WO2011074431A1 - リチウムイオン電池用正極及びその製造方法、並びに、リチウムイオン電池 - Google Patents
リチウムイオン電池用正極及びその製造方法、並びに、リチウムイオン電池 Download PDFInfo
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- WO2011074431A1 WO2011074431A1 PCT/JP2010/071724 JP2010071724W WO2011074431A1 WO 2011074431 A1 WO2011074431 A1 WO 2011074431A1 JP 2010071724 W JP2010071724 W JP 2010071724W WO 2011074431 A1 WO2011074431 A1 WO 2011074431A1
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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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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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
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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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- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
Definitions
- the present invention relates to a positive electrode for a lithium ion battery, a method for producing the same, and a lithium ion battery.
- Lithium-containing transition metal oxides are generally used as positive electrode active materials for lithium ion batteries. Specifically, lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate (LiMn 2 O 4 ), etc., improved characteristics (higher capacity, cycle characteristics, storage characteristics, reduced internal resistance) In order to improve the charge / discharge characteristics) and safety, it is underway to combine them.
- lithium ion batteries for large applications such as in-vehicle use and load leveling are required to have characteristics different from those for conventional mobile phones and personal computers. Specifically, high capacity and low resistance are required for in-vehicle use, and high capacity and long life are required for load leveling.
- a positive electrode of a lithium ion battery is formed by mixing a positive electrode active material and a conductive material in an organic solvent in which a binder is dissolved, applying a paste to an aluminum foil, drying and pressing.
- the binder is necessary for maintaining the adhesion of the positive electrode active material, the conductive material, and the aluminum foil (current collector).
- the conductive material is mixed for the purpose of imparting conductivity to the positive electrode active material having poor conductivity.
- the positive electrode for lithium ion batteries described in Patent Document 1 is formed by applying a positive electrode active material paste to an aluminum foil for a current collector whose surface has been subjected to hydration oxidation treatment.
- the positive electrode active material paste used here contains a positive electrode active material, a conductive agent such as carbon black or graphite, a binder such as PTFE, and a solvent such as water (in the specification of Patent Document 1). Paragraphs 0016-0025, etc.).
- Patent Document 2 describes a lithium ion comprising an aluminum foil provided with a film containing a compound having ion permeability and carbon fine particles in a lower layer, and an upper layer provided with a film containing a binder, carbon fine particles and a positive electrode active material.
- a positive electrode for a battery is described (paragraph 0009 in the specification of Patent Document 2).
- the positive electrode for lithium ion batteries described in Patent Document 3 is formed by applying a positive electrode active material composition to an Al alloy positive electrode current collector.
- the positive electrode active material composition used here is manufactured by dispersing a positive electrode active material, a polyvinylidene fluoride binder, and a carbon conductive agent in an N-methylpyrrolidone solvent (paragraph of the specification of Patent Document 3). 0031 and 0032 etc.).
- a positive electrode for a lithium ion battery is formed on a current collector such as an aluminum foil by applying a positive electrode active material mixed with a conductive material or a binder
- the uneven distribution of the conductive material or the binder covers the positive electrode active material. Deactivation or the like may occur to increase the contact resistance of the battery, resulting in a problem that the output characteristics of the battery deteriorate.
- an object of the present invention is to provide a positive electrode for a lithium ion battery that suppresses the contact resistance of the battery and realizes good output characteristics. Moreover, this invention makes it another subject to provide the manufacturing method of the said positive electrode for lithium ion batteries. Furthermore, this invention makes it another subject to provide the lithium ion battery using the said positive electrode for lithium ion batteries.
- This inventor used the positive electrode active material which does not contain an electroconductive material and a binder by paying attention to the electroconductivity of the positive electrode active material and the aluminum foil which is a collector, and their adhesion method, and studying earnestly.
- the present inventors have found that a positive electrode for a lithium ion battery having a configuration and characteristics different from those of conventional ones can be formed.
- the present invention completed on the basis of the above knowledge includes, in one aspect, a mixed layer composed of a metal that forms a current collector and a positive electrode active material dispersed in layers in the metal that forms the current collector.
- This is a positive electrode for a lithium ion battery.
- the positive electrode for a lithium ion battery according to the present invention includes a layer made of only the metal, and the mixed layer is formed on a layer made of only the metal.
- the metal is aluminum or an aluminum alloy.
