WO2015072702A1 - 불소 고분자를 이용하여 표면처리한 리튬 이차전지용 양극 활물질 및 이의 제조방법 - Google Patents

불소 고분자를 이용하여 표면처리한 리튬 이차전지용 양극 활물질 및 이의 제조방법 Download PDF

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Publication number
WO2015072702A1
WO2015072702A1 PCT/KR2014/010651 KR2014010651W WO2015072702A1 WO 2015072702 A1 WO2015072702 A1 WO 2015072702A1 KR 2014010651 W KR2014010651 W KR 2014010651W WO 2015072702 A1 WO2015072702 A1 WO 2015072702A1
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Prior art keywords
active material
lithium
fluorine
metal oxide
positive electrode
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Ceased
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PCT/KR2014/010651
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English (en)
French (fr)
Inventor
박병천
정왕모
오상승
박성빈
김지혜
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LG Chem Ltd
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LG Chem Ltd
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Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to US15/032,178 priority Critical patent/US10418634B2/en
Priority to EP14861667.5A priority patent/EP3043407B1/en
Priority to CN201480059278.4A priority patent/CN105684199B/zh
Priority to JP2016550444A priority patent/JP6621210B2/ja
Publication of WO2015072702A1 publication Critical patent/WO2015072702A1/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Definitions

  • the present invention provides a cathode active material and a lithium secondary battery capable of repeated layer discharge.
  • Lithium secondary batteries are important for the development of ubiquitous society. Lithium secondary batteries have higher operating voltages and energy densities than other secondary batteries, and can be used for a long time, resulting in complex and complex equipment.
  • lithium secondary battery technology has made efforts to expand the field of application as well as environmentally friendly hydrogen systems such as electric vehicles, as well as electric power storage.
  • Korean Patent Laid-Open No. 10-2005-0114516 discloses dissimilar metal oxides on surfaces.
  • a cathode active material for a lithium secondary battery made of a coated lithium-containing composite oxide.
  • Korean Patent Publication No. 10-0479900 discloses that a part of manganese (Mn) is Ni, Co, Fe, Cr and
  • a spinel-type lithium-containing transition metal oxide is disclosed which is substituted with at least one metal element selected from the group consisting of Cu and at least one metal element selected from the group consisting of silicon (Si) and titanium (Ti).
  • the present invention utilizes fluorine polymer to form the surface of lithium-containing metal oxide particles.
  • cathode active material for a lithium secondary battery of a novel structure and other active material.
  • the compound of 10-0479900 has a high operating potential of 4.5 V or higher, so that electrolytes are decomposed even in the normal operating range of the battery, and the performance of the battery is degraded due to side reaction with the electrolyte. It was confirmed that the "elution of ions" occurred. This problem is caused by the operating voltage of 4V region.
  • the present invention uses a fluorine polymer to solve the surface of a spinel-structured lithium-containing metal oxide. I want to solve it by processing.
  • the positive electrode active material for a lithium secondary battery includes: lithium-containing metal oxide particles; formed on the surface of the lithium-containing metal oxide particles, and formed of fluorine-doped metal oxides and fluorine-doped metal hydroxides. And a first surface treatment layer containing at least one compound selected from the group consisting of: and a second surface treatment layer formed on the surface of the first surface treatment layer and containing fluorine polymer. do.
  • the positive electrode active material according to the present invention includes a first surface treatment layer and a second surface treatment layer each containing fluorine, and are particularly present in the second surface treatment layer.
  • CF -Fluoride
  • the first surface treatment layer may cover the entire surface of the lithium-containing metal oxide particles, and the second surface treatment layer may cover part or the entire surface of the first surface treatment layer.
  • the first surface treatment layer covers a part of the surface of the lithium-containing metal oxide, and in this case, the second surface treatment layer is a part of the surface of the lithium-containing metal oxide and a part of the surface of the first surface treatment layer. Or it may cover the whole.
  • the positive electrode active material mixes lithium-containing metal oxide particles with fluorine polymer in the range of 0.05% by weight to less than 5.00% by weight based on the total weight of the positive electrode active material.
  • the fluorine-doped metal oxide may be a fluorine-doped lithium-containing metal oxide in which a part of oxygen of the lithium-containing metal oxide is replaced with fluorine.
  • the content of the fluorine polymer is, in detail, a positive electrode active material. It may be more than 0.05% by weight to less than 3% by weight of the total weight, more specifically, may be more than 0.10% by weight to less than 1.00% by weight, more specifically, more than 0.20% by weight to less than 1.00% by weight.
  • the positive electrode active material according to the present invention has a critical effect when the content of the fluorine polymer is 0.05% by weight or more and less than 5.00% by weight based on the total amount of the positive electrode active material.
  • the fluorine-doped metal oxide may be present on the surface of the lithium-containing metal oxide particles in the form of particles. Further, the fluorine polymer may be present on the surface of the first surface treatment layer in the form of particles (FIG. 1 and In this case, the average particle diameter (D50) of the fluorine-doped lithium-containing metal oxide particles may be in the range of the average thickness of the first surface treatment layer, the average of the fluorine-containing polymer particles
  • the particle diameter D50 may be in the range of the average thickness of the second surface treatment layer.
  • the average particle diameter (D50) of the particles may be within the range mentioned above, for example, from 1 nm to 1500 nm, respectively, in detail from 10 nm to 1000 nm. If the average particle diameter (D50) of the fluorine-doped metal hydroxide particles is less than 1 nm each, the particles may be enormously small and are not preferable. If the particle size is more than 1500 nm, the efficiency of the manufacturing process is not desirable.
  • the positive electrode active material comprises lithium oxide containing metal oxide, metal hydroxide or metal oxide and metal hydroxide in the range of 0.05% to 2.00% by weight relative to the total weight of the positive electrode active material. It can be manufactured by mixing with fluorine polymer in the range of 0.05% by weight or more and less than 5.00% by weight based on the total amount of positive electrode active material and heat-treating in an air atmosphere.
  • the fluorine-doped metal oxide is a portion of the oxygen of the oxide of one metal selected from the group consisting of Al, Mg, Ni, Co, Ti, Cr, Mo, Bi, Zn ⁇ Zr, Ru and W.
  • the fluorine-doped metal hydroxide may be a fluorine-substituted hydroxide of a metal hydroxide selected from the group consisting of Al, Mg, Ni, Co, Ti, Cr, Mo, Bi, Zn, Zr, Ru, and W. Some of them may be replaced with fluorine.
  • the content of the fluorine-doped metal oxide may range from 0.05% by weight to less than 2.00% by weight based on the total weight of the positive electrode active material, and the content of the fluorine-doped metal hydroxide may be 0.05 based on the total amount of the positive electrode active material. It may range from more than% by weight to less than 2.00% by weight.
  • the content of the fluorine polymer may be in the range of 0.05% by weight to more than 5.00% by weight based on the total weight of the positive electrode active material, more specifically, in the range of 0.05% by weight to 3% by weight, more specifically, 0.10% by weight. It may be greater than or equal to% and less than 1.00 weight%, and more specifically, greater than or equal to 0.20 weight% and less than 1.00 weight%.
  • the positive electrode active material according to the present invention has a critical effect when the content of fluorine polymer is 0.05% by weight or more and less than 5.00% by weight based on the total weight of the positive electrode active material.
  • the fluorine-doped metal oxide and the fluorine-doped metal hydroxide may be present on the surface of the lithium-containing metal oxide particle in the form of particles.
  • the fluorine polymer may also be present on the surface of the first surface treatment layer in the form of particles.
  • the average particle diameter (D50) of the fluorine-doped metal oxide particles and the fluorine-doped metal hydroxide particles may be in the range of the average thickness of the first surface treatment layer, and the average particle diameter (D50) of the fluorine polymer particles , The average thickness of the second surface treatment layer may be within the range.
