WO2011108659A1 - 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 - Google Patents
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 Download PDFInfo
- Publication number
- WO2011108659A1 WO2011108659A1 PCT/JP2011/054942 JP2011054942W WO2011108659A1 WO 2011108659 A1 WO2011108659 A1 WO 2011108659A1 JP 2011054942 W JP2011054942 W JP 2011054942W WO 2011108659 A1 WO2011108659 A1 WO 2011108659A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ion battery
- positive electrode
- lithium ion
- active material
- lithium
- Prior art date
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a positive electrode active material for a lithium ion battery, a positive electrode for a lithium ion battery, and a lithium ion battery.
- Lithium ion batteries that use lithium as a material with a low specific gravity and a tendency to cause an electrochemical reaction can store 2 to 3 times the energy of the same weight compared to nickel-cadmium batteries and nickel-metal hydride batteries. While the lithium ion battery has such excellent advantages, it has a problem in terms of safety.
- Patent Document 1 discloses a lithium-containing composite oxide, a lithium-containing composite oxide having a layered rock salt structure, a material for a lithium secondary battery positive electrode containing a mixture of lithium-containing composite oxide having a spinel structure, the lithium-containing composite oxide is represented by the general formula Li p Co x M y O z F a (where, M Represents at least one element selected from the group consisting of transition metal elements other than Co, Al, Sn, and alkaline earth metal elements: 0.9 ⁇ p ⁇ 1.1, 0.97 ⁇ x ⁇ 1.00.
- a lithium secondary battery positive electrode material comprising a lithium-containing composite oxide, it has been described as.
- Patent Document 2 discloses that in a positive electrode active material for a non-aqueous electrolyte secondary battery composed of at least a spinel-structure lithium transition metal composite oxide, the heat generation start temperature by differential scanning calorimetry of the lithium transition metal composite oxide is:
- a positive electrode active material for a non-aqueous electrolyte secondary battery is disclosed, wherein the lithium transition metal composite oxide has a calorific value of 700 to 900 mJ / mg at 220 ° C. or higher. ing.
- the positive electrode active material for non-aqueous-electrolyte secondary batteries which has the outstanding battery characteristic also in the severer use environment can be provided.
- Patent Document 3 discloses a lithium secondary in which a positive electrode using a lithium manganese composite oxide having a spinel structure as a positive electrode active material and a negative electrode using a carbon material as a negative electrode active material are infiltrated into a non-aqueous electrolyte.
- a lithium secondary battery is disclosed in which the total amount of heat generated by the differential scanning calorimeter of the lithium manganese composite oxide is 1.0 kJ / g or less. And it is described that according to this, the non-aqueous-electrolyte secondary battery excellent in safety can be provided.
- an object of the present invention is to provide a positive electrode active material for a lithium ion battery that realizes a lithium ion battery excellent in safety.
- the present inventor has found that there is a close correlation between the shape of the DSC (differential scanning calorimetry) exothermic curve of the positive electrode active material and the safety of the produced battery. That is, for the positive electrode active material, when the difference between the respective first exothermic peak temperatures measured in the DSC (Differential Scanning Calorimetry) exothermic curve relating to the battery charged to two different voltages is below a certain value It was found that the battery generated heat gently and thermal runaway could be suppressed well.
- DSC differential scanning calorimetry
- the present invention completed on the basis of the above knowledge has a composition formula: Li x (Ni y M 1-y ) O z (In the formula, M is Mn and Co, x is 0.9 to 1.2, y is 0.8 ⁇ 0.025, and z is 1.8 to 2.4.) Lithium ion using a positive electrode active material for a lithium ion battery having a layer structure represented by: a positive electrode active material prepared in a weight ratio of 91% positive electrode active material, 4.2% binder and 4.8% conductive material 1M-LiPF 6 was added to ethylene carbonate (1.0 mg of positive electrode mixture) for a first lithium ion battery charged to 4.4 V and a second lithium ion battery charged to 4.1 V.
- First lithium obtained by differential scanning calorimetry (DSC) performed at a heating rate of 5 ° C./min with an electrolyte dissolved in a mixed solvent of EC) -dimethyl carbonate (DMC) (volume ratio 1: 1).
- the difference ⁇ T T41 ⁇ T44 between the first exothermic peak temperature T44 (° C.) of the ion battery and the first exothermic peak temperature T41 (° C.) of the second lithium ion battery satisfies ⁇ T ⁇ 15 (° C.). It is a positive electrode active material for a be a lithium-ion battery.
