JP2015103331A - 正極活物質、およびリチウムイオン二次電池 - Google Patents
正極活物質、およびリチウムイオン二次電池 Download PDFInfo
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- JP2015103331A JP2015103331A JP2013241551A JP2013241551A JP2015103331A JP 2015103331 A JP2015103331 A JP 2015103331A JP 2013241551 A JP2013241551 A JP 2013241551A JP 2013241551 A JP2013241551 A JP 2013241551A JP 2015103331 A JP2015103331 A JP 2015103331A
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- active material
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- OQTQHQORDRKHFW-UHFFFAOYSA-L manganese(2+);sulfate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Mn+2].[O-]S([O-])(=O)=O OQTQHQORDRKHFW-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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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
- H01M4/52—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
-
- 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
-
- 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
-
- 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
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Abstract
【解決手段】X線回折において、(104)面の回折ピーク強度I(104)と、(003)面の回折ピーク強度I(003)との比I(003)/(104)が、1.05以上1.25以下であり、かつ、(003)面の半値幅FWHM(003)が、0.12以上0.155以下であり、かつ、平均2次粒子径であるD50が、3μm以上9μm以下であり、かつ、比表面積が、0.38m2/g以上1.05m2/g以下であり、下記一般式(1)で示される組成を有するリチウム複合酸化物を含む、正極活物質。
(化1)
LiaNixCoyMzO2・・・(1)
【選択図】図1
Description
(化1)
LiaNixCoyMzO2・・・(1)
前記一般式(1)において、Mは、Al、Mn、Cr、Fe、V、Mg、Ti、Zr、Nb、Mo、W、Cu、Zn、Ga、In、Sn、La、Ceからなる群から選択される1種または2種以上の金属元素であり、
aは、0.20≦a≦1.20であり、
xは、0.80≦x<1.00であり、
yは、0<y≦0.20であり、
zは、0≦z≦0.10であり、
x+y+z=1である。
xは、0.80≦x<1.00であり、
yは、0<y≦0.15であり、
zは、0<z≦0.05であり、
x+y+z=1であってもよい。
まず、本発明の一実施形態に係るリチウムイオン二次電池の概要について、本発明の背景技術を交えながら説明を行う。
以下では、図1を参照して、上記で説明した本発明の一実施形態に係るリチウムイオン二次電池10の具体的な構成について説明を行う。図1は、本発明の一実施形態に係るリチウムイオン二次電池の構成を説明する説明図である。
LiaNixCoyMzO2・・・(1)
aは、0.20≦a≦1.20であり、
xは、0.80≦x<1.00であり、
yは、0<y≦0.20であり、
zは、0≦z≦0.10であり、
x+y+z=1である。
xは、0.80≦x<1.00であり、
yは、0<y≦0.15であり、
zは、0<z≦0.05であり、
x+y+z=1であってもよい。
[3−1.高Ni比率のリチウムニッケル複合酸化物の製造方法]
次に、本発明の一実施形態に係る高Ni比率のリチウムニッケル複合酸化物の製造方法について説明する。本発明の一実施形態に係るリチウムニッケル複合酸化物の製造方法は、特に制限されないが、例えば、共沈法を用いることできる。以下では、かかる共沈法を用いたリチウムニッケル複合酸化物の製造方法について、一例を挙げて説明を行う。
続いて、リチウムイオン二次電池10の製造方法について説明する。なお、本発明では、上述した製造方法による高Ni比率のリチウムニッケル複合酸化物に正極活物質を変更した以外は、従来のリチウムイオン二次電池と同様の製造方法にて、リチウムイオン二次電池10を製造することができる。本発明の一実施形態に係るリチウムイオン二次電池10の製造方法は概略的には以下のとおりである。
