WO2020111404A1 - Procédé de fabrication d'oxyde de lithium-métal de transition utilisant un analogue de bleu de prusse, oxyde de lithium-métal de transition et batterie rechargeable au lithium - Google Patents

Procédé de fabrication d'oxyde de lithium-métal de transition utilisant un analogue de bleu de prusse, oxyde de lithium-métal de transition et batterie rechargeable au lithium Download PDF

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WO2020111404A1
WO2020111404A1 PCT/KR2019/004680 KR2019004680W WO2020111404A1 WO 2020111404 A1 WO2020111404 A1 WO 2020111404A1 KR 2019004680 W KR2019004680 W KR 2019004680W WO 2020111404 A1 WO2020111404 A1 WO 2020111404A1
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transition metal
lithium
metal oxide
formula
pba
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Korean (ko)
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송태섭
박현중
김정헌
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한양대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/60—Compounds characterised by their crystallite size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/38—Particle morphology extending in three dimensions cube-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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 secondary battery, and more particularly, to a lithium secondary battery.
  • Secondary battery refers to a battery that can be used repeatedly because it can be charged as well as discharge.
  • the representative lithium secondary battery among the secondary batteries is the lithium ions contained in the positive electrode active material is transferred to the negative electrode through the electrolyte and then inserted into the layered structure of the negative electrode active material (charging), and then the lithium ions that have been inserted into the layered structure of the negative electrode active material again It works through the principle of returning to the anode (discharging).
  • These lithium secondary batteries are currently commercialized and used as small power sources such as mobile phones and notebook computers, and are expected to be used as large power sources such as hybrid vehicles, and the demand is expected to increase.
  • a typical lithium transition metal oxide mainly used as a positive electrode active material in a lithium secondary battery has a disadvantage of high rate characteristics, that is, low output characteristics.
  • the problem to be solved by the present invention is to provide a new method for manufacturing a lithium transition metal oxide used as a positive electrode active material for a lithium secondary battery, and to provide a lithium transition metal oxide capable of improving the high rate characteristics of a lithium secondary battery. .
  • an aspect of the present invention provides a method for manufacturing a lithium-transition metal oxide.
  • the method for producing a lithium-transition metal oxide includes forming prussian blue analogue (hereinafter referred to as PBA) particles represented by Chemical Formula 1 below.
  • PBA particles are dispersed in an aqueous solution in which lithium salt is dissolved, filtered and dried to coat the PBA particles with lithium salt.
  • the lithium salt-coated PBA particles are oxidized or pyrolyzed in an air atmosphere to change CN bridges (-CN-) in the PBA to oxygen bridges (-O-).
  • the result of the oxidation step is calcined to obtain a lithium-transition metal oxide.
  • M 1 and M 2 are transition metals having a divalent oxidation number and are Ni, Mn, Co, Fe, Ti, V, or Cr regardless of each other, and M 3 is a transition metal having a trivalent oxidation number.
  • Ni, Mn, Co, Fe, Ti, V, or Cr, c is 1 to 5, and a and b have positive values to make the compound of Formula 1 electrically neutral.
  • the aqueous solution of the salt of the first transition metal and the salt of the second transition metal may further include sodium citrate.
  • the lithium salt may be LiOH.
  • the PBA particles coated with the lithium salt are dispersed in an aqueous transition metal precursor solution, filtered and dried to form PBA particles coated with a lithium salt and a transition metal precursor in turn.
  • the transition metal precursor may include precursors of transition metals constituting the PBA.
  • the pyrolysis temperature may be 400 to 500 degrees.
  • a phase transition occurs in the calcination step, and the calcination step includes a primary calcination step and a secondary calcination step, and may include a cooling step between the primary calcination step and the secondary calcination step.
  • the primary calcination may be performed at 800 to 900 degrees, and the secondary calcination may be performed at 750 to 850 degrees.
  • the lithium-transition metal oxide may be a lithium-transition metal oxide represented by the following Chemical Formula 2.
  • the ratio of x:y:z may be the same as the ratio of a:b:c in Formula 1.
  • the lithium-transition metal oxide has a regular shape of a particle and is represented by the following Chemical Formula 2.
  • the lithium transition metal oxide exhibits a hexagonal layered structure in which the transition metal oxide layer and the lithium layer are arranged repeatedly, and in the crystal of the lithium transition metal oxide, the c-axis length is larger than the a-axis length.