- ⁇ T satisfies ⁇ T ⁇ 10 (° C.).
- ⁇ T satisfies ⁇ T ⁇ 7 (° C.).
- the present invention is a positive electrode for a lithium ion battery using the positive electrode active material for a lithium ion battery according to the present invention.
- 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 active material for a lithium ion battery that realizes a lithium ion battery excellent in safety.
- Example 6 is a DSC heat generation curve according to Example 3.
- lithium cobaltate LiCoO 2
- lithium-containing transition metal oxides such as lithium nickelate (LiNiO 2 ) and lithium manganate (LiMn 2 O 4 ).
- the positive electrode active material for a lithium ion battery of the present invention produced using such a material has a composition formula: Li x (Ni y M 1-y ) O z (In the formula, M is Mn and Co, x is 0.9 to 1.2, y is 0.8 ⁇ 0.025, and z is 1.8 to 2.4.) It has the layer structure represented by these.
- the ratio of lithium to all metals in the positive electrode active material for a lithium ion battery is 0.9 to 1.2. When the ratio is less than 0.9, it is difficult to maintain a stable crystal structure. This is because the high capacity cannot be secured.
- the positive electrode active material for a lithium ion battery is composed of primary particles, secondary particles formed by aggregation of primary particles, or a mixture of primary particles and secondary particles.
- the positive electrode active material for a lithium ion battery preferably has an average particle diameter of primary particles or secondary particles of 2 to 15 ⁇ m. When the average particle size is less than 2 ⁇ m, it becomes difficult to apply to the current collector. When the average particle size is more than 15 ⁇ m, voids are likely to occur during filling, and the filling property is lowered.
- the average particle size is more preferably 3 to 12 ⁇ m.
- the positive electrode for a lithium ion battery includes, for example, a positive electrode mixture prepared by mixing a positive electrode active material for a lithium ion battery having the above-described configuration, a conductive additive, and a binder from an aluminum foil or the like.
- the current collector has a structure provided on one side or both sides.
- the lithium ion battery which concerns on embodiment of this invention is equipped with the positive electrode for lithium ion batteries of such a structure.
- the lithium ion battery produced using the positive electrode active material for a lithium ion battery of the present invention is defined as follows by differential scanning calorimetry.
- the differential scanning calorimetry (Differential scanning calorimetry) is to measure the heat amount difference between a sample and a reference material accompanying a temperature change as a function of temperature.
- a curve (DSC exothermic curve) drawn with a value measured at a rate of temperature increase of 5 ° C./min for a lithium ion battery charged to two predetermined voltages, the difference between the first exothermic peak temperatures is described later.
- the battery using the positive electrode active material for a lithium ion battery generates heat gently and can suppress thermal runaway well.
- a lithium ion battery using a positive electrode mixture produced in a weight ratio of 91% of a positive electrode active material, 4.2% of a binder and 4.8% of a conductive material according to the present invention, up to 4.4V.
- 1 M-LiPF 6 was added to ethylene carbonate (EC) -dimethyl carbonate (DMC) (1.0 mg) with respect to 1.0 mg of the positive electrode mixture.
- First exothermic peak temperature T44 of the first lithium ion battery respectively obtained by differential scanning calorimetry (DSC) performed at a heating rate of 5 ° C./min together with the electrolyte dissolved in the mixed solvent of volume ratio 1: 1).
- the difference ⁇ T T41 ⁇ T44 between (° C.) and the first exothermic peak temperature T41 (° C.) of the second lithium ion battery satisfies ⁇ T ⁇ 15 (° C.).
- ⁇ T ⁇ 10 (° C.) is preferable, and ⁇ T ⁇ 7 (° C.) is more preferable.
- a metal salt solution is prepared.
- the metals are Ni, Co and Mn.
- the metal salt is sulfate, chloride, nitrate, acetate, etc., and nitrate is particularly preferable. This is because even if it is mixed as an impurity in the firing raw material, it can be fired as it is, so that the washing step can be omitted, and nitrate functions as an oxidant, and promotes the oxidation of the metal in the firing raw material.
- Each metal contained in the metal salt is adjusted so as to have a desired molar ratio. Thereby, the molar ratio of each metal in the positive electrode active material is determined.
