WO2019078672A2 - Procédé de production d'un matériau actif d'électrode positive pour batterie secondaire, et batterie secondaire l'utilisant - Google Patents

Procédé de production d'un matériau actif d'électrode positive pour batterie secondaire, et batterie secondaire l'utilisant Download PDF

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WO2019078672A2
WO2019078672A2 PCT/KR2018/012415 KR2018012415W WO2019078672A2 WO 2019078672 A2 WO2019078672 A2 WO 2019078672A2 KR 2018012415 W KR2018012415 W KR 2018012415W WO 2019078672 A2 WO2019078672 A2 WO 2019078672A2
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transition metal
tungsten
metal oxide
hydroxide
active material
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English (en)
Korean (ko)
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WO2019078672A3 (fr
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백현희
반성호
엄준호
박나리
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020180125222A external-priority patent/KR102165119B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to JP2020513773A priority Critical patent/JP7046410B2/ja
Priority to CN201880033908.9A priority patent/CN110662718B/zh
Priority to US16/615,527 priority patent/US11437609B2/en
Publication of WO2019078672A2 publication Critical patent/WO2019078672A2/fr
Publication of WO2019078672A3 publication Critical patent/WO2019078672A3/fr
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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

Definitions

  • the present invention relates to a method for producing a cathode active material for a secondary battery and a secondary battery using the same, and more particularly, to a cathode active material manufacturing method capable of improving the lifetime characteristics of a battery by suppressing loss of a doped compound .
  • Lithium-containing cobalt oxide (LiCoO 2 ) is mainly used as a positive electrode active material of a lithium secondary battery, and a lithium-containing manganese oxide such as LiMnO 2 having a layered crystal structure and LiMn 2 O 4 having a spinel crystal structure, The use of LiNiO 2 , which is a non-aqueous electrolyte, is also considered.
  • LiCoO 2 is most widely used because of its excellent lifetime characteristics and charge / discharge efficiency.
  • LiCoO 2 is expensive because of its small capacity and resource limitations of cobalt used as a raw material. Therefore, it is used as a power source for mid- There is a disadvantage in that price competitiveness is limited.
  • Lithium manganese oxides such as LiMnO 2 and LiMn 2 O 4 are advantageous in that they are rich in manganese resources used as raw materials, are inexpensive, environmentally friendly, and excellent in thermal stability. However, they have small capacity, high temperature characteristics, This is a poor problem.
  • Ni rich system Ni rich system
  • the nickel rich active material has a high capacity, it has a higher cation mixing ratio at a high temperature, and is produced at a lower temperature than other cathode active materials in order to suppress it.
  • the cathode active material when the cathode active material is manufactured at a low temperature, lithium impurities that have not participated in the synthesis reaction of the cathode active material are left in a larger amount, and the lithium impurities are removed from the gel by applying a composition containing the cathode active material to the cathode current collector gel is induced, and electrode surface defects may occur due to agglomeration during electrode coating.
  • residual lithium impurities vaporize during charging / discharging of the battery, causing the battery case to swell, which may deteriorate battery stability and life performance.
  • the present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a method for manufacturing a cathode active material in which lithium doping is removed through a washing process, .
  • a method of forming a tungsten-doped lithium transition metal oxide comprising: forming a tungsten-doped lithium transition metal oxide; And a step of washing the lithium-transition metal oxide with a wash water.
  • a hydroxide compound is added to the washing liquid during washing, thereby providing a method for producing the cathode active material .
  • the present invention provides a positive electrode and a lithium secondary battery including the positive electrode active material.
  • the tungsten-doped lithium transition metal oxide according to the present invention may be washed with a wash water to prevent lithium impurities from remaining on the surface of the lithium transition metal oxide, thereby improving lifetime characteristics and safety of the battery.
