WO2017207878A1 - Method of producing non-conductive lithium metal phosphates - Google Patents

Method of producing non-conductive lithium metal phosphates Download PDF

Info

Publication number
WO2017207878A1
WO2017207878A1 PCT/FI2017/050412 FI2017050412W WO2017207878A1 WO 2017207878 A1 WO2017207878 A1 WO 2017207878A1 FI 2017050412 W FI2017050412 W FI 2017050412W WO 2017207878 A1 WO2017207878 A1 WO 2017207878A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
solution
metal
phosphate
carbon
Prior art date
Application number
PCT/FI2017/050412
Other languages
English (en)
French (fr)
Inventor
Olle SIRÉN
Pekka A. TANSKANEN
Original Assignee
Keliber Oy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Keliber Oy filed Critical Keliber Oy
Publication of WO2017207878A1 publication Critical patent/WO2017207878A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to lithium metal phosphates.
  • the present invention concerns a method of producing non-conductive lithium transition metal phosphates, such as lithium iron phosphate (LiFePC ⁇ ).
  • lithium iron phosphate as an electrode material is well-known in the art. It was first proposed for use as a cathode in lithium ion batteries by A. K. Padhi et al. and later on as a positive electrode for secondary lithium batteries in WO 02/099913.
  • Lithium metal phosphates can be synthesised by a number of methods, such as solid-phase synthesis, emulsion drying, sol-gel processing, solution co -precipitation, vapor phase deposition, electrochemical synthesis, electron beam irradiation, microwave processing, hydrothermal synthesis, ultrasonic pyrolysis, and spray pyrolysis, as discussed by Zhang et al.
  • a preferred source of lithium ions is lithium hydroxide.
  • WO 2014/004386 discloses a method in which lithium hydroxide is combined with other precursor materials including sources of transition metal ions, phosphate ions, carbonate, hydrogen carbonate, formate or acetate ions in water and a cosolvent to form a lithium transition metal phosphate.
  • EP 2 612 839 discloses a method in which a lithium ion source, a divalent transition metal ion source and a phosphate ion source undergo a conversion reaction in the presence of a polar solvent to produce a lithium metal phosphate.
  • CN 1013982 discloses a method for preparing lithium iron phosphate coated with carbon in which an iron salt, a metallic compound, citric acid and a phosphorous compound are mixed in water and reacted to yield a precipitate. A carbon source and lithium are then added to the washed precipitate and reacted and baked to provide lithium iron phosphate coated with carbon.
  • the present invention is based on the concept of producing non-conductive lithium metal phosphates directly from lithium bicarbonate in an aqueous solution.
  • Lithium bicarbonate solutions are already at hand in industrial lithium processes.
  • suitable starting materials arise during separation and purification of intermediate process flows when lithium is leached from spodumene by sodium carbonate pressure leaching.
  • the aqueous lithium bicarbonate solution is preferably purified to high purity.
  • the lithium or lithium compound existing in the solution can readily be converted to lithium metal phosphate by reacting with metal ions and phosphate ions in the solution. A precipitate is formed, which can be recovered and purified. More specifically, the method according to the present invention is characterized by what is stated in claim 1.
  • a lithium metal phosphate can be prepared from a lithium containing starting material (raw-material) in a process, for example a continuous process, without the need for converting the lithium material first to L1 2 CO 3 or LiOH or other lithium compound, for example by precipitation, resulting in increased energy, time and material efficiency and lower investment and operational costs.
  • the lithium metal phosphate can be characterized as non-conductive and can be converted into a conductive lithium metal phosphate in a separate process.
  • the method of converting the lithium metal phosphate into conductive form can be selected depending on the actual application.
  • the present lithium metal phosphate can be milled into a suitable particle size before coating with, for example, a carbon source, which is then converted into conductive form.
  • the purified lithium bicarbonate solution obtained can be used both for the production of the present lithium metal phosphates and also for the production of lithium carbonate.
