WO2014061892A1 - Novel method of preparing olivine-type electrode material using formic acid derivative - Google Patents

Novel method of preparing olivine-type electrode material using formic acid derivative Download PDF

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WO2014061892A1
WO2014061892A1 PCT/KR2013/005304 KR2013005304W WO2014061892A1 WO 2014061892 A1 WO2014061892 A1 WO 2014061892A1 KR 2013005304 W KR2013005304 W KR 2013005304W WO 2014061892 A1 WO2014061892 A1 WO 2014061892A1
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olivine
electrode material
group
type electrode
elements
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French (fr)
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Seong Jae Lim
Sei Ung Park
Kyu Ho Song
Kee Do Han
Ki Taeg Jung
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Hanwha Chemical Corporation
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    • 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
    • H01M4/04—Processes of manufacture in general
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/008—Processes carried out under supercritical conditions
    • 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
    • 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
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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 a novel method of preparing an olivine-type electrode material using a formic acid derivative.
  • lithium secondary batteries are broad-sense secondary batteries including secondary batteries using lithium metal and lithium ion secondary batteries.
  • a lithium secondary battery is one of the most remarkable secondary batteries because it has high voltage and high energy density.
  • Such a lithium secondary battery essentially includes three constituents of a cathode, an anode and an electrolyte.
  • dry calcination, wet precipitation or the like has been used as a method of preparing an electrode material for a cathode or an anode.
  • an electrode material is prepared by a process including the steps of: mixing a transition metal oxide or hydroxide such as cobalt (Co) oxide or hydroxide with lithium carbonate or lithium hydroxide as a lithium supply source; and calcinating the mixture at a high temperature of 700 to 1000°C for 5 to 48 hours.
  • the dry calcination is advantageous in that it can easily conducted because it has been used traditionally and frequently in order to prepare metal oxides, but is disadvantageous in that it is difficult to obtain single-phase products because raw materials are difficult to uniformly mix, and in that, in the case of a multi-component electrode material consisting of two or more kinds of transition metals, it is difficult to uniformly arrange two or more kinds of elements at an atomic level.
  • an electrode material is prepared by a process including the steps of: dissolving a transition metal (cobalt (Co) or the like)-containing salt in water and then adding an alkali to the solution to form a transition metal hydroxide precipitate; filtering and drying the precipitate; mixing the filtered and dried precipitate with lithium carbonate or lithium hydroxide as a lithium supply source; and calcinating the mixture at a high temperature of 700 to 1000°C for 1 to 48 hours.
  • the wet precipitation is known to easily obtain a uniform mixture by coprecipitating two or more kinds of transition metals, but is problematic in that the precipitation reaction must be conducted for a long period of time, processes are complicated, and waste acids and the like are formed as side products.
  • sucrose was generally used as a reductant.
  • a reductant sucrose or the like
  • a filter or a concentrator is plugged during a feed supply process, a feed synthesis process or a subsequent process, and thus it is difficult to continuously operate processes for a long period of time.
  • the severest problem is that non-degradable chemical oxygen demand (COD)-causing materials are generated by high-temperature decomposition during a synthesis reaction process, and thus the COD in wastewater become high, thereby increasing the cost and time necessary for wastewater treatment.
  • COD chemical oxygen demand
  • an object of the present invention is to provide a method of preparing an olivine-type electrode material, which can prevent the oxidation of a raw material in a raw material supply process because a novel reductant is used in an olivine-type electrode material synthesis process using high-temperature and high-pressure hydrothermal synthesis, which can prevent a pipe arrangement from being plugged because the novel reductant is completely decomposed to inhibit the formation of side products, and which can prevent a filter or a concentrator from being plugged in subsequent processes.
  • Another object of the present invention is to provide a method of preparing an olivine-type electrode material, wherein wastewater treatment equipment is not required because the COD in wastewater is lowered by the complete decomposition of the novel reductant, so a post-treatment process can be simplified, and process costs can be greatly reduced at the time of mass production.
  • Still another object of the present invention is to provide a method of preparing an olivine-type electrode material, which can provide an olivine-type electrode material having excellent electrochemical characteristics because the oxidation of a raw material can be prevented by the complete decomposition of the novel reductant in a synthesis process.