- the positive electrode active material is a lithium-containing transition metal oxide.
- the transition metal in the lithium-containing transition metal oxide is one or more selected from the group consisting of Ni, Mn, Co, and Fe. is there.
- the crystal structure of the positive electrode active material in the mixed layer has a layered structure or a spinel structure.
- the present invention provides a method for producing a positive electrode for a lithium ion battery, comprising providing a powder of a positive electrode active material in a mold and pouring molten metal onto the powder in the mold.
- the present invention is a lithium ion battery using the positive electrode for a lithium ion battery according to the present invention.
- the present invention it is possible to provide a positive electrode for a lithium ion battery that suppresses the contact resistance of the battery and realizes good output characteristics.
- a positive electrode for a lithium ion battery includes a mixed layer composed of a metal that forms a current collector and a positive electrode active material dispersed in layers in the metal that forms the current collector. .
- the mixed layer may constitute a positive electrode alone.
- the mixed layer is formed on the metal layer forming the current collector, and the two layers may constitute a positive electrode.
- the positive electrode active material is not particularly limited, and compounds useful as a positive electrode active material for a general positive electrode for a lithium ion battery can be widely used.
- lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO) 2 ), lithium-containing transition metal oxides such as lithium manganate (LiMn 2 O 4 ) are preferably used.
- the transition metal in a lithium containing transition metal oxide is 1 type, or 2 or more types selected from the group which consists of Ni, Mn, Co, and Fe.
- the ratio of lithium to all metals in the lithium-containing transition metal oxide is preferably more than 1.0 and less than 1.3.
- the crystal structure of the positive electrode active material in such a mixed layer is not particularly limited as long as it is a structure capable of inserting and extracting lithium, but a layered structure or a spinel structure is preferable.
- the current collector is formed of a conductive member made of a highly conductive metal. As described later, since the conductive member is melted and poured onto the powder of the positive electrode active material in the positive electrode manufacturing process as described later, it is not preferable that the melting point of the conductive member is a temperature that adversely affects the characteristics of the positive electrode active material. Further, it is necessary that the metal has a greater ionization tendency than the metal element constituting the positive electrode active material. Therefore, as the conductive member constituting the current collector, aluminum, magnesium, manganese, zinc, or an alloy containing at least one of them can be used. Among these, aluminum and aluminum alloys (for example, Al—Mn, Al—Mg, and Al—Zn—Mg) are particularly preferable.
- the shape of the current collector is not particularly limited, and may be a foil shape or a plate shape.
- the mixed layer is formed by laying a powdered positive electrode active material on a mold, and pouring a molten metal serving as a constituent material of the current collector on the mold, followed by solidification, and the positive electrode active material and the current collector It is the mixed layer of the metal which comprises.
- the mixed layer has a configuration in which a metal enters between the particles of the positive electrode active material and is solidified.
- the positive electrode active material in the mixed layer is dispersed in layers within the metal forming the current collector.
- the positive electrode active material dispersed in a layered form is not particularly limited, but is preferably dispersed evenly.
- the positive electrode for a lithium ion battery includes the mixed layer of the metal constituting the positive electrode active material and the current collector as described above, the positive electrode active material does not include a binder or a conductive material. However, it has good adhesion to the current collector and electrical conductivity.
- the thickness of the mixed layer varies depending on the size of the positive electrode to be formed, the average particle size of the powder of the positive electrode active material, the hardness of the surface of the positive electrode active material spread on the mold, the material of the molten metal to be poured, the amount and temperature, etc. For example, 10 to 60 ⁇ m.
- the composition of the mixed layer can be determined by quantitative analysis of each element (Li, Ni, Mn, etc.) of the material by ICP-MS (ICP mass spectrometer). Moreover, the thickness of the mixed layer can be determined by SEM (scanning electron microscope) observation.
- a positive electrode active material powder is formed.
- a method of oxidizing a mixture or coprecipitate containing a metal constituting the positive electrode active material can be used.
- the mixture may be prepared by mixing compounds of each element by a general method, and the coprecipitate can also be prepared by a general method (coprecipitation with hydroxide or carbonate).
- various raw materials are mixed so that the metal elements constituting the crystal of the positive electrode active material are present in the crystal structure at a target composition ratio to obtain a raw material mixture.
- the raw materials include lithium compounds and other metal element compounds.
