FI128092B - Process for the preparation of non-conductive lithium metal phosphates - Google Patents

Process for the preparation of non-conductive lithium metal phosphates Download PDF

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FI128092B
FI128092B FI20165457A FI20165457A FI128092B FI 128092 B FI128092 B FI 128092B FI 20165457 A FI20165457 A FI 20165457A FI 20165457 A FI20165457 A FI 20165457A FI 128092 B FI128092 B FI 128092B
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lithium
solution
metal
phosphate
metal phosphate
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FI20165457A7 (en
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Olle Sirén
Pekka Tanskanen
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Keliber Oy
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    • 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 iron, with or without oxygen or hydrogen, and containing two or more other elements
    • 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
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    • 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

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Abstract

Esillä oleva keksintö koskee menetelmää ei-johtavan litiummetallifosfaatin valmistamiseksi litiumia sisältävistä raaka-aineista, jonka menetelmän mukaan tuotetaan teollisesta prosessivirrasta liuos, joka sisältää litiumbikarbonaattia, litiumbikarbonaatti saatetaan liuoksessa reagoimaan metalli-ionien ja fosfaatti-ionien kanssa, litiumbikarbonaattia sisältävästä liuoksesta erotetaan kiintoaineet kiintoaine-nesteerotuksella ja kiintoaineet lämpökäsitellään litiummetallifosfaatin aikaansaamiseksi. Menetelmää voidaan käyttää jatkuvatoimisesti litiumionikatodi-kemikaalien valmistamiseksi etenkin elektrokemiallisen teollisuuden tarpeisiin, esim. ionikatodikemikaaleiksi.The present invention relates to a process for the preparation of a non-conductive lithium metal phosphate from lithium-containing raw materials, which process comprises preparing a solution containing lithium bicarbonate from an industrial process stream, reacting the solution solids are heat treated to provide lithium metal phosphate. The process can be used continuously for the preparation of lithium ion cathode chemicals, particularly for the needs of the electrochemical industry, e.g., ion cathode chemicals.

Description

Method of Producing Non-Conductive Lithium Metal Phosphates
Technical Field
The present invention relates to lithium metal phosphates. In particular, the present invention concerns a method of producing non-conductive lithium transition metal phosphates, such as lithium iron phosphate (LiFePCL).
Background Art
The use of 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.
Conventionally, a preferred source of lithium ions is lithium hydroxide. For example, 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.
Processes utilising diverse sources of lithium ions are also known in the art. Thus, US 2013/0047423 teaches a method of manufacturing lithium iron phosphate starting from lithium hydroxide monohydrate or lithium carbonate, iron tetrahydrate, and ammonium dihydrogen phosphate. Similarly, US 2011/0200508 discloses the use of purified lithium hydroxide for producing lithium iron phosphate.
CN 102496711 discloses a method in which a lithium carbonate solution is fed with carbon dioxide, and the resulting lithium bicarbonate solution is then reacted with a mixed solution of phosphoric acid and ferrous sulphate.
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.
In the late 1990s it was discovered that the application of a carbon coating to lithium metal phosphates had beneficial effects to their uses as cathodic materials.
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.
A similar technology is described in an article by Liang et al. in Journal of Power Sources, February 2008.
In addition to carbon coatings various other coatings on lithium metal phosphates are known. For example US 2009/028772 relates to a method of coating lithium iron phosphate with an oxide carbon complex. Lu et al. disclose enhancement of F-doping on the electrochemical behaviour of carbon-coated LiFePCf nanoparticles prepared by hydrothermal route in an article in Electrochimica Acta, July 2011.
The main drawback associated with the existing techniques of producing carbon-coated lithium metal phosphates is the great number of steps required to carry out the processes. Production of precursors from natural resources is carried out in a separate process. For example, lithium hydroxide monohydrate, lithium hydroxide or lithium carbonate must be pre produced as solid chemicals. This leads to high investment, energy and material costs.
Thus, the complexity and inefficiency of the known processes make them expensive and undesirable, and result in an economically expensive lithium metal phosphate product.
Summary of Invention
Technical Problem
It is an aim of the present invention to provide a simplified method for the production of non-conductive lithium metal phosphates which are suitable as intermediates for the production of conductive lithium metal phosphates.
