Mo, W, Nb, Si, Al, V, and Cr.

91. The method of claim 89 or 90, wherein the lithium ion-containing ionic melt comprises at least one member selected from the group consisting of LiCl, LiF, LiBr, Lil, LiNCh, L12CO3, LiOH, L1CIO4, L1C2H3O2, L1BO2, L1B4O7, LIPF6, LiTFSl, and LiFSl.

92. The method of any one of claims 89-91, wherein the composition comprises the formula LixMnyOz, where x ranges from 0.02 to 5.5, y ranges from 0.20 to 6.80, and z ranges from 2 to 16.

93. The method of any one of claims 89-91, wherein the composition comprises at least one member selected from the group consisting of LiCoCh, Li MnCh, LiMmCL, LiNiMnCoCh, LINICOA1O2, L14T15O12.

94. The method of any one of claims 89-93, wherein the composition comprises a cubic, orthorhombic, rhombohedral, or hexagonal crystalline structure.

95. The method of any one of claims 89-94, wherein a polarization is applied to the metal oxide.

96. The method of claim 95, wherein the polarization applied to the metal oxide is from -3.5 V to -0.1 V, optionally from -3 V to -0.1 V relative to a reference electrode immersed in the lithium ion-containing ionic melt.

97. A system, comprising: a container comprising a lithium ion-containing ionic melt; a movable shaft; and a phosphorous-containing reactant attached to the movable shaft, wherein the movable shaft is configured to immerse and remove the phosphorous- containing reactant from the lithium ion-containing ionic melt.

98. The system of claim 97, wherein the container, the phosphorous-containing reactant, and at least a portion of the movable shaft are disposed in a reactor; and the reactor comprises a gas port.

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