  • the c-axis length/a-axis length represents a value of 1.4 to 1.5.
  • M 1 may be Ni
  • M 2 may be Mn
  • M 3 may be Co
  • the lithium secondary battery may include a positive electrode including a positive electrode active material, which is a lithium-transition metal oxide defined by Chemical Formula 2; A negative electrode containing a negative electrode active material; And an electrolyte disposed between the positive electrode and the negative electrode.
  • a positive electrode active material which is a lithium-transition metal oxide defined by Chemical Formula 2
  • a negative electrode containing a negative electrode active material and an electrolyte disposed between the positive electrode and the negative electrode.
  • the lithium-transition metal oxide produced thereby has a stable structure during charging/discharging, thereby exhibiting excellent battery performance, particularly high rate characteristics. You can...
  • FIG. 1 is a schematic diagram schematically showing an active material manufacturing method according to an embodiment of the present invention.
  • Figure 8 is a graph showing the discharge capacity change according to the rate of crate (c-rate) of the half-cell according to Comparative Example 1, half-cell comparison Example 1, and half-cell comparison.
  • FIG. 1 is a schematic diagram schematically showing an active material manufacturing method according to an embodiment of the present invention.
  • metal hexacyanometallates represented by Chemical Formula 1 may be formed.
  • the metal hexacyanometallate may also be referred to as a prussian blue analogue (hereinafter referred to as PBA).
  • PBA prussian blue analogue
  • the Prussian Blue analog is a type of metal organic structure, and the iron ion is replaced with another metal ion based on the structure (Prussian Blue) formed through chemical bonding between iron and cyano (CN) groups. It means the group of materials.
  • M 1 and M 2 are transition metals having a divalent oxidation number, and may be Ni, Mn, Co, Fe, Ti, V, or Cr regardless of each other, and M 3 is a transition having a trivalent oxidation number
  • the metal may be Ni, Mn, Co, Fe, Ti, V, or Cr.
  • M 1 may be Ni
  • M 2 may be Mn
  • M 3 may be Co
  • c may be 1 to 5.
  • a and b may have a positive value to make the compound of Formula 1 electrically neutral.
  • the PBA may be Ni 2 Mn[Co(CN) 6 ] 2 or NiMn 2 [Co(CN) 6 ] 2 .
  • the PBA may have a particle shape, and the shape of the particle may be, for example, a cube surrounded by a rectangle, and a cube.
  • the cube may mean that all sides have the same length within an error range of 5%, and all angles are equal within an error range of 5%.
  • the PBA represented by Chemical Formula 1 may be formed using a co-precipitation method.
  • an aqueous transition metal salt solution is mixed with an aqueous solution of K 3 M 3 (CN) 6 (M 3 is as defined in Chemical Formula 1), and then the mixed solution is aged to form a precipitate, and the precipitate is filtered to obtain
  • the PBA represented by Chemical Formula 1 can be formed.
  • the transition metal salt may include a salt of a first transition metal (M 1 defined in Formula 1) and a salt of a second transition metal (M 2 defined in Formula 1).
  • the first transition metal and the second transition metal may be the same or different transition metals.
  • the salt of the first transition metal and the salt of the second transition metal may be nitrate or sulfate regardless of each other.
  • the aqueous transition metal salt solution may further include a shape control agent.
  • the shape control agent serves to help form a Prussian blue crystal structure, and may be PVP (Polyvinylpyrrolidone), PDDA (Poly(diallyldimethylammonium chloride)), CTAB (Cetyl trimethylammonium bromide), or sodium citrate. Can be.
  • the temperature for aging the mixed solution may be room temperature, and the aging time may be 3 to 5 weeks.
  • the PBA particles can be dispersed in an aqueous solution in which the lithium salt is dissolved, filtered and dried to coat the PBA particles with a lithium salt. At this time, the surface and internal pores of the PBA particles may be coated with a lithium salt.
  • the lithium salt may be LiOH or LiCO 3 as an example.
  • the PBA particles coated with lithium salt are dispersed in an aqueous transition metal precursor solution, filtered and dried to coat the PBA particles coated with lithium salt (PBA@alkaline salt) again with a transition metal precursor.
  • PBA@lithium salt@transition metal precursor PBA@lithium salt@transition metal precursor
  • the surface and internal pores of the PBA particles may be coated in turn with a lithium salt and a transition metal precursor.
  • the transition metal precursor coating step may be omitted in some cases.