- lithium carbonate is suspended in pure water, and then the metal salt solution of the metal is added to prepare a metal carbonate solution slurry. At this time, fine particles of lithium-containing carbonate precipitate in the slurry. If the lithium compound does not react during heat treatment such as sulfate or chloride as a metal salt, it is washed with a saturated lithium carbonate solution and then filtered off. When the lithium compound reacts as a lithium raw material during heat treatment, such as nitrate or acetate, it can be used as a calcining precursor without being washed, filtered off as it is, and dried. Next, the lithium-containing carbonate separated by filtration is dried to obtain a powder of a lithium salt composite (a precursor for a lithium ion battery positive electrode active material).
- a lithium salt composite a precursor for a lithium ion battery positive electrode active material
- a firing container having a predetermined capacity is prepared, and this firing container is filled with a precursor powder for a lithium ion battery positive electrode active material.
- the firing container filled with the precursor powder for the lithium ion battery positive electrode active material is transferred to a firing furnace and fired. Firing is performed by heating and holding in an oxygen atmosphere for a predetermined time. Further, it is preferable to perform baking under a pressure of 101 to 202 KPa because the amount of oxygen in the composition further increases.
- the firing temperature is appropriately set according to the amount of Li in the positive electrode active material precursor used as a raw material. Specifically, since sintering is likely to proceed when the amount of Li is large, the optimum value of the firing temperature is shifted to a lower side than when Li is small.
- the positive electrode for a lithium ion battery according to the present invention is a current collector made of an aluminum foil or the like made of a positive electrode mixture prepared by mixing a positive electrode active material prepared as described above, a conductive additive, and a binder.
- the lithium ion battery of the present invention is manufactured using this positive electrode for a lithium ion battery.
- Examples 1 to 4 First, after suspending lithium carbonate of the input amount shown in Table 1 in 3.2 liters of pure water, 4.8 liter of metal salt solution was charged. Here, the nitrate hydrate of each metal was adjusted so that each metal might become the composition ratio of Table 1, and the total metal mole number might be set to 14 mol.
- the suspended amount of lithium carbonate was such that the product (lithium ion secondary battery positive electrode material, ie, positive electrode active material) was Li x (Ni y M 1-y ) O z and x was the value shown in Table 1. Are respectively calculated by the following equations.
- W (g) 73.9 ⁇ 14 ⁇ (1 + 0.5X) ⁇ A
- “A” is a numerical value to be multiplied in order to subtract the amount of lithium from the lithium compound other than lithium carbonate remaining in the raw material after filtration from the amount of suspension in addition to the amount necessary for the precipitation reaction. is there.
- “A” is 0.9 when lithium salt reacts as a firing raw material such as nitrate or acetate, and “1” when lithium salt does not react as a firing raw material such as sulfate or chloride. 0.
- fine particles of lithium-containing carbonate were precipitated in the solution, and this precipitate was filtered off using a filter press.
- the precipitate was dried to obtain a lithium-containing carbonate (precursor for a lithium ion battery positive electrode active material).
- a firing container was prepared, and this firing container was filled with a lithium-containing carbonate.
- the firing container is placed in an oxygen atmosphere furnace under atmospheric pressure, heated up to the firing temperature shown in Table 1 over 6 hours, heated and held for 2 hours, and then cooled to cool the oxide. Obtained.
- the obtained oxide was crushed to obtain a lithium ion secondary battery positive electrode active material powder.
- Example 5 As Example 5, the same processing as in Examples 1 to 4 was performed, except that each metal of the raw material had a composition as shown in Table 1 and calcination was performed not under atmospheric pressure but under a pressure of 120 KPa. Further, as Example 6, the same processing as in Example 5 was performed, except that each metal of the raw material had a composition as shown in Table 1 and firing was performed under a pressure of 180 KPa.
- Comparative Examples 1 and 2 As Comparative Examples 1 and 2, the same treatment as in Examples 1 to 4 was performed, except that the amount of lithium carbonate suspended and the firing temperature were changed.