  • the method for producing a cathode active material according to the present invention includes the steps of (1) forming a tungsten-doped lithium transition metal oxide; and (2) washing the lithium transition metal oxide. After washing with water, (3) the above-mentioned cathode active material according to the present invention can be prepared by further drying and heat-treating the tungsten-doped lithium transition metal oxide.
  • the tungsten-doped lithium transition metal oxide can be prepared by a known method and is not particularly limited, but may be a method of mixing 1) a lithium compound, a transition metal precursor and a tungsten-doped source together and firing the mixture, 2) A method in which a tungsten-doped transition metal precursor is mixed and then calcined, and 3) a method in which a lithium compound and a transition metal precursor are mixed and calcined, and then the calcined product is mixed with a tungsten doping source and then re- One or more methods can be selected and formed.
  • a lithium compound, a transition metal precursor, and a tungsten doping source are mixed together and then fired to form a tungsten-doped lithium transition metal oxide.
  • the lithium compound is a compound containing lithium and is not particularly limited as long as it can be used as a lithium source.
  • the lithium compound may be at least one or more selected from the group consisting of lithium carbonate (Li 2 CO 3 ), lithium hydroxide (LiOH), lithium nitrate (LiNO 3 ) and lithium hydrate (LiOH ⁇ H 2 O) .
  • the transition metal precursor may include at least one transition metal cation selected from the group consisting of Ni, Co, and Mn.
  • the transition metal precursor may include at least one transition metal cation selected from the group consisting of Ni, Co, and Mn, and may include a hydroxide, a carbonate, or a nitrate including the transition metal cation.
  • the transition metal precursor includes transition metal cations of nickel (Ni), cobalt (Co), and manganese (Mn), and contains at least 80 mol%, preferably 85 mol% , More preferably at least 88 mol%, and when the transition metal cation of nickel (Ni) is contained within the above range, a high capacity can be realized.
  • the lithium compound and the transition metal precursor may be mixed at a molar ratio of 1.01: 1 to 1.07: 1, preferably 1.01: 1 to 1.06: 1, more preferably 1.02: 1 to 1.05: 1.
  • the lithium compound it can easily be volatilized at a high temperature and an excess amount relative to the transition metal precursor should be added. Therefore, it is preferable to mix within the above range.
  • the tungsten doping source may include 0.1 to 20% by weight, preferably 0.1 to 10% by weight based on the combined weight of the lithium compound and the transition metal precursor.
  • the tungsten doping source may vary depending on the doping condition and doping amount, but it is preferable that the tungsten doping source is included within the above range in view of economical efficiency and the like.
  • a conventional dry process, a dry process, and a wet process may be used without any limitation, and general mixing may be performed for uniform mixing.
  • the mixture that has undergone the above-described mixing process may be fired to form a lithium-transition metal oxide doped with tungsten.
  • the temperature condition of the firing step for forming the lithium transition metal oxide is performed at 700 to 900 DEG C, preferably 700 to 880 DEG C, more preferably 700 to 850 DEG C for 8 to 12 hours Lt; / RTI >
  • the lithium compound and the transition metal precursor react sufficiently to prevent the lithium impurity from remaining.
  • the tungsten doping source can be stably doped to the inside and the surface of the lithium transition metal oxide.
  • the water washing step includes the steps of 1) charging the washing solution with a tungsten-doped lithium transition metal oxide and then firstly stirring the solution, 2) adding a hydroxide compound to the washing solution after the primary stirring, And stirring the mixture.
  • a lithium transition metal oxide is not formed and residual lithium impurity is present.
  • the transition metal of the high-Ni system system it is preferable that the residual amount of the lithium impurity is larger than that of the case of using another kind of transition metal, and the lithium transition metal oxide is washed and washed.
  • the lithium impurity can be removed by washing the tungsten-doped lithium transition metal oxide
  • the tungstate anion for example, WO 4 2-
  • the wash water There is a problem.