- lithium compounds include, but are not limited to, lithium carbonate, lithium hydroxide, lithium oxide, lithium chloride, lithium nitrate, lithium sulfate, lithium hydrogen carbonate, lithium acetate, lithium fluoride, lithium bromide, lithium iodide, A lithium oxide is mentioned.
- lithium carbonate is preferable because it is easy to handle and inexpensive.
- Ni, Mn, Co, Mg, Al, Ti, Cr, Fe, Cu, or Zr is adopted as the other metal element contained in the positive electrode active material, their carbonates, nitrates, hydroxides, Chlorides, oxides and the like can be used as raw materials.
- the mixing method is not limited, and examples thereof include a method of mixing powdery raw materials as they are, and a method of mixing after dissolving or suspending the raw materials in water and / or an organic solvent.
- the powder of the positive electrode active material according to the present invention is obtained by subjecting the obtained raw material mixture to oxidation treatment (calcination in an oxidizing atmosphere, etc.) under appropriate conditions.
- the average particle size of the positive electrode active material powder used varies depending on the characteristics required of the battery, but is preferably 10 ⁇ m or less. This is because when the average particle size is 10 ⁇ m or less, the molten metal and the powder of the positive electrode active material are mixed well when the molten metal is poured. In addition, the characteristics required for the battery can be generally satisfied.
- the mold is prepared, and the positive electrode active material powder is uniformly spread in the mold.
- the mold may have any shape / size.
- the constituent material of the mold is not particularly limited, and examples thereof include cast iron, copper alloy, aluminum alloy, steel, and other special alloys.
- molten metal as a constituent material of the current collector is poured onto the powder in the mold.
- the melting point is 660 ° C.
- the characteristics of the positive electrode active material are not adversely affected.
- the poured molten metal enters the positive electrode active material powder in the mold.
- the molten metal and the positive electrode active material are mixed, and a mixed layer in which the positive electrode active material is dispersed in layers is formed.
- the positive electrode active material and the molten metal are cooled in a mold, thereby forming a positive electrode for a lithium ion battery including a mixed layer formed by solidifying a mixture composed of the positive electrode active material and the molten metal. . Further, when a part of the molten metal is provided so as to further overlap on the mixture as described above, a metal-only layer for forming a current collector is further formed on the mixed layer.
- the positive electrode for a lithium ion battery according to the present invention is formed by providing a powdered positive electrode active material in a mold and pouring molten metal thereon, and includes a conductive material and a binder. Absent. For this reason, the contact resistance of a battery is suppressed and an output characteristic becomes favorable. Therefore, it is particularly useful in large-scale applications that require high capacity, low resistance, and long life such as in-vehicle use and load leveling.
- a carbonate which is a precursor was prepared by a wet coprecipitation method using a nitrate solution of Ni, Mn and Co and lithium carbonate. This was dried and then oxidized to prepare a positive electrode active material powder.
- the positive electrode active material powder was evenly dispersed on the bottom of a horizontal mold having a thickness of 100 ⁇ m, and molten aluminum was poured onto the mold, followed by cooling to produce a positive electrode for a lithium ion battery.
- Comparative example As a comparative example, the same positive electrode active material as that of the example was prepared. Next, carbon black was prepared as a conductive material, and PVDF was prepared as a binder. Next, these positive electrode active materials, conductive materials and binders were weighed at a ratio of 85: 8: 7. Subsequently, a binder dissolved in an organic solvent (N-methylpyrrolidone) is mixed with a positive electrode active material and a conductive material to form a paste, applied onto an aluminum foil as a current collector, dried, and then pressed. Thus, a positive electrode for a lithium ion battery was obtained. The thickness of the positive electrode was approximately 100 ⁇ m.
- evaluation 2032 type coin cells having a counter electrode of Li were prepared.
- a 1M-LiPF6 dissolved in EC-DMC (1: 1) was used as an electrolyte, and charging / discharging was performed with a charging condition of 4.3 V and a discharging condition of 3.0 V.
- the resistance was estimated by the voltage drop at the end of charging and the beginning of discharging. As a result, the electrode resistance was 0.5 m ⁇ for the example, and the electrode resistance was 1.3 m ⁇ for the comparative example.