- FIG. 1 shows a DSC heat generation curve according to Example 3 shown in Table 1.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
(式中、MはMn及びCoであり、xは0.9~1.2であり、yは0.8±0.025であり、zは1.8~2.4である。)
で表される層構造を有するリチウムイオン電池用正極活物質であり、正極活物質91%、バインダー4.2%及び導電材4.8%の重量比で作製した正極合材を用いたリチウムイオン電池であって、4.4Vまで充電した第1のリチウムイオン電池及び4.1Vまで充電した第2のリチウムイオン電池について、正極合材1.0mgに対して、1M-LiPF6をエチレンカーボネート(EC)-ジメチルカーボネート(DMC)(体積比1:1)の混合溶媒に溶解した電解液と共に昇温速度5℃/分で行った示差走査熱量測定(DSC)でそれぞれ得られた第1のリチウムイオン電池の第一発熱ピーク温度T44(℃)と、第2のリチウムイオン電池の第一発熱ピーク温度T41(℃)との差ΔT=T41-T44が、ΔT≦15(℃)を満たすリチウムイオン電池用正極活物質である。
本発明のリチウムイオン電池用正極活物質の材料としては、一般的なリチウムイオン電池用正極用の正極活物質として有用な化合物を広く用いることができるが、特に、コバルト酸リチウム(LiCoO2)、ニッケル酸リチウム(LiNiO2)、マンガン酸リチウム(LiMn2O4)等のリチウム含有遷移金属酸化物を用いるのが好ましい。このような材料を用いて作製される本発明のリチウムイオン電池用正極活物質は、組成式:Lix(NiyM1-y)Oz
(式中、MはMn及びCoであり、xは0.9~1.2であり、yは0.8±0.025であり、zは1.8~2.4である。)
で表される層構造を有している。
リチウムイオン電池用正極活物質における全金属に対するリチウムの比率が0.9~1.2であるが、これは、0.9未満では、安定した結晶構造を保持し難く、1.2超では電池の高容量が確保できなくなるためである。
平均粒径が2μm未満であると集電体への塗布が困難となる。平均粒径が15μm超であると充填時に空隙が生じやすくなり、充填性が低下する。また、平均粒径は、より好ましくは3~12μmである。
本発明の実施形態に係るリチウムイオン電池用正極は、例えば、上述の構成のリチウムイオン電池用正極活物質と、導電助剤と、バインダーとを混合して調製した正極合剤をアルミニウム箔等からなる集電体の片面または両面に設けた構造を有している。また、本発明の実施形態に係るリチウムイオン電池は、このような構成のリチウムイオン電池用正極を備えている。
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活物質の製造方法について詳細に説明する。
まず、金属塩溶液を作製する。当該金属は、Ni、Co及びMnである。また、金属塩は硫酸塩、塩化物、硝酸塩、酢酸塩等であり、特に硝酸塩が好ましい。これは、焼成原料中に不純物として混入してもそのまま焼成できるため洗浄工程が省けることと、硝酸塩が酸化剤として機能し、焼成原料中の金属の酸化を促進する働きがあるためである。金属塩に含まれる各金属を所望のモル比率となるように調整しておく。これにより、正極活物質中の各金属のモル比率が決定する。
次に、濾別したリチウム含有炭酸塩を乾燥することにより、リチウム塩の複合体(リチウムイオン電池正極活物質用前駆体)の粉末を得る。
その後、焼成容器から粉末を取り出し、粉砕を行うことにより正極活物質の粉体を得る。
また、本発明のリチウムイオン電池用正極は、上述のようにして作製した正極活物質と、導電助剤と、バインダーとを混合して調製した正極合剤をアルミニウム箔等からなる集電体の片面または両面に設けることで作製され、さらに、本発明のリチウムイオン電池は、このリチウムイオン電池用正極を用いて作製される。
まず、表1に記載の投入量の炭酸リチウムを純水3.2リットルに懸濁させた後、金属塩溶液を4.8リットル投入した。ここで、金属塩溶液は、各金属の硝酸塩の水和物を、各金属が表1に記載の組成比になるように調整し、また全金属モル数が14モルになるように調整した。
なお、炭酸リチウムの懸濁量は、製品(リチウムイオン二次電池正極材料、すなわち正極活物質)をLix(NiyM1-y)Ozでxが表1の値となる量であって、それぞれ次式で算出されたものである。
W(g)=73.9×14×(1+0.5X)×A
上記式において、「A」は、析出反応として必要な量の他に、ろ過後の原料に残留する炭酸リチウム以外のリチウム化合物によるリチウムの量をあらかじめ懸濁量から引いておくために掛ける数値である。「A」は、硝酸塩や酢酸塩のように、リチウム塩が焼成原料として反応する場合は0.9であり、硫酸塩や塩化物のように、リチウム塩が焼成原料として反応しない場合は1.0である。
この処理により溶液中に微小粒のリチウム含有炭酸塩が析出したが、この析出物を、フィルタープレスを使用して濾別した。
続いて、析出物を乾燥してリチウム含有炭酸塩(リチウムイオン電池正極活物質用前駆体)を得た。
次に、焼成容器を準備し、この焼成容器内にリチウム含有炭酸塩を充填した。次に、焼成容器を、大気圧下、酸素雰囲気炉に入れて、表1に記載の焼成温度まで6時間かけて昇温させた後、2時間加熱保持し、続いて冷却して酸化物を得た。次に、得られた酸化物を解砕し、リチウムイオン二次電池正極活物質の粉末を得た。
実施例5として、原料の各金属を表1に示すような組成とし、焼成を大気圧下ではなく120KPaの加圧下で行った以外は、実施例1~4と同様の処理を行った。さらに実施例6として、原料の各金属を表1に示すような組成とし、焼成を180KPaの加圧下で行った以外は、実施例5と同様の処理を行った。
比較例1~2として、炭酸リチウム懸濁量、焼成温度を変えた以外は、実施例1~4と同様の処理を行った。
各正極活物質中のLi、Ni、Mn及びCo含有量は、誘導結合プラズマ発光分光分析装置(ICP-AES)で測定し、各金属の組成比(モル比)を算出した。また、X線回折により、結晶構造は層状構造であることを確認した。
