WO2015026108A1 - 리튬 복합 전이금속 산화물 제조용 전구체, 그 제조방법 및 이를 이용한 리튬 복합 전이금속 산화물 - Google Patents
리튬 복합 전이금속 산화물 제조용 전구체, 그 제조방법 및 이를 이용한 리튬 복합 전이금속 산화물 Download PDFInfo
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- WO2015026108A1 WO2015026108A1 PCT/KR2014/007613 KR2014007613W WO2015026108A1 WO 2015026108 A1 WO2015026108 A1 WO 2015026108A1 KR 2014007613 W KR2014007613 W KR 2014007613W WO 2015026108 A1 WO2015026108 A1 WO 2015026108A1
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- 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
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- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
- C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
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- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
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- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/56—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO3]2-, e.g. Li2[CoxMn1-xO3], Li2[MyCoxMn1-x-yO3
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- 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
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- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/56—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO3]2-, e.g. Li2[NixMn1-xO3], Li2[MyNixMn1-x-yO3
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a precursor for preparing a lithium composite transition metal oxide, a method for preparing the same, and a lithium composite transition metal oxide using the same. More specifically, a basic material is added to an aqueous transition metal solution having a specific composition and mixed with a transition metal-containing salt.
- the present invention relates to a transition metal precursor, a method for producing the same, and a lithium composite transition metal oxide using the same.
- lithium secondary batteries As the development and demand for mobile devices increases, the demand for secondary batteries as energy sources is increasing rapidly. Among them, many researches have been conducted on lithium secondary batteries with high energy density and discharge voltage. It is widely used. Among them, lithium secondary batteries are the most used batteries due to their excellent electrode life and high fast charge and discharge efficiency.
- lithium secondary batteries include lithium-containing cobalt oxide (LiCoO 2 ) as a positive electrode active material.
- lithium-containing manganese oxides such as LiMnO 2 having a layered crystal structure and LiMn 2 O 4 having a spinel crystal structure, and lithium-containing materials
- nickel oxide LiNiO 2
- LiCoO 2 is widely used because of its excellent physical properties such as excellent cycle characteristics, but has a low safety and high cost due to resource limitations of cobalt as a raw material.
- Li-Ni-based oxides such as LiNiO 2 have a lower discharge capacity than LiCoO 2 and have a high discharge capacity when charged to 4.25V, but have high production cost, swelling due to gas generation in a battery, low chemical stability, and high pH.
- Have problems such as;
- lithium manganese oxides such as LiMnO 2 and LiMn 2 O 4 have the advantage of using a resource-rich and environmentally friendly manganese as a raw material, attracting a lot of attention as a cathode active material that can replace LiCoO 2 , in particular
- LiMn 2 O 4 has advantages such as relatively low price and high power, but has a disadvantage in that energy density is lower than that of LiCoO 2 and three-component active materials.
- the present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
- the inventors of the present application developed a transition metal precursor having a specific composition and improved crystallinity, powder sphericity, and tap density.
- a positive electrode active material it was confirmed that not only the electrode process was easy but also the electrochemical characteristics of the secondary battery based on such a lithium composite transition metal oxide were improved, and thus the present invention was completed.
- the transition metal precursor according to the present invention has a composition represented by the following Chemical Formula 1, and is characterized in that it is prepared in a state in which a basic material is added to an aqueous transition metal solution containing a transition metal-containing salt.
- M is at least one selected from the group consisting of Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn and bicycle transition metals;
- A is at least one selected from the group consisting of anions of PO 4 , BO 3 , CO 3 , F and NO 3 ,
- x may be 0.2 or more and less than 0.5, and more specifically, 0.3 or more and less than 0.5.
- the oxidation number of the Mn may be +2 to +3.5.
- the transition metal precursor according to the present invention may be prepared by coprecipitation in one specific example.
- the coprecipitation method is a method for preparing two or more transition metal elements simultaneously by using a precipitation reaction in an aqueous solution.
- a transition metal precursor including two or more transition metals may be prepared by mixing transition metal-containing salts in a desired molar ratio in consideration of the content of the transition metal to prepare an aqueous solution, followed by a strong base such as sodium hydroxide, Therefore, it can be prepared by adding an additive such as an ammonia source or the like and coprecipitation while maintaining the pH to be basic.
- the pH range is 9 to 13 and in particular 9 to 12, and in some cases, the reaction may be carried out in multiple stages.