  • an aspect of the present invention provides a method of preparing an olivine-type electrode material using hydrothermal synthesis, including the steps of: (a) providing a raw material mixture including a metal precursor of at least one selected from among group II elements, transition metals, group XII elements and group XIII elements, a lithium precursor, an alkalinizing agent and a reductant represented by Formula 1 below; and (b) mixing and reacting the raw material mixture with high-temperature and high-pressure water to prepare an olivine-type electrode material:
  • R is a hydrogen atom, or , and R’ is an alkyl group of C 1 to C 30 .
  • Another aspect of the present invention provides a method of preparing an olivine-type electrode material using hydrothermal synthesis, including the steps of: (a-1) providing a nonbasic mixture including a metal precursor of at least one selected from among group II elements, transition metals, group XII elements and group XIII elements, and a reductant represented by Formula 1 below; (a-2) providing a basic mixture including a lithium precursor and an alkalizing agent; and (b-1) mixing and reacting the nonbasic mixture and the basic mixture with high-temperature and high-pressure water to prepare an olivine-type electrode material:
  • R is a hydrogen atom, or , and R’ is an alkyl group of C 1 to C 30 .
  • the reductant may be at least one selected from among formic acid, formic anhydride, and acetic formic anhydride.
  • the raw material mixture may further include a polyacid compound.
  • the nonbasic mixture may further include a polyacid compound.
  • the polyacid compound may be at least one selected from the group consisting of H 3 PO 4 , NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 and P 2 O 5 .
  • the transition metal precursor may be a precursor of at least one selected from among Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo.
  • the iron (Fe) precursor may be at least one selected from the group consisting of FeSO 4 ⁇ 7H 2 O, FeC 2 O 4 ⁇ 2H 2 O and FeCl 2 .
  • the lithium (Li) precursor may be at least one selected from the group consisting of Li 2 CO 3 , LiOH, LiOH ⁇ H 2 O and LiNO 3 .
  • the alkalinizing agent may be at least one selected from the group consisting of alkali metal hydroxides, alkali earth-metal hydroxides and ammonia compounds.
  • the step of preparing the olivine-type electrode material may be performed at a pressure of 150 to 700 bar and a temperature of 200 to 700°C.
  • the step of preparing the olivine-type electrode material may be performed under a subcritical condition or a supercritical condition, and preferably under a supercritical condition.
  • the high-temperature and high-pressure water may be subcritical water or supercritical water, and preferably supercritical water.
  • the olivine-type electrode material is a cathode active material.
  • the olivine-base electrode material may be represented by Formula 2 below:
  • M may be represented by Formula 3 below, and A may be P, Ti, V, Si or the like:
  • M A may be at least one selected from the group consisting of group II elements
  • M B may be selected from the group consisting of group XIII elements
  • M T may be at least one selected from the group consisting of Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo, 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.575, 0 ⁇ t ⁇ 1, 0 ⁇ (a+b) ⁇ 1, and 0 ⁇ (a+b+t) ⁇ 1.
  • the method may be performed by a continuous reaction apparatus or a batch reaction apparatus, and preferably a continuous reaction apparatus.
  • the present invention can provide a method of preparing an olivine-type electrode material, which can prevent the oxidation of a raw material in a raw material supply process because a novel reductant is used in an olivine-type electrode material synthesis process using high-temperature and high-pressure hydrothermal synthesis, which can prevent a pipe arrangement from being plugged because the novel reductant is completely decomposed to inhibit the formation of side products, and which can prevent a filter or a concentrator from being plugged in subsequent processes.
  • the present invention can provide a method of preparing an olivine-type electrode material, wherein wastewater treatment equipment is not required because the COD in wastewater is lowered by the complete decomposition of the novel reductant, so a post-treatment process can be simplified, and process costs can be greatly reduced at the time of mass production.
  • the present invention can provide a method of preparing an olivine-type electrode material, which can provide an olivine-type electrode material having excellent electrochemical characteristics because the oxidation of a raw material can be prevented by the complete decomposition of the novel reductant in a synthesis process.
  • FIG. 1 is a graph showing XRD data of a crystal structure of LiFePO 4 synthesized in Example 1;
  • FIG. 2 shows a photograph (FIG. 2(b)) of wastewater of Example 1 and a photograph (FIG. 2(a)) of wastewater of Comparative Example 1.