  • the doped tungsten is not ionized by tungstate anion, it may be unstable when it is subjected to a washing process and may be eluted during charging and discharging of the battery, and as a part of the doped tungsten precipitates, cycle characteristics of the secondary battery deteriorate .
  • the present inventors have studied a method for preventing the loss of doped tungsten while removing residual lithium impurities existing on the surface of the tungsten-doped lithium transition metal oxide.
  • the lithium-transition metal oxide doped with tungsten is first washed with a wash water, and then washed with a washing solution in which a hydroxide compound is added to the washed lithium-transition metal oxide doped with tungsten .
  • the tungstate anion and the hydroxide compound can stably form a complex compound in a state where impurities are removed from the surface of the lithium-transition metal oxide doped with tungsten.
  • the primary stirring step is a step in which a lithium transition metal oxide doped with tungsten is added to the washing solution and then stirred.
  • the washing liquid includes distilled water, and the temperature of the washing liquid may be 5 to 30 ⁇ , preferably 5 to 25 ⁇ , more preferably 10 to 25 ⁇ .
  • the temperature of the washing liquid may be 5 to 30 ⁇ , preferably 5 to 25 ⁇ , more preferably 10 to 25 ⁇ .
  • the step is carried out by adding 20 to 60% by volume, preferably 20 to 50% by volume, more preferably 20 to 40% by volume of the wash liquid to the reactor volume in the 1 L reactor, With stirring at 100 to 500 rpm, preferably 100 to 400 rpm, more preferably 100 to 300 rpm, for 10 to 30 minutes, preferably 10 to 25 minutes, more preferably 10 to 20 minutes .
  • the step may include forming a coating on the surface of the tungsten-doped lithium transition metal oxide particle, wherein the metal cation of the hydroxide-based compound and the tungstate anion eluted from the tungsten-doped lithium transition metal oxide .
  • the hydroxide compound is a compound capable of forming a coated portion on the surface of the lithium-transition metal oxide by reacting with the tungstate anion eluted from the tungsten-doped lithium-transition metal oxide.
  • hydroxide- OH < - & gt ;
  • the hydroxide (hydroxide) compound is aluminum hydroxide (Al (OH) 3), magnesium hydroxide (Mg (OH) 2), cobalt hydroxide (Co (OH) 2), calcium hydroxide (Ca (OH) 2 ), barium hydroxide (Ba (OH) 2 ) and strontium hydroxide (Sr (OH) 2 ).
  • the hydroxide compound in the reactor is a mixture of metal cation of tungsten and hydroxide compound doped in the lithium transition metal oxide in a weight ratio of 1: 0.3 to 1: 0.6 Can be input. More preferably, the metal cation of the tungsten and hydroxide compound doped in the lithium transition metal oxide is in a weight ratio of 1: 0.4 to 1: 0.6, more preferably 1: 0.4 to 1: 0.5, A hydroxide-based compound can be added.
  • the tungstic acid anion and the hydroxide (hydroxide) are added to the surface of the tungsten-doped lithium transition metal oxide particle while maintaining the capacity of the cathode active material using the hydroxide compound.
  • Based compound can form a stable coated portion.
  • the hydroxide compound is added to the 1 L reactor for 10 to 30 minutes, preferably 10 to 25 minutes, more preferably 10 to 20 minutes, Lt; / RTI > min.
  • the step of filtering the lithium transition metal oxide from the wash liquor may be further roughened.
  • the filtering may be performed according to a conventional filtration process.
  • the drying process may be performed according to a conventional drying method, and may be performed by hot air injection, vacuum drying, or the like at a temperature of 80 to 200 ° C, more preferably 100 to 180 ° C, 1 to 3 hours, more preferably 1 to 2 hours.
  • the dried lithium-transition metal oxide doped with tungsten may be heat-treated to produce a cathode active material.
  • the heat treatment may be performed at a temperature of 250 to 600 ° C, preferably 300 to 600 ° C, more preferably 300 to 550 ° C for 1 to 5 hours, preferably 1 to 4 hours, Preferably 2 to 4 hours.