次に、この正極活物質について、DSC発熱カーブを以下のようにして測定した。まず、正極活物質91%、バインダー4.2%及び導電材4.8%の重量比で秤量し、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、正極活物質と導電材とを混合してスラリー化して正極合材とし、Al箔上に塗布して乾燥後にプレスして正極とした。この正極において、正極合材の重量は10.0~10.2mgとなるように打ち抜かれている。続いて、対極をLiとした評価用の2032型コインセルを作製し、電解液に1M-LiPF6をエチレンカーボネート(EC)-ジメチルカーボネート(DMC)(体積比1:1)に溶解したものを用いて、(A)電流密度0.2Cにて4.3Vまで充電した後、3.0Vまで放電し、再び4.4Vまで充電したもの、及び、同様に(B)電流密度0.2Cにて4.3Vまで充電した後、3.0Vまで放電し、再び4.1Vまで充電したものをそれぞれ準備した。
次に、このコインセルから上述の(A)及び(B)でそれぞれ準備した電極を取り出し、ジメチルカーボネート(DMC)で洗浄した後、正極合材を削りとった。この正極合材1.0mgを1M-LiPF6をエチレンカーボネート(EC)-ジメチルカーボネート(DMC)(体積比1:1)に溶解した電解液と共にSUS製のサンプルパンに封入し、セイコーインスツルメント社製DSC6200を用いて昇温速度5℃/分にて、示差走査熱量測定を行った。これによりDSC発熱カーブが得られ、さらにこのDSC発熱カーブから、上述の(A)で準備した電極に係る第一の発熱ピーク温度T44(℃)、(B)で準備した電極に係る第一の発熱ピーク温度T41(℃)、及び、それらの差ΔTを得た。また、上述の(A)で準備した電池に対し、25℃の室内で2mm径の釘を電池の厚さ方向に貫通させて発熱させ、30秒後の電池表面の温度を測定した。
これらの結果を表1に示す。また、図1に、表1に示した実施例3に係るDSC発熱カーブを示す。
Claims (5)
- 組成式:Lix(NiyM1-y)Oz
(式中、MはMn及びCoであり、xは0.9~1.2であり、yは0.8±0.025であり、zは1.8~2.4である。)
で表される層構造を有するリチウムイオン電池用正極活物質であり、該正極活物質91%、バインダー4.2%及び導電材4.8%の重量比で作製した正極合材を用いたリチウムイオン電池であって、4.4Vまで充電した第1のリチウムイオン電池及び4.1Vまで充電した第2のリチウムイオン電池について、該正極合材1.0mgに対して、1M-LiPF6をエチレンカーボネート(EC)-ジメチルカーボネート(DMC)(体積比1:1)の混合溶媒に溶解した電解液と共に昇温速度5℃/分で行った示差走査熱量測定(DSC)でそれぞれ得られた該第1のリチウムイオン電池の第一発熱ピーク温度T44(℃)と、該第2のリチウムイオン電池の第一発熱ピーク温度T41(℃)との差ΔT=T41-T44が、ΔT≦15(℃)を満たすリチウムイオン電池用正極活物質。 - 前記ΔTが、ΔT≦10(℃)を満たす請求項1に記載のリチウムイオン電池用正極活物質。
- 前記ΔTが、ΔT≦7(℃)を満たす請求項2に記載のリチウムイオン電池用正極活物質。
- 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活物質を用いたリチウムイオン電池用正極。
- 請求項4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。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020127017342A KR101330843B1 (ko) | 2010-03-04 | 2011-03-03 | 리튬 이온 전지용 정극 활물질, 리튬 이온 전지용 정극, 및 리튬 이온 전지 |
US13/582,089 US20120326099A1 (en) | 2010-03-04 | 2011-03-03 | Positive Electrode Active Material For Lithium Ion Battery, Positive Electrode For Lithium Ion Battery, And Lithium Ion Battery |
CN201180009077.XA CN102754255B (zh) | 2010-03-04 | 2011-03-03 | 锂离子电池用正极活性物质、锂离子电池用正极及锂离子电池 |
JP2012503258A JPWO2011108659A1 (ja) | 2010-03-04 | 2011-03-03 | 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 |
EP11750768.1A EP2544279A4 (en) | 2010-03-04 | 2011-03-03 | POSITIVE ELECTRODE ACTIVE MATERIAL FOR LITHIUM-ION BATTERY, POSITIVE ELECTRODE FOR LITHIUM-ION BATTERY, AND LITHIUM-ION BATTERY |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010048187 | 2010-03-04 | ||
JP2010-048187 | 2010-03-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011108659A1 true WO2011108659A1 (ja) | 2011-09-09 |
Family
ID=44542306
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/054942 WO2011108659A1 (ja) | 2010-03-04 | 2011-03-03 | 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 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20120326099A1 (ja) |
EP (1) | EP2544279A4 (ja) |
JP (1) | JPWO2011108659A1 (ja) |
KR (1) | KR101330843B1 (ja) |
CN (1) | CN102754255B (ja) |
TW (1) | TWI423509B (ja) |
WO (1) | WO2011108659A1 (ja) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5373889B2 (ja) | 2009-03-31 | 2013-12-18 | 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 |