  • a singular number includes a plural number as long as they are not clearly different from each other, and the terms “have”, “include”, “comprise” and the like are used to differentiate a certain component from other components, but the configuration of such components should not be construed to be limited by the terms.
  • high-temperature and high-pressure water means a stream including the high-temperature and high-pressure water without relation to the name thereof.
  • alkyl group means an aliphatic hydrocarbon group unless otherwise specified.
  • the alkyl group may be a saturated alkyl group that does not have any double bond and triple bond. Further, the alkyl group may be an unsaturated alkyl group that has at least one double bond or triple bond. Further, the alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group.
  • the alkyl group may be an alkyl group of C 1 to C 30 or an alkyl group of C 1 to C 20 . More preferably, the alkyl group may be an alkyl group of C 1 to C 10 , C 1 to C 6 or C 1 to C 3 .
  • transition metal includes cadmium (Cd) and mercury (Hg) unless otherwise specified.
  • olivine-type electrode material (a) providing a raw material mixture including a metal precursor of at least one selected from among group II elements, transition metals, group XII elements and group XIII elements, a lithium precursor, an alkalinizing agent and a reductant represented by Formula 1 below; and (b) mixing and reacting the raw material mixture with high-temperature and high-pressure water to prepare an olivine-type electrode material:
  • R is a hydrogen atom, or , and R’ is an alkyl group of C 1 to C 30 .
  • the process of mixing and reacting the raw material mixture with high-temperature and high-pressure water can be performed by various methods.
  • step (a) is conducted, and then, in step (b), the raw material mixture of step (a) is mixed and reacted with high-temperature and high-pressure water.
  • step (a) and step (b) are conducted at the same place and time, and thus a metal precursor of at least one selected from among group II elements, transition metals, group XII elements and group XIII elements, a lithium precursor, an alkalinizing agent and a reductant represented by Formula 1 above are mixed and reacted with high-temperature and high-pressure water.
  • a method of preparing an olivine-type electrode material using hydrothermal synthesis includes the steps of: (a-1) providing a nonbasic mixture including a metal precursor of at least one selected from among group II elements, transition metals, group XII elements and group XIII elements, and a reductant represented by Formula 1 above; (a-2) providing a basic mixture including a lithium precursor and an alkalizing agent; and (b-1) mixing and reacting the nonbasic mixture and the basic mixture with high-temperature and high-pressure water to prepare an olivine-type electrode material.
  • the process of mixing and reacting the nonbasic mixture and the basic mixture with high-temperature and high-pressure water can be performed by various methods.
  • step (a-1) and step (a-2) are conducted, and then, in step (b-1), the nonbasic mixture of step (a-1) and the basic mixture of step (a-2) are mixed and reacted with high-temperature and high-pressure water.
  • step (a-1), step (a-2) and step (b-1) are conducted at the same place and time, and thus a metal precursor of at least one selected from among group II elements, transition metals, group XII elements and group XIII elements, a lithium precursor, an alkalinizing agent and a reductant represented by Formula 1 above are mixed and reacted with high-temperature and high-pressure water.
  • a raw material mixture including a metal precursor of at least one selected from among group II elements, transition metals, group XII elements and group XIII elements, a lithium precursor, an alkalinizing agent and a reductant represented by Formula 1 above is provided (step (a)).
  • a raw material solution which is obtained by dissolving a raw material of an olivine-type electrode material in water, may be used.
  • step (a) may be divided into step (a-1) of providing a nonbasic mixture including the metal precursor and the reductant represented by Formula 1 above, and step (a-2) of providing a basic mixture including the lithium precursor and the alkalizing agent.
  • a nonbasic mixture a nonbasic mixture solution, which is obtained by dissolving a nonbasic raw material of an olivine-type electrode material in water, may be used.
  • a basic mixture solution which is obtained by dissolving a basic raw material of an olivine-type electrode material in water, may be used.
  • a reductant can be used in order to prevent the oxidation of a precursor or the like of a raw material of an olivine-type electrode material during a hydrothermal synthesis reaction process and to prevent the oxidation of the prepared olivine-type electrode material.
  • oxalic acid sucrose, fructose, ascorbic acid (vitamin C) or the like was used.