  • the process can be operated such as to produce lithium carbonate during a first period of time and then non-conductive lithium metal phosphate during a second period of time and optionally to produce both lithium carbonate and non-conductive lithium metal phosphate during a third period of time.
  • Such multipurpose operation ensures proper utilisation of the valuable lithium raw material, and it is economically advantageous.
  • the lithium metal phosphates of the present invention can be used in several applications of the electrochemical industry after a suitable surface treatment or other modification process to convert it into conductive form.
  • a carbon-coated lithium metal phosphate is used as cathode material in a battery.
  • a lithium metal phosphate coated with a layer formed by carbon is used in the preparation of a lithium metal phosphate cathode.
  • the cathodic material and/or the cathode is used in a battery comprising at least one electrochemical cell, said electrochemical cell comprising a cathode and an anode.
  • the method is used for producing a carbon-coated lithium metal phosphate suitable as cathode material in a battery.
  • such a lithium metal phosphate cathode is used in a battery comprising at least one electrochemical cell, said electrochemical cell comprising a cathode and an anode.
  • a battery comprising at least one electrochemical cell, said electrochemical cell comprising a cathode and an anode.
  • Figure 1 is an overview of an embodiment of a process of refining a lithium mineral raw- material to lithium chemicals by sodium carbonate leaching;
  • Figure 2 is a simplified process scheme of an embodiment of producing non-conductive lithium transition metal phosphate from lithium bicarbonate according to the present technology
  • Figure 3 shows an XRD of LiFeP0 4 ;
  • Figure 4 shows the specific capacity of carbon coated LiFeP0 4 according to an embodiment of the present invention. Description of Embodiments
  • bicarbonate is used synonymously with “hydrogen carbonate”.
  • the present invention relates to a method for producing "non-conductive" lithium metal phosphate starting from a lithium bicarbonate solution prepared during, and preferably directly obtained from, an extraction process of lithium from natural minerals and other natural resources, or from an industrial purification process of pre-produced lithium carbonate.
  • non-conductive and essentially non-conductive are interchangeably used with reference to the lithium metal phosphate provided by the present technology for designating lithium metal phosphate which does not have a sufficiently high electrical conductivity for making it suitable as an electrode material, for example as a cathode in a battery.
  • the terms “non-conductive” and “essentially non-conductive” are not to be interpreted as meaning that the lithium metal phosphate would be an insulating material. Rather the terms simply refer to the feature that the lithium metal phosphate cannot - conventionally - be used as such, i.e. unmodified, in applications of the kind wherein lithium compounds are typically utilized by virtue of their properties of electrical conductivity.
  • the "non-conductive" lithium metal phosphate provided by the present invention needs to be subjected to further processing steps to convert it into a form which is sufficiently conductive for practical applications.
  • One conventional process is to provide the material with a carbon coating, as will be discussed below.
  • the present lithium metal phosphate can also be characterized as "uncoated” or “non-coated” lithium metal phosphate.
  • the method generally comprises the steps of
  • lithium bicarbonate by solid-liquid separation, - optionally heat treating the solids to provide lithium metal phosphate, and
  • non-conductive (or essentially non-conductive) lithium metal phosphate can be converted into conductive form by deposition of a conductive material on the surface thereof or by another modification step.
  • the conductive material comprises carbon.
  • the L1HCO 3 solution obtained by extraction of lithium from natural minerals and other resources is used directly for producing lithium transition metal phosphate L1MPO 4 .
  • lithium minerals or by purification of an industrial grade lithium carbonate solution, does not involve a separate step wherein a solid material, typically lithium carbonate or lithium hydroxide, is prepared and optionally purified, and which solid material is the dissolved again.
  • a solid material typically lithium carbonate or lithium hydroxide