  • the average particle diameter (D50) of the particles may be within the ranges mentioned above, for example, between 1 nm and less than 1500 nm, and more specifically between 10 nm and 1000 nm. If the average particle diameter (D50) of the fluorine-doped metal hydroxide particles is less than 1 nm, the particles may be excessively small in size, which is not preferable. If the particle size is more than 1500 nm, the efficiency of manufacturing process is not desirable.
  • the fluorine polymer serves as a source of fluorine element of the metal oxide or the metal hydroxide constituting the first surface treatment layer.
  • the fluorine polymer may include, but is not limited to, polyvinylfluoride, polyvinylidene fluoride,
  • It may be one or more selected from the group consisting of Perfluorosulfonic acid.
  • the lithium-containing metal oxide may be a layered lithium transition metal oxide or a spinel structure lithium transition metal oxide.
  • the lithium-containing metal oxide may be lithium cobalt oxide (LiCo0 2 ) or lithium nickel oxide (LiNi0 2 ).
  • Layered compounds such as compounds substituted with one or more transition metals; and Li l + y Mn 2 . y 0 4 (where y is 0 to 0.33), LiMn0 3 , LiMn 2 0 3 , LiMn0 2 lithium manganese oxide; lithium copper oxide (Li 2 Cu 0 2 ), formula LiNi ,.
  • the spinel-structured lithium transition metal oxide is It may be a compound having a composition represented by the following formula (1).
  • M is at least one selected from Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zn, and a group consisting of five transition metals in the periodic table; -0.1 ⁇ a ⁇ 0.1, 0.3 ⁇ x ⁇ 0.8.
  • the spinel structure lithium transition metal oxide of Formula (1) may be a compound having a composition represented by the following Formula (2).
  • M is Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zn and 5 cycles of the periodic table
  • One or more selected from the group consisting of transition metals -0.1 ⁇ a ⁇ 0.1, 0.3 ⁇ b ⁇ 0.6, 0 ⁇ c ⁇ 0.2.
  • the present invention can also provide a cathode for a lithium secondary battery in which an electrode mixture layer containing the cathode active material and the conductive material and binder is also included on a current collector.
  • an electrode assembly having a structure including a cathode, an anode, and a polymer film interposed between the anode and the cathode may be stored in a battery case, and a sealed lithium secondary battery may be provided. It may contain an electrolyte.
  • the lithium secondary battery may be a lithium ion battery, a lithium ion polymer battery, or a lithium polymer battery.
  • the positive electrode or the negative electrode disperses or dissolves the binder in a solvent to form a binder solution.
  • an electrode slurry by mixing the binder solution, an electrode active material, and a conductive material; coating the electrode slurry on a current collector;
  • It can be manufactured by a manufacturing method including drying the electrode; and compressing the electrode to a certain thickness. In some cases, the method may further include drying the rolled electrode.
  • the binder solution manufacturing process is a process of preparing a binder solution by dispersing or dissolving the binder in a solvent.
  • the binder may be all binders known in the industry, specifically, polyvinylidene fluoride (PVdF) or
  • Fluororesin binder containing polytetrafluoroethylene (/ (yieira ⁇ / ZMoroei / iy / ene, PTFE), Styrene-butadiene rubber, Acrylonitrile-butydiene rubber, Rubber-based binder including styrene-isoprene rubber,
  • the solvent may be selectively used depending on the type of the binder. For example, organic solvents such as isopropyl alcohol, N-methylpyrrolidone (NMP) and acetone may be used.
  • PVdF may be dispersed / dissolved in NMP (N-methyl pyrrolidone) to prepare anode binder solution, and SBR (Styrene-Butadiene Rubber) / CMC (Carboxy Methyl Cellulose). Can also be dispersed / dissolved in water to produce a negative binder solution.
  • NMP N-methyl pyrrolidone
  • SBR Styrene-Butadiene Rubber
  • CMC Carboxy Methyl Cellulose
  • An electrode slurry can be prepared by mixing / dispersing an electrode active material and a conductive material in the binder solution.
  • the prepared electrode slurry can be transferred to a storage tank and stored until the coating process. In order to prevent the electrode slurry from freezing, the electrode slurry can be stirred continuously.
  • the electrode active material may be the cathode active material or the cathode active material described below.
  • the negative electrode active material is, for example, carbon such as non-graphitized carbon, graphite-based carbon; Li x Fe 2 0 3 (0 ⁇ x ⁇ l), Li x WO 2 (0 ⁇ x ⁇ l), Sn x Me ,.
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical changes to the battery.
  • graphite such as natural graphite or artificial graphite
  • conductive fibers such as carbon fiber and metal fiber
  • metal powder such as carbon fluoride, aluminum and nickel powder
  • conductive whiskey such as zinc oxide and potassium titanate
  • titanium oxide Conductive metal oxides such as; conductive materials such as polyphenylene derivatives; and the like.
  • the electrode slurry may optionally be added with a layer cleaner as needed.
  • the filler is not particularly limited as long as it is a fibrous material without inducing chemical changes in the battery.
  • an olefinic polymer such as polyethylene or polypropylene may be used; fibrous materials such as glass fiber and carbon fiber may be used.
  • the coating of the electrode slurry on the current collector is a process of coating the electrode slurry on the current collector with a predetermined pattern and a predetermined thickness by passing through a coater head.
  • the method of coating the electrode slurry on the current collector may be performed by distributing the electrode slurry on the current collector and uniformly dispersing the same using a doctor blade, die casting, or comma. It can be used for coating, screen printing, etc.
  • the electrode slurry can be bonded to the current collector by pressing or lamination.
  • the current collector has high conductivity without causing chemical changes in the battery. It does not have particular limitation, if it has, for example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel surface treated with carbon, nickel, titanium, silver, etc., aluminum-cadmium Alloys and the like can be used.
  • the positive electrode current collector can form fine irregularities on the surface to strengthen the bonding strength of the positive electrode active material, and can be used in various forms such as film, sheet, foil, net, porous body, foam, and nonwoven fabric.
  • the positive electrode current collector may be a metal current collector including aluminum
  • the negative electrode current collector may be a metal current collector including copper.
  • the electrode current collector may be a metal foil and aluminum (A1) foil. Or copper (Cu) foil.
  • the drying process is a process of removing solvent and water in slurry to dry the coated slurry on the metal current collector.
  • the drying process is carried out in a vacuum oven at 50 to 20 ° C. within 1 day. .
  • the preheating process is a process of preheating the electrodes before they are introduced into each other to increase the compression effect of the electrodes.
  • the electrode after the rolling process has completed the temperature above the melting point of the binder.
  • the rolled electrode may be cut to a certain length and then dried.
  • the cooling process may be further included.
  • the polymer membrane is a separation membrane that separates between the positive electrode and the negative electrode.
  • the solid electrolyte may also serve as the separation membrane.
  • the separator is an insulating thin film having high ion permeability and mechanical strength.
  • the pore diameter of the separator is generally ⁇ -10 and the thickness is generally 5-300.
  • Such separators include, for example, olefin polymers such as chemical and hydrophobic polypropylenes; sheets or nonwovens made of glass fibers or polyethylene; Kraft papers are used.
  • olefin polymers such as chemical and hydrophobic polypropylenes
  • sheets or nonwovens made of glass fibers or polyethylene Kraft papers are used.
  • Typical examples currently on the market include Celgard series (Celgard R 2400, 2300 (manufactured by Hoechest Celanese Corp.), polypropylene separator (manufactured by Ube Industries Ltd. or Pall RAI), and polyethylene group (Tonen). Or Entek).
  • a gel polymer electrolyte may be coated on the separator in order to increase the stability of the cell.
  • Polyethylene oxide polyvinylidene fluoride, polyacrylonitrile and the like.
  • the electrode assembly may be a jelly-type electrode assembly (or a structure known in the art). Wound electrode assemblies), stacked electrode assemblies (or stacked electrode assemblies) or stacked & folding electrode assemblies.
  • the stack and folding electrode assembly is configured to fold or wind the separator sheet after arranging unit cells having a separator structure between the anode and the cathode on the separator sheet.