  • a carbon-containing material such as sucrose or the like, was added and used in an amount of 1 to 30 wt% based on the weight of a metal precursor.
  • a formic acid derivative represented by Formula 1 above may be used as a reductant.
  • formic acid, formic anhydride, acetic formic anhydride or a combination thereof may be used as the reductant.
  • formic acid may be used as the reductant.
  • the novel reductant is used in the process of preparing an olivine-type electrode material using hydrothermal synthesis at high temperature and high pressure, the oxidation of a raw material is prevented in a raw material supply process, and the formation of side products is prevented due to the complete decomposition of the novel reductant, so that it is possible to prevent a pipe arrangement from being plugged, and it is possible to prevent a filter or concentrator from being plugged in subsequent processes.
  • the novel reductant since the novel reductant is completely decomposed, the COD in wastewater becomes low, and thus wastewater treatment equipment is not additionally required, so that post-treatment processes can be simplified, and operation costs can be greatly reduced at the time of mass production.
  • the amount of the novel reductant is not limited. However, in consideration of the COD value in wastewater and economical efficiency, the amount thereof may be 0.01 ⁇ 50 wt%, preferably 0.05 ⁇ 40 wt%, and more preferably 0.1 ⁇ 30 wt%, based on the amount of the metal precursor. When the amount thereof is less than 0.01 wt%, a reduction effect may be insufficient. Further, when the amount thereof is more than 50 wt%, the COD value in waste water may become high.
  • the oxidation of a raw material can be prevented by the complete decomposition of the novel reductant in a synthesis process, and thus an olivine-type electrode material having excellent electrochemical characteristics can be synthesized.
  • the metal precursor precursors of group II elements, transition metals, group XII elements and group XIII elements may be used, independently or in a combination thereof.
  • the transition metal includes zinc (Zn), cadmium (Cd) and mercury (Hg).
  • transition metal precursor precursors of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo may be used independently or in a combination thereof.
  • the metal precursor compound is not limited as long as it is a salt containing the metal and is a compound that can be ionized.
  • the metal precursor compound may be a water-soluble compound.
  • the transition metal precursor compound may include a metal alkoxide, a metal nitrate, a metal acetate, a metal halogenide, a metal hydroxide, a metal oxide, a metal carbonate, a metal oxalate, a metal sulfate, and combinations thereof.
  • a metal nitrate, a metal sulfate and a metal acetate may be used.
  • compounds including the transition metals or combination thereof for example, Ni-Mn, Ni-Co, Ni-Mn-Co, etc. may also be used.
  • iron (Fe) precursor FeSO 4 ⁇ 7H 2 O, FeC 2 O 4 ⁇ 2H 2 O, FeCl 2 or a combination thereof, and preferably FeSO 4 , may be used.
  • step (a) may be divided into step (a-1) of providing a nonbasic mixture including the metal precursor and the reductant represented by Formula 1 above, and step (a-2) of providing a basic mixture including the lithium precursor and the alkalizing agent.
  • water may be used in an amount 3 to 100 times, preferably, 4 to 200 times the total weight of the iron (Fe) precursor and the following polyacid compound.
  • the raw material mixture in the step (a) may further include a polyacid compound, and the nonbasic mixture in the step (a-1) may also further include a polyacid compound.
  • the polyacid compound may include at least one element selected from among P, Ti, V and Si.
  • H 3 PO 4 NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 , P 2 O 5 or a combination thereof, preferably H 3 PO 4 , may be used.
  • This polyacid compound may be used as a raw material of an olivine-type electrode material.
  • lithium (Li) precursor Li 2 CO 3 , Li(OH), Li(OH) ⁇ H 2 O, LiNO 3 or a combination thereof may be used.
  • the lithium (Li) precursor is not limited thereto.
  • the basic mixture may be provided in the form of an aqueous solution.
  • water may be used in an amount of 10 to 1000 times, preferably, 100 to 700 times the weight of the lithium (Li) precursor.
  • the raw material mixture of an olivine-type electrode material may be provided in the form of an aqueous solution.
  • water may be used in an amount of 10 to 1200 times, preferably, 100 to 900 times the weight of the lithium (Li) precursor.
  • the alkalinizing agent may be at least one selected from the group consisting of alkali metal hydroxides, alkali earth-metal hydroxides and ammonia compounds.