  • the heat treatment process is performed within the above temperature range, the crystallinity of the lithium transition metal oxide is improved and the structure thereof can be stably formed.
  • the coating portion that has been formed through the water washing step can be formed more stably, and the performance and lifetime characteristics of the battery can also be improved.
  • the positive electrode comprising the positive electrode active material produced according to the above production method will be described.
  • the anode includes a cathode current collector and a cathode active material layer formed on the cathode current collector and including the cathode active material.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • carbon, nickel, titanium, , Silver or the like may be used.
  • the cathode current collector may have a thickness of 3 to 500 ⁇ , and fine unevenness may be formed on the surface of the current collector to increase the adhesive force of the cathode active material.
  • it can be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the cathode active material layer may include a conductive material and a binder together with the cathode active material described above.
  • the cathode active material may be contained in an amount of 70 to 99.8% by weight, preferably 75 to 99.8% by weight, and more preferably 80 to 99.8% by weight based on the total weight of the cathode active material layer.
  • the conductive material is used for imparting conductivity to the electrode.
  • the conductive material can be used without particular limitation as long as it has electron conductivity without causing chemical change. Specific examples thereof include graphite such as natural graphite and artificial graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black and carbon fiber; Metal powder or metal fibers such as copper, nickel, aluminum and silver; Conductive whiskey such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; And polyphenylene derivatives. These may be used alone or in admixture of two or more.
  • the conductive material may be contained in an amount of 0.1 to 30% by weight, preferably 0.1 to 25% by weight, more preferably 0.1 to 20% by weight based on the total weight of the cathode active material layer.
  • the binder serves to improve the adhesion between the positive electrode active material particles and the adhesion between the positive electrode active material and the current collector.
  • specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethylcellulose ), Starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluororubber, and various copolymers thereof.
  • PVDF polyvinylidene fluoride
  • PVDF-co-HFP vinylidene fluoride-hexafluoropropylene copolymer
  • PVDF-co-HFP polyvinyl
  • the binder may be contained in an amount of 0.1 to 30% by weight, preferably 0.1 to 25% by weight, more preferably 0.1 to 20% by weight based on the total weight of the cathode active material layer.
  • the positive electrode may be manufactured according to a conventional positive electrode manufacturing method, except that the positive electrode active material described above is used. Specifically, a composition for forming a cathode active material layer in the form of a slurry including the above-mentioned cathode active material and optionally a binder and a conductive material may be applied on the cathode current collector, followed by drying and rolling. At this time, the types and contents of the cathode active material, the binder, and the conductive material are as described above.
  • the solvent examples include dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone, and the like. Water and the like, and one kind or a mixture of two or more kinds can be used.
  • the amount of the solvent to be used is determined by dissolving or dispersing the cathode active material, the conductive material and the binder in consideration of the coating thickness and the production yield of the composition for forming the cathode active material layer, It is enough to have it.
  • the positive electrode may be produced by casting the composition for forming the positive electrode active material layer on a separate support, then peeling off the support from the support, and laminating the obtained film on the positive electrode current collector.
  • lithium secondary battery including the positive electrode, the negative electrode, the separator interposed between the positive electrode and the negative electrode, and the electrolyte will be described.
  • the lithium secondary battery includes a positive electrode, a negative electrode disposed opposite to the positive electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte.
  • the positive electrode is as described above.
  • the lithium secondary battery may further include a battery container for housing the electrode assembly of the anode, the cathode, and the separator, and a sealing member for sealing the battery container.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery.
  • the negative electrode current collector may be formed on the surface of copper, stainless steel, aluminum, nickel, titanium, sintered carbon, Carbon, nickel, titanium, silver or the like, aluminum-cadmium alloy, or the like may be used.