  • the nonaqueous electrolyte may be a nonaqueous electrolyte, a solid electrolyte, or an inorganic solid electrolyte.
  • non-aqueous electrolyte for example, N-methyl-2-pyrrolidinone and propylene
  • the organic solid electrolyte may be, for example, polyethylene derivatives or polyethylene.
  • Polymeric columns containing oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, poly agitation lysine, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, and silver dissociates can be used.
  • the lithium salt is a good material to be dissolved in the non-aqueous electrolyte, for example, LiCl, LiBr, Lil, LiC10 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 S0 3 , LiCF 3 C0 2, LiAsF 6, LiSbF 6, LiAlCl 4> CH 3 S0 3 Li, CF 3 S0 3 Li, LiSCN, LiC (CF 3 S0 2) 3, (CF 3 S0 2) 2 NLi, chloro borane lithium, lower aliphatic carboxylic Lithium phosphate, lithium phenyl borate, imide and the like can be used.
  • the electrolyte has a purpose of improving charge and discharge characteristics and flame retardancy, for example,
  • a halogen-containing solvent may be further included, and a carbon dioxide gas may be further included to improve high temperature preservation characteristics, and fluoro-ethylene carbonate (FEC), propene sultone (PRS) and fluoro-propylene carbonate (FPC) may be added.
  • FEC fluoro-ethylene carbonate
  • PRS propene sultone
  • FPC fluoro-propylene carbonate
  • the lithium secondary battery according to the present invention can not only be used as a power source for small devices, but also for medium and large battery models including a large number of lithium secondary batteries.
  • the present invention provides a battery pack including the battery modules as a power source for a medium and large device, and the medium and large device includes an electric vehicle (EV) and a hybrid electric vehicle (Hybrid Electric).
  • Electric vehicles and power storage devices including, but not limited to, vehicles, HEVs, and Plug-in Hybrid Electric Vehicles (PHEVs).
  • the battery modules and battery packs may be manufactured by the structure and manufacturing method known in the art, and are not particularly limited.
  • FIG. 1 is an SEM image of the positive electrode active material of Non-limiting Example 1 of the present invention.
  • FIG. 2 is a SEM image of the positive electrode active material of Non-limiting Comparative Example 1 of the present invention.
  • the positive electrode active material The conductive material: The amount of the binder is 95: 2.5: 2.5, and weighed in an NMP, mixed to prepare a positive electrode mixture, and coated the positive electrode mixture on aluminum foil of 20 ⁇ thickness. The anode was then prepared by rolling and drying.
  • the lithium secondary battery positive electrode prepared above lithium metal foil as a counter electrode (cathode), a polyethylene film (Celgard, thickness: 20 ⁇ ⁇ ) as a separator, ethylene carbonate, dimethylene carbonate, diethyl carbonate, 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: 2: 1.
  • a coin coin cell was manufactured in the same manner as in Example 1, except that the amount of PVdF was 0.5% by weight.
  • Example 3 A coin coin cell was manufactured in the same manner as in Example 1, except that the amount of PVdF was 1.0% by weight.
  • a coin coin was manufactured in the same manner as in Example 1, except that a positive electrode material of LiNi 0.44Mn 1 56 O 4 was mixed with 0.5% by weight of PVdF and 0.25% by weight of 70 nm in size of A1 20 3 . .
  • a coin coin cell was manufactured in the same manner as in Example 4, except that 70 nm ZrO having a 0.25 increase of ⁇ 7 ° instead of A1 2 0 3 was mixed.
  • a 2016 coin battery was manufactured in the same manner as in Example 4.
  • the coin cell of 2016 was manufactured by the method of Example 1 using the positive electrode material of ⁇ ⁇ ⁇ , ⁇ which was not surface-treated using PVdF.
  • a coin coin was manufactured in the same manner as in Example 1, except that A1 2 0 3 having a size of 2 / mm3 was used instead of the magnesium oxide of Example 4.
  • the battery according to Examples 1 to 6 of the present invention can be seen that the initial charge and discharge efficiency is significantly improved compared to the batteries according to Comparative Examples 2 and 3, in the case of the battery of Comparative Example 1 Although the initial charge and charging efficiency is relatively high, it can be seen that the initial layer capacity itself is low.
  • the cathode active material of the battery according to Examples 1 to 6 of the present invention is the first surface treatment layer and the second surface treatment containing fluorine.
  • the fluorinated polymer mainly present in the second surface treatment layer increases the concentration of lithium ions by electrochemical reactions, thereby making it easier to move the lithium ions generated during charging and discharging on the surface of the lithium-containing metal oxide. Because of losing.
  • the battery according to Examples 1 to 6 of the present invention is superior to the high temperature life characteristics compared with the batteries according to Comparative Examples 1 and 2.
  • This embodiment 1 of the present invention The positive electrode active material of the battery according to 6 to 6 has a predetermined surface treatment layer containing fluorine, thereby suppressing side reaction of the surface of the positive electrode active material and the electrolyte and dissolution of manganese at high voltage.
  • the self-discharge amount and the gas generation rate were evaluated by evacuating one layer in the voltage range of 3.5 ⁇ 4.9V and storing it for 2 weeks at 45 ° C.
  • the results are shown in Table 3 below.
  • Comparative Example 2 24.2 5.7 According to Table 2, it can be seen that the cells according to Examples 1 to 6 of the present invention are relatively low in self-discharge and gas generation compared with the batteries according to Comparative Examples 1 and 2.
  • the positive electrode active material of the battery according to Examples 1 to 6 has predetermined surface treatment layers containing fluorine, which can suppress the surface reaction of the positive electrode active material and the side reaction of the electrolyte and the elution of manganese at high voltage.
  • the present invention uses a fluorine polymer to form a cathode active material for lithium secondary batteries.
  • Electrode treatment provides a novel cathode active material having a first surface treatment layer of a fluorine-doped metal oxide layer and / or a fluorine-doped metal hydroxide layer and a second surface treatment layer comprising fluorine polymers. Therefore, lithium may promote silver migration at the surface of the lithium-containing metal oxide during layer discharge.
  • the content of fluorine polymer is less than 5% by weight relative to the total increase of the positive electrode active material.
  • the reaction between the surface of the positive electrode active material and the electrolyte at a high voltage is higher than that of a compound in which a part of manganese is replaced with a metal element such as Ni. And by suppressing the elution of manganese, there is an advantage that can provide a high voltage lithium secondary battery.

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Abstract

본 발명은 리튬 함유 금속 산화물 입자; 상기 리튬 함유 금속 산화물 입자의 표면에 형성되어 있고， 불소 도핑 금속 산화물들과 불소 도핑 금속 수산화물들로 이루어진 군에서 선택되는 하나 이상의 화합물을 포함하고 있는 제 1표면처리 층; 및 상기 제 1표면처리층의 표면에 형성되어 있고, 불소 고분자를 포함하고 있는 제 2표면처리층; 을 포함하는 것을 특징으로 하는 리륨 이차전지용 양극 활물질 및 이의 제조방법에 관한 것이다.

Description

명세서
발명의명칭:불소고분자를이용하여표면처리한리튬이차전지용 양극활물질및이의제조방법
기술분야
[1] 본발명은반복적인층방전이가능한리튬이차전지의양극활물질및
이의제조방법에관한것이다.
배경기술
[2] IT(Information Technology)기술이눈부시게발달함에따라다양한휴대형
정보통신기기의확산이이뤄짐으로써 , 21세기는시간과장소에구애받지않고 고품질의정보서비스가가능한 '유비쿼터스사회 '로발전되고있다.이러한 유비쿼터스사회로의발전기반에는,리륨이차전지가중요한위치를차지하고 있다.리튬이차전지는다른이차전지에비해작동전압및에너지밀도가높을 뿐아니라오래사용할수있어기기의다양화와복합화에따른복잡한
요구조건을충족시킬수있는특성이있다.최근기존의리튬이차전지기술을 더욱발전시켜전기자동차등친환경수소시스템뿐만아니라，전력저장등으로 , 응용분야를확대하기위한노력이전세계적으로활발히진행되고있다.