- the transition metal precursor may be prepared by further including a reducing agent in the aqueous transition metal solution to prevent oxidation of Mn to have a uniform particle size.
- the reducing agent may be included in 0.1 to 30 mol% relative to the molar amount of the aqueous solution of the transition metal, and in detail, may be included in 1.0 to 10 mol%. If the reducing agent is less than 0.1 mol%, the amount is too small to exert its effect. If the reducing agent is more than 30 mol%, the tendency to suppress precipitation of the transition metal hydroxide becomes stronger, which may result in deterioration of powder characteristics. not.
- the reducing agent may be at least one selected from the group consisting of hydrazine, oxalic acid, ascorbic acid, and a sugar-based material, and in detail, may be a sugar-based material.
- the sugar-based material is, for example, fructose (fructose), sucrose (sucrose), glucose (glucose), galactose (galactose), lactose (lactose), maltose (starch), and dextrin (dextrin) may be one or more selected from the group consisting of.
- the sugar-based material When used as the reducing agent, the sugar-based material is present on the surface of the transition metal-containing salt to prevent particles from agglomerating, thereby making it possible to prepare a transition metal precursor having a high porosity and a large specific surface area. In addition, it may be present in the interior voids or particle surface of the transition metal precursor, and the reducing agent trapped therein may be partially carbonized and thus exhibit the carbon treatment effect of the transition metal precursor, resulting in an improvement in electrochemical properties after firing.
- the inventors of the present application recognize these problems, and after extensive research based on numerous experiments, the preparation of the anion sites in the preparation of transition metal precursors containing high manganese content of PO 4 , BO 3 , CO 3 , When substituted with anions such as F and NO 3 , in spite of the addition of a reducing agent, the transition metal hydroxide is more easily precipitated and the cohesion of the particles is improved to improve the crystallinity, sphericity and tap density of the transition metal precursor. When the lithium composite transition metal oxide is manufactured using the same, the secondary battery including the electrode process is easy and the cathode active material is excellent in initial discharge capacity and efficiency, and the output characteristics are newly found.
- the amount of anion substitution exceeds 0.02, there is a problem in that charge and discharge capacity and efficiency are greatly reduced. Therefore, it is not preferable that the amount of anion substitution is 0.02 or less.
- the transition metal-containing salt may be sulfate, nitrate or carbonate, preferably having an anion that is easily decomposed and volatilized upon firing.
- Specific examples thereof include, but are not limited to, nickel sulfate, manganese sulfate, nickel nitrate, manganese nitrate, nickel carbonate, manganese carbonate, and the like.
- the basic material may include sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like, and preferably sodium hydroxide, but is not limited thereto.
- the present invention also provides a method of preparing the transition metal precursor.
- It may be prepared by a method comprising a.
- the anion may be added by mixing with a material such as a transition metal-containing salt within a range that does not cause other side reactions during the synthesis of the precursor, or may be added separately, but mixed with other materials in terms of cost savings in the process It is desirable to be.
- the anion in the process (ii) may be mixed by further adding a reducing agent.
- the reducing agent may be added simultaneously with a material such as a transition metal-containing salt, or may be added separately.
- the amount and concentration of the reducing agent per hour may be important variables in forming the precursor.
- the concentration of the reducing agent may be 2.0 mol% to 7.0 mol%. If the concentration of the reducing agent is less than 2.0 mol%, the effect is insignificant, and if it exceeds 7.0 mol%, the formation of precursor precipitates is excessively suppressed, which is not preferable.
- additives and / or alkali carbonates capable of forming a complex with a transition metal may be further added during the coprecipitation of step (iii).
- an ammonium ion source for example, an ethylene diamine compound, a citric acid compound, or the like can be used.
- the ammonium ion source include aqueous ammonia, aqueous ammonium sulfate solution and aqueous ammonium nitrate salt.
- the alkali carbonate may be selected from the group consisting of ammonium carbonate, sodium carbonate, potassium carbonate and lithium carbonate. In some cases, these may be used by mixing two or more thereof.
- the addition amount of the additive and alkali carbonate can be appropriately determined in consideration of the amount of transition metal-containing salt, pH, and the like.
- the present invention also provides a lithium composite transition metal oxide prepared from the transition metal precursor.
- the transition metal precursor and the lithium precursor may be mixed and calcined in an oxidizing atmosphere to prepare a lithium composite transition metal oxide which is a cathode active material for a lithium secondary battery.