US8993160B2 (en) | 2009-12-18 | 2015-03-31 | Jx Nippon Mining & Metals Corporation | Positive electrode for lithium ion battery, method for producing said positive electrode, and lithium ion battery |
WO2011077932A1 (ja) | 2009-12-22 | 2011-06-30 | 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、リチウムイオン電池用正極及びそれを用いたリチウムイオン電池、並びに、リチウムイオン電池用正極活物質前駆体 |
WO2011096525A1 (ja) | 2010-02-05 | 2011-08-11 | 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、リチウムイオン電池用正極、及び、リチウムイオン電池 |
CN102804461B (zh) | 2010-02-05 | 2016-03-02 | Jx日矿日石金属株式会社 | 锂离子电池用正极活性物质、锂离子电池用正极和锂离子电池 |
KR101450422B1 (ko) | 2010-03-04 | 2014-10-13 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | 리튬 이온 전지용 정극 활물질, 리튬 이온 전지용 정극, 및 리튬 이온 전지 |
US9090481B2 (en) | 2010-03-04 | 2015-07-28 | Jx Nippon Mining & Metals Corporation | Positive electrode active material for lithium-ion battery, positive electrode for lithium-ion battery, and lithium-ion battery |
US9240594B2 (en) | 2010-03-04 | 2016-01-19 | Jx Nippon Mining & Metals Corporation | Positive electrode active substance for lithium ion batteries, positive electrode for lithium ion batteries, and lithium ion battery |
US9225020B2 (en) | 2010-03-04 | 2015-12-29 | Jx Nippon Mining & Metals Corporation | Positive electrode active substance for lithium ion batteries, positive electrode for lithium ion batteries, and lithium ion battery |
TWI423504B (zh) | 2010-03-05 | 2014-01-11 | Jx Nippon Mining & Metals Corp | A positive electrode active material for a lithium ion battery, a positive electrode for a lithium ion battery, a lithium ion battery, and a method for producing a positive electrode active material for a lithium ion battery |
CN105514420A (zh) | 2010-12-03 | 2016-04-20 | Jx日矿日石金属株式会社 | 锂离子电池用正极活性物质、锂离子电池用正极及锂离子电池 |
EP2696406B1 (en) | 2011-01-21 | 2018-05-30 | JX Nippon Mining & Metals Corporation | Method for producing positive-electrode active material for lithium-ion battery |
TWI513663B (zh) | 2011-03-29 | 2015-12-21 | Jx Nippon Mining & Metals Corp | Production method of positive electrode active material for lithium ion battery and positive electrode active material for lithium ion battery |
WO2012133434A1 (ja) | 2011-03-31 | 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、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 |
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 |
KR101729824B1 (ko) | 2012-09-28 | 2017-04-24 | 제이엑스금속주식회사 | 리튬 이온 전지용 정극 활물질, 리튬 이온 전지용 정극 및 리튬 이온 전지 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003007299A (ja) * | 2001-06-14 | 2003-01-10 | Samsung Sdi Co Ltd | 電池用活物質及びその製造方法、並びに電池の製造方法 |
JP2004006264A (ja) | 2002-04-17 | 2004-01-08 | Shin Kobe Electric Mach Co Ltd | リチウム二次電池 |
JP2004227790A (ja) | 2003-01-20 | 2004-08-12 | Nichia Chem Ind Ltd | 非水電解液二次電池用正極活物質 |
JP2006107845A (ja) * | 2004-10-01 | 2006-04-20 | Sumitomo Metal Mining Co Ltd | 非水系電解質二次電池用正極活物質およびこれを用いた非水系電解質二次電池およびその製造方法 |