硫酸ニッケル6水和物(NiSO4・6H2O)、硫酸コバルト5水和物(CoSO4・5H2O)、および硝酸アルミニウム(Al(NO3)3)をイオン交換水に溶解させ、混合水溶液を製造した。ここで、硫酸ニッケル6水和物、硫酸コバルト5水和物、および硝酸アルミニウムの総質量は、混合水溶液の総質量に対して、20質量%とした。また、硫酸ニッケル6水和物、硫酸コバルト5水和物、および硝酸アルミニウムの混合比は、Ni、Co、およびAlの各元素のモル比が、それぞれの実施例において、Ni:Co:Al=80〜84:15:1〜5となるように混合した。
混合水溶液を硫酸ニッケル6水和物、硫酸コバルト5水和物、および硫酸マンガン7水和物(MnSO4・7H2O)で製造した以外は、上述した実施例1〜3および比較例1〜4と同様の方法で、実施例4、5および比較例5、6に係るリチウムニッケル複合酸化物を製造した。なお、硫酸ニッケル6水和物、硫酸コバルト5水和物、および硫酸マンガン7水和物の混合比は、Ni、Co、およびMnの各元素のモル比がNi:Co:Mn=80〜85:10〜15:4〜10となるように混合した。
上記で製造した実施例1〜5および比較例1〜6に係るリチウムニッケル複合酸化物のX線回折試験を行ったところ、回折角(2θ)18°付近に(003)面のピークが検出され、回折角(2θ)44°付近に(104)面のピークが検出された。かかるピークに基づいて、(003)面および(104)面の回折ピーク強度比I(003)/(104)、および(003)面の半値幅FWHM(003)を算出した。
さらに、リチウムイオン二次電池を以下のように製造した。まず、上述した製造方法によって、それぞれ製造されたリチウムニッケル複合酸化物と、アセチレンブラックと、ポリフッ化ビニリデンとを95:2:3の質量比で混合した。そして、この混合物をN−メチル−2−ピロリドンに分散させることでスラリーを形成した。
以上で説明した方法にて製造された実施例1〜5および比較例1〜6に係るリチウムイオン二次電池の充放電評価を行った。具体的には、以下の表1に示す充放電レート(rate)、カットオフ(cut off)電圧にてサイクル試験を行った。
20 正極
21 集電体
22 正極活物質層
30 負極
31 集電体
32 負極活物質層
40 セパレータ層
Claims (3)
- X線回折において、(003)面の回折ピーク強度I(003)と、(104)面の回折ピーク強度I(104)との比I(003)/(104)が、1.05以上1.25以下であり、かつ、(003)面の半値幅FWHM(003)が、0.12以上0.155以下であり、かつ、平均2次粒子径であるD50が、3μm以上9μm以下であり、かつ、比表面積が、0.38m2/g以上1.05m2/g以下であり、
下記一般式(1)で示される組成を有するリチウム複合酸化物を含む、正極活物質。
(化1)
LiaNixCoyMzO2・・・(1)
前記一般式(1)において、Mは、Al、Mn、Cr、Fe、V、Mg、Ti、Zr、Nb、Mo、W、Cu、Zn、Ga、In、Sn、La、Ceからなる群から選択される1種または2種以上の金属元素であり、
aは、0.20≦a≦1.20であり、
xは、0.80≦x<1.00であり、
yは、0<y≦0.20であり、
zは、0≦z≦0.10であり、
x+y+z=1である。 - 前記一般式(1)において、Mは、AlまたはMnであり、
xは、0.80≦x<1.00であり、
yは、0<y≦0.15であり、
zは、0<z≦0.05であり、
x+y+z=1である、請求項1に記載の正極活物質。 - 請求項1または2に記載の正極活物質を含む、リチウムイオン二次電池。
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JP2017193471A (ja) * | 2016-04-22 | 2017-10-26 | ユミコア | ニッケルリチウム金属複合酸化物の製造方法 |
CN110462894A (zh) * | 2018-03-07 | 2019-11-15 | 日立金属株式会社 | 锂离子二次电池用正极活性物质和锂离子二次电池 |
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CN110462894A (zh) * | 2018-03-07 | 2019-11-15 | 日立金属株式会社 | 锂离子二次电池用正极活性物质和锂离子二次电池 |
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CN112042011B (zh) * | 2018-03-28 | 2024-02-13 | 尤米科尔公司 | 作为用于可再充电锂二次蓄电池的正电极活性材料的锂过渡金属复合氧化物 |
WO2023050044A1 (zh) * | 2021-09-28 | 2023-04-06 | 宁德新能源科技有限公司 | 一种电化学装置和电子装置 |
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CN116960276B (zh) * | 2023-09-20 | 2023-12-29 | 中创新航科技集团股份有限公司 | 一种正极极片、包含该正极极片的电化学装置和电子装置 |
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