It is a particular aim to provide a method for the production of lithium metal phosphates from an aqueous solution of a lithium raw material in a continuous process.
It is a further aim of the present invention to provide carbon-coated lithium metal phosphates using non-conductive lithium metal phosphates as a starting compound.
Solution to Problem
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. For example, 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.
Use of the method of the present invention is characterized by what is stated in claim 22.
Advantageous Effects of Invention
The invention provides several advantages. By means of the invention 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 Li2CO3 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. Thus, typically, 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. Thus, 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. In one embodiment, a carbon-coated lithium metal phosphate is used as cathode material in a battery.
In a further embodiment, a lithium metal phosphate coated with a layer formed by carbon is used in the preparation of a lithium metal phosphate cathode.
In a further embodiment 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.
In a further embodiment, the method is used for producing a carbon-coated lithium metal phosphate suitable as cathode material in a battery.
In a further embodiment, 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.
Not only does the method increase time and energy efficiency as mentioned above but it also increases material efficiency. The solution containing unreacted material can be recycled for further use in the method.
Other features and advantages will become apparent from the following description of preferred embodiments.
Brief Description of Drawings
Figure 1 is an overview of an embodiment of a process of refining a lithium mineral rawmaterial 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 LiFePCf; and
Figure 4 shows the specific capacity of carbon coated LiFePCf according to an embodiment of the present invention.
Description of Embodiments
In the present context, the term “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.
In the present context, the terms “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.
Typically, 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. Thus, with respect to such a modification process, the present lithium metal phosphate can also be characterized as “uncoated” or “non-coated” lithium metal phosphate.
The method generally comprises the steps of
- providing a solution containing lithium bicarbonate,
- reacting the lithium bicarbonate in the solution with metal ions and phosphate ions,
- separating the solids from the solution which contains, or which has contained lithium bicarbonate, by solid-liquid separation,
- optionally heat treating the solids to provide lithium metal phosphate, and
- recovering the lithium metal phosphate in a non-conductive form.
As stated above, the 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.
Conventionally, the conductive material comprises carbon.
In one embodiment, the L1HCO3 solution obtained by extraction of lithium from natural minerals and other resources is used directly for producing lithium transition metal phosphate L1MPO4.
Thus, in preferred embodiments, the production of lithium transition metal phosphate L1MPO4 from the L1HCO3 solution obtained by extraction of lithium raw-materials (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.
L1MPO4 can be used for example as a starting material for preparing L1MPO4-C which is suitable as an electrode (e.g. cathode) in a battery.
According to a preferred embodiment, 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. Optionally any non-dissolved material is separated. In addition unwanted ionic species are removed from the solution.
Thus, to mention some examples, the lithium bicarbonate solution can be obtained
- by pressure dissolution of lithium from a lithium mineral with sodium carbonate, in particular in the form of a lithium carbonate followed by treatment of the lithium carbonate containing mother liquid with carbon dioxide,
- by extraction of a lithium mineral with a mineral acid to yield a lithium carbonate composition, which is treated with carbon dioxide to form a lithium bicarbonate solution, or
- by purification of an industrial grade lithium carbonate solution with carbon dioxide to form a high purity lithium bicarbonate solution.
Naturally, it is also possible to combine lithium bicarbonate solutions obtained from different sources.
In one embodiment, 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.
Typically, 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 nonconductive 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.
In one embodiment, 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 %.
Thus, in one embodiment of the present technology, 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 (lithium transition metal phosphate/lithium carbonate) can vary between 1:100 to 100:1 depending on the actual commercial demand for particular compounds.
Figure 1 gives an overview of the process of producing L12CO3 and L1MPO4.
As will appear from the scheme, 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.
In Figure 1, 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. Also 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. Thus, one of the preferred raw-materials is spodumene which occurs in nature as monoclinic alfa-spodumene. For further processing, before leaching, 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 (2)-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. In the present case, 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 strong mineral acid, such as sulphuric acid. A solution suitable for further treatment can also be obtained by an extraction process.
The leaching can be carried out as a batch process, or preferably as a continuously operated process.
In the case of spodumene, 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 highpressure 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:
LiAI(SiO3)2+ Na2CO3+ H2O 2NaAI(SiO3)2-H2O + Li2CO3 I
NaAI(SiO3)2-H2O, also known as analcime, is a zeolite-like crystal material. It is separated by filtering and can be recovered. Analcime can be used for example as a chemical filter material.