[3] 대한민국공개특허제 10-2005-0114516호는，표면에이종금속산화물을
코팅된리튬함유복합산화물로이루어진리튬이차전지용양극활물질을 개시하고있다.
[4] 대한민국특허공보제 10-0479900호는，망간 (Mn)의일부를 Ni,및 Co, Fe, Cr및
Cu로이투어진군으로부터선택되는 1종이상의금속원소와실리콘 (Si)과 티타늄 (Ti)으로이루어진군에서선택되는 1종이상의금속원소로치환한 스피넬구조의리톱함유전이금속산화물을개시하고있다.
발명의상세한설명
기술적과제
[5] 본발명은불소고분자를이용하여리튬함유금속산화물입자의표면을
처리함으로써，대한민국공개특허제 10-2005-0114516호에개시된양극
활물질과다른신규한구조의리튬이차전지용양극활물질을제공하고자한다.
[6] 또한,본출원의발명자들이확인한바에따르면，스피넬구조의리튬함유망간 산화물의망간의일부를니켈등의금속으로치환한대한민국특허공보제
10-0479900호의화합물은， 4.5 V이상의높은작동전위를가지는까닭에 , 전지의정상작동범위에서도전해액이분해되고전해액과의부반응으로 인해서전지의성능이저하되는문제가있음을확인하였다.또한， Mn이온의 " 용출이발생함을확인하였다.이러한문제는， 4V영역의작동전압을가지는
LiMn204에서는발견할수없었던문제였다.본발명은，이러한문제점을불소 고분자를이용하여스피넬구조의리튬함유금속산화물의표면을 처리함으로써해결하고자한다.
과제해결수단
[7] 본발명의비제한적인예에따른리튬이차전지용양극활물질은,리튬함유 금속산화물입자;상기리튬함유금속산화물입자의표면에형성되어있고， 불소도핑금속산화물들과블소도핑금속수산화물들로이루어진군에서 선택되는하나이상의화합물을포함하고있는제 1표면처리층;및상기제 1 표면처리층의표면에형성되어있고,불소고분자를포함하고있는제 2 표면처리층;을포함하는것을특징으로한다.
[8] 본발명에따른양극활물질은각각불소를포함하는제 1표면처리층및제 2 표면처리층올포함하며,특히，제 2표면처리층에주로존재하는
-CF (불소고분자)는전기화학반웅으로인해양극활물질표면의리튬이온의 농도를높여주기때문에리튬함유금속산화물의표면에서층방전시일어나는 리튬이온의이동을더욱용이하게해줄수있으므로,결과적으로,고전압에서의 양극활물질표면과전해액의부반웅및망간의용출을억제함으로써，고전압용 리튬이차전지를제공할수있다.
[9] 상기제 1표면처리층은상기리튬함유금속산화물입자의표면의전부를 덮고있을수있고，상기제 2표면처리층은상기제 1표면처리층의표면의 일부또는전부를덮고있을수있다.또한，상기제 1표면처리층은상기리튬 함유금속산화물의표면의일부를덮고있고,이경우,상기제 2표면처리층은 상기리튬함유금속산화물의표면의일부와상기제 1표면처리층의표면의 일부또는전부를덮고있을수있다.
[10] 본발명의비제한적인예에따라서，상기한양극활물질은,리튬함유금속 산화물입자를양극활물질전체중량대비 0.05중량 %이상내지 5.00증량 % 미만의범위의불소고분자와흔합하고,공기분위기에서열처라함으로써 제조할수있다.이경우，상기불소도핑금속산화물은상기리튬함유금속 산화물의산소증일부를불소로치환한불소도핑리튬함유금속산화물일수 있다.상기불소고분자의함량은상세하게는,양극활물질전체중량대비 0.05 중량 %이상내지 3중량 %이하일수있고，더욱상세하게는 0.10증량 %이상 내지 1.00중량 %미만일수있고,좀더상세하게는 0.20중량 %이상내지 1.00 중량 %미만일수있다.
[11] 본발명의구체적인실험예를참고할때，불소고분자의함량이 0.05중량 % 미만일경우,소망하는효과를발휘할수없고，불소고분자의함량이 5.00 중량 %이상인경우，초기방전용량과 45°C고온수명특성이저하되고， 45°C고온 저장시가스발생으로인한자가방전이증가함을확인할수있다.
[12] 따라서,본발명에따른양극활물질은，불소고분자의함량이양극활물질의 전체증량을기준으로 0.05증량 %이상내지 5.00중량 %미만일때,임계적 효과를가진다. [13] 상기불소도핑금속산화물은입자형태로상기리튬함유금속산화물입자의 표면에존재할수있다.또한，상기불소고분자는입자형태로상기제 1 표면처리층의표면에존재할수있다 (도 1및 2의 SEM이미지참고).이경우, 상기불소도핑리튬함유금속산화물입자의평균입경 (D50)은，제 1표면처리 층의평균두께의범위이내일수있고，상기블소고분자입자의평균
입경 (D50)은，제 2표면처리층의평균두께의범위이내일수있다.
[14] 상세하게는상기불소도핑금속산화물입자와불소도핑금속수산화물
입자의평균입경 (D50)은상기에서언급한범위이내에서 ,예를들어，각각 1 nm 이상내지 1500 nm미만일수있으며，상세하게는 10 nm이상내지 1000 nm 이하일수있다.상기불소도핑금속산화물입자와불소도핑금속수산화물 입자의평균입경 (D50)이각각 1 nm미만일경우，지나치게작은크기로 입자들이웅집될수있어바람직하지않으며， 1500 nm이상일경우，제조공정상 효율성이떨어지는바바람직하지않다.
[15] 본발명의비제한적인예에서，상기한양극활물질은,리튬함유금속산화물 입자를양극활물질전체중량대비 0.05증량 %내지 2.00증량%범위의금속 산화물,금속수산화물또는금속산화물및금속수산화물과양극활물질전체 증량대비 0.05증량 %이상내지 5.00중량 %미만의범위의불소고분자와 혼합하고，공기분위기에서열처리함으로써제조할수있다.
[16] 이경우，상기불소도핑금속산화물은， Al, Mg, Ni, Co, Ti, Cr, Mo, Bi, Znᅳ Zr, Ru 및 W로이루어진군에서선택된하나의금속의산화물의산소의일부를불소로 치환한것일수있고，상기불소도핑금속수산화물은, Al, Mg, Ni, Co, Ti, Cr, Mo, Bi, Zn, Zr, Ru및 W로이루어진군에서선택된하나의금속의수산화물의 수산화기의일부를불소로치환한것일수있다.
[17] 상기불소도핑금속산화물의함량은양극활물질의전체중량을기준으로 0.05중량 %이상내지 2.00증량 %미만의범위일수있고，상기불소도핑금속 수산화물의함량은양극활물질의전체증량을기준으로 0.05중량 %이상내지 2.00중량 %미만의범위일수있다.
[18] 상기불소고분자의함량은양극활물질전체중량대비 0.05중량 %이상내지 5.00중량 %미만의범위일수있고，상세하게는， 0.05중량 %이상내지 3증량 % 이하일수있고，더욱상세하게는 0.10증량 %이상내지 1.00중량 %미만일수 있고,좀더상세하게는 0.20중량 %이상내지 1.00중량 %미만일수있다.
[19] 본발명의구체적인실험예를참고할때，불소고분자의함량이 0.05증량 % 미만일경우，소망하는효과를발휘할수없고，불소고분자의함량이 5.00증량 % 이상인경우,초기방전용량및 45°C고온수명특성이저하되고, 45°C고온저장 시가스발생으로인한자가방전이증가함을확인할수있다.