- the contact resistance of the battery is better when the positive electrode for a lithium ion battery (Example) produced by the manufacturing method according to the present invention is used than for the positive electrode for a lithium ion battery (Comparative Example) produced by a conventional coating method. Is small. Therefore, it can be seen that when the positive electrode for a lithium ion battery according to the present invention is used, the contact resistance of the battery is suppressed and the output characteristics are improved.
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Abstract
Description
本発明の実施形態に係るリチウムイオン電池用正極は、集電体を形成する金属と、集電体を形成する金属内に層状に分散した正極活物質とで構成された混合層を備えている。混合層は、単独で正極を構成していてもよい。また、混合層は、集電体を形成する金属の層上に形成されており、これらの2層で正極を構成していてもよい。
本発明の実施形態に係るリチウムイオン電池用正極は、上述のように正極活物質及び集電体を構成する金属の混合層を備えるため、正極活物質は、バインダーや導電材を含んでいなくても良好な集電体との接着性及び導電性を有している。
混合層の厚さは、形成する正極の大きさ、正極活物質の粉体の平均粒径、鋳型に敷き詰めた正極活物質表面の硬さ、流し込む溶融金属の材料、量及び温度等によって異なるが、例えば、10~60μmである。
混合層の組成は、材料の各元素(Li、Ni、Mn等)をICP-MS(ICP質量分析装置)による定量分析で決定することができる。また、混合層の厚さは、SEM(走査型電子顕微鏡)観察で決定することができる。
次に、本発明の実施形態に係るリチウムイオン電池用正極の製造方法について説明する。
まず、正極活物質の粉体を形成する。正極活物質の粉体の形成については、本発明では、正極活物質を構成する金属を含む混合物又は共沈物を酸化する方法を用いることができる。混合物は各元素の化合物を一般的な方法で混合して作製したものでよく、共沈物についても一般的な方法(水酸化物もしくは炭酸塩での共沈)で作製することができる。
リチウム化合物としては、限定的ではないが、炭酸リチウム、水酸化リチウム、酸化リチウム、塩化リチウム、硝酸リチウム、硫酸リチウム、炭酸水素リチウム、酢酸リチウム、フッ化リチウム、臭化リチウム、ヨウ化リチウム、過酸化リチウムが挙げられる。中でも、取り扱いが容易であること、安価であることの理由から、炭酸リチウムが好ましい。
次に、得られた原料混合物を適正条件下で酸化処理(酸化雰囲気中での焼成等)することにより本発明に係る正極活物質の粉体が得られる。
また、使用する正極活物質の粉体の平均粒径は、電池に求められる特性によって変わるが、10μm以下であるのが好ましい。平均粒径が10μm以下の場合には、溶融金属を流し込んだときに、溶融金属と正極活物質の粉体とが良好に混じり合うためである。また、電池に求められる特性をおおむね満足できるためである。
本発明に係るリチウムイオン電池用正極は、上述のように、粉体状の正極活物質を鋳型内に設けておき、その上から溶融金属を流し込んで形成されており、導電材やバインダーを含まない。このため、電池の接触抵抗が抑制され、出力特性が良好となる。従って、車載用やロードレベリング用といった、高容量、低抵抗及び長寿命が要求される大型用途において、特に有用である。
Ni,Mn及びCoの硝酸塩溶液、及び、炭酸リチウムを使用した湿式共沈法によって前駆体である炭酸塩を作製した。これを乾燥後、酸化処理して、正極活物質の粉体を作製した。正極活物質の粉体のLi、Ni、Mn及びCo含有量は、ICP-MSで測定し、Ni:Mn:Co=1:1:1であり、Liと全金属との比(Li/全金属比)は、1.05であることを確認した。また、XRD(X線回折装置)により、正極活物質が層状構造であることを確認した。さらに、レーザー回折式粒度分布により、正極活物質の粉体の平均粒径が6μmであることを確認した。
この正極活物質の粉体を、水平にした厚さ100μmの鋳型の底に均等に分散し、この上に溶融したアルミニウムを流し込んだ後、冷却することにより、リチウムイオン電池用正極を作製した。
比較例として、実施例と同じ正極活物質を作製した。次に、導電材としてカーボンブラックを、バインダーとしてPVDFを準備した。次に、これらの正極活物質、導電材及びバインダーを、85:8:7の割合で秤量した。続いて、バインダーを有機溶媒(N-メチルピロリドン)に溶解したものに、正極活物質及び導電材を混合してペースト化し、集電体としてのアルミニウム箔上に塗布して乾燥した後、プレスしてリチウムイオン電池用正極とした。正極の厚さはほぼ100μmであった。
Claims (8)
- 集電体を形成する金属と、該集電体を形成する金属内に層状に分散した正極活物質とで構成された混合層を備えたリチウムイオン電池用正極。