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 CO2 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
Li2CO3+CO2+H2O A2 LiHCO3 II
Carbonation according to formula II of a solution of lithium carbonate is preferably performed using carbon dioxide in an excess amount. According to one embodiment of the present invention the carbonation of the solution containing lithium carbonate is performed at ambient temperature, typically at a temperature of 5 to 40 °C. According to an embodiment of the present invention the carbonation of the solution containing lithium carbonate is performed under atmospheric or higher pressure.
Various process applications are possible. Thus, 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.
As mentioned above, the lithium bicarbonate solution, in particular when produced from spodumene, has the attractive feature that it can be purified to a high purity.
Thus, after carbonation, solids are separated from the solution containing lithium bicarbonate by any suitable solid-liquid separation method. Examples of 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. Preferably trivalent or divalent metal ions, such as calcium, magnesium, aluminium and iron, or combinations thereof, are used.
In addition to solution purification by ion exchange stages, 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.
A suitable method is disclosed in WO 2010/103173 the contents of which are herewith incorporated by reference.
After the purifying step, 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
LiHCO3 +heat = Li2CO3+ CO2+ H2O
III
Lithium bicarbonate can also originate from pre-produced solid L12CO3 chemical, dissolved in water with the aid of pressurized CO2 gas to form L1HCO3 water solution. The production of lithium carbonate by crystallization from a purified lithium bicarbonate solution is discussed in WO 2013/140039A, the contents of which are herewith incorporated by reference.
In an embodiment, 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. And reference numeral 12 refers to the reagents, viz. transition metal source and a phosphate source.
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: “ L1HCO3 (aq)”. The abbreviation “aq” indicates that the lithium bicarbonate is dissolved in the aqueous solution which contains at least residues of dissolved carbon dioxide gas.
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.
In a further embodiment, the metal ions are transition metal ions, preferably iron ions.
The transition metal source is typically iron sulphate (FeSCU) or manganese sulphate (MnSCU) or any other transition metal sulfate (MSO4, 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 (NH4H2PO4) and mixtures thereof, phosphoric acid (H3PO4) 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 CO2. 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.
In one embodiment, 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. By addition of ammonia (NH3) pH will be increased to about 9. Increasing the pH of the reaction provides the added benefit of increasing the rate of reaction.
The addition of an alkali or base causes Li3PO4(OH) to precipitate as a turquoise coloured sediment.
During the addition of the reactants, carbon dioxide is released from the solution as the lithium begins to react with the phosphate ions to form Li3PO4.
After formation of Li3PO4(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 L1MPO4 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 (LIMPO4) 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 L1MPO4 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 N2 atmosphere.
The L1MPO4 thus obtained is separated from the solution, which can undergo recycling.
After precipitation 18 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; L1MPO4-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; L1MPO4-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.
Thus, the non-conductive lithium metal phosphate can be coated with carbon. For that purpose, 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 H2 as a reducing gas.
Diverse sources of carbon can be used in the method ranging from mineral sources to various biological sources. In an embodiment 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.
In preferred embodiments, the carbon source is selected from glucose (CeH^Oe), citric acid (CeHgO?), and ascorbic acid (CeHgOe) 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.
Thus, in an embodiment, 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.
Thus, by the present method, 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%.
Before any modification for turning non-conductive lithium metal phosphate into conductive form, the lithium metal phosphate recovered in the form of larger granules or grains is milled or ground to form a finely divided material. Such a material has a large surface and is suitable as a substrate for a conductive lithium metal phosphate material. Preferably milling is carried out in a jet mill.
The non-conductive lithium metal phosphate is suitable 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.
Based on the above, the following embodiments are illustrative:
1. A method for producing lithium metal phosphate comprising
- providing a solution containing purified lithium bicarbonate,
- reacting the lithium bicarbonate in the solution with metal ions and phosphate ions to produce a solid precipitate;
- separating the solids from the solution containing lithium bicarbonate by solidliquid separation;
- mixing and milling the non-conductive lithium metal phosphate with carbon source; and
- heat treating the mixture to provide a conductive carbon coated lithium metal phosphate.
2. The method according to embodiment 1, wherein the 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 bicarbonate and optionally by separating any non-dissolved material.