JP2006107818A (ja) * | 2004-10-01 | 2006-04-20 | Sumitomo Metal Mining Co Ltd | 非水系電解質二次電池用正極活物質およびこれを用いた非水系電解質二次電池およびその製造方法 |
JP2006164758A (ja) | 2004-12-07 | 2006-06-22 | Seimi Chem Co Ltd | リチウム二次電池用正極材料 |
JP2007048744A (ja) * | 2005-07-14 | 2007-02-22 | Matsushita Electric Ind Co Ltd | リチウム二次電池用正極およびそれを用いたリチウム二次電池 |
JP2007095443A (ja) * | 2005-09-28 | 2007-04-12 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
WO2009060603A1 (ja) * | 2007-11-06 | 2009-05-14 | Panasonic Corporation | 非水電解質二次電池用正極活物質ならびにそれを用いた非水電解質二次電池 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002289261A (ja) * | 2001-01-16 | 2002-10-04 | Matsushita Electric Ind Co Ltd | 非水電解質二次電池 |
JP2002124261A (ja) * | 1999-11-29 | 2002-04-26 | Mitsui Chemicals Inc | リチウム二次電池用正極活物質および電池 |
US6929883B2 (en) * | 2000-05-30 | 2005-08-16 | Seimi Chemical Co., Ltd. | Lithium-transition metal composite oxide |
US6984469B2 (en) * | 2000-09-25 | 2006-01-10 | Samsung Sdi Co., Ltd. | Positive active material for rechargeable lithium batteries and method of preparing same |
CN1263184C (zh) * | 2001-11-20 | 2006-07-05 | Tdk株式会社 | 电极活性材料及其制法、电极、锂离子二次电池及其制法 |
KR100437339B1 (ko) * | 2002-05-13 | 2004-06-25 | 삼성에스디아이 주식회사 | 전지용 활물질의 제조방법 및 그로부터 제조되는 전지용활물질 |
TWI279019B (en) * | 2003-01-08 | 2007-04-11 | Nikko Materials Co Ltd | Material for lithium secondary battery positive electrode and manufacturing method thereof |
JP4954451B2 (ja) * | 2004-07-05 | 2012-06-13 | 株式会社クレハ | リチウム二次電池用正極材およびその製造方法 |
KR20070009447A (ko) * | 2005-07-14 | 2007-01-18 | 마츠시타 덴끼 산교 가부시키가이샤 | 리튬 2차 전지용 양극 및 이를 이용한 리튬 2차 전지 |
CN100502106C (zh) * | 2006-05-12 | 2009-06-17 | 盐光科技(嘉兴)有限公司 | 二次电池正极材料及制备方法 |
EP2350879A1 (en) * | 2008-09-19 | 2011-08-03 | Oracle International Corporation | Hash join using collaborative parallel filtering in intelligent storage with offloaded bloom filters |
JP5373889B2 (ja) * | 2009-03-31 | 2013-12-18 | 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 |
TWI423504B (zh) * | 2010-03-05 | 2014-01-11 | Jx Nippon Mining & Metals Corp | A positive electrode active material for a lithium ion battery, a positive electrode for a lithium ion battery, a lithium ion battery, and a method for producing a positive electrode active material for a lithium ion battery |
-
2011
- 2011-03-03 EP EP11750768.1A patent/EP2544279A4/en not_active Withdrawn
- 2011-03-03 US US13/582,089 patent/US20120326099A1/en not_active Abandoned
- 2011-03-03 TW TW100107081A patent/TWI423509B/zh active
- 2011-03-03 WO PCT/JP2011/054942 patent/WO2011108659A1/ja active Application Filing
- 2011-03-03 KR KR1020127017342A patent/KR101330843B1/ko active IP Right Grant
- 2011-03-03 CN CN201180009077.XA patent/CN102754255B/zh active Active
- 2011-03-03 JP JP2012503258A patent/JPWO2011108659A1/ja active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003007299A (ja) * | 2001-06-14 | 2003-01-10 | Samsung Sdi Co Ltd | 電池用活物質及びその製造方法、並びに電池の製造方法 |
