Lithium metal composite oxide powder

Patent metadata

Field	Value
Publication number	US-10312508-B2
Application number	US-201515508184-A
Country	US
Kind code	B2
Filing date	Sep 3, 2015
Priority date	Sep 3, 2014
Publication date	Jun 4, 2019
Grant date	Jun 4, 2019

Abstract

A positive electrode active material comprising a lithium metal composite oxide having a layered crystal structure provides a novel lithium metal composite oxide powder which can suppress the reaction with an electrolytic solution and raise the charge-discharge cycle ability of a battery, and can improve the output characteristics of a battery. A lithium metal composite oxide powder comprises a particle having a surface portion where one or a combination of two or more (“surface element A”) of the group consisting of Al, Ti and Zr is present, on the surface of a particle comprising a lithium metal composite oxide having a layered crystal structure, wherein the amount of surface LiOH is smaller than 0.10% by weight, and the amount of surface Li 2 CO 3 is smaller than 0.25% by weight; in an X-ray diffraction pattern, the ratio of an integral intensity of the (003) plane of the lithium metal composite oxide to that of the (104) plane thereof is higher than 1.15; and the amount of S obtained by a measurement using ICP is smaller than 0.10% by weight of the lithium metal composite oxide powder (100% by weight).

First claim

The invention claimed is:

1. A lithium metal composite oxide powder, comprising a particle having a surface portion where one or a combination of two or more (referred to as “surface element A”) of the group consisting of Al, Ti and Zr is present, on a surface of a particle comprising a lithium metal composite oxide having a layered crystal structure,
wherein an amount of surface LiOH measured by the following measuring method is smaller than 0.10% by weight of the lithium metal composite oxide powder, and an amount of surface Li 2 CO 3 measured by the following measuring method is smaller than 0.25% by weight of the lithium metal composite oxide powder;
in an X-ray diffraction pattern obtained by X-ray diffraction using CuKα radiation, a ratio of an integral intensity of the (003) plane of the lithium metal composite oxide to that of the (104) plane thereof is higher than 1.15; and
an amount of S obtained by a measurement using an inductively coupled plasma (ICP) atomic emission spectrometer is smaller than 0.10% by weight of the lithium metal composite oxide powder (100% by weight),
wherein the amount of surface LiOH and the amount of surface Li 2 CO 3 are measured by a titration that is carried out according to the following procedure by reference to a Winkler method, wherein 10.0 g of a sample is dispersed in 50 ml of ion-exchanged water, immersed therein for 15 min, and thereafter filtered; and the filtrate is titrated with hydrochloric acid; and at this time, by using phenolphthalein and bromophenol blue as indicators, the amount of the surface LiOH and the amount of the surface Li 2 CO 3 are calculated based on the discoloration of the filtrate and an amount of titration at this time,
the lithium metal composite oxide is a lithium metal composite oxide represented by the general formula: Li 1+x M 1−x O 2 , wherein x=0 to 0.07 and M is one or a combination of two or more (referred to as “constituent element M”) of the group consisting of Mn, Co, Ni, transition elements in the third group elements through and including the 11th group elements of the periodic table, and elements in the first period through and including the third period of the periodic table, and
a ratio (C A /C M ) of a concentration (at %) referred to as “C A ”; in the case where the surface element A contains two or more elements, the total concentration of the surface element A to a concentration (at %) referred to as “C M ”; in the case where the constituent element M contains two or more elements, the total concentration of the constituent element M is higher than 0 and lower than 0.8, as measured by X-ray photoelectron spectroscopy (XPS).

2. The lithium metal composite oxide powder according to claim 1 , wherein a tap density (TD) thereof is higher than 2.0 g/cm 3 .