3. The method according to embodiment 1 or 2, wherein the lithium bicarbonate solution is obtained
- by pressure dissolution of a lithium mineral with sodium carbonate, the lithium bicarbonate solution being recovered after separation and purification using carbon dioxide,
- by extraction of a lithium mineral with a mineral acid to yield a lithium carbonate composition, which is treated with carbon dioxide to form a lithium bicarbonate solution, or
- by purification of an industrial grade lithium carbonate solution with carbon dioxide to form a high purity lithium bicarbonate solution.
4. The method according to any of the preceding embodiments, wherein the lithium bicarbonate is obtained from spodumene, petalite, lepidolite or mixtures thereof, or natural lithium containing brines, in particular spodumene.
5. The method according to any of the preceding embodiments, wherein the lithium bicarbonate solution is obtained from the production of a lithium chemical 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.
The following non-limiting example illustrates the invention:
Example 1
L12CO3 was dissolved in water (about 2 g/70 ml H2O) under pressurised CO2 (lObar) in an autoclave to prepare a L1HCO3 solution. At the same time, to a round-bottomed flask containing H2O (25ml), in a nitrogen atmosphere was added FeSO4 7H20 (12.38 g), H3PO4 solution (85 %)(3.2 ml) and ascorbic acid (Ig). The L1HCO3 solution was pipetted into the round-bottomed flask with stirring until the lithium was present in a stoichiometric excess of about 20 %. An aqueous solution of ammonia (25 %, 25 ml) and a surfactant (IGEPAL® CA-630) (0.1 ml) were added to the round-bottomed flask. The formed slurry was poured into the autoclave reactor and reacted in CO2 at 170 °C for 3 h. The contents were cooled. The solids were separated from the solution by suction and dried under vacuum at 40 °C.
2.3 g of the hydrothermally formed L1MPO4 solids were mixed with a carbon source, containing 0.23 g of glucose dissolved in 10 ml of water. The mixture was agitated by ultrasound for 20 minutes after which the water was evaporated by heating the mixture to 110 °C for a 60 minute period of time.
Glucose coated L1MPO4 was dried in a vacuum furnace for 60 minutes.
The resultant solids were heat treated at 675 °C in a reducing Ar-H2 atmosphere for 3 h to convert the glucose coating into carbon coating.
Resultant particles were milled to smaller than a diameter of 40 pm to yield LiFePCL-C
According to the XRD analysis the non-conductive form of lithium iron phosphate contained 95.9 wt% LiFePCL and 3.1 wt% L13PO4. The XRD scan is shown in Figure 3.
The measured reversible specific capacity for the final carbon coated material LiFePCL-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.
List of Reference Signs mining, crushing, grinding and concentration conversion of crystal structure pressure leaching
CO2 treatment filtration and purification crystallization and drying lithium solution reagents mixing precipitation filtration filtrate lithium metal phosphate heat treatment lithium metal phosphate