- the lithium precursor is not particularly limited, and examples thereof include lithium hydroxide, lithium carbonate, lithium oxide, and the like, and preferably lithium carbonate (Li 2 CO 3 ) and / or lithium hydroxide (LiOH).
- the lithium composite transition metal oxide may be represented by the following formula (2).
- M is at least one selected from the group consisting of Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn and bicycle transition metals;
- A is at least one selected from the group consisting of anions of PO 4 , BO 3 , CO 3 , F and NO 3 ,
- the lithium complex transition metal oxide in which an anion site is substituted decreases the structure change due to the gas generated in the battery activation step as well as improving the ion conductivity by the anion.
- the lithium composite transition metal oxide represented by Chemical Formula 2 may be a solid solution or a composite form. In some cases, they may be present in a mixed form thereof.
- the lithium composite transition metal oxide can be effectively synthesized using the transition metal precursor according to the present invention, and when used as a cathode active material of a lithium secondary battery, it is not only stable at high voltage.
- the initial discharge capacity and efficiency are excellent, and the output characteristics and life characteristics are improved.
- the lithium composite transition metal oxide may be preferably used as an electrode active material for a lithium secondary battery, and these may be used alone or in combination with another known electrode active material for a lithium secondary battery.
- the present invention also provides a cathode including the lithium composite transition metal oxide as a cathode active material and a lithium secondary battery including the same.
- the positive electrode is prepared by, for example, applying a mixture of the positive electrode active material, the conductive material, and the binder according to the present invention onto a positive electrode current collector, followed by drying, and, if necessary, further adding a filler to the mixture.
- the positive electrode current collector is generally made to a thickness of 3 to 500 ⁇ m. Such a positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery.
- a positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery.
- the surface of stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel Surface treated with carbon, nickel, titanium, silver, or the like can be used.
- the current collector may form fine irregularities on its surface to increase the adhesion of the positive electrode active material, and may be in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
- the conductive material is typically added in an amount of 1 to 20 wt% based on the total weight of the mixture including the positive electrode active material.
- a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
- the binder is a component that assists in bonding the active material and the conductive material to the current collector, and is generally added in an amount of 1 to 20 wt% based on the total weight of the mixture including the positive electrode active material.
- binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene , Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers and the like.
- the filler is optionally used as a component for inhibiting expansion of the positive electrode, and is not particularly limited as long as it is a fibrous material without causing chemical change in the battery.
- the filler include olefinic polymers such as polyethylene and polypropylene; Fibrous materials, such as glass fiber and carbon fiber, are used.
- the lithium secondary battery is generally composed of the positive electrode, the negative electrode, the separator and the lithium salt-containing nonaqueous electrolyte, other components of the lithium secondary battery according to the present invention will be described below.
- the negative electrode is manufactured by applying and drying a negative electrode material on the negative electrode current collector, and if necessary, the components as described above may be further included.
- the negative electrode material may be, for example, carbon such as hardly graphitized carbon or graphite carbon; Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), Sn x Me 1-x Me ' y O z (Me: Mn, Fe, Pb, Ge; Me' Metal complex oxides such as Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen, 0 ⁇ x ⁇ 1; 1 ⁇ y ⁇ 3; 1 ⁇ z ⁇ 8); Lithium metal; Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , and metal oxides such as Bi 2 O 5 ;
- the negative electrode current collector is generally made to a thickness of 3 to 500 ⁇ m.
- a negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
- the surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface treated with carbon, nickel, titanium, silver, or the like, aluminum-cadmium alloy, or the like can be used.
- fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may 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 separator is interposed between the anode and the cathode, and an insulating thin film having high ion permeability and mechanical strength is used.
- the pore diameter of the separator is generally from 0.01 to 10 ⁇ m ⁇ m, thickness is generally 5 ⁇ 300 ⁇ m.
- a separator for example, olefin polymers such as chemical resistance and hydrophobic polypropylene; Sheets or non-woven fabrics made of glass fibers or polyethylene are used.
- a solid electrolyte such as a polymer
- the solid electrolyte may also serve as a separator.
- the lithium-containing non-aqueous electrolyte consists of a nonaqueous electrolyte and lithium.
- a nonaqueous electrolyte a nonaqueous electrolyte, a solid electrolyte, an inorganic solid electrolyte, and the like are used.
- organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, Polymers containing ionic dissociating groups and the like can be used.
- Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Li 4 SiO 4 -LiI-LiOH, Li 3 PO 4 -Li 2 has a nitride, halides, sulfates, such as Li, such as S-SiS 2 can be used.
- the lithium salt is a good material to be dissolved in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate and imide have.
- pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, etc.
- halogen-containing solvents such as carbon tetrachloride and ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics.
- the present invention also provides a battery module including the lithium secondary battery as a unit cell, and provides a battery pack including the battery module.
- the battery pack may be used as a power source for devices requiring high voltage stability, long cycle characteristics, high rate characteristics, and the like.
- Preferred examples of the device include a power tool that is driven by an electric motor; Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like; Electric motorcycles including electric bicycles (E-bikes) and electric scooters (E-scooters); Electric golf carts; Power storage systems and the like, but is not limited thereto.
- Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like
- Electric motorcycles including electric bicycles (E-bikes) and electric scooters (E-scooters); Electric golf carts; Power storage systems and the like, but is not limited thereto.
- Example 1 is a photograph taken with the FE-SEM (Hitachi S-4800 model) of the SEM image of the precursor prepared in Example 1;
- Example 2 is a photograph taken with a FE-SEM (Model Hitachi S-4800) of the precursor prepared in Example 2;
- Manganese sulphate, nickel sulphate and cobalt sulphate were mixed in a ratio (molar ratio) of 0.50: 0.45: 0.05 to prepare an aqueous solution of a transition metal at a concentration of 1.5 M, to which phosphate 0.5, which can provide the PO 4 anion, is substituted for the anion site. Mole% and 4.0 mole% sucrose were mixed together. Separately, 3M aqueous sodium hydroxide solution was prepared. The transition metal aqueous solution was continuously pumped with a metering pump to the tank for the wet reactor at 0.18 L / hr.
- the aqueous sodium hydroxide solution was pumped in conjunction with the control equipment to adjust the pH of the distilled water in the tank, so that the distilled water in the wet reactor tank pH 11.5 is maintained. At this time, a 14% concentration of ammonia solution as an additive was continuously pumped together into the reactor at a rate of 0.04 L / hr.
- the average residence time of the solution in the wet reactor tank was about 6 hours, and after the reaction in the tank reached the steady state, Given these, more complex composite transition metal precursors were synthesized.
- a manganese-nickel composite transition metal precursor prepared by continuously reacting transition metal ions of the transition metal aqueous solution, sodium hydroxide ion of sodium hydroxide, and ammonia ion of the ammonia solution for 20 hours was installed at the upper side of the tank. It is obtained continuously through the overflow pipe.
- the composite transition metal precursor thus obtained was washed several times with distilled water and dried in a 120 ° C. constant temperature dryer for 24 hours to obtain a manganese-nickel composite transition metal precursor.
- a transition metal precursor was prepared in the same manner as in Example 1 except that sucrose was not mixed with the aqueous transition metal solution.
- a transition metal precursor was prepared in the same manner as in Example 1 except that ginseng salt was not mixed with the aqueous transition metal solution.
- a transition metal precursor was prepared in the same manner as in Example 1 except that sucrose and ginseng salt were not mixed in the aqueous transition metal solution.
- prepared slurry was prepared by mixing Denka as a conductive material and KF1100 as a binder in a weight ratio of 88: 6: 6 to the prepared positive electrode active material powder, and uniformly coated on an aluminum foil having a thickness of 20 ⁇ m. This was dried to 130 °C to prepare a positive electrode for a lithium secondary battery.
- a 2016 coin battery was manufactured using a liquid electrolyte in which LiPF 6 was dissolved in 1 M in a solvent mixed with 1.
- the battery evaluation was performed by measuring the charge and discharge capacity in the applied current of 0.1C and a voltage range of 3.0 to 4.4 V and the discharge capacity and the charge and discharge efficiency results are shown in Table 2 below.
- the transition metal precursor for preparing a lithium composite transition metal oxide according to the present invention is prepared by coprecipitation in the state of adding a reducing agent to prevent oxidation of Mn, so that the specific surface area of the precursor having a uniform particle size Synthesis is possible.
- a reducing agent to prevent oxidation of Mn
- the specific surface area of the precursor having a uniform particle size Synthesis is possible.