[20] 따라서，본발명에따른양극활물질은,불소고분자의함량이양극활물질의 전체중량을기준으로 0.05중량 %이상내지 5.00중량 %미만인때，임계적 효과를가진다. [21] 상기블소도핑금속산화물과상기불소도핑금속수산화물은입자형태로 상기리톱함유금속산화물입자의표면에존재할수있다.또한,상기불소 고분자는입자형태로상기제 1표면처리층의표면에존재할수있다.이경우, 상기불소도핑금속산화물입자와불소도핑금속수산화물입자의평균 입경 (D50)은，제 1표면처리층의평균두께의범위이내일수있고,상기불소 고분자입자의평균입경 (D50)은，제 2표면처리층의평균두께의범위이내일 수있다.
[22] 상세하게는상기불소도핑금속산화물입자와불소도핑금속수산화물
입자의평균입경 (D50)은상기에서언급한범위이내에서,예를들어， 1 nm이상 내지 1500 nm미만일수있으며，더욱상세하게는 10 nm이상내지 1000 nm 이하일수있다.상기불소도핑금속산화물입자와불소도핑금속수산화물 입자의평균입경 (D50)이 1 nm미만일경우，지나치게작은크기로입자들이 웅집될수있어바람직하지않으며， 1500 nm이상일경우，제조공정상효율성이 떨어지는바바람직하지않다.
[23] 본발명은,상기한불소고분자가제 1표면처리층을구성하는금속산화물 또는금속수산화물의불소원소공급원으로작용한다.
[24] 상기불소고분자는,비제한적으로，폴리비닐플루오라이드 (polyvinylfluoride), 폴리비닐리덴플루오라이드 (polyvinylidene fluoride),
폴리테트라플루오로에틸렌 (polytetrafluoroethylene),
폴리클로로트리플루오르에틸렌 (polychlorotrifluoroethylene),
퍼플루오로알콕시폴리머 (perfluoroalkoxy polymer),플루오르화
에틸렌-프로필렌 (fluorinated ethylene-propylene),
폴리에틸렌테트라플루오로에틸렌 (polyethylenetetrafluoroethylene),
폴리에틸렌클로로트리플루오로에틸렌 (polyethylenechlorotrifluoroethylene), 퍼플루오로엘라스토머 (Perfluoroelastomer),플루오로카본 (Fluorocarbon), 퍼플루오로폴리에틸렌 (Perfluoropolyether)，및
퍼플루오로술폰산 (Perfluorosulfonic acid)으로이루어진군에서선택되는하나 이상일수있다.
[25] 상기리튬함유금속산화물은，층상구조의리튬전이금속산화물또는스피넬 구조의리튬전이금속산화물일수있다.상기리튬함유금속산화물은，리튬 코발트산화물 (LiCo02),리튬니켈산화물 (LiNi02)등의층상화합물이나 1또는 그이상의전이금속으로치환된화합물;화학식 Lil+yMn2.y04 (여기서， y는 0 ~ 0.33임 )， LiMn03, LiMn203, LiMn02둥의리튬망간산화물;리튬동산화물 (Li2 Cu02),화학식 LiNi,.yMy02 (여기서， M = Co, Mn, Al, Cu, Fe, Mg, B또는 Ga이고, y = 0.01 - 0.3임)으로표현되는 Ni사이트형리튬니켈산화물;화학식 LiMn2.yMy02 (여기서， M = Co, Ni, Fe, Cr, Zn또는 Ta이고, y = 0.01 ~ 0.1임 )또는 Li2Mn3M08 (여기서， M = Fe, Co, Ni, Cu또는 Zn임)으로표현되는리튬망간복합산화물; 둥일수있고，구체적인예에서，상기스피넬구조의리튬전이금속산화물은 하기화학식 (1)로표현되는조성을가지는화합물일수있다.
[26] Li1+aMxMn2.x04 (1)
[27] 상기식에서, M은， Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zn및주기율표상 5주기의 전이금속들로이루어진군에서선택되는하나이상이고 ; -0.1≤a≤0.1, 0.3≤x≤0.8 이다.
[28] 더욱구체적으로,상기화학식 (1)의스피넬구조의리튬전이금속산화물은 하기화학식 (2)로표현되는조성을가지는화합물일수있다.
[29] LiI+aNibMcMn2.(b+c)04 (2)
[30] 상기식에서, M은 Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zn및주기율표상 5주기의
전이금속들로이루어진군에서선택되는하나이상이고 ; -0.1≤a≤0.1, 0.3≤b≤0.6, 0≤c≤0.2이다.
[31] 본발명은,또한，상기한양극활물잘과，도전재및바인더를포함하고있는 전극합제층이전류집전체상에도포되어있는리튬이차전지용양극을제공할 수있다.
[32] 또한ᅳ양극,음극및양극과음극사이에고분자막을개재시킨구조의전극 조립체를전지케이스에수납하고밀봉한구조의리튬이차전지를제공할수 있다.상기리튬이차전지는리튬염함유비수계전해질을포함할수있다.
상기한리튬이차전지는리튬이온전지일수있고，리튬이온폴리머전지일수 있고，리튬폴리머전지일수있다.
[33] 양극또는음극은,바 더를용매에분산또는용해시켜바인더용액을
제조하는과정;상기바인더용액과전극활물질및도전재를혼합하여전극 술러리를제조하는과정;상기전극슬러리를집전체상에코팅하는과정;
전극을건조하는과정;및전극을일정한두께로압축하는과정을포함하는 제조방법으로제조할수있다.경우에따라서는，압연한전극을건조하는과정을 더포함할수있다.
[34] 상기바인더용액제조과정은,바인더를용매에분산또는용해시켜바인더 용액을제조하는과정이다.
[35] 상기바인더는, ¾해업계에서공지된모든바인더들일수있고,구체적으로는， 폴리불화비닐리덴 (polyvinylidene fluoride, PVdF)또는
폴리테트라플루오로에틸렌 (/ (yieiraᅳ /ZMoroei/iy/ene, PTFE)을포함하는불소 수지계바인더，스티렌-부타디엔고무，아크릴로니트릴 -부티디엔고무， 스티렌 -이소프렌고무를포함하는고무계바인더，
카르복시메틸셀를로우즈 (CMC),전분，히드록시프로필샐를로우즈,재생 셀를로우즈를포함하는셀를로오스계바인더，폴리알코올계바인더， 폴리에틸렌，폴리프로필렌를포함하는폴리올레핀계바인더，폴리이미드계 바인더，폴리에스테르계바인더,흥합접착제,실란계바인더로이루어진 군에서선택된하나또는 2종이상의바인더들의흔합물이거나공중합체일수 있다. [36] 상기용매는，바인더의종류에따라선택적으로사용될수있고，예를들어， 이소프로필알코올， N-메틸피롤리돈 (NMP),아세톤등의유기용매와물둥이 사용될수있다.
[37] 본발명의하나의구체적인실시예로서 , PVdF를 NMP(N-methyl pyrrolidone)에 분산 /용해시켜양극용바인더용액을제조할수도있고， SBR(Styrene-Butadiene Rubber)/CMC(Carboxy Methyl Cellulose)를물에분산 /용해시켜음극용바인더 용액을제조할수도있다.
[38] 전극활물질및도전재를상기바인더용액에혼합 /분산시켜서전극슬러리를 제조할수있다.이렇게제조된전극슬러리는，저장탱크로이송하여코팅과정 이전까지보관할수있다.상기저장탱크내에서는,전극슬러리가굳는것을 방지하기위하여，계속하여전극슬러리를교반할수있다.
[39ᅵ 상기전극활물질은，상기의양극활물질또는하기의음극활물질일수있다. 상기음극활물질은，예를들어,난흑연화탄소，흑연계탄소등의탄소; LixFe203 (0<x≤l), LixWO2(0<x≤l), SnxMe,.xMe'yOz (Me: Mn, Fe, Pb, Ge; Me': Al, B, P, Si, 주기율표의 1족， 2족, 3족원소,할로겐; 0<x<l ; l<y<3; 1<ζ<8)등의금속복합 산화물;리튬금속;리튬합금;규소계합금;주석계합금; SnO, Sn02, PbO, Pb02, Pb203, Pb304, Sb203, Sb204, Sb205, GeO, Ge02, Bi203, Bi204) Bi205등의금속 산화물;폴리아세틸렌등의도전성고분자; Li-Co-Ni계재료등일수있다.