- 前記金属のみで構成された層を備えると共に、前記混合層が、該金属のみで構成された層上に形成されている請求項1に記載のリチウムイオン電池用正極。
- 前記金属が、アルミニウム又はアルミニウム合金である請求項1又は2に記載のリチウムイオン電池用正極。
- 前記正極活物質が、リチウム含有遷移金属酸化物である請求項1~3のいずれかに記載のリチウムイオン電池用正極。
- 前記リチウム含有遷移金属酸化物における遷移金属が、Ni、Mn、Co及びFeよりなる群から選択される1種又は2種以上である請求項4に記載のリチウムイオン電池用正極。
- 前記正極活物質の結晶構造が、層状構造又はスピネル構造を有する請求項1~5のいずれかに記載のリチウムイオン電池用正極。
- 正極活物質の粉体を鋳型内に設け、該鋳型内の該粉体上に溶融金属を流し込むことを含むリチウムイオン電池用正極の製造方法。
- 請求項1~6のいずれかに記載のリチウムイオン電池用正極を用いたリチウムイオン電池。
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WO2012132072A1 (ja) | 2011-03-29 | 2012-10-04 | Jx日鉱日石金属株式会社 | リチウムイオン電池用正極活物質の製造方法及びリチウムイオン電池用正極活物質 |
EP2704237B1 (en) | 2011-03-29 | 2016-06-01 | JX Nippon Mining & Metals Corporation | Production method for positive electrode active material for lithium ion batteries and positive electrode active material for lithium ion batteries |
US9214676B2 (en) | 2011-03-31 | 2015-12-15 | Jx Nippon Mining & Metals Corporation | Positive electrode active material for lithium ion batteries, positive electrode for lithium ion batteries, and lithium ion battery |
JP5812682B2 (ja) | 2011-05-19 | 2015-11-17 | Jx日鉱日石金属株式会社 | リチウムイオン電池用正極活物質及びその製造方法 |
JP6292738B2 (ja) | 2012-01-26 | 2018-03-14 | Jx金属株式会社 | リチウムイオン電池用正極活物質、リチウムイオン電池用正極、及び、リチウムイオン電池 |
JP6292739B2 (ja) | 2012-01-26 | 2018-03-14 | Jx金属株式会社 | リチウムイオン電池用正極活物質、リチウムイオン電池用正極、及び、リチウムイオン電池 |
JP6159514B2 (ja) | 2012-09-19 | 2017-07-05 | Jx金属株式会社 | リチウムイオン電池用正極活物質、リチウムイオン電池用正極、及び、リチウムイオン電池 |
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- 2010-12-03 CN CN201080055329.8A patent/CN102668184B/zh not_active Expired - Fee Related
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2001266851A (ja) * | 1999-10-22 | 2001-09-28 | Sanyo Electric Co Ltd | リチウム二次電池用電極の製造方法 |
JP2002216745A (ja) * | 2001-01-23 | 2002-08-02 | Sanyo Electric Co Ltd | リチウム二次電池 |
JP2005183366A (ja) * | 2003-11-27 | 2005-07-07 | Matsushita Electric Ind Co Ltd | エネルギーデバイス及びその製造方法 |
JP2008181708A (ja) * | 2007-01-23 | 2008-08-07 | Matsushita Electric Ind Co Ltd | 非水電解質二次電池用電極の製造方法、非水電解質二次電池用電極、および非水電解質二次電池 |
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US8993160B2 (en) | 2015-03-31 |
EP2515364A1 (en) | 2012-10-24 |
JPWO2011074431A1 (ja) | 2013-04-25 |
CN102668184A (zh) | 2012-09-12 |
TWI466368B (zh) | 2014-12-21 |
US20120244434A1 (en) | 2012-09-27 |
KR20120069770A (ko) | 2012-06-28 |
TW201125193A (en) | 2011-07-16 |
KR101450978B1 (ko) | 2014-10-15 |
JP5661646B2 (ja) | 2015-01-28 |
CN102668184B (zh) | 2015-06-24 |
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