  • the negative electrode collector may have a thickness of 3 to 500 ⁇ , and similarly to the positive electrode collector, fine unevenness may be formed on the surface of the collector to enhance the binding force of the negative electrode active material.
  • it can be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the anode active material layer optionally includes a binder and a conductive material together with the anode active material.
  • the negative electrode active material layer may be formed, for example, by applying a negative electrode active material composition on a negative electrode collector and, optionally, a slurry composition for forming a negative electrode, which includes a binder and a conductive material, and drying the composition or drying the composition for negative electrode formation on a separate support Casting, and then laminating a film obtained by peeling from the support onto an anode current collector.
  • a compound capable of reversible intercalation and deintercalation of lithium may be used.
  • Specific examples thereof include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber and amorphous carbon;
  • Metal compounds capable of alloying with lithium such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloys, Sn alloys or Al alloys;
  • Metal oxides capable of doping and dedoping lithium such as SiO x (0 ⁇ x ⁇ 2), SnO 2 , vanadium oxide, and lithium vanadium oxide;
  • a composite containing the metallic compound and the carbonaceous material such as Si-C composite or Sn-C composite, and any one or a mixture of two or more thereof may be used.
  • a metal lithium thin film may be used as the negative electrode active material.
  • the carbon material may be both low-crystalline carbon and high-crystallinity carbon.
  • Examples of the low-crystalline carbon include soft carbon and hard carbon.
  • Examples of the highly crystalline carbon include natural graphite, artificial graphite, artificial graphite or artificial graphite, Kish graphite graphite, pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, mesophase pitches and petroleum or coal tar coke derived cokes).
  • metal lithium may be used as the cathode.
  • the binder and the conductive material may be the same as those described above for the anode.
  • the separation membrane separates the cathode and the anode and provides a passage for lithium ion.
  • the separation membrane can be used without any particular limitation as long as it is used as a separation membrane in a lithium secondary battery. Particularly, It is preferable to have a low resistance and an excellent electrolyte wettability.
  • porous polymer films such as porous polymer films made of polyolefin-based polymers such as ethylene homopolymers, propylene homopolymers, ethylene / butene copolymers, ethylene / hexene copolymers and ethylene / methacrylate copolymers, May be used.
  • a nonwoven fabric made of a conventional porous nonwoven fabric for example, glass fiber of high melting point, polyethylene terephthalate fiber, or the like may be used.
  • a coated separator containing a ceramic component or a polymer material may be used, and the separator may be selectively used as a single layer or a multilayer structure.
  • Examples of the electrolyte used in the present invention include an organic-based liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel-type polymer electrolyte, a solid inorganic electrolyte, and a molten inorganic electrolyte that can be used in the production of a lithium secondary battery. It is not.
  • the electrolyte may include an organic solvent and a lithium salt.
  • the organic solvent may be used without limitation as long as it can act as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • examples of the organic solvent include ester solvents such as methyl acetate, ethyl acetate,? -Butyrolactone and?
  • Ether solvents such as dibutyl ether or tetrahydrofuran; Ketone solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; Dimethyl carbonate (DMC), diethylcarbonate (DEC), methylethylcarbonate (MEC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), propylene carbonate PC) and the like; Alcohol solvents such as ethyl alcohol and isopropyl alcohol; R-CN (R is a straight, branched or cyclic hydrocarbon group of C2 to C20, which may contain a double bond aromatic ring or an ether bond); Amides such as dimethylformamide; Dioxolanes such as 1,3-dioxolane; Or sulfolane may be used.
  • Ether solvents such as dibutyl ether or tetrahydrofuran
  • Ketone solvents such as cyclohexanone
  • a carbonate-based solvent is preferable, and a cyclic carbonate (for example, ethylene carbonate or propylene carbonate) having a high ionic conductivity and a high dielectric constant, for example, such as ethylene carbonate or propylene carbonate, For example, ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate) is more preferable.