  • L1MPO 4 can be used for example as a starting material for preparing L1MPO 4 -C which is suitable as an electrode (e.g. cathode) in a battery.
  • an electrode e.g. cathode
  • the lithium bicarbonate solution is obtained by purification of an industrial composition containing lithium carbonate by contacting it with carbon dioxide to dissolve lithium carbonate into aqueous phase in the form of lithium bicarbonate.
  • any non-dissolved material is separated.
  • unwanted ionic species are removed from the solution.
  • the lithium bicarbonate solution can be obtained
  • non-conductive lithium metal phosphate is prepared from lithium bicarbonate obtained from lithium raw-materials, such as lithium mineral or industrial grade lithium carbonate, without an intervening conversion of the lithium bicarbonate to another lithium compound.
  • the lithium bicarbonate is purified in situ in the solution. The purified lithium bicarbonate is then converted to lithium metal phosphate which is recovered in non- conductive form.
  • the method can be carried out in one continuous process from the extraction of the lithium from raw material and preparation of the lithium bicarbonate solution up to the production and recovery of the lithium metal phosphate.
  • the purification process of the product is also continuously carried out.
  • a particular feature of the present process is that the filtered and purified lithium
  • bicarbonate solution is also useful for the production of lithium carbonate, which may have a purity of more than 99.9 % or even more than 99.99 % by weight.
  • the process is used for simultaneous production of lithium transition metal phosphate and non-conductive lithium carbonate utilizing the same intermediate aqueous bicarbonate solution.
  • a part of the solution is used for producing the phosphate by reaction with suitable metal sources, whereas another part is used for producing lithium carbonate by crystallization and drying.
  • the weight ratios between the two components produced can vary between 1 : 100 to 100: 1 depending on the actual commercial demand for particular compounds.
  • the term "industrial grade”, when used for lithium carbonate, stands for a lithium carbonate material which is obtained from an industrial process, i.e. a process carried out on an industrial scale. Such a material contains impurities, and "industrial grade lithium carbonate” stands for lithium carbonate that still needs to be purified to reach a purity of more than 99.9 % or even more than 99.99 % by weight.
  • the purity of the industrial grade lithium carbonate is less than the 99.9 % by weight, given above for the purified lithium carbonate.
  • the purity of the industrial grade lithium carbonate is about 99 % by weight, conventionally at least 95 %, for example 98 to 99.5 % or 99 to 99.2 % by weight.
  • Figure 1 gives an overview of the process of producing L1 2 CO 3 and L1MPO 4 .
  • the process comprises a number of steps (1 to 5), which in combination will produce not only lithium metal phosphate but also, as important sidestreams, analcime and lithium carbonate.
  • reference numeral 1 refers collectively to the various processing steps needed to provide a raw-material suitable for extraction of lithium for the preparation of lithium carbonate and lithium bicarbonate.
  • the starting material of the present process i.e. the raw material for the lithium compound, can be any lithium containing mineral, such as spodumene, petalite, lepidolite or mixtures thereof.
  • natural lithium containing brines can be used as raw materials. Spodumene is preferred in view of its relatively high content of lithium and ease of processing by leaching. Further, industrial grade low purity lithium carbonate can also be obtained.
  • the processing steps 1 to 3 typically include 1 mining and crushing, 2 concentration by gravimetric and magnetic separation, grinding and flotation. During the above-described process can also include an optional step 3 of changing the crystal form of the lithium mineral.
  • one of the preferred raw-materials is spodumene which occurs in nature as monoclinic alfa-spodumene.
  • the alfa-form needs to be converted into tetragonal beta-spodumene. This can for example be carried out by heating the alfa-spodumene or concentrate of alfa-spodumene to a temperature of approximately 1000-1100 °C for a suitable period of time in a rotational furnace or fluidized bed reactor.
  • the mined, crushed, ground and concentrated raw material is then pulped 4 in water for producing a slurry.