JP2004006264A (ja) | 2002-04-17 | 2004-01-08 | Shin Kobe Electric Mach Co Ltd | リチウム二次電池 |
JP2004227790A (ja) | 2003-01-20 | 2004-08-12 | Nichia Chem Ind Ltd | 非水電解液二次電池用正極活物質 |
JP2006107845A (ja) * | 2004-10-01 | 2006-04-20 | Sumitomo Metal Mining Co Ltd | 非水系電解質二次電池用正極活物質およびこれを用いた非水系電解質二次電池およびその製造方法 |
JP2006107818A (ja) * | 2004-10-01 | 2006-04-20 | Sumitomo Metal Mining Co Ltd | 非水系電解質二次電池用正極活物質およびこれを用いた非水系電解質二次電池およびその製造方法 |
JP2006164758A (ja) | 2004-12-07 | 2006-06-22 | Seimi Chem Co Ltd | リチウム二次電池用正極材料 |
JP2007048744A (ja) * | 2005-07-14 | 2007-02-22 | Matsushita Electric Ind Co Ltd | リチウム二次電池用正極およびそれを用いたリチウム二次電池 |
JP2007095443A (ja) * | 2005-09-28 | 2007-04-12 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
WO2009060603A1 (ja) * | 2007-11-06 | 2009-05-14 | Panasonic Corporation | 非水電解質二次電池用正極活物質ならびにそれを用いた非水電解質二次電池 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2544279A4 * |
Also Published As
Publication number | Publication date |
---|---|
KR20120094087A (ko) | 2012-08-23 |
TWI423509B (zh) | 2014-01-11 |
CN102754255A (zh) | 2012-10-24 |
EP2544279A4 (en) | 2015-01-07 |
EP2544279A1 (en) | 2013-01-09 |
US20120326099A1 (en) | 2012-12-27 |
KR101330843B1 (ko) | 2013-11-18 |
JPWO2011108659A1 (ja) | 2013-06-27 |
TW201136011A (en) | 2011-10-16 |
CN102754255B (zh) | 2014-11-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5934089B2 (ja) | 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 | |
WO2011108659A1 (ja) | 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 | |
JP5934088B2 (ja) | 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 | |
WO2011108658A1 (ja) | 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 | |
TWI423503B (zh) | A positive electrode active material for a lithium ion battery, a positive electrode for a lithium ion battery, and a lithium ion battery | |
JP5313392B2 (ja) | 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 | |
JP5843753B2 (ja) | 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 | |
WO2011108598A1 (ja) | 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 | |
JPWO2012128288A1 (ja) | 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 | |
JP6026404B2 (ja) | 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 | |
WO2011108657A1 (ja) | 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 | |
WO2011108655A1 (ja) | 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 | |
WO2011108652A1 (ja) | 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 | |
JP2011187178A (ja) | リチウムイオン電池用正極及びその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180009077.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11750768 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012503258 Country of ref document: JP |
|
ENP | Entry into the national phase |
Ref document number: 20127017342 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13582089 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011750768 Country of ref document: EP |