  • a cyclic carbonate for example, ethylene carbonate or propylene carbonate
  • ethylene carbonate or propylene carbonate for example, ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate
  • the performance of the electrolyte may be excellent.
  • the lithium salt can be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
  • the lithium salt LiPF 6, LiClO 4, LiAsF 6, LiBF 4, LiSbF 6, LiAl0 4, LiAlCl 4, LiCF 3 SO 3, LiC 4 F 9 SO 3, LiN (C 2 F 5 SO 3) 2 , LiN (C 2 F 5 SO 2) 2, LiN (CF 3 SO 2) 2.
  • LiCl, LiI, or LiB (C 2 O 4 ) 2 may be used.
  • the concentration of the lithium salt is preferably in the range of 0.1 to 2.0 M. When the concentration of the lithium salt is within the above range, the electrolyte has an appropriate conductivity and viscosity, so that it can exhibit excellent electrolyte performance and the lithium ion can effectively move.
  • the electrolyte may contain, for example, a haloalkylene carbonate-based compound such as difluoroethylene carbonate or the like, pyridine, triethanolamine, or the like for the purpose of improving lifetime characteristics of the battery, Ethyl phosphite, triethanol amine, cyclic ether, ethylenediamine, glyme, hexametriamide, nitrobenzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, At least one additive such as benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, The additive may be included in an amount of 0.1 to 5% by weight based on the total weight of the electrolyte.
  • the lithium secondary battery including the cathode active material according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity retention rate, it can be used in portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles hybrid electric vehicle (HEV)).
  • portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles hybrid electric vehicle (HEV)).
  • HEV hybrid electric vehicles hybrid electric vehicle
  • a battery module including the lithium secondary battery as a unit cell and a battery pack including the same.
  • the battery module or the battery pack may include a power tool; An electric vehicle including an electric vehicle (EV), a hybrid electric vehicle, and a plug-in hybrid electric vehicle (PHEV); Or a power storage system, as shown in FIG.
  • a power tool including an electric vehicle (EV), a hybrid electric vehicle, and a plug-in hybrid electric vehicle (PHEV); Or a power storage system, as shown in FIG.
  • EV electric vehicle
  • PHEV plug-in hybrid electric vehicle
  • a lithium compound (LiOH) and the transition metal precursor (... Ni 0 90 Co 0 07 Mn 0 03 (OH) 2) 1.03: a mixture of 1 molar ratio of 200g to prepare and, after addition of 1.2 g of WO 3 Plastic Neta And then mixed at 2000 rpm for 10 minutes to prepare a mixture. The mixture was calcined at 760 ° C for 12 hours to prepare a tungsten-doped lithium transition metal oxide.
  • the tungsten-doped lithium transition metal oxide was dried at 130 DEG C for 1 hour. Then, the dried lithium transition metal oxide was heat-treated at 500 DEG C for 2 hours under an oxygen atmosphere to prepare a cathode active material.
  • a cathode active material was prepared in the same manner as in Example 1 except that 0.6 g of WO 3 was added.
  • a cathode active material was prepared in the same manner as in Example 1, except that 0.43 g of Al (OH) 3 was added.
  • a cathode active material was prepared in the same manner as in Example 1, except that 0.47 g of Co (OH) 3 was added.
  • a cathode active material was prepared in the same manner as in Example 1, except that Al (OH) 3 was not added in the washing step.
  • Example 2 In the washing step in Example 1, Al (OH) 3 was not added but only water was distilled at 20 ° C. Thereafter, the washed lithium transition metal oxide was dried at 130 ° C. for 1 hour, and then 0.87 g of Al (OH) 3 was added thereto. The mixture was placed in a planetary mill and mixed at 2000 rpm for 10 minutes to prepare a mixture. Then, the mixture was heat-treated at 500 ° C for 2 hours to prepare a cathode active material.