[40] 상기도전재는,당해전지에화학적변화를유발하지않으면서도전성을가진 것이라면특별히제한되는것은아니며，예를들어,천연흑연이나인조흑연 등의흑연;카본블랙，아세틸렌블랙,케첸블랙,채널블랙，퍼네이스블랙，램프 블랙，서머블랙등의카본블랙;탄소섬유나금속섬유등의도전성섬유;불화 카본，알루미늄,니켈분말등의금속분말;산화아연,티탄산칼륨등의도전성 위스키;산화티탄등의도전성금속산화물;폴리페닐렌유도체등의도전성 소재등이사용될수있다.
[41] 상기전극슬러리에는，필요에따라층진제등이선택적으로추가될수있다. 상기충진제는，당해전지에화학적변화를유발하지않으면서섬유상재료라면 특별히제한되는것은아니며，예를들어,폴리에틸렌，폴리프로필렌등의 올리핀계증합제;유리섬유，탄소섬유등의섬유상물질등이사용될수있다.
[42] 상기전극슬러리를집전체상에코팅하는과정은,전극술러리를코터 (coater) 헤드를통과시켜정해진패턴및일정한두께로집전체상에코팅하는과정이다
[43] 상기전극술러리를집전체상에코팅하는방법은,전극슬리러를집전체위에 분배시킨후닥터블레이드 (doctor blade)등을사용하여균일하게분산시키는 방법，다이캐스팅 (die casting),콤마코팅 (comma coating),스크린프린팅 (screen printing)둥의방법등을들수있다.또한，별도의기재 (substrate)위에성형한후 프레싱또는라미네이션방법에의해전극슬러리를집전체와접합시킬수도 있다.
[44] 상기집전체는，당해전지에화학적변화를유발하지않으면서높은도전성을 가지는것이라면특별히제한되는것은아니며，예를들어 ,구리 ,스테인리스 스틸,알루미늄，니켈,티탄,소성탄소，구리나스테인리스스틸의표면에카본, 니켈，티탄,은등으로표면처리한것，알루미늄-카드뮴합금등이사용될수 있다.양극집전체는,표면에미세한요철을형성하여양극활물질의결합력을 강화시킬수도있으며，필름，시트,호일，네트,다공질체，발포체，부직포체등 다양한형태로사용될수있다.구체적으로,양극집전체는，알루미늄을 포함하는금속집전체일수있고,음극집전체는,구리를포함하는금속 집전체일수있다.상기전극집전체는금속호일일수있고，알루미늄 (A1)호일 또는구리 (Cu)호일일수있다.
[45] 상기건조공정은，금속집전체에코팅된술러리를건조하기위하여슬러리 내의용매및수분을제거하는과정으로,구체적인실시예에서 , 50내지 20°C의 진공오븐에서 1일이내로건조한다.
[46] 코팅과정이끝난전극의용량밀도를높이고집전체와활물질들간의
접착성을증가시키기위해서,고은가열된 2개의롤사이로전극을통과시켜 원하는두께로압축할수있다.이과정을압연과정이라한다.
[47] 상기전극을고온가열된 2개의롤사이로통과시키기전에，상기전극은
예열될수있다.상기예열과정은，전극의압축효과를높이기위해서를로 투입되기전에전극을예열하는과정이다.
[48] 상기와같이압연과정이완료된전극은，바인더의융점이상의온도를
만족하는범위로서 50내지 200°C의진공오본에서 1일이내로건조할수있다. 압연된전극은일정한길이로절단된후건조될수도있다.
[49] 상기건조과정이후에는，냉각과정을더포함할수있다.
[50] 상기고분자막은,양극과음극사이를격리시키는분리막이고，전해질로서 폴리머등의고체전해질이사용되는경우에는고체전해질이분리막을겸할 수도있다.
[51] 상기분리막은높은이온투과도와기계적강도를가지는절연성의얇은
박막이사용된다.분리막의기공직경은일반적으로 αοι - 10 이고，두께는 일반적으로 5 - 300 이다.
[52] 이러한분리막으로는，예를들어，내화학성및소수성의폴리프로필렌등의 올레핀계폴리머；유리섬유또는폴리에틸렌등으로만돌어진시트나부직포; 크라프트지등이사용된다.현재시판중인대표적인예로는셀가드계열 (Celgard R 2400， 2300(Hoechest Celanese Corp.제품)，폴리프로필렌분리막 (Ube Industries Ltd.제품또는 Pall RAI사제품)，폴리에틸렌계열 (Tonen또는 Entek)둥이있다.
[53] 경우에따라서 ,상기분리막위에는전지의안정성을높이기위하여겔폴리머 전해질이코팅될수있다.이러한겔폴리머의대표적인예로는
폴리에틸렌옥사이드,폴리비닐리덴플투라이드，폴리아크릴로나이트릴등을들 수있다.
[54] 상기전극조립체는,당해업계에서공지된구조의젤리 -를형전극조립체 (또는 권취형전극조립체),스택형전극조립체 (또는적층형전극조립체)또는스택 & 폴딩형전극조립체등을모두포함할수있다.
[55] 본명세서에서，상기스택 &폴딩형전극조립체는，분리막시트상에양극과 음극사이에분리막이개재된구조의단위셀을배열한후，분리막시트를 접거나 (folding)권취 (winding)하는방법으로제조하는스택 &폴딩형
전극조립체를포함하는개념으로이해할수있다.
[56] 상기비수계전해질로는비수전해액,고체전해질，무기고체전해질등이
사용된다.
[57] 상기비수전해액으로는,예를들어， N-메틸 -2-피롤리디논，프로필렌
카르보네이트，에틸렌카르보네이트,부틸렌카르보네이트，디메틸
카르보네이트，디에틸카르보네이트，에틸메틸카보네이트,감마-부틸로락톤， 1,2-디메록시에탄， 1，2-디에톡시에탄,테트라히드록시프랑 (franc), 2-메틸 테트라하이드로푸란，디메틸술폭시드， 1,3-디옥소런, 4-메틸 -1,3-디옥센， 디에틸에테르，포름아미드，디메틸포름아미드,디옥소런，아세토니트릴, 니트로메탄,포름산메틸，초산메틸，인산트리에스테르,트리메특시메탄, 디옥소런유도체,설포란，메틸설포란， 1,3-디메틸 -2-이미다졸리디논,프로필렌 카르보네이트유도체,테트라하이드로푸란유도체，에테르，피로피온산메틸， 프로피은산에틸둥의비양자성유기용매가사용될수있다.
[58] 상기유기고체전해질로는,예를들어，폴리에틸렌유도체,폴리에틸렌
옥사이드유도체，폴리프로필렌옥사이드유도체,인산에스테르폴리머,폴리 에지테이션리신 (agitation lysine),폴리에스테르술파이드,폴리비닐알코을， 폴리불화비닐리덴，이은성해리기를포함하는중합체둥이사용될수있다.
[59] 상기무기고체전해질로는，예를들어, Li3N, Lil, Li5NI2, Li3N-LiI-LiOH, LiSi04, LiSi04.LiI-LiOH, Li2SiS3, Li4Si04, Li4Si04-LiI-LiOHᅳ Li3P04ᅳ Li2S-SiS2등의 Li의 질화물，할로겐화물,황산염등이사용될수있다.
[60] 상기리튬염은상기비수계전해질에용해되기좋은물질로서,예를들어， LiCl, LiBr, Lil, LiC104, LiBF4, LiB10Cl10, LiPF6, LiCF3S03, LiCF3C02, LiAsF6, LiSbF6, LiAlCl4> CH3S03Li, CF3S03Li, LiSCN, LiC(CF3S02)3, (CF3S02)2NLi,클로로보란 리튬，저급지방족카르본산리튬， 4페닐붕산리튬,이미드등이사용될수있다.