  • the lithium raw material is leached or extracted from the suspended solid matter to yield a suitable lithium compound, such as lithium carbonate, which in turn can be used for further processing.
  • the lithium carbonate is used for producing lithium bicarbonate but, in addition, it can be used for production of other lithium compounds.
  • the leaching or extraction of the starting material can be carried out with sodium carbonate by pressure leaching or by using a mineral acid, such as a strong mineral acid.
  • mineral acids include sulphuric acid.
  • Other mineral acids and organic acids, preferably strong organic acids, can also be used.
  • a caustic material for example an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide.
  • a solution suitable for further treatment can also be obtained by other extraction processes.
  • the leaching can be carried out as a batch process, or preferably as a continuously operated process.
  • the leaching of a slurry containing lithium can be performed in an autoclave or in a cascade of autoclaves in the presence of sodium carbonate and high- pressure steam.
  • Leaching is typically performed at a temperature of 160 to 250 °C.
  • the presence of sodium carbonate and the process conditions give rise to the formation of lithium carbonate.
  • the reaction can be depicted with formula I:
  • the lithium carbonate is preferably purified 5 after first converting it into lithium bicarbonate. In one embodiment, during the purification, lithium is kept dissolved in water with the aid of pressurized C0 2 gas mixed in the solution.
  • Lithium bicarbonate solution can be produced from the lithium carbonate by reacting the carbonate with carbon dioxide according to formula II
  • Carbonation according to formula II of a solution of lithium carbonate is preferably performed using carbon dioxide in an excess amount.
  • the carbonation of the solution containing lithium carbonate is performed at ambient temperature, typically at a temperature of 5 to 40 °C.
  • the carbonation of the solution containing lithium carbonate is performed under atmospheric or higher pressure.
  • carbonation of lithium carbonate can be performed by feeding the carbon dioxide counter-currently with respect to the flow direction of the solution containing lithium carbonate.
  • the lithium bicarbonate solution in particular when produced from spodumene, has the attractive feature that it can be purified to a high purity.
  • solids are separated from the solution containing lithium bicarbonate by any suitable solid-liquid separation method.
  • separation methods include thickening, filtering and combinations thereof.
  • Purification of the lithium bicarbonate solution is then typically continued with ion exchange, for example using cation exchange resin.
  • ion exchange resin Preferably trivalent or divalent metal ions, such as calcium, magnesium, aluminium and iron, or combinations thereof, are used.
  • a proper purification process includes the regeneration of impurity metals bound to the resin. It typically comprises washing the resin with water, elution with acid solution, washing with water, and neutralisation with an alkali solution, such as sodium hydroxide solution, and washing with water.
  • the lithium bicarbonate can be subjected to a reaction step, as disclosed below, for producing lithium metal phosphate. However, it is also possible to recover lithium carbonate of high purity by crystallization thereof.
  • the lithium bicarbonate containing solution is heated in a crystallization unit 6 and a lithium carbonate precipitate is formed according to the reaction III
  • LiHCOs +heat Li 2 C0 3 + C0 2 + H 2 0 III
  • Lithium bicarbonate can also originate from pre-produced solid Li 2 C0 3 chemical, dissolved in water with the aid of pressurized C0 2 gas to form LiHC0 3 water solution.
  • the separated solution containing lithium bicarbonate is purified by distillation. A purified solution containing lithium bicarbonate is thus obtained. Lithium carbonate crystals can be recovered from the purified solution containing lithium bicarbonate by crystallization.
  • Figure 2 depicts a simplified flow scheme of a process according to the present technology for producing lithium transition metal phosphate from the purified lithium bicarbonate solution.
  • Reference numeral 11 refers to the starting material of the lithium reactant, viz. the purified lithium bicarbonate solution.
  • reference numeral 12 refers to the reagents, viz.
  • the lithium solution 11 contains water, carbon dioxide and a lithium source.
  • the lithium source of the aqueous solution, lithium hydrogen carbonate, can also be designated:
  • the reagent mixture 12 contains one or more transition metal sources, and one or more phosphate sources.
  • the metal ions can be obtained from compounds selected from the group consisting of metal phosphates, metal sulphates, metal oxides, metal nitrates, metal nitrites, metal sulphites, metal halides, metal carbonates and mixtures thereof.
  • the metal ions are transition metal ions, preferably iron ions.
  • the transition metal source is typically iron sulphate (FeS0 4 ) or manganese sulphate (MnS0 4 ) or any other transition metal sulfate (MS0 4 , wherein M stands for transition metal) and mixtures thereof.
  • the phosphate source is typically a compound selected from the group consisting of metal phosphates, phosphoric acid, ammonium hydrogen phosphate (NH 4 H 2 P0 4 ) and mixtures thereof, phosphoric acid (H 3 P0 4 ) being particularly preferred.
  • the lithium bicarbonate solution is mixed with the reagent mixture at step 13. Mixing can be made in a reaction vessel or autoclave 14. Reagents are added into lithium solution slowly, for preventing excessive gasification of C0 2 . The pH of the solution will be changing to about 6 by the addition of the reagents.
  • the reaction is typically carried out at a pH in excess of 7, preferably at a pH less than 14.
  • the pH is increased by addition of an alkali or a base selected from the group of ammonia, metal hydroxides, metal oxides or a mixture thereof.
  • an alkali or a base selected from the group of ammonia, metal hydroxides, metal oxides or a mixture thereof.
  • ammonia (NH 3 ) pH will be increased to about 9.
  • Increasing the pH of the reaction provides the added benefit of increasing the rate of reaction.
  • Li 3 P0 4 (OH) the reactor is sealed and pressurised to overpressure with an inert gas, such as carbon dioxide or nitrogen, for preventing oxidation of the reagents.
  • the reaction to produce lithium transition metal phosphate LiMP0 4 is realized at a temperature in excess of 130 °C, preferably at 130 to 220 °C, for example 140-200 °C, e.g. about 170 °C, and at a pressure in excess of 5 bar, preferably at a pressure in the range of 6 to 20 bar, in particular at a pressure of 12-16 bar.
  • Reaction time is typically can be 3-24 hours, preferably 3-6 hours.
  • the temperature of the reaction is related to reaction pressure.
  • the lithium metal phosphate (LIMP0 4 ) is precipitated in the form of fine grains.
  • the reaction mixture is subjected to filtration 15 to yield a leachate 16 and solid lithium transition metal phosphate LiMP0 4 19.
  • Filtration is typically carried out at a room temperature or at an elevated temperature of 50 up to 90 °C, e.g. 80° C, and protective N 2 atmosphere.
  • the LiMP0 4 thus obtained is separated from the solution, which can undergo recycling.
  • the lithium transition metal phosphate is mixed with carbon source aiming to generate a conducting carbon coated form of the the lithium transition metal phosphate; L1MPO 4 -C.
  • Lithium transition metal phosphate carbon source mixture is heat treated in a furnace 19 to to produce a conducting carbon coated form of the the lithium transition metal phosphate; LiMP0 4 -C.
  • Steps 13, 14, 15 and optionally 17 and optionally 18 and optionally 19 are preferably carried out in equipment capable of continuous operation.
  • One embodiment of the invention comprises uncoated lithium metal phosphate.
  • the uncoated metal phosphate is essentially non-conductive and can be subjected to further processing in order to convert it into conductive form, suitable for use for example in lithium ion battery electrode applications.
  • the non-conductive lithium metal phosphate can be coated with carbon.
  • the lithium metal phosphate is contacted in liquid phase, preferably in an aqueous phase, with a source of carbon which is deposited on the surface of the lithium metal phosphate.
  • the carbon source covering the lithium metal phosphates is converted to carbon cover by heating in inert atmosphere composed for example argon or inert argon atmosphere containing 3 ⁇ 4 as a reducing gas.
  • the carbon source is selected from the group consisting of glucose, fructose, sucrose, maltose, dextrose, saccharose, ascorbic acid, pantothenic acid, sodium ascorbate, calcium ascorbate, potassium ascorbate, ascorbyl palmitate, ascorbyl stearate, pteroic acid, paraminobenzoic acid, glutamic acid, pteroylglutamic acid and mixtures thereof.
  • These sources of carbon have the added advantage that they are inexpensive, easy to handle and no pretreatment is required before use in the method of the present invention.
