WO2011108656A1 - 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
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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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- C01G53/00—Compounds of nickel
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- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- 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
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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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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, when the positive electrode active material has a difference between the first exothermic peak temperature measured in the DSC (Differential Scanning Calorimetry) exothermic curve and the temperature that is 1 ⁇ 2 of the first exothermic peak intensity, the battery is Was found to generate mild heat and suppress thermal runaway 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 After the battery was charged to 4.3 V, 1M-LiPF 6 was dissolved in a mixed solvent of ethylene carbonate (EC) -dimethyl carbonate (DMC) (volume ratio 1: 1) with respect to 1.0 mg of the positive electrode mixture.
- EC ethylene carbonate
- DMC dimethyl carbonate
- First exothermic peak temperature T1 (° C.) obtained by differential scanning calorimetry (DSC) performed at a heating rate of 5 ° C./min with the liquid, and temperature T2 (° C.) that is 1 ⁇ 2 of the first exothermic peak intensity Is a positive electrode active material for a lithium ion battery in which the difference ⁇ T (where T2 ⁇ T1) satisfies ⁇ T ⁇ 13 (° C.).
- ⁇ T satisfies ⁇ T ⁇ 15 (° C.).
- the positive electrode active material for a lithium ion battery according to the present invention satisfies ⁇ T ⁇ 18 (° C.).
- the positive electrode active material for a lithium ion battery according to the present invention has T1 of 230 ° C. or higher.
- 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.
- 6 is a DSC heat generation curve according to Example 3. 6 is a DSC heat generation curve according to Comparative Example 4.
- 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.
- the battery In the curve drawn by the measured value (DSC exothermic curve) at this time, when the difference between the first exothermic peak temperature and the temperature that is 1 ⁇ 2 of the first exothermic peak intensity is equal to or greater than a predetermined value described later, the battery is gentle. It generates heat and can suppress thermal runaway well. This is because the thermal runaway occurs when the heat release cannot catch up with the heat generation, and generally, the more slowly the heat generation increases as the temperature rises, the more heat release is available.
- T2 ⁇ T1 between the first exothermic peak temperature T1 (° C.) obtained by differential scanning calorimetry (DSC) performed in step 1 and a temperature T2 (° C.) that is 1 ⁇ 2 of the first exothermic peak intensity. Satisfies ⁇ T ⁇ 13 (° C.). Further, ⁇ T ⁇ 15 (° C.) is preferable, and ⁇ T ⁇ 18 (° C.) is more preferable.
- the first exothermic peak temperature T1 (° C.) is preferably 230 ° C. or higher.
- 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 5 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 6 As Example 6, the same processing as in Examples 1 to 5 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 7, the same processing as in Example 6 was performed, except that each material 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 to 5 As Comparative Examples 1 to 5, the same treatment as in Examples 1 to 5 was performed, except that the lithium carbonate suspension amount and the firing temperature were changed.
- the electrode was taken out from the coin cell, washed with dimethyl carbonate (DMC), and then the positive electrode mixture was scraped off. 1.0 mg of this positive electrode mixture was sealed in a sample pan made of SUS together with an electrolytic solution in which 1M-LiPF 6 was dissolved in ethylene carbonate (EC) -dimethyl carbonate (DMC) (volume ratio 1: 1), and Seiko Instruments Inc. Differential scanning calorimetry was performed using a DSC6200 manufactured by the company at a temperature elevation rate of 5 ° C./min. As a result, a DSC exothermic curve is obtained.