[61] 또한,전해액에는충방전특성,난연성등의개선을목적으로,예를들어，
피리딘，트리에틸포스파이트，트리에탄올아민,환상에테르,에틸렌디아민, n-글라임 (glyme),핵사인산트리아미드，니트로벤젠유도체，유황，퀴논이민 염료, N-치환옥사졸리디논， Ν,Ν-치환이미다졸리딘，에틸렌글리콜디알킬 에테르，암모늄염,피를, 2-메톡시에탄올,삼염화알투미늄등이첨가될수도 있다.경우에따라서는,불연성을부여하기위하여，사염화탄소，삼불화에틸렌 등의할로겐함유용매를더포함시킬수도있고,고온보존특성을향상시키기 위하여이산화탄산가스를더포함시킬수도있으며， FEC(fluoro-ethylene carbonate), PRS(propene sultone), FPC(fluoro-propylene carbonate)등을더 포함시킬수있다.
[62] 본발명에따른리튬이차전지는소형디바이스의전원으로사용될수있을 뿐만아니라，다수의리튬이차전지를포함하는중대형전지모들의
단위전지로도바람직하게사용될수있다.또한,본발명은상기전지모들을 중대형디바이스의전원으로포함하는전지팩을제공하고，상기중대형 디바이스는전기자동차 (Electric Vehicle, EV),하이브리드전기자동차 (Hybrid Electric Vehicle, HEV),플러그-인하이브리드전기자동차 (Plug-in Hybrid Electric Vehicle, PHEV)등을포함하는전기차및전력저장장치등을들수있으나，이에 한정되는것은아니다.
[63] 상기전지모들과전지팩은당해업계의공지의구조및제작방법으로제작할 수있고，특별히한정되지않는다.
도면의간단한설명
[64] 도 1은，본발명의비제한적인실시예 1의양극활물질의 SEM이미지이다;및, [65] 도 2는,본발명의비제한적인비교예 1의양극활물질의 SEM이미지이다. 발명의실시를위한형태
[66] 이하，실시예를통해본발명을더욱상술하지만,하기실시예는본발명을 예시하기위한것이며,본발명의범주가이들만으로한정되는것은아니다.
[67]
[68] <실시예 1>
[69] LiNio.^MnLseOi의양극재와 ().2중량 %의 PVdF(Kynar£E FLEX)의흔합물을 페인트쉐이커 (paint shaker)(Red Devil, 1400 model)을사용하여 1000 rpm의 회전수로한시간동안혼합하였다.혼합결과물을공기분위기에의전기로에서 300oC의온도로 5시간동안열처리하여불소고분자로표면처리한양극 활물질을제조하였다.
[70] 상기양극활물질：도전재 :바인더의양이 95： 2.5： 2.5가되도록계량한후 NMP에넣고믹싱 (mixing)하여양극합제를제조하고， 20 βϊα두께의알루미늄 호일에상기양극합제를코팅한후압연및건조하여양극을제조하였다.
[71] 상기에서제조된리륨이차전지용양극과，상대전극 (음극)으로서리튬메탈 박과，분리막으로서폴리에틸렌막 (Celgard,두께: 20 μη\),및에틸렌카보네이트， 디메틸렌카보네이트，디에틸카보네이트가 1 : 2: 1로흔합된용매에 LiPF6가 1M로녹아있는액체전해액을사용하여， 2016코인전지를제조하였다.
[72]
[73] <실시예 2>
[74] PVdF의함량이 0.5중량%인것을제외하고는실시예 1과동일한방법으로 2016코인전지를제조하였다.
[75]
[76] <실시예 3> [77] PVdF의함량이 1.0증량 %인것을제외하고는실시예 1과동일한방법으로 2016코인전지를제조하였다.
[78]
[79] <실시예 4>
[80] LiNi0.44Mn1 56O4의양극재와 0.5증량%의 PVdF및 0.25중량 %의 70 nm크기의 A1 203를혼합한것을제외하고는실시예 1과동일한방법으로 2016코인전지를 제조하였다.
[81]
[82] <실시예 5>
[83] A1203대신에 0.25증량 <7。의 70 nm크기의 ZrO를혼합한것을제외하고는실시예 4와동일한방법으로 2016코인전지를제조하였다.
[84]
[85] <실시예 6>
[86] A1203대신에 0.25중량 %의 70 nm크기의 Ti02를흔합한것을제외하고는
실시예 4와동일한방법으로 2016코인전지를제조하였다.
[87]
[88] <비교예 1>
[89] PVdF를이용하여표면처리하지않은 ΠΝία^Μη,^ 의양극재를사용하여 실시예 1의방법으로 2016코인전지를제조하였다.
[90]
[91] <비교예 2>
[92] PVdF의함량이 5.0중량 %인것을제외하고는실시예 1과동일한방법으로
2016코인전지를제조하였다.
[93]
[94] <비교예 3>
[95] 실시예 4의산화마그네슘대신 2 /皿크기의 A1203을사용한것을제외하고는 실시예 1과동일한방법으로 2016코인전지를제조하였다.
[96]
[97] <실험예 1 >초기충방저특성
[98]
[99] 실시예 1내지 6및비교예 1내지 3에서각각제조된코인전지들에대해, 0.1C 전류로 3.5 4.9V의전압범위에서 1회충방전하여층방전특성을평가하였다. 그결과를하기표 1에나타내었다.
[100]
[101] 표 1 [Table 1]
Figure imgf000012_0001
[102] 상기표 1에따르면본발명의실시예 1내지 6에따른전지는비교예 2및 3에 따른전지와비교하여초기충방전효율이상대적으로향상된것을확인할수 있고，비교예 1의전지의경우초기충반전효율이상대적으로높지만，초기층전 용량자체가낮은것을확인할수있다.이는본발명의실시예 1내지 6에따른 전지의양극활물질은불소를포함하는제 1표면처리층및제 2표면처리층을 가지는바,특히,제 2표면처리층에주로존재하는불소고분자는전기화학 반웅으로리튬이온의농도를높여주기때문에리튬함유금속산화물의 표면에서충방전시일어나는리튬이온의이동을더욱용이해지기때문이다.
[103] <실험예 2> ,
[104] 고온수명특성
[105] 실시예 1내지 6및비교예 1내지 2에서각각제조된코인전지들에대해,
45°C의온도에서 1.0C의전류로 200회층방전하여수명특성을평가하였다.그 결과를하기표 2에나타내었다.
[106] 표 2
[Table 2]
Figure imgf000013_0001
[107] 상기표 2에따르면본발명의실시예 1내지 6에따른전지는비교예 1및 2에 따른전지와비교하여고온수명특성이상대적으로우수한것을확인할수 있다.이는본발명의실시예 1내지 6에따른전지의양극활물질은불소를 포함하는소정의표면처리층들을가지는바，이로인하여，고전압에서의양극 활물질표면과전해액의부반웅및망간의용출을억제할수있기때문이다.
[108] <실험예 3>
[109] 고온저장시자가방저량
[110] 실시예 1내지 6및비교예 1내지 2에서각각제조된코인전지들을 0.1C
전류로 3.5 ~ 4.9V의전압범위에서 1회층전하고ᅳ 45°C의은도에서 2주간보관한 후자가방전량및가스발생량을평가하였다.그결과를하기표 3에
나타내었다.