  • the alkalizing agent serves to provide a condition under which one or more transition metal compounds are hydrolyzed into transition metal oxides to be easily precipitated, and is not particularly limited as long as it can make a reaction solution into an alkaline reaction solution.
  • the alkalizing agent may include alkali metal hydroxides (NaOH, KOH, etc.), alkali earth-metal hydroxides (Ca(OH) 2 , Mg(OH) 2 , etc.), ammonia compounds (ammonia water, ammonium nitrate, etc.), and mixtures thereof.
  • the metal compound be a nitrate
  • the alkalizing agent be an ammonia compound.
  • the reason for this is that most nitrate ions, which are obtained as side products, can be decomposed in the same process, and residual nitrate ions can also be easily removed by water-washing, drying or calcination in a subsequent process after a synthesis process.
  • the alkalizing agent may be included in the same amount as that of a catalyst for reaction.
  • the method of preparing an olivine-type electrode material according to the present invention includes the step (b) of mixing and reacting a raw material mixture with high-temperature and high-pressure water to prepare an olivine-type electrode material, wherein the raw material includes a metal precursor of at least one selected from among group II elements, transition metals, group XII elements and group XIII elements, a lithium precursor, an alkalinizing agent and a reductant represented by Formula 1 above.
  • the method of preparing an olivine-type electrode material according to the present invention may include the steps of: providing the nonbasic mixture; providing the basic mixture; and mixing and reacting the nonbasic mixture and the basic mixture with high-temperature and high-pressure water to prepare an olivine-type electrode material.
  • the high-temperature and high-pressure water may be subcritical water or supercritical water, and preferably supercritical water.
  • the high-temperature and high-pressure water means a stream including the high-temperature and high-pressure water without relation to the name thereof.
  • the subcritical water means a stream including the subcritical water without relation to the name thereof
  • the supercritical water means a stream including the supercritical water without relation to the name thereof.
  • the step (b) of preparing the olivine-type electrode material may be performed at a pressure of 150 to 700 bar, preferably, 230 to 400 bar, and at a temperature of 200 to 700°C, preferably 250 to 500°C.
  • a pressure of 150 bar preferably, 230 to 400 bar
  • a temperature of 200 to 700°C preferably 250 to 500°C.
  • step (b) when the step (b) is performed at a temperature of lower than 200°C, it is difficult to synthesize nanosized particles, and when the step (b) is performed at a temperature of higher than 700°C, equipment cost is excessively increased because equipment is additionally required.
  • the step (b) of preparing the olivine-type electrode material may be performed under a subcritical condition or a supercritical condition, and preferably under a supercritical condition.
  • the supercritical point of water is 374°C and 220 bar.
  • supercritical water means water existing under the condition of a temperature of 374°C or higher, and preferably may exist at a pressure of 220 bar or higher.
  • subcritical water means water existing under the condition of a temperature of 250°C or higher, and preferably may exist at a pressure of 200 bar or higher.
  • the olivine-type electrode material prepared by the method of the present invention can be obtained in the form of a slurry at the rear end of the apparatus.
  • reaction apparatus for conducting a hydrothermal reaction a batch reaction apparatus or a continuous (fluidized) reaction apparatus, and preferably a continuous reaction apparatus, may be used.
  • the olivine-type electrode material may be a cathode active material.
  • olivine-base electrode material may be represented by Formula 2 below:
  • M may be represented by Formula 3 below, and A may be P, Ti, V, Si or the like:
  • M A may be at least one selected from the group consisting of group II elements
  • M B may be selected from the group consisting of group XIII elements
  • M T may be at least one selected from the group consisting of Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo, 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.575, 0 ⁇ t ⁇ 1, 0 ⁇ (a+b) ⁇ 1, and 0 ⁇ (a+b+t) ⁇ 1.
  • Iron sulfate (FeSO 4 ⁇ 7H 2 O), phosphoric acid (H 3 PO 4 ) and formic acid were mixed such that the molar ratio of phosphoric acid (H 3 PO 4 ) to iron sulfate (FeSO 4 ⁇ 7H 2 O) was 1:1 and the weight ratio of formic acid to iron sulfate (FeSO 4 ⁇ 7H 2 O) was 0.1 wt%, so as to obtain an aqueous solution of iron sulfate (FeSO 4 ⁇ 7H 2 O), phosphoric acid (H 3 PO 4 ) and formic acid.