  • the carbon source is selected from glucose (C 6 H 12 O 6 ), citric acid (CeHsOy), and ascorbic acid (CeHsOe) and mixtures thereof.
  • the lithium metal phosphate can, after mixing with the carbon source, then be heat treated to allow for the formation of a layer of carbon.
  • the carbon is present in an amount of at least 0.01 wt%, typically about 1.0 to 10 wt%, of the lithium metal phosphate.
  • the lithium transition metal phosphate containing a carbon source cover (or lithium transition metal phosphate mixed with the carbon source) is heated, preferably in a reducing gas atmosphere, and during the heat treatment the temperature is in excess of 400 °C, particularly in excess of 500 °C, suitably in excess of 600 °C, most suitably at about 675 °C, typically at not more than 1000 °C, to provide a carbon coated lithium metal phosphate.
  • carbon coated conducting lithium metal phosphates of high purity can be produced.
  • the carbon coated lithium metal phosphate typically has a carbon content of up to 10 wt%, preferably 5 wt% or less, for example about 0.01 to 2.5 wt%.
  • the lithium metal phosphate recovered in the form of larger granules or grains is milled or ground to form a finely divided material.
  • a material has a large surface and is suitable as a substrate for a conductive lithium metal phosphate material.
  • milling is carried out in a jet mill.
  • the non-conductive lithium metal phosphate is suitably milled into a finely divided material having an average particle size in the range of 0.01 to 0.5 mm.
  • the non-conductive lithium metal phosphate and the carbon source are mixed prior the milling enabling good mixing and full covering of the particles with the carbon source.
  • a method for producing lithium metal phosphate comprising or consisting of or consisting essentially of the steps of
  • lithium bicarbonate solution is obtained by purification of an industrial lithium carbonate composition by contacting it with carbon dioxide to dissolve lithium carbonate into aqueous phase as lithium
  • lithium bicarbonate is obtained from spodumene, petalite, lepidolite or mixtures thereof, or natural lithium containing brines, in particular spodumene.
  • the lithium bicarbonate solution is obtained from the production of a lithium chemical, such as lithium carbonate, from spodumene, wherein lithium carbonate is dissolved in aqueous solution with carbon dioxide to allow for the separation of analcime and optionally for the purification of the remaining lithium compounds.
  • L1 2 CO 3 was dissolved in water (about 2 g/70 ml H 2 0) under pressurised C0 2 (lObar) in an autoclave to prepare a L1HCO 3 solution.
  • C0 2 lObar
  • FeSO 4 '7H 2 0 (12.38 g)
  • H 3 PO 4 solution 85 %(3.2 ml)
  • ascorbic acid lg
  • Glucose coated L1MPO 4 was dried in a vacuum furnace for 60 minutes.
  • the resultant solids were heat treated at 675 °C in a reducing Ar-H 2 atmosphere for 3 h to convert the glucose coating into carbon coating.
  • the non-conductive form of lithium iron phosphate contained 95.9 wt% LiFePC ⁇ and 3.1 wt% L1 3 PO 4 .
  • the XRD scan is shown in Figure 3.
  • the measured reversible specific capacity for the final carbon coated material LiFeP0 4 -C was measured to be 145.9 mAh/g for charge and 129.8 mAh/g for discharge, cf. the specific capacity curve in Figure 4.
  • the present invention finds applications in the chemical industry e.g. in the preparation of lithium ion cathode chemicals for the electrochemical industry, e.g. for the preparation of lithium ion batteries for use in diverse applications, such as in electric vehicles, in batteries and battery banks for the storage of energy harnessed from the sun, waves or wind, from tidal energy and from hydroelectric power plants, or indeed any power plants.
  • Citation List e.g. in the preparation of lithium ion cathode chemicals for the electrochemical industry, e.g. for the preparation of lithium ion batteries for use in diverse applications, such as in electric vehicles, in batteries and battery banks for the storage of energy harnessed from the sun, waves or wind, from tidal energy and from hydroelectric power plants, or indeed any power plants.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
PCT/FI2017/050412 2016-06-01 2017-06-01 Method of producing non-conductive lithium metal phosphates WO2017207878A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20165457A FI128092B (sv) 2016-06-01 2016-06-01 Förfarande för framställning av icke-ledande litiummetallfosfater
FI20165457 2016-06-01