  • Example 1 0.2395 g of LiOH was dissolved in 300 mL of distilled water at 20 ⁇ ⁇ to prepare a washing solution, which was then placed in a 1 L reactor. Thereafter, 150 g of the tungsten-doped lithium transition metal oxide prepared as in Example 1 (1) was charged, and the stirring speed in the reactor was maintained at 200 rpm and stirred for 25 minutes. The stirred tungsten-doped lithium transition metal oxide was filtered. Then, the cathode active material was dried and heat-treated in the same manner as in (3) of Example 1 to prepare a cathode active material.
  • a cathode active material was prepared in the same manner as in Comparative Example 3, except that 0.6995 g of LiNO 3 was dissolved instead of LiOH.
  • a lithium secondary battery (coin half cell) was prepared using the cathode active materials prepared in Examples 1 to 4 and Comparative Examples 1 to 4, respectively.
  • the cathode active material, the carbon black conductive material and the PVDF binder prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were mixed in a N-methylpyrrolidone solvent at a weight ratio of 96.5: 1.5: 2.0
  • a composition for forming an anode (viscosity: 5000 mPa ⁇ ⁇ ) was prepared, applied to an aluminum current collector, dried at 130 ⁇ ⁇ and rolled to prepare a positive electrode.
  • Lithium metal was used as the cathode.
  • a lithium secondary battery (coin half cell) was fabricated by preparing an electrode assembly between the positive electrode and the negative electrode prepared as described above through a separator of porous polyethylene, positioning the electrode assembly inside the case, and then injecting electrolyte into the case. .
  • each of the cathode active materials prepared according to Examples 1 to 4 and Comparative Examples 1 to 4 was subjected to ICP analysis and the resulting tungsten content was shown in Table 1 below.
  • a predetermined amount of the cathode active material (about 0.1 g) was precisely weighed, and 2 ml of hydrochloric acid was added thereto. The mixture was heated on a hot plate to dissolve the cathode active material. Thereafter, hydrogen peroxide was added thereto and heated to dissolve the solution.
  • the tungsten content was measured using an inductively coupled plasma spectrometer (ICP, PerkinElmer OPTIMA 8000).
  • Coin half cells (using a cathode of Li metal) each produced using the cathode active materials prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were charged at a constant current of 0.2 C in a voltage range of 2.5 to 4.25 V After charging and discharging, the coin half cell was disassembled by charging to 4.25 V at a current of 0.2C.
  • the anode obtained in the disassembled coin half cell was immersed in a container containing 15 mL of electrolyte and stored for 2 weeks in a 60 ° C thermostatic chamber. The content of tungsten eluted into the electrolyte was analyzed by ICP (PerkinElmer OPTIMA 8000) Respectively.
  • LiOH ion dissociation was low due to the cathode active material containing excess lithium which was thought to be unreacted, and consequently it was confirmed that a large amount of ionization that could form a complex was not achieved.
  • LiNO 3 showed the same phenomenon as LiOH.
  • the coin half cell (cathode of Li metal) prepared using the cathode active materials prepared in Examples 1 to 4 and Comparative Examples 1 to 4 was charged at 25 ° C. until the constant current (CC) of 0.2 C reached 4.25 V Then, the battery was charged at a constant voltage (CV) of 4.25 V and the first charge was performed until the charge current became 0.05 mAh, and the charge capacity was measured. Thereafter, the battery was allowed to stand for 20 minutes and then discharged at a constant current of 0.2 C until it reached 2.5 V to measure the discharge capacity at the first cycle. The charge / discharge efficiency of the first cycle was evaluated. The rate characteristics were evaluated by different discharge conditions at 2C. The results are shown in Table 3.