Industrial Applicability
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
Patent Literature
CN 102496711
US 2013047423
EP 2612839
CN 1013982
US 2009028772
WO 2014004386
WO 02/099913
US 2011200508
Non Patent Literature
A. K. Padhi, K. S. Nanjundaswamy, and J. B. Goodenough, J. Electrochem. Soc., 144 (1996)1188-1194.
Y. Zhang, Q. Huo, P. Du, L. Wang, A. Zhang, Y. Song, Y. Lv, G. Li, Synthetic Metals 162 (2012)1315-1326.
G. Liang, L. Wang, X. Ou, X Zhao, and S. Xu, Journal of Power Sources, 184 (2008), p. 538-542.
F. Lu, Y. Zhou, J. Liu, and Y. Pan, Electrochimica Acta, 56 (2011), p. 8833-8838.

Claims (22)

Patenttivaatimukset:Claims: 1. Menetelmä litiummetallifosfaatin valmistamiseksi, jossa menetelmässäA process for the preparation of lithium metal phosphate, which process - tuotetaan puhdistettua litiumbikarbonaattia sisältävä liuos,- producing a solution containing purified lithium bicarbonate, - saatetaan litiumbikarbonaatti liuoksessa reagoimaan metalli-ionien ja fosfaattiionien kanssa kiinteän saostuman valmistamiseksi,- reacting the lithium bicarbonate in solution with metal ions and phosphate ions to form a solid precipitate, - erotetaan kiintoaineet liuoksesta kiintoaine-neste-erotuksella ja- separating the solids from the solution by solid-liquid separation, and - otetaan talteen päällystämätön, ei-johtava litiummetallifosfaatti, jolloin litiumbikarbonaattiliuos saadaan uuttamalla litiumia luonnonmineraaleista ja mainittua litiumbikarbonaattiliuosta käytetään suoraan litiumsiirtymämetallifosfaatin valmistamiseen.- recovering the uncoated, non-conductive lithium metal phosphate, wherein the lithium bicarbonate solution is obtained by extraction of lithium from natural minerals and said lithium bicarbonate solution is used directly for the preparation of lithium transition metal phosphate. 2. Patenttivaatimuksen 1 mukainen menetelmä, jossa litiumbikarbonaattiliuos saadaanThe method of claim 1, wherein the lithium bicarbonate solution is obtained - paineliuottamalla litiummineraalia natriumkarbonaattiliuoksella ja ottamalla talteen litiumbikarbonaattiliuos hiilidioksidilla suoritetun erottamisen ja puhdistamisen jälkeen.- pressure leaching of the lithium mineral with sodium carbonate solution and recovery of the lithium bicarbonate solution after separation and purification with carbon dioxide. 3. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, jossa litiumbikarbonaatti saadaan spodumeenista, petaliitista, lepidoliitista tai jostain näiden seoksesta, tai suolavettä sisältävästä luonnon litiumista, erityisesti spodumeenista.The process according to any one of the preceding claims, wherein the lithium bicarbonate is obtained from spodumene, petalite, lepidolite or a mixture thereof, or natural lithium containing brine, in particular spodumene. 4. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, jossa litiumbikarbonaattiliuos saadaan litiumkemikaalin tuotannosta spodumeenista, jossa tuotannossa litiumkarbonaatti liuotetaan vesipitoiseen liuokseen hiilidioksidilla analsiimin erottamiseksi ja valinnaisesti jäljellä olevien litiumyhdisteiden puhdistamiseksi.The method according to any one of the preceding claims, wherein the lithium bicarbonate solution is obtained from the production of lithium chemical from spodumene, in which the lithium carbonate is dissolved in an aqueous solution with carbon dioxide to separate the analyte and optionally purify the remaining lithium compounds. 5. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, jossa metalli-ionit saadaan yhdisteistä, jotka on valittu ryhmästä, joka koostuu metallifosfaateista, metallisulfaateista, metallioksideista, metallinitraateista, metallinitriiteistä, metallisulfiiteista, metallihalideista, metallikarbonaateista ja jostain näiden seoksesta.The process according to any one of the preceding claims, wherein the metal ions are obtained from compounds selected from the group consisting of metal phosphates, metal sulfates, metal oxides, metal nitrates, metal nitrites, metal sulfites, metal halides, metal carbonates, and mixtures thereof. 6. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, jossa metalli-ionit ovat siirtymämetalli-ioneja, edullisesti rautaioneja.The process according to any one of the preceding claims, wherein the metal ions are transition metal ions, preferably iron ions. 7. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, jossa fosfaatti-ionit saadaan yhdisteistä, jotka valitaan ryhmästä, joka koostuu metallifosfaateista, fosforihaposta, ammoniumvetyfosfaatista ja jostain näiden seoksesta.The process according to any one of the preceding claims, wherein the phosphate ions are obtained from compounds selected from the group consisting of metal phosphates, phosphoric acid, ammonium hydrogen phosphate and mixtures thereof. 8. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, jossa reagointi suoritetaan vesifaasissa yli 130 °C:ssa, edullisesti 140-200 °C:ssa.The process according to any one of the preceding claims, wherein the reaction is carried out in an aqueous phase above 130 ° C, preferably 140-200 ° C. 9. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, jossa reagointi suoritetaan yli 5 bar, edullisesti 6-20, erityisesti noin 10 bar, paineessa.The process according to any one of the preceding claims, wherein the reaction is carried out at a pressure of more than 5 bar, preferably 6-20, in particular about 10 bar. 10. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, jossa reagointi suoritetaan pH:n ollessa yli 7, edullisesti alle 14, tyypillisesti 7,5-12.The process according to any one of the preceding claims, wherein the reaction is carried out at a pH above 7, preferably below 14, typically 7.5 to 12. 11. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, jossa pH:ta nostetaan lisäämällä alkalia tai emästä, joka on valittu ryhmästä, joka koostuu ammoniakista, metallihydroksideista, metallioksideista ja jostain näiden seokset.The process according to any one of the preceding claims, wherein the pH is increased by the addition of an alkali or a base selected from the group consisting of ammonia, metal hydroxides, metal oxides and mixtures thereof. 12. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, jossa litiumbikarbonaattia sisältävä erotettu liuos puhdistetaan suodattamalla, jolloin saadaan puhdistettu litiumbikarbonaattia sisältävä liuos, ja litiumkarbonaattikiteet otetaan talteen puhdistetusta litiumbikarbonaattia sisältävästä liuoksesta kiteyttämällä.The process according to any one of the preceding claims, wherein the lithium bicarbonate-containing separated solution is purified by filtration to obtain a purified lithium bicarbonate-containing solution, and the lithium carbonate crystals are recovered from the purified lithium bicarbonate-containing solution. 13. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, jossa johtamaton litiummetallifosfaatti muunnetaan johtavaan muotoon kerrostamalla sen pinnalle johtavaa materiaalia, joka käsittää edullisesti hiiltä.The process according to any one of the preceding claims, wherein the non-conductive lithium metal phosphate is converted into a conductive form by deposition on its surface of a conductive material, preferably comprising carbon. 14. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, jossaThe method of any preceding claim, wherein - litiumfosfaatti sekoitetaan hiililähteen kanssa; jalithium phosphate is mixed with the carbon source; and - seos lämmitetään hiililähteen muuntamiseksi hiilipäällysteeksi hiilellä päällystetyn litiummetallifosfaatin valmistamiseksi.heating the mixture to convert the carbon source into a carbon coating to produce carbon coated lithium metal phosphate. 15. Patenttivaatimuksen 14 mukainen menetelmä, jossa hiililähde kerrostetaan litiummetallifosfaatille ja päällystetty litiummetallifosfaatti lämmitetään hiililähteen muuntamiseksi hiilipäällysteeksi.The method of claim 14, wherein the carbon source is deposited on lithium metal phosphate and the coated lithium metal phosphate is heated to convert the carbon source to a carbon coating. 16. Jonkin patenttivaatimuksen 13-15 mukainen menetelmä, jossa litiummetallifosfaatti saatetaan kontaktiin nestefaasissa, edullisesti vesifaasissa, litiummetallifosfaatin pinnalle kerrostetun hiililähteen kanssa ja hiililähde muunnetaan hiilipäällysteeksi lämmittämällä inertissä ilmakehässä, esimerkiksi inertissä argonista koostuvassa ilmakehässä, tai inertissä argonilmakehässä, joka sisältää pelkistävää kaasua, kuten H2.A process according to any one of claims 13 to 15, wherein the lithium metal phosphate is contacted in a liquid phase, preferably an aqueous phase, with a carbon source deposited on the lithium metal phosphate and the carbon source is converted to a carbon coating by heating in an inert atmosphere such as inert 17. Menetelmä, jossa ainakin yksi, edullisesti kaikki, seuraavista vaiheistaA process comprising at least one, preferably all, of the following steps - tuotetaan puhdistettua litiumbikarbonaattia sisältävä liuos,- producing a solution containing purified lithium bicarbonate, - saatetaan litiumbikarbonaatti liuoksessa reagoimaan metalli-ionien ja fosfaattiionien kanssa kiinteän saostuman valmistamiseksi,- reacting the lithium bicarbonate in solution with metal ions and phosphate ions to form a solid precipitate, - erotetaan kiintoaineet erotetaan litiumbikarbonaattia sisältävästä liuoksesta