  • ammonia water and lithium hydroxide were mixed such that the molar ratio of ammonia water to iron sulfate (FeSO 4 ⁇ 7H 2 O) was 1:1.1 and the molar ratio of lithium hydroxide (LiOH ⁇ H 2 O) to iron sulfate (FeSO 4 ⁇ 7H 2 O) was 1:2, so as to obtain another aqueous solution of ammonia water and lithium hydroxide (LiOH ⁇ H 2 O).
  • the two aqueous solutions were respectively pressurized and pumped into a mixer at a flow rate of 8 g/min at a pressure of 250 bar at room temperature, and were then mixed in the mixer to form a lithium iron phosphate (LiFePO 4 ) precursor.
  • LiFePO 4 lithium iron phosphate
  • Ultrapure water heated to about 450°C was pressurized and pumped into the mixer at a flow rate of 96 g/min at a pressure of 250 bar, and was then mixed with the lithium iron phosphate (LiFePO 4 ) precursor to form a mixed solution.
  • the mixed solution was introduced into a reactor at 386°C and 250 bar to obtain lithium iron phosphate (LiFePO 4 ), and then the LiFePO 4 -containing stream was introduced into a heat exchanger to be cooled to 50°C.
  • the cooled LiFePO 4 -containing stream was introduced into a concentrator to be concentrated such that the amount of LiFePO 4 particles was 20 wt%, so as to prepare a LiFePO 4 cathode active material.
  • a LiFePO 4 cathode active material was prepared in the same manner as in Example 1, except that the weight ratio of formic acid to iron sulfate (FeSO 4 ⁇ 7H 2 O) was adjusted to 10 wt% to obtain an aqueous solution of iron sulfate (FeSO 4 ⁇ 7H 2 O), phosphoric acid (H 3 PO 4 ) and formic acid.
  • the XRD-Rietveld analysis of the LiFePO 4 powder was conducted. As a result, it can be ascertained that the LiFePO 4 powder exists in the form of single-phase LiFePO 4 crystals having no defect structure.
  • a LiFePO 4 cathode active material was prepared in the same manner as in Example 1, except that the weight ratio of formic acid to iron sulfate (FeSO 4 ⁇ 7H 2 O) was adjusted to 30 wt% to obtain an aqueous solution of iron sulfate (FeSO 4 ⁇ 7H 2 O), phosphoric acid (H 3 PO 4 ) and formic acid.
  • the XRD-Rietveld analysis of the LiFePO 4 powder was conducted. As a result, it can be ascertained that the LiFePO 4 powder exists in the form of single-phase LiFePO 4 crystals having no defect structure.
  • a LiFePO 4 cathode active material was prepared in the same manner as in Example 1, except that formic anhydride was used as a reductant instead of formic acid, and the weight ratio of formic anhydride to iron sulfate (FeSO 4 ⁇ 7H 2 O) was adjusted to 10 wt% to obtain an aqueous solution of iron sulfate (FeSO 4 ⁇ 7H 2 O), phosphoric acid (H 3 PO 4 ) and formic anhydride.
  • the XRD-Rietveld analysis of the LiFePO 4 powder was conducted. As a result, it can be ascertained that the LiFePO 4 powder exists in the form of single-phase LiFePO 4 crystals having no defect structure.
  • a LiFePO 4 cathode active material was prepared in the same manner as in Example 1, except that acetic formic anhydride was used as a reductant instead of formic acid, and the weight ratio of acetic formic anhydride to iron sulfate (FeSO 4 ⁇ 7H 2 O) was adjusted to 10 wt% to obtain an aqueous solution of iron sulfate (FeSO 4 ⁇ 7H 2 O), phosphoric acid (H 3 PO 4 ) and acetic formic anhydride.
  • the XRD-Rietveld analysis of the LiFePO 4 powder was conducted. As a result, it can be ascertained that the LiFePO 4 powder exists in the form of single-phase LiFePO 4 crystals having no defect structure.