3. A lithium metal composite oxide powder comprising a particle having a surface portion where one or a combination of two or more (referred to as “surface element A”) of the group consisting of Al, Ti and Zr is present, on a surface of a particle comprising a lithium metal composite oxide having a layered crystal structure,
wherein an amount of surface LiOH measured by the following measuring method is smaller than 0.10% by weight of the lithium metal composite oxide powder, and an amount of surface Li 2 CO 3 measured by the following measuring method is smaller than 0.25% by weight of the lithium metal composite oxide powder;
in an X-ray diffraction pattern obtained by X-ray diffraction using CuKα radiation, a ratio of an integral intensity of the (003) plane of the lithium metal composite oxide to that of the (104) plane thereof is higher than 1.15; and
an amount of S obtained by a measurement using an inductively coupled plasma (ICP) atomic emission spectrometer is smaller than 0.10% by weight of the lithium metal composite oxide powder (100% by weight),
wherein the amount of surface LiOH and the amount of surface Li 2 CO 3 are measured by a titration that is carried out according to the following procedure by reference to a Winkler method, wherein 10.0 g of a sample is dispersed in 50 ml of ion-exchanged water, immersed therein for 15 min, and thereafter filtered; and the filtrate is titrated with hydrochloric acid; and at this time, by using phenolphthalein and bromophenol blue as indicators, the amount of the surface LiOH and the amount of the surface Li 2 CO 3 are calculated based on the discoloration of the filtrate and an amount of titration at this time,
the lithium metal composite oxide is a lithium metal composite oxide represented by the general formula: Li 1+x M 1−x O 2 , wherein x=0 to 0.07 and M is one or a combination of two or more (referred to as “constituent element M”) of the group consisting of Mn, Co, Ni, transition elements in the third group elements through and including the 11th group elements of the periodic table, and elements in the first period through and including the third period of the periodic table, and
a ratio (C A /C Ni ,) of a concentration (at %) (referred to as “C A ”; in the case where the surface element A contains two or more elements, the total concentration) of the surface element A to a concentration (at %) (referred to as “C Ni ,”) of a constituent element Ni is higher than 0 and lower than 1.0, as measured by X-ray photoelectron spectroscopy (XPS).

4. A lithium metal composite oxide powder comprising a particle having a surface portion where one or a combination of two or more (referred to as “surface element A”) of the group consisting of Al, Ti and Zr is present, on a surface of a particle comprising a lithium metal composite oxide having a layered crystal structure,
wherein an amount of surface LiOH measured by the following measuring method is smaller than 0.10% by weight of the lithium metal composite oxide powder, and an amount of surface Li 2 CO 3 measured by the following measuring method is smaller than 0.25% by weight of the lithium metal composite oxide powder;
in an X-ray diffraction pattern obtained by X-ray diffraction using CuKα radiation, a ratio of an integral intensity of the (003) plane of the lithium metal composite oxide to that of the (104) plane thereof is higher than 1.15; and
an amount of S obtained by a measurement using an inductively coupled plasma (ICP) atomic emission spectrometer is smaller than 0.10% by weight of the lithium metal composite oxide powder (100% by weight),
wherein the amount of surface LiOH and the amount of surface Li 2 CO 3 are measured by a titration that is carried out according to the following procedure by reference to a Winkler method, wherein 10.0 g of a sample is dispersed in 50 ml of ion-exchanged water, immersed therein for 15 min, and thereafter filtered; and the filtrate is titrated with hydrochloric acid; and at this time, by using phenolphthalein and bromophenol blue as indicators, the amount of the surface LiOH and the amount of the surface Li 2 CO 3 are calculated based on the discoloration of the filtrate and an amount of titration at this time,
the lithium metal composite oxide is a lithium metal composite oxide represented by the general formula: Li 1+x M 1−x O 2 , wherein x=0 to 0.07 and M is one or a combination of two or more (referred to as “constituent element M”) of the group consisting of Mn, Co, Ni, transition elements in the third group elements through and including the 11th group elements of the periodic table, and elements in the first period through and including the third period of the periodic table, and
a concentration (at %) (referred to as “C M ”; in the case where the constituent element M contains two or more elements, the total concentration) of the constituent element M is higher than 0 at % and lower than 50 at %; a concentration (at %) (referred to as “C A ”; in the case where the surface element A contains two or more elements, the total concentratio

Assignees

• Mitsui Mining & Smelting Co

Inventors

• Mitsumoto Tetsuya
• Washida Daisuke
• Matsuyama Toshikazu
• Inoue Daisuke
• Matsushima Hideaki
• Hata Yoshimi
• Ide Hitohiko
• Kagei Shinya

Classifications

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title

• C01G53/50 Primary

  of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• C01P2004/62

  Submicrometer sized, i.e. from 0.1-1 micrometer · CPC title

• H01M4/366 Primary

  as layered products · CPC title