- anion sites by substituting anion sites, the problem of inhibiting precipitation due to the addition of a reducing agent can be solved, thereby improving the crystallinity, sphericity and tap density of the precursor.
- the lithium composite transition metal oxide prepared using this as a positive electrode active material not only the electrode process is facilitated, but also the secondary battery based thereon can exhibit excellent initial discharge capacity and efficiency, improved output characteristics, and lifetime characteristics. have.
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Abstract
Description
Claims (25)
- 하기 화학식 1로 표현되는 조성을 가지며, 전이금속 함유 염이 혼합된 전이금속 수용액에 염기성 물질을 첨가한 상태에서 제조되는 것을 특징으로 하는 전이금속 전구체:MnaMb(OH1-x)2-yAy (1)상기 식에서,M은 Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn 및 2주기 전이금속들로 이루어진 군에서 선택되는 하나 이상이고;A는 PO4, BO3, CO3, F 및 NO3의 음이온으로 이루어진 군에서 선택되는 하나 이상이며,0.5≤a≤1.0;0≤b≤0.5;a + b = 1;0<x<1.0;0<y≤0.02이다.
- 제 1 항에 있어서, 상기 x는 0.2 이상 내지 0.5 미만인 것을 특징으로 하는 전이금속 전구체.
- 제 1 항에 있어서, 상기 Mn의 산화수는 +2 내지 +3.5인 것을 특징으로 하는 전이금속 전구체.
- 제 1 항에 있어서, 상기 전이금속 전구체는 Mn의 산화를 방지하기 위해 상기 전이금속 수용액에 환원제를 더 포함하여 제조되는 것을 특징으로 하는 전이금속 전구체.
- 제 4 항에 있어서, 상기 환원제는 상기 전이금속 수용액의 몰량 대비 0.1 내지 30 몰%인 것을 특징으로 하는 전이금속 전구체.
- 제 4 항에 있어서, 상기 환원제는 상기 전이금속 수용액의 전이금속 몰 대비 1.0 내지 10 몰%인 것을 특징으로 하는 전이금속 전구체.
- 제 4 항에 있어서, 상기 환원제의 농도는 2.0 내지 7.0 몰%인 것을 특징으로 하는 전이금속 전구체.
- 제 4 항에 있어서, 상기 환원제는 히드라진(hydrazine), 옥살산, 아스코르브 산, 수소, 탄소, 탄화수소, 및 기타 설탕계 물질로 이루어진 군에서 선택되는 하나 이상인 것을 특징으로 하는 전이금속 전구체.
- 제 4 항에 있어서, 상기 환원제는 설탕계 물질인 것을 특징으로 하는 전이금속 전구체.
- 제 9 항에 있어서, 상기 설탕계 물질은 프락토스(fructose), 슈크로오스(sucrose), 글루코오스(glucose), 갈락토스(galactose), 락토스(lactose), 말토오스(maltose), 녹말(starch), 및 덱스트린(dextrin)으로 이루어진 군에서 선택되는 하나 이상인 것을 특징으로 하는 전이금속 전구체.
- 제 1 항에 있어서, 상기 전이금속 함유 염은 황산염, 질산염 및 탄산염으로 이루어진 군에서 선택되는 어느 하나 이상인 것을 특징으로 하는 전이금속 전구체.
- 제 1 항에 있어서, 상기 염기성 물질은 수산화 나트륨, 수산화 칼륨 및 수산화 리튬으로 이루어진 군에서 선택되는 어느 하나 이상인 것을 특징으로 하는 전이금속 전구체
- 제 1 항에 있어서, 상기 전이금속 전구체는 공침법으로 제조되는 것을 특징으로 하는 전이금속 전구체.
- 제 1 항에 따른 전이금속 전구체를 제조하는 방법으로서,(i) 전구체 제조용 전이금속 함유 염을 포함하는 전이금속 수용액을 준비하는 과정;(ii) 상기 전이금속 수용액에 상기 전구체의 음이온 자리를 치환하도록 음이온을 혼합하는 과정; 및(iii) 과정(ii)의 혼합 후 강염기를 첨가하여 공침시키는 과정;을 포함하는 것을 특징으로 하는 전이금속 전구체의 제조 방법.
- 제 14 항에 있어서, 상기 과정(ii)에서 음이온 이외에 환원제를 더 첨가하여 혼합하는 것을 특징으로 하는 전이금속 전구체의 제조 방법.