  • a LiFePO 4 cathode active material was prepared in the same manner as in Example 1, except that sucrose was used as a reductant instead of formic acid, and the weight ratio of sucrose to iron sulfate (FeSO 4 ⁇ 7H 2 O) was adjusted to 10 wt% to obtain an aqueous solution of iron sulfate (FeSO 4 ⁇ 7H 2 O), phosphoric acid (H 3 PO 4 ) and sucrose.
  • the present invention can provide a method of preparing an olivine-type electrode material, which can prevent the oxidation of a raw material in a raw material supply process because a novel reductant is used in an olivine-type electrode material synthesis process using high-temperature and high-pressure hydrothermal synthesis, which can prevent a pipe arrangement from being plugged because the novel reductant is completely decomposed to inhibit the formation of side products, and which can prevent a filter or a concentrator from being plugged in subsequent processes.
  • the present invention can provide a method of preparing an olivine-type electrode material, wherein wastewater treatment equipment is not required because the COD in wastewater is lowered by the complete decomposition of the novel reductant, so a post-treatment process can be simplified, and process costs can be greatly reduced at the time of mass production.
  • the present invention can provide a method of preparing an olivine-type electrode material, which can provide an olivine-type electrode material having excellent electrochemical characteristics because the oxidation of a raw material can be prevented by the complete decomposition of the novel reductant in a synthesis process.

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PCT/KR2013/005304 2012-10-17 2013-06-17 Novel method of preparing olivine-type electrode material using formic acid derivative WO2014061892A1 (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
FR3054541A1 (fr) * 2016-08-01 2018-02-02 Centre National De La Recherche Scientifique Procede de preparation d'arsenates et/ou de phosphates de metaux de transition de structure olivine

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EP1094532A1 (en) * 1999-04-06 2001-04-25 Sony Corporation Method for manufacturing active material of positive plate and method for manufacturing nonaqueous electrolyte secondary cell
US20010055718A1 (en) * 2000-04-25 2001-12-27 Guohua Li Positive electrode active material and non-aqueous electrolyte cell
JP2011001221A (ja) * 2009-06-18 2011-01-06 Toyota Motor Corp 窒化リン酸リチウム化合物含有シートの製造方法
US20110037019A1 (en) * 2008-04-25 2011-02-17 Sumitomo Osaka Cement Co.,Ltd. Method for producing cathode active material for lithium ion batteries, cathode active material for lithium ion batteries obtained by the production method, lithium ion battery electrode, and lithium ion battery
JP2011213587A (ja) * 2010-03-19 2011-10-27 Toda Kogyo Corp リン酸マンガン鉄リチウム粒子粉末の製造方法、リン酸マンガン鉄リチウム粒子粉末、及び該粒子粉末を用いた非水電解質二次電池

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Publication number Priority date Publication date Assignee Title
EP1094532A1 (en) * 1999-04-06 2001-04-25 Sony Corporation Method for manufacturing active material of positive plate and method for manufacturing nonaqueous electrolyte secondary cell
US20010055718A1 (en) * 2000-04-25 2001-12-27 Guohua Li Positive electrode active material and non-aqueous electrolyte cell
US20110037019A1 (en) * 2008-04-25 2011-02-17 Sumitomo Osaka Cement Co.,Ltd. Method for producing cathode active material for lithium ion batteries, cathode active material for lithium ion batteries obtained by the production method, lithium ion battery electrode, and lithium ion battery
JP2011001221A (ja) * 2009-06-18 2011-01-06 Toyota Motor Corp 窒化リン酸リチウム化合物含有シートの製造方法
JP2011213587A (ja) * 2010-03-19 2011-10-27 Toda Kogyo Corp リン酸マンガン鉄リチウム粒子粉末の製造方法、リン酸マンガン鉄リチウム粒子粉末、及び該粒子粉末を用いた非水電解質二次電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3054541A1 (fr) * 2016-08-01 2018-02-02 Centre National De La Recherche Scientifique Procede de preparation d'arsenates et/ou de phosphates de metaux de transition de structure olivine
WO2018024979A1 (fr) * 2016-08-01 2018-02-08 Centre National De La Recherche Scientifique Procédé de préparation d'arséniates et/ou de phosphates de métaux de transition de structure olivine

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KR20140050125A (ko) 2014-04-29
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TWI481104B (zh) 2015-04-11

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