[111] 표 3
[Table 3]
자가방전량 (%) 가스발생량 (ml/g)
실시예 1 18.7 7.4
실시예 2 17.4 6.2
실시예 3 15.1 6.1
실시예 4 15.4 6.8
실시예 5 15.8 7.1
실시예 6 15.7 6.5
비교예 1 29.4 18.4
비교예 2 24.2 5.7 [112] 상기표 2에따르면본발명의실시예 1내지 6에따른전지는비교예 1및 2에 따른전지와비교하여자가방전량및가스발생량이상대적으로낮은것을 확인할수있다.이는본발명의실시예 1내지 6에따른전지의양극활물질은 불소를포함하는소정의표면처리층들을가지는바，이로인하여,고전압에서의 양극활물질표면과전해액의부반웅및망간의용출을억제할수있기 때문이다.
산업상이용가능성
[113] 본발명은，불소고분자를이용하여라튬이차전지용양극활물질을
표면처리함으로써，불소원소가도핑된금속산화물층및 /또는불소원소가 도핑된금속수산화물층의제 1표면처리층과불소고분자를포함하는제 2 표면처리층을가진신규한구조의양극활물질을제공하므로층방전시리튬 함유금속산화물의표면에서리튬이은의이동을촉진할수있다.
[114] 특히,불소고분자의함량이양극활물질의전체증량대비 5중량 %미만
인경우，초기충방전특성,고온수명특성및고온저장특성이향상됨을확인할 수있다.
[115] 또한,스피넬구조의상기화학식 (1)의리튬함유전이금속산화물의경우， 망간의일부를 Ni등의금속원소로치환한구조의화합물에비해서, 고전압에서의양극활물질표면과전해액의부반웅및망간의용출을 억제함으로써，고전압용리튬이차전지를제공할수있는장점이있다.

Claims

청구범위
리튬함유금속산화물입자;
상기리튬함유금속산화물입자의표면에형성되어있고,불소 도핑금속산화물들과불소도핑금속수산화물들로이루어진 군에서선택되는하나이상의화합물을포함하고있는제 1 표면처리층;및
상기제 1표면처리층의표면에형성되어있고，불소고분자를 포함하고있는제 2표면처리층;
을포함하는것을특징으로하는리튬이차전지용양극활물질. 제 1항에있어서，
상기불소도핑금속산화물은상기리튬함유금속산화물의산소 증일부를불소로치환한불소도핑리튬함유금속산화물인것을 특징으로하는리톱이차전지용양극활물질.
제 1항에있어서，
상기불소도핑금속산화물은， Al, Mg, Ni, Co, Ti, Cr, Mo, Bi, Zn, Zr, Ru및 W로이루어진군에서선택된하나의금속의산화물의 산소의일부를불소로치환한것을특징으로하는리튬
이차전지용양극활물질.
제 3항에있어서，상기불소도핑금속산화물의함량은양극 활물질의전체증량을기준으로 0.05증량 %이상내지 2.00중량 «¾ 미만의범위인것을특징으로하는양극활물질.
제 1항에있어서，
상기블소도핑금속수산화물은， Al, Mg, Ni, Co, Ti, Cr, Mo, Bi, Zn, Zr, Ru및 W로이루어진군에서선택된하나의금속의수산화물의 수산화기의일부를불소로치환한것을특징으로하는리튬 이차전지용양극활물질.
제 5항에있어서，상기불소도핑금속수산화물의함량은양극 활물질의전체중량을기준으로 0.05중량 %이상내지 2.00증량 % 미만의범위인것을특징으로하는양극활물질.
제 1항에있어서，상기불소고분자는,
폴리비닐플루오라이드 (polyvinylfluoride),
폴리비닐리덴플루오라이드 (polyvinylidene fluoride),
폴리테트라플루오로에틸렌 (polytetrafluoroethylene),
폴리클로로트리플루오르에틸렌 (polychlorotrifluoroethylene), 퍼플루오로알콕시폴리머 (perfluoroalkoxy polymer),플루오르화 에틸렌-프로필렌 (fluorinated ethylene-propylene),
폴리에틸렌테트라플루오로에틸렌 (polyethylenetetrafluoroethylene), 폴리에틸렌클로로트리플루오로에틸렌
(polyethylenechlorotrifluoroethylene),
퍼플루오로엘라스토머 (Perfluoroelastomer),
플루오로^ ]■본 (Fluorocarbon),
퍼플루오로폴리에틸렌 (Perfluoropolyether),및
퍼플루오로술폰산 (Perfluorosulfonic acid)으로이루어진군에서 선택되는하나이상인것을특징으로하는양극활물질.
제 1항에있어서,
상기리튬함유금속산화물은，층상구조의리튬전이금속산화물 또는스피넬구조의리튬전이금속산화물인것을특징으로하는 리튬이차전지용양극활물질.
제 8항에있어서,상기스피넬구조의리륨전이금속산화물은 하기화학식 (1)로표현되는조성을가지는것을특징으로하는 리튬이차전지용양극활물질:
Li,+aMxMn2.x04 (1)
상기식에서,
M은, Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zn및주기율표상 5주기의 전이금속들로이루어진군에서선택되는하나이상이고;
-0.1<a≤0.1, 0.3<x<0.8이다.
제 9항에있어서，상기스피넬구조의리튬전이금속산화물은 하기화학식 (2)로표현되는조성을가지는것을특징으로하는 리튬이차전지용양극활물질:
Lii+aNibMcMn2.(b+c)04 (2)
상기식에서,
M은 Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zn및주기율표상 5주기의 전이금속들로이루어진군에서선택되는하나이상이고;
-0.1<a<0.1, 0.3<b<0.6, 0<c<0.2이다.
제 1항에있어서，
상기제 1표면처리층은상기리튬함유금속산화물의표면의 전부를덮고있고，상기제 2표면처리층은상기쎄 1표면처리 층의표면의전부를덮고있는것을특징으로하는양극활물질. 제 1항에있어서，
상기제 1표면처리층은상기리튬함유금속산화물의표면의 일부를덮고있고,상기제 2표면처리층은상기리튬함유금속 산화물의표면의일부와상기제 1표면처리층의표면의전부를 덮고있는것을특징으로하는양극활물질.
제 1항에있어서，
상기불소도핑금속산화물과상기불소도핑금속수산화물은 입자형태로상기리튬함유금속산화물의표면에존재하는것을 특징으로하는양극활물질.
제 13항에있어서,
상기불소도핑금속산화물과상기불소도핑금속수산화물 입자의평균입경은각각 1 nm이상내지 1800 nm미만인것을 특징으로하는양극활물질.
제 1항에있어서，
상기불소고분자는입자형태로상기제 1표면처리층의표면에 존재하는것을특징으로하는양극활물질.
제 1항에따른양극활물질,도전재및바인더를포함하고있는 전극합제층이전류집전체상에도포되어있는리튬이차전지용 양극.
제 16항에따른양극을포함하는것을특징으로하는리튬 이차전지.
제 17항에따른리튬이차전지를포함하는것을특징으로하는 전지팩.
제 18항에따른전지팩을전원으로이용하는전기차.
리튬함유금속산화물입자를양극활물질전체중량대비 0.05 중량 %이상내지 5.00증량 %미만범위의불소고분자와 흔합하고，공기분위기에서열처리하여제 1항에따른양극 활물질을제조하는제조방법 .
제 20항에있어서,양극활물질전체증량대비 0.05증량 %내지 2.00증량 <¾범위의금속산화물，금속수산화물또는금속산화물 및금속수산화물을더흔합하고，공기분위기에서열처리하는 것을특징으로하는제조방법 .
PCT/KR2014/010651 2013-11-18 2014-11-07 불소 고분자를 이용하여 표면처리한 리튬 이차전지용 양극 활물질 및 이의 제조방법 Ceased WO2015072702A1 (ko)

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CN201480059278.4A CN105684199B (zh) 2013-11-18 2014-11-07 经含氟共聚物表面处理的锂二次电池用正极活性材料及其制造方法
JP2016550444A JP6621210B2 (ja) 2013-11-18 2014-11-07 フッ素高分子を用いて表面処理したリチウム二次電池用正極活物質及びその製造方法

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US20160260979A1 (en) 2016-09-08
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US10418634B2 (en) 2019-09-17
EP3043407B1 (en) 2020-04-22
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