kiintoaine-neste-erotuksella,- separating the solids from the solution containing lithium bicarbonate by solid-liquid separation, - otetaan talteen litiummetallifosfaattikiintoaineet, ja valinnaisesti seuraavat vaiheet- recovering the lithium metal phosphate solids, and optionally the following steps - litiumfosfaatti sekoitetaan hiililähteen kanssa, jalithium phosphate is mixed with the carbon source, and - seos lämmitetään hiililähteen muuntamiseksi hiilipäällysteeksi hiilipäällystetyn litiummetallifosfaatin valmistamiseksi, suoritetaan jatkuvana prosessina.heating the mixture to convert the carbon source to a carbon coating to produce carbon coated lithium metal phosphate is performed in a continuous process. 18. Jonkin patenttivaatimuksen 13-17 mukainen menetelmä, jossa hiililähde valitaan ryhmästä, joka koostuu glukoosista, fruktoosista, sukroosista, maltoosista, dekstroosista, sakkaroosista, askorbiinihaposta, pantoteenihaposta, natriumaskorbaatista, kalsiumaskorbaatista, kaliumaskorbaatista, askorbyylipalmitaatista, askorbyylistearaatista, pteridiinihaposta, paraminobentsoehaposta, glutamiinihaposta, pteroyyliglutamiinihaposta ja jostain näiden seoksesta.18. A method according to any one of claims 13-17, wherein the carbon source is selected from the group consisting of glucose, fructose, sucrose, maltose, dextrose, sucrose, ascorbic acid, pantothenic acid, sodium ascorbate, calcium ascorbate, kaliumaskorbaatista, ascorbyl palmitate, ascorbyl stearate, pteroic, paraminobentsoehaposta, glutamic acid, pteroyyliglutamiinihaposta and some mixture of these. 19. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, jossa litiumbikarbonaattiliuo sThe method of any preceding claim, wherein the lithium bicarbonate solution is s - saadaan uuttamalla litiumraaka-aineita tai puhdistamalla teollislaatuista litiumkarbonaattiliuosta, ja- obtained by extraction of the lithium raw materials or purification of an industrial grade lithium carbonate solution, and - näin saatua litiumbikarbonaattiliuosta käytetään sellaisenaan, vaihtoehtoisesti puhdistuksen jälkeen, ei-johtavan litiummetallifosfaatin valmistamiseen.the lithium bicarbonate solution thus obtained is used as such, alternatively after purification, for the preparation of non-conductive lithium metal phosphate. 20. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, jossa litiummetallifosfaatti valmistetaan litiumbikarbonaatista, joka saadaan litiumraaka-aineista ilman litiumbikarbonaatin välimuuntamista toiseksi litiumyhdisteeksi, esimerkiksi saostamalla.The process according to any one of the preceding claims, wherein the lithium metal phosphate is prepared from lithium bicarbonate obtained from lithium raw materials without conversion of lithium bicarbonate to another lithium compound, for example by precipitation. 1010 21. Jonkin patenttivaatimuksen 13-20 mukaisen menetelmän käyttö akun katodimateriaaliksi soveltuvan hiilipäällystetyn litiummetallifosfaatin tuottamiseksi.Use of a process according to any one of claims 13 to 20 for the production of carbon-coated lithium metal phosphate suitable as a cathode battery material. 22. Patenttivaatimuksen 21 mukainen käyttö, jossa litiummetallifosfaattikatodia käytetään akussa, joka käsittää ainakin yhden sähkökemiallisen kennon, joka käsittää katodin jaUse according to claim 21, wherein the lithium metal phosphate cathode is used in a battery comprising at least one electrochemical cell comprising a cathode and 15 anodin.15 anodes.
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US6048507A (en) 1997-12-09 2000-04-11 Limtech Process for the purification of lithium carbonate
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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
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CN102947225A (en) 2010-02-17 2013-02-27 辛博尔股份有限公司 Processes for preparing highly pure lithium carbonate and other highly pure lithium containing compounds
CA2810132C (en) 2010-09-03 2015-03-17 Showa Denko K.K. Method for producing lithium metal phosphate
KR102156726B1 (en) 2011-08-29 2020-09-16 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Method of manufacturing positive electrode active material for lithium ion battery
CN102332581B (en) 2011-10-20 2013-06-19 四川天齐锂业股份有限公司 Method for producing lithium ferrous phosphate by using lithium mine as lithium source
CN102496711B (en) 2011-12-13 2013-04-10 海门容汇通用锂业有限公司 Method for preparing micron-level lithium iron phosphate with large specific surface area
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EA201491632A1 (en) 2012-03-19 2015-03-31 Оутотек (Финлэнд) Ой METHOD FOR EXTRACTING LITHIUM CARBONATE
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