  • Example 1 232.8 207.6 89.9 87.9
  • Example 2 236.6 213.0 90.0 85.2
  • Example 3 233.9 211.3 90.3 86.0
  • Example 4 231.5 209.2 90.3 86.4 Comparative Example 1 235.9 213.3 90.5 84.8 Comparative Example 2 231.3 207.6 89.7 84.5 Comparative Example 3 234.6 205.4 87.6 84.9 Comparative Example 4 235.0 199.4 84.9 84.0
  • Capacity retention (%) was measured while charging the battery to 45 ° C. in a CCCV mode until the battery reached 0.3 C and 4.55 V, discharged at 3 V at a constant current of 1.0 C, and subjected to 30 charge / And the results are shown in Table 4 below.

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  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

La présente invention concerne un procédé de production d'un matériau actif d'électrode positive, une électrode positive comprenant un matériau actif d'électrode positive produit selon ce procédé, et une batterie secondaire le comprenant. Le procédé comprend : une étape de formation d'un oxyde de métal de transition de lithium dopé au tungstène ; et une étape de lavage de l'oxyde de métal de transition de lithium. Dans l'étape de lavage, un composé à base d'hydroxyde est introduit dans la solution de lavage pendant le lavage.
PCT/KR2018/012415 2017-10-20 2018-10-22 Procédé de production d'un matériau actif d'électrode positive pour batterie secondaire, et batterie secondaire l'utilisant Ceased WO2019078672A2 (fr)

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JP2020513773A JP7046410B2 (ja) 2017-10-20 2018-10-22 二次電池用正極活物質の製造方法、及びこれを用いる二次電池
CN201880033908.9A CN110662718B (zh) 2017-10-20 2018-10-22 制备二次电池用正极活性材料的方法和使用其的二次电池
US16/615,527 US11437609B2 (en) 2017-10-20 2018-10-22 Method of preparing positive electrode active material for secondary battery and secondary battery using the same

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KR20170136900 2017-10-20
KR10-2017-0136900 2017-10-20
KR10-2018-0125222 2018-10-19
KR1020180125222A KR102165119B1 (ko) 2017-10-20 2018-10-19 이차전지용 양극활물질 제조방법 및 이를 이용하는 이차전지

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Cited By (3)

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CN111453778A (zh) * 2020-04-13 2020-07-28 浙江帕瓦新能源股份有限公司 一种掺钨的三元前驱体及其制备方法
CN111710843A (zh) * 2020-06-24 2020-09-25 河南福森新能源科技有限公司 一种高压实锂电池正极材料镍钴锰酸锂的制作方法
CN120646920A (zh) * 2025-08-12 2025-09-16 淮北师范大学 钴掺杂钼钨硫化物及其制备方法与等离子体处理方法和应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101841114B1 (ko) * 2014-12-02 2018-03-22 주식회사 엘지화학 양극 활물질의 제조방법 및 이로부터 제조되는 양극 활물질
KR101888180B1 (ko) * 2015-12-22 2018-08-14 주식회사 포스코 리튬 이차 전지용 양극 활물질의 제조 방법 및 이를 포함하는 리튬 이차 전지
KR101919516B1 (ko) * 2015-12-23 2018-11-16 주식회사 포스코 리튬 이차 전지용 양극 활물질의 제조 방법 및 이를 포함하는 리튬 이차 전지
US10361423B2 (en) * 2016-01-18 2019-07-23 Grst International Limited Method of preparing battery electrodes
KR101892612B1 (ko) * 2016-03-25 2018-08-28 주식회사 에코프로비엠 리튬이차전지 양극활물질의 제조 방법 및 이에 의하여 제조된 리튬이차전지 양극활물질

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111453778A (zh) * 2020-04-13 2020-07-28 浙江帕瓦新能源股份有限公司 一种掺钨的三元前驱体及其制备方法
CN111710843A (zh) * 2020-06-24 2020-09-25 河南福森新能源科技有限公司 一种高压实锂电池正极材料镍钴锰酸锂的制作方法
CN120646920A (zh) * 2025-08-12 2025-09-16 淮北师范大学 钴掺杂钼钨硫化物及其制备方法与等离子体处理方法和应用

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