Publications (1)

Publication Number Publication Date
WO2017207878A1 true WO2017207878A1 (en) 2017-12-07

Family

ID=59298472

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2017/050412 WO2017207878A1 (en) 2016-06-01 2017-06-01 Method of producing non-conductive lithium metal phosphates

Country Status (2)

Country Link
FI (1) FI128092B (sv)
WO (1) WO2017207878A1 (sv)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113213445A (zh) * 2021-02-02 2021-08-06 江西赣锋锂业股份有限公司 一种电池级磷酸锂的制备方法

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999029624A1 (en) 1997-12-09 1999-06-17 Limtech Process for the purification of lithium carbonate
WO2002099913A1 (en) 2001-05-23 2002-12-12 N.V. Umicore S.A. Lithium transition-metal phosphate powder for rechargeable batteries
US20090028772A1 (en) 2007-07-27 2009-01-29 Nippon Chemical Industrial Co., Ltd. Method for manufacturing lithium-iron-phosphorus compound oxide carbon complex and method for manufacturing coprecipitate containing lithium, iron, and phosphorus
CN101393982A (zh) 2008-10-28 2009-03-25 南京海泰纳米材料有限公司 一种沉淀法制备碳包覆的纳米级磷酸铁锂的方法
WO2010103173A1 (en) 2009-03-11 2010-09-16 Outotec Oyj Method for purifying lithium bicarbonate
CN102030320A (zh) 2009-09-25 2011-04-27 上海中锂实业有限公司 磷酸锂制备方法
US20110200508A1 (en) 2010-02-17 2011-08-18 Simbol Mining Corp. Processes for preparing highly pure lithium carbonate and other highly pure lithium containing compounds
CN102496711A (zh) 2011-12-13 2012-06-13 海门容汇通用锂业有限公司 一种高比表面积微米级磷酸亚铁锂的制造方法
CN102522555A (zh) * 2011-12-23 2012-06-27 彩虹集团公司 不同锂源磷酸铁锂锂离子电池正极材料的制备方法
US20130047423A1 (en) 2011-08-29 2013-02-28 Semiconductor Energy Laboratory Co., Ltd. Method of manufacturing positive electrode active material for lithium ion battery
CN102332581B (zh) 2011-10-20 2013-06-19 四川天齐锂业股份有限公司 以锂矿为锂源生产磷酸亚铁锂的方法
EP2612839A1 (en) 2010-09-03 2013-07-10 Showa Denko Kabushiki Kaisha Method for producing lithium metal phosphate
WO2013140039A1 (en) 2012-03-19 2013-09-26 Outotec Oyj Method for recovering lithium carbonate
WO2014004386A2 (en) 2012-06-27 2014-01-03 Dow Global Technologies Llc Low-cost method for making lithium transition metal olivines with high energy density

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999029624A1 (en) 1997-12-09 1999-06-17 Limtech Process for the purification of lithium carbonate
WO2002099913A1 (en) 2001-05-23 2002-12-12 N.V. Umicore S.A. Lithium transition-metal phosphate powder for rechargeable batteries
US20090028772A1 (en) 2007-07-27 2009-01-29 Nippon Chemical Industrial Co., Ltd. Method for manufacturing lithium-iron-phosphorus compound oxide carbon complex and method for manufacturing coprecipitate containing lithium, iron, and phosphorus
CN101393982A (zh) 2008-10-28 2009-03-25 南京海泰纳米材料有限公司 一种沉淀法制备碳包覆的纳米级磷酸铁锂的方法
WO2010103173A1 (en) 2009-03-11 2010-09-16 Outotec Oyj Method for purifying lithium bicarbonate
CN102030320A (zh) 2009-09-25 2011-04-27 上海中锂实业有限公司 磷酸锂制备方法
US20110200508A1 (en) 2010-02-17 2011-08-18 Simbol Mining Corp. Processes for preparing highly pure lithium carbonate and other highly pure lithium containing compounds
EP2612839A1 (en) 2010-09-03 2013-07-10 Showa Denko Kabushiki Kaisha Method for producing lithium metal phosphate
US20130047423A1 (en) 2011-08-29 2013-02-28 Semiconductor Energy Laboratory Co., Ltd. Method of manufacturing positive electrode active material for lithium ion battery
CN102332581B (zh) 2011-10-20 2013-06-19 四川天齐锂业股份有限公司 以锂矿为锂源生产磷酸亚铁锂的方法
CN102496711A (zh) 2011-12-13 2012-06-13 海门容汇通用锂业有限公司 一种高比表面积微米级磷酸亚铁锂的制造方法
CN102522555A (zh) * 2011-12-23 2012-06-27 彩虹集团公司 不同锂源磷酸铁锂锂离子电池正极材料的制备方法
WO2013140039A1 (en) 2012-03-19 2013-09-26 Outotec Oyj Method for recovering lithium carbonate
WO2014004386A2 (en) 2012-06-27 2014-01-03 Dow Global Technologies Llc Low-cost method for making lithium transition metal olivines with high energy density