  • the transition metal precursor may include precursors of transition metals constituting the PBA.
  • the transition metal precursor when the PBA contains nickel, manganese, and cobalt, is a nickel precursor specifically nickel nitrate or nickel sulfate, a manganese precursor specifically manganese nitrate or manganese sulfate, and a cobalt precursor specifically cobalt nitrate Or cobalt sulfate.
  • the thermal decomposition temperature may be about 400 to 500 degrees, and the thermal decomposition time may be about 2 to 4 hours.
  • the CN bridges between transition metals are oxidized and converted to oxygen bridges, so that the distance between the transition metals becomes close and collapse of the particle shape may occur.
  • the aging time is set to 3 weeks to 5 weeks as an example, as described above, it is possible to sufficiently reduce the occurrence of crystal defects in the PBA particles, in the thermal decomposition process.
  • the collapse of the particle shape can be greatly reduced or the collapse of the particle shape can be prevented.
  • the temperature rise rate during thermal decomposition proceeds relatively slowly to 0.5 to 1.5°C/min to maintain the shape of the particles.
  • M 1 , M 2 and M 3 may be Ni, Mn, Co, Fe, Ti, V, or Cr, regardless of each other.
  • M 1, M 2 and M 3 are M 1, M 2, and are the same oxidation state transition metal, respectively, and M 3 in the formula (1) of the general formula (2) may or may not be equal.
  • M 1 may be Ni
  • M 2 may be Mn
  • M 3 may be Co.
  • the ratio of x:y:z may be the same as the ratio of a:b:c in Chemical Formula 1 above. However, it is not limited thereto.
  • the lithium transition metal oxide represented by Chemical Formula 2 may exhibit a hexagonal layered structure in which the transition metal oxide layer and the lithium layer are repeatedly arranged, and O3 among the layered structures. Structure.
  • the c-axis length/a-axis length that is, I (003) /I (104) in the XRD graph may exhibit a value of more than 1, further 1.2 or more, further 1.4 or more, and 1.5 or less.
  • cation mixing which is a phenomenon in which other transition metal cations (especially nickel ions) are inserted instead of lithium ions, can be suppressed.
  • the shape of the particles of the lithium transition metal oxide represented by Chemical Formula 2 may be, for example, a cube surrounded by a rectangle, and a cube.
  • the surface area may be larger at the same volume than when the particle shape is spherical. This can be seen as an increase in capacity due to an increase in the reaction area.
  • the cube may mean that all sides have the same length within an error range of 5%, and all angles are equal within an error range of 5%. Meanwhile, the length of each side of the cube may be about 50 to 150 nm.
  • the calcination may include a primary calcination step and a secondary calcination step, and may include cooling to room temperature before starting the secondary calcination after terminating the primary calcination.
  • the calcination can be performed in an air atmosphere.
  • the temperature for the primary calcination may be 800 to 900 degrees, and the treatment time may be about 3 to 6 hours.
  • the obtained resultant lithium-transition metal oxide powder may be ground at room temperature and then subjected to the second calcination.
  • the temperature for the second calcination can be 750 to 850 degrees, and the treatment time can be about 4 to 5 hours.
  • the temperature increase rate can be relatively slow to 4 to 6°C/min to maintain the shape of the particles.
  • the transition metal precursor coated on the particles may maintain the shape of the particles stably despite the phase transition during calcination in the thermal decomposition process.
  • the active material which is a lithium-transition metal oxide, is used as a positive electrode active material for a lithium secondary battery, which will be described later, so that the particle structure can be stably maintained even when the lithium secondary battery is driven, so that efficiency and high rate characteristics can be excellent.
  • the lithium secondary battery according to an embodiment of the present invention may include a positive electrode containing the active material described above as a positive electrode active material, a negative electrode containing a negative electrode active material capable of deintercalating lithium ions, and an electrolyte positioned therebetween. .
  • a positive electrode material may be obtained by mixing the positive electrode active material, a conductive material, and a binder.
  • the conductive material may be natural graphite, artificial graphite, coke, carbon black, carbon nanotubes, graphene, and other carbon materials.
  • Binders include thermoplastic resins such as polyvinylidene fluoride, polytetrafluoroethylene, ethylene tetrafluoride, vinylidene fluoride copolymers, fluorine resins such as propylene hexafluoride, and/or polyolefin resins such as polyethylene and polypropylene. It can contain.
  • the positive electrode material may be coated on the positive electrode current collector to form the positive electrode.