- 제 15 항에 있어서, 상기 환원제의 농도는 2.0 내지 7.0 몰%인 것을 특징으로 하는 전이금속 전구체의 제조 방법.
- 제 1 항에 따른 전이금속 전구체를 사용하여 제조된 것을 특징으로 하는 리튬 복합 전이금속 산화물.
- 제 17 항에 있어서, 상기 리튬 복합 전이금속 산화물은 하기 화학식 2로 표현되는 것을 특징으로 하는 리튬 복합 전이금속 산화물.(1-x)LiM'O2-yAy -xLi2MnO3-y'Ay' (2)상기 식에서,M'은 MnaMb이고;M은 Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn 및 2주기 전이금속들로 이루어진 군에서 선택되는 하나 이상이며;A는 PO4, BO3, CO3, F 및 NO3의 음이온으로 이루어진 군에서 선택되는 하나 이상이고,0<x<1;0<y≤0.02;0<y'≤0.02;0.5≤a≤1.0;0≤b≤0.5;a + b = 1 이다.
- 제 18 항에 있어서, 상기 리튬 복합 전이금속 산화물은 고용체(solid solution) 또는 복합체(composite) 형태인 것을 특징으로 하는 리튬 복합 전이금속 산화물
- 제 17 항에 따른 리튬 복합 전이금속 산화물을 양극 활물질로서 포함하는 것을 특징으로 하는 양극.
- 제 20 항에 따른 양극을 포함하는 것을 특징으로 하는 리튬 이차전지.
- 제 21 항에 따른 리튬 이차전지를 단위전지로 포함하는 것을 특징으로 하는 전지모듈.
- 제 22 항에 따른 전지모듈을 포함하는 것을 특징으로 하는 전지팩.
- 제 23 항에 따른 전지팩을 포함하는 것을 특징으로 하는 디바이스.
- 제 24 항에 있어서, 상기 디바이스는 전기자동차, 하이브리드 전기자동차, 플러그-인 하이브리드 전기자동차, 또는 전력저장용 시스템인 것을 특징으로 하는 디바이스.
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JP2016527951A JP6342488B2 (ja) | 2013-08-20 | 2014-08-18 | リチウム複合遷移金属酸化物製造用前駆体、その製造方法及びそれを用いたリチウム複合遷移金属酸化物 |
CN201480043166.XA CN105452171B (zh) | 2013-08-20 | 2014-08-18 | 锂复合过渡金属氧化物制造用前体、其制造方法、及由其获得的锂复合过渡金属氧化物 |
EP14837239.4A EP3009404B1 (en) | 2013-08-20 | 2014-08-18 | Precursor for preparing lithium composite transition metal oxide, method for preparing same, and lithium composite transition metal oxide using same |
US16/394,624 US10903489B2 (en) | 2013-08-20 | 2019-04-25 | Precursor for preparation of lithium composite transition metal oxide, method for preparing the same and lithium composite transition metal oxide obtained from the same |
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KR20130090341A (ko) * | 2012-02-03 | 2013-08-13 | 주식회사 엘지화학 | 리튬 이차전지용 리튬 복합 전이금속 산화물의 전구체 입자들 및 이를 포함하는 양극 활물질 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2018012385A1 (ja) * | 2016-07-14 | 2018-01-18 | 株式会社Gsユアサ | 非水電解質二次電池用正極活物質、遷移金属水酸化物前駆体、遷移金属水酸化物前駆体の製造方法、非水電解質二次電池用正極活物質の製造方法、非水電解質二次電池用電極、非水電解質二次電池及び蓄電装置 |
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KR20150021417A (ko) | 2015-03-02 |
TWI520424B (zh) | 2016-02-01 |
US10903489B2 (en) | 2021-01-26 |
JP6342488B2 (ja) | 2018-06-13 |
US10355275B2 (en) | 2019-07-16 |
EP3009404A4 (en) | 2017-02-22 |
JP2016530193A (ja) | 2016-09-29 |
CN105452171B (zh) | 2018-01-12 |
US20190252679A1 (en) | 2019-08-15 |
EP3009404B1 (en) | 2020-01-22 |
TW201523989A (zh) | 2015-06-16 |
KR101608632B1 (ko) | 2016-04-05 |
US20160164087A1 (en) | 2016-06-09 |
CN105452171A (zh) | 2016-03-30 |
EP3009404A1 (en) | 2016-04-20 |
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