- DMC dimethyl carbonate
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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を4.3Vまで充電した後、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)で得られた第一発熱ピーク温度T1(℃)と第一発熱ピーク強度の1/2となる温度T2(℃)との差ΔT(ただしT2<T1)が、ΔT≧13(℃)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。
第一発熱ピーク温度T1(℃)は、230℃以上であるのが好ましい。
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、焼成を大気圧下ではなく120KPaの加圧下で行った以外は、実施例1~5と同様の処理を行った。さらに実施例7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6と同様の処理を行った。
比較例1~5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1~5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、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4.3Vまで充電した。
次に、このコインセルから電極を取り出し、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発熱カーブから第一ピークのピーク温度T1(℃)、このピーク高さの1/2となる温度T2(℃)、及び、それらの差ΔT(ただしT2<T1)を得た。また、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及び2に、それぞれ表1に示した実施例3及び比較例4に係るDSC発熱カーブを示す。
Claims (6)
- 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を4.3Vまで充電した後、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℃/分で行なった示差走査熱量測定(DSC)で得られた第一発熱ピーク温度T1(℃)と第一発熱ピーク強度の1/2となる温度T2(℃)との差ΔT(ただしT2<T1)が、ΔT≧13(℃)を満たすリチウムイオン電池用正極活物質。 - 前記ΔTが、ΔT≧15(℃)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≧18(℃)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。
- 前記T1が230℃以上である請求項1~3のいずれかに記載のリチウムイオン電池用正極活物質。
- 請求項1~4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5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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US8748041B2 (en) | 2009-03-31 | 2014-06-10 | Jx Nippon Mining & Metals Corporation | Positive electrode active material for lithium ion battery |
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CN102668185B (zh) | 2009-12-22 | 2015-07-08 | 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使用其的锂离子电池、及锂离子电池用正极活性物质前驱体 |
US9231249B2 (en) | 2010-02-05 | 2016-01-05 | Jx Nippon Mining & Metals Corporation | Positive electrode active material for lithium ion battery, positive electrode for lithium ion battery, and lithium ion battery |
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EP2544273A4 (en) | 2010-03-04 | 2014-06-25 | Jx Nippon Mining & Metals Corp | POSITIVE ACTIVE ELECTRODE MATERIAL FOR LITHIUM ION BATTERIES, POSITIVE ELECTRODE FOR LITHIUM ION BATTERIES AND LITHIUM ION BATTERY |
CN102754254B (zh) | 2010-03-04 | 2016-01-20 | 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 |
US9216913B2 (en) | 2010-03-04 | 2015-12-22 | Jx Nippon Mining & Metals Corporation | Positive electrode active substance for lithium ion batteries, positive electrode for lithium ion batteries, and lithium ion battery |
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US20120319039A1 (en) * | 2010-03-04 | 2012-12-20 | Jx Nippon Mining & Metals Corporation | Positive Electrode Active Material For Lithium Ion Battery, Positive Electrode For Lithium Ion Battery, 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 |
US9221693B2 (en) | 2011-03-29 | 2015-12-29 | Jx Nippon Mining & Metals Corporation | Method for producing positive electrode active material for lithium ion batteries and positive electrode active material for lithium ion batteries |
EP2693536B1 (en) | 2011-03-31 | 2017-05-03 | JX Nippon Mining & Metals Corporation | Positive electrode active material for lithium ion batteries, positive electrode for lithium ion battery, and lithium ion battery |
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 |
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KR101729824B1 (ko) | 2012-09-28 | 2017-04-24 | 제이엑스금속주식회사 | 리튬 이온 전지용 정극 활물질, 리튬 이온 전지용 정극 및 리튬 이온 전지 |
JP6301619B2 (ja) * | 2013-09-20 | 2018-03-28 | 株式会社東芝 | 非水電解質二次電池、電池パック及び車 |
CN111634961A (zh) * | 2020-06-28 | 2020-09-08 | 蜂巢能源科技有限公司 | 锂离子电池用正极材料及其制备方法 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11307094A (ja) * | 1998-04-20 | 1999-11-05 | Chuo Denki Kogyo Co Ltd | リチウム二次電池用正極活物質とリチウム二次電池 |