  • the positive electrode current collector may be a conductor such as Al, Ni, and stainless steel.
  • Applying the positive electrode material on the positive electrode current collector may be a method of forming a paste using pressure molding or an organic solvent, and then applying the paste onto the current collector and pressing to fix it.
  • Organic solvents include amines such as N,N-dimethylaminopropylamine and diethyltriamine; Ether systems such as ethylene oxide and tetrahydrofuran; Ketone systems such as methyl ethyl ketone; Ester systems such as methyl acetate; Aprotic polar solvents such as dimethylacetamide and N-methyl-2-pyrrolidone.
  • Applying the paste on the positive electrode current collector can be performed using, for example, a gravure coating method, a slit die coating method, a knife coating method, or a spray coating method.
  • the negative electrode active material is a metal, a metal alloy, a metal oxide, a metal fluoride, a metal sulfide, and natural graphite, artificial graphite, coke, carbon black, carbon nanotube, graphene, which can deintercalate or convert lithium ions. It can also be formed using a carbon material such as fin.
  • a negative electrode material can be obtained by mixing a negative electrode active material, a conductive material, and a binder.
  • the conductive material may be natural graphite, artificial graphite, coke, carbon black, carbon nanotubes, graphene, and other carbon materials.
  • Binders include thermoplastic resins such as polyvinylidene fluoride, polytetrafluoroethylene, ethylene tetrafluoride, vinylidene fluoride copolymers, fluorine resins such as propylene hexafluoride, and/or polyolefin resins such as polyethylene and polypropylene. It can contain.
  • the negative electrode material may be coated on the negative electrode current collector to form a negative electrode.
  • the negative electrode current collector may be a conductor such as Al, Ni, and stainless steel.
  • Applying the negative electrode material on the negative electrode current collector may be a method of forming a paste using pressure molding or an organic solvent, and then applying the paste onto the current collector and pressing it to fix it.
  • Organic solvents include amines such as N,N-dimethylaminopropylamine and diethyltriamine; Ether systems such as ethylene oxide and tetrahydrofuran; Ketone systems such as methyl ethyl ketone; Ester systems such as methyl acetate; Aprotic polar solvents such as dimethylacetamide and N-methyl-2-pyrrolidone.
  • Applying the paste on the negative electrode current collector may be performed using, for example, a gravure coating method, a slit die coating method, a knife coating method, or a spray coating method.
  • the electrolyte may be a liquid electrolyte containing a lithium salt and a solvent dissolving it.
  • the solvent may be an organic solvent.
  • an organic solvent for example, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, isopropyl methyl carbonate , Carbonates such as vinylene carbonate, 4-trifluoromethyl-1,3-dioxolan-2-one and 1,2-di(methoxycarbonyloxy)ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropylmethyl ether, 2,2,3,3-tetrafluoropropyldifluoromethyl ether, tetrahydrofuran, 2-methyltetrahydro Ethers such as furan; Esters such as methyl formate, methyl acetate, and ⁇ -butyrolactone; Nitriles such as acetonitrile and butyronitrile; Amides such as N,N-dimethylformamide and N,N-dimethylacet
  • the electrolyte is not limited thereto, and the liquid electrolyte may be a polymer solid electrolyte or a ceramic solid electrolyte impregnated into the polymer.
  • the polymer may be a polymer compound containing at least one of a polyethylene oxide-based polymer compound, a polyorganosiloxane chain, or a polyoxyalkylene chain.
  • the ceramic type solid electrolyte may also use inorganic ceramics such as sulfide, oxide, and phosphate of the metal.
  • the solid electrolyte may serve as a separator to be described later, and in that case, a separator may not be required.
  • a separator may be disposed between the anode and the cathode.
  • the separator may be a material having a form of a porous film made of a material such as polyethylene, polypropylene, polyolefin resin, fluorine resin, or nitrogen-containing aromatic polymer, nonwoven fabric, woven fabric, or the like.
  • the thickness of the separator is preferably as thin as possible, as long as the mechanical strength is maintained, in that the bulk energy density of the battery increases and the internal resistance decreases.
  • a positive electrode, a separator, and a negative electrode may be stacked in order to form an electrode group, and then, if necessary, the electrode group may be rolled and stored in a battery can, and a lithium secondary battery may be manufactured by impregnating the electrode group with an electrolyte solution.