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
A. K. PADHI; K. S. NANJUNDASWAMY; J. B. GOODENOUGH, J. ELECTROCHEM. SOC., vol. 144, 1996, pages 1188 - 1194
F. LU; Y. ZHOU; J. LIU; Y. PAN, ELECTROCHIMICA ACTA, vol. 56, 2011, pages 8833 - 8838
G. LIANG; L. WANG; X. OU; X ZHAO; S. XU, JOURNAL OF POWER SOURCES, vol. 184, 2008, pages 538 - 542
LIANG ET AL., JOURNAL OF POWER SOURCES, February 2008 (2008-02-01)
LU ET AL.: "disclose enhancement of F-doping on the electrochemical behaviour of carbon-coated LiFeP0 nanoparticles prepared by hydrothermal route in an article in", ELECTROCHIMICA ACTA, July 2011 (2011-07-01)
SEUNG-AH HONG ET AL: "Carbon coating on lithium iron phosphate (LiFePO): Comparison between continuous supercritical hydrothermal method and solid-state method", CHEMICAL ENGINEERING JOURNAL, ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 198, 18 May 2012 (2012-05-18), pages 318 - 326, XP028451422, ISSN: 1385-8947, [retrieved on 20120527], DOI: 10.1016/J.CEJ.2012.05.058 *
Y. ZHANG; Q. HUO; P. DU; L. WANG; A. ZHANG; Y. SONG; Y. LV; G. LI, SYNTHETIC METALS, vol. 162, 2012, pages 1315 - 1326

Also Published As

Publication number Publication date
FI128092B (sv) 2019-09-13
FI20165457A (sv) 2017-12-02

Similar Documents

Publication Publication Date Title
EP3227943B1 (en) Method of producing lithium metal phosphates
CN113735087B (zh) 一种废旧磷酸铁锂电池正极物料回收的方法
JP5587500B2 (ja) リチウム含有溶液からリチウムを抽出する方法
US9169125B2 (en) Method for producing high-purity lithium carbonate
CA3143966C (en) Methods for extracting lithium from spodumene
US20150247216A1 (en) Method for the hydrometallurgical recovery of lithium, nickel and cobalt from the lithium transition metal oxide-containing fraction of used galvanic cells
CN107055575B (zh) 一种电池级氢氧化锂的生产工艺
CA2644092A1 (en) Extraction of lithium from lithium bearing minerals by caustic leaching
KR20210108966A (ko) 리튬 화학물질 및 금속성 리튬의 제조
EA032897B1 (ru) Гидрометаллургический способ получения чистого металлического магния и различных побочных продуктов
KR102408888B1 (ko) 폐 양극재 반응용기로부터 유가금속 및 제올라이트 함유 물질의 회수방법
JP2019526523A (ja) 塩化リチウムの製造方法および炭酸リチウムの製造方法
JP2023073298A (ja) 水酸化リチウムの製造方法
TW202134182A (zh) 純化鋰鹽的方法
KR101889457B1 (ko) 수산화 리튬 수용액의 제조 방법 및 이를 이용한 탄산 리튬의 제조 방법
CN109264748B (zh) 一种以粗制磷酸锂制备碳酸锂的方法
CN115806279B (zh) 一种利用含铁废料制备磷酸铁的方法
Quintero et al. Development of a co-precipitation process for the preparation of magnesium hydroxide containing lithium carbonate from Li-enriched brines
KR101944518B1 (ko) 탄산리튬으로부터 고농도 리튬 수용액 제조방법
JP2023522285A (ja) 水酸化リチウムの製造方法
KR101944522B1 (ko) 인산리튬으로부터 고농도 리튬 수용액 제조 방법
Shin et al. Recovery of lithium from LiAlO2 in waste box sagger through sulfation to produce Li2SO4 and sequential wet conversion to Li3PO4, LiCl and Li2CO3
CN112725621B (zh) 基于碳酸根固相转换法从废旧锂电池分离镍钴锰的方法
FI128092B (sv) Förfarande för framställning av icke-ledande litiummetallfosfater
Berdikulova et al. Methods for lithium-bearing raw materials processing

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17737307

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17737307

Country of ref document: EP

Kind code of ref document: A1