JP2002063901A (ja) * | 2000-08-14 | 2002-02-28 | Mitsui Chemicals Inc | リチウム二次電池用正極活物質、その製法およびそれを用いた電池 |
JP2002164053A (ja) * | 2000-09-25 | 2002-06-07 | Samsung Sdi Co Ltd | リチウム二次電池用正極活物質及びその製造方法 |
WO2002086993A1 (fr) * | 2001-04-20 | 2002-10-31 | Yuasa Corporation | Matiere active anodique et son procede de production, anode pour pile secondaire a electrolyte non aqueux et pile secondaire a electrolyte non aqueux |
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 |
JP2005302628A (ja) * | 2004-04-15 | 2005-10-27 | Toshiba Corp | 非水電解質電池用正極活物質、正極及び非水電解質電池 |
JP2005332707A (ja) * | 2004-05-20 | 2005-12-02 | Toshiba Corp | 非水電解質電池用正極及び非水電解質電池 |
JP2006156126A (ja) * | 2004-11-29 | 2006-06-15 | Sumitomo Metal Mining Co Ltd | 非水系二次電池用正極活物質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 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5393622A (en) * | 1992-02-07 | 1995-02-28 | Matsushita Electric Industrial Co., Ltd. | Process for production of positive electrode active material |
JPH08138669A (ja) * | 1994-11-02 | 1996-05-31 | Toray Ind Inc | 正極活物質、その製造方法およびそれを用いた非水溶媒系二次電池 |
JP3471244B2 (ja) * | 1999-03-15 | 2003-12-02 | 株式会社東芝 | 非水電解液二次電池の製造方法 |
KR100437339B1 (ko) * | 2002-05-13 | 2004-06-25 | 삼성에스디아이 주식회사 | 전지용 활물질의 제조방법 및 그로부터 제조되는 전지용활물질 |
TWI286849B (en) * | 2003-03-25 | 2007-09-11 | Nichia Corp | Positive electrode active material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
KR100570616B1 (ko) * | 2004-02-06 | 2006-04-12 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 양극 활물질, 그의 제조 방법 및 그를포함하는 리튬 이차 전지 |
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 |
EP1831943B1 (en) | 2004-12-31 | 2014-12-10 | IUCF-HYU (Industry-University Cooperation Foundation Hanyang University) | Method for preparing double-layer cathode active materials for lithium secondary batteries |
CN100362681C (zh) * | 2005-03-23 | 2008-01-16 | 中南大学 | 一种锂离子电池正极材料锂镍钴锰氧及其制备方法 |
CN100466364C (zh) * | 2005-12-15 | 2009-03-04 | 中国电子科技集团公司第十八研究所 | 一种安全锂离子电池 |
CN102983322A (zh) * | 2006-05-10 | 2013-03-20 | 株式会社Lg化学 | 用于高性能锂二次电池的材料 |
CN101281965A (zh) * | 2008-05-29 | 2008-10-08 | 复旦大学 | 一种锂离子电池正极材料及其制备方法 |
CN101308925B (zh) * | 2008-07-04 | 2011-02-02 | 深圳市贝特瑞新能源材料股份有限公司 | 锂离子电池复合包覆正极材料及其制备方法 |
-
2011
- 2011-03-03 CN CN2011800123260A patent/CN102782912A/zh active Pending
- 2011-03-03 CN CN201510009493.XA patent/CN104600291B/zh active Active
- 2011-03-03 KR KR1020127025196A patent/KR20120132527A/ko not_active Application Discontinuation
- 2011-03-03 EP EP11750765.7A patent/EP2544277A4/en not_active Withdrawn
- 2011-03-03 WO PCT/JP2011/054938 patent/WO2011108656A1/ja active Application Filing
- 2011-03-03 TW TW100107074A patent/TWI423506B/zh active
- 2011-03-03 US US13/582,067 patent/US20120326102A1/en not_active Abandoned
- 2011-03-03 JP JP2012503255A patent/JP5934089B2/ja active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11307094A (ja) * | 1998-04-20 | 1999-11-05 | Chuo Denki Kogyo Co Ltd | リチウム二次電池用正極活物質とリチウム二次電池 |
JP2002063901A (ja) * | 2000-08-14 | 2002-02-28 | Mitsui Chemicals Inc | リチウム二次電池用正極活物質、その製法およびそれを用いた電池 |
JP2002164053A (ja) * | 2000-09-25 | 2002-06-07 | Samsung Sdi Co Ltd | リチウム二次電池用正極活物質及びその製造方法 |
WO2002086993A1 (fr) * | 2001-04-20 | 2002-10-31 | Yuasa Corporation | Matiere active anodique et son procede de production, anode pour pile secondaire a electrolyte non aqueux et pile secondaire a electrolyte non aqueux |
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 |
JP2005302628A (ja) * | 2004-04-15 | 2005-10-27 | Toshiba Corp | 非水電解質電池用正極活物質、正極及び非水電解質電池 |
JP2005332707A (ja) * | 2004-05-20 | 2005-12-02 | Toshiba Corp | 非水電解質電池用正極及び非水電解質電池 |
JP2006156126A (ja) * | 2004-11-29 | 2006-06-15 | Sumitomo Metal Mining Co Ltd | 非水系二次電池用正極活物質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 |
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