  • a positive electrode, a solid electrolyte, and a negative electrode may be stacked to form an electrode group, and then, if necessary, the electrode group may be rolled and stored in a battery can to manufacture a metal secondary battery.
  • PBA@LiOH@NCM powder in a crucible was treated in a furnace in an air atmosphere at 450°C for 1 hour/min for 3 hours to oxidize CN ligands in the PBA, and then for 5 hours at 5°C/min up to 850°C gave. Thereafter, after pulverizing the powder, further heat treatment was performed at 5°C/min for 5 hours to 800°C to obtain a Li[Ni 0.4 Co 0.4 Mn 0.2 ]O 2 powder.
  • An active material (Li-NCM oxide) was prepared in the same manner as the active material preparation example, except that the transition metal precursor coating step was omitted.
  • FIG. 2 shows SEM (scanning electron microscope) photographs of the active material according to Preparation Example 1
  • FIG. 3 shows SEM photographs of the active material according to Preparation Example 2.
  • FIG. 4 shows an SEM photograph of an active material according to Comparative Example 1 of the active material
  • FIG. 5 shows an SEM photograph of an active material according to Comparative Example 2 of the active material. It can be seen that many defects occurred in the active material after firing. This is because the aging time in the PBA powder manufacturing step, that is, the synthesis time according to the co-precipitation method is short, so many crystal defects in the PBA occur, and when the CN ligands are oxidized in the firing step, the CN bridges are converted into oxygen bridges. The gap was narrowed and it was estimated that the structure was difficult to maintain due to the Ostwald ripening phenomenon.
  • the active material according to the comparative example 1 of the active material maintains the particle shape of the cube even after firing.
  • the aging time was greatly increased to minimize the formation of crystal defects in the PBA, so the CN bridges due to oxidation of the CN ligands appearing in the firing process are converted into oxygen bridges, and thus the interval between the metals is It was presumed that the particle structure was maintained despite the shrinking and Ostwald life.
  • the particle size is also larger than the active material particles according to Comparative Example 2, which was judged because the crystal growth was sufficiently achieved.
  • the active material according to Comparative Example 1 and Active Material Comparative Example 2 was subjected to heat treatment at 450° C. for 3 hours (first), heat treatment at 800° C. for 3 hours (second), and heat treatment at 800° C. for 5 hours (third).
  • first heat treatment
  • second heat treatment
  • third heat treatment
  • the second heat treatment is heat treated at 850° C. for 5 hours as in the case of the active material preparation example 1
  • the aging time is short as 2 weeks as in the active material comparative example 1
  • the collapse of the structure occurs more severely or it is aged as in the active material comparative example 2 Even when the time was increased to 4 weeks, structural collapse was observed.
  • the active material according to the active material preparation example 1 relatively maintains the shape of the particles, that is, the shape of the cube, even after the heat treatment step.
  • the length of one side of the particle is about 1 um, and irregular hexahedral nanoparticles on the surface of the particle are identified.
  • the active material according to Preparation Example 1 of the active material is nano-sized. It can be seen that the primary particles are secondary particles generated by aggregation.
  • the active material according to the active material preparation example 2 has a somewhat collapsed particle shape compared to the active material production example 1 (FIG. 2 ), which is a heat treatment process (450° C.) without adding a transition metal precursor in the manufacturing process. It was estimated that 3 hours heat treatment (first), 850°C 5 hours heat treatment (second), and 800°C 5 hours heat treatment (third) were performed. From these results, it can be seen that when the transition metal precursor is added in the active material manufacturing process and then the heat treatment process is performed, the collapse of the particle structure can be suppressed.
  • the XRD pattern of the active material obtained in Preparation Example 1 shows (003) peak and (104) peak, and (003) peak intensity (I 003 ) is (104) peak intensity (I 104 ) It can be seen that it shows a larger value than.
  • the ratio of I 003 /I 104 is greater than 1, furthermore 1.2 or more, further 1.4 or more, and 1.5 or less Specifically, it represents a value of 1.47.
  • the ratio of I 003 /I 104 is an index for determining cation mixing, which is a phenomenon in which other transition metal cations (especially nickel ions) are inserted instead of lithium ions at the lithium ion site, and the ratio of I 003 /I 104 It is known that when it is more than 1, cation mixing becomes low, and further, when it is 1.2 or more, cation mixing becomes sufficiently low. Accordingly, it can be seen that the active material according to the active material preparation example 1 sufficiently suppressed the cation mixing phenomenon, and it was estimated that capacity and efficiency could be improved.
  • a semi-prepared paper was manufactured through the same process as the semi-prepared paper manufacturing example, except that the active material prepared in Comparative Example 1 was used as the positive electrode active material instead of the positive electrode active material prepared in Preparation Example 1.
  • a semi-prepared paper was prepared through the same process as the semi-prepared paper manufacturing example, except that the active material prepared in Comparative Example 2 was used as the positive electrode active material instead of the positive electrode active material prepared in Preparation Example 1.
  • FIG. 7 is a graph showing charging and discharging characteristics in the first cycle of the reverse cells according to Comparative Example 1, Semi-Compared Paper Comparative Example 1, and Comparative Paper 2. At this time, the capacity was measured while charging was performed at 0.1C to 4.4V and discharge was performed at 0.1C to 3.0V.
  • a half-sheet according to Preparation Example 1 that is, a half-sheet using the active material according to Preparation Example 1, a half-sheet according to Comparative Examples, and an active material according to Comparative Examples
  • the initial charge capacity and discharge capacity are relatively low compared to the reverse cells using, while the ratio of charge capacity/discharge capacity, that is, cycle efficiency is excellent. This was estimated because the capacity of the active material according to Comparative Examples increased due to the increase in porosity due to the collapse of the particle structure as described above, but the efficiency decreased. It was estimated that the capacity was relatively small, but the efficiency was excellent because it could be kept stable.
  • Figure 8 is a graph showing the discharge capacity change according to the rate of crate (c-rate) of the half-cell according to Comparative Example 1, half-cell comparison Example 1, and half-cell comparison.
  • the 1st to 3rd cycles are 0.1C, 0.2C, and the 4th to 6th cycles at 0.5C, the 7th to 9th cycles at 2C, the 10th to 12th cycles at 4C, and the 13th to 15th cycles again.
  • Charging from 1C to 4.4V and discharging to 3.0V were repeated.
  • the reverse paper according to Preparation Example 1 that is, the reverse material using the active material according to Preparation Example 1
  • the reverse paper according to the comparison examples of the reverse paper that is, the active material according to the comparative examples
  • the active material according to the active material preparation example 1 was estimated to have excellent high rate characteristics because the particle structure can be stably maintained.

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un oxyde de lithium-métal de transition. Le procédé de fabrication d'un oxyde de lithium-métal de transition comprend une étape de formation de particules d'un analogue de bleu de Prusse (appelé PBA ci-après) représenté par la formule chimique 1 ci-dessous. Les particules de PBA sont dispersées dans une solution aqueuse d'un sel de lithium, filtrées et séchées pour revêtir les particules de PBA par le sel de lithium. Les particules de PBA revêtues de sel de lithium sont pyrolysées sous une atmosphère d'air pour oxyder des ponts CN dans le PBA en ponts oxygène. Le produit résultant qui a subi l'étape d'oxydation est calciné pour obtenir un oxyde de lithium-métal de transition. [Formule chimique 1] M1 aM2 b[M3(CN)6]c , où M1 et M2 représentent des métaux de transition présentant chacun un nombre d'oxydation de 2 et représentant indépendamment Ni, Mn, Co, Fe, Ti, V ou Cr ; M3 représente un métal de transition présentant un nombre d'oxydation de 3 et représente Ni, Mn, Co, Fe, Ti, V ou Cr ; c vaut 1 à 5 ; et a et b ont des valeurs positives pour neutraliser électriquement le composé de formule chimique 1.
PCT/KR2019/004680 2018-11-27 2019-04-18 Procédé de fabrication d'oxyde de lithium-métal de transition utilisant un analogue de bleu de prusse, oxyde de lithium-métal de transition et batterie rechargeable au lithium WO2020111404A1 (fr)

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CN115520848A (zh) * 2022-09-28 2022-12-27 广东邦普循环科技有限公司 一种磷酸铁锂正极材料及其制备方法和应用
CN117457902A (zh) * 2023-12-25 2024-01-26 宁波容百新能源科技股份有限公司 一种普鲁士蓝类正极材料及其制备方法、电池
WO2024026991A1 (fr) * 2022-08-01 2024-02-08 广东邦普循环科技有限公司 Dérivé de prusse modifié, son procédé de préparation et son utilisation

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CN117457902A (zh) * 2023-12-25 2024-01-26 宁波容百新能源科技股份有限公司 一种普鲁士蓝类正极材料及其制备方法、电池

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