JP2018530113A - 二次電池の正極形成用組成物、及びこれを用いて製造した二次電池用正極並びに二次電池 - Google Patents
二次電池の正極形成用組成物、及びこれを用いて製造した二次電池用正極並びに二次電池 Download PDFInfo
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- JP2018530113A JP2018530113A JP2018515444A JP2018515444A JP2018530113A JP 2018530113 A JP2018530113 A JP 2018530113A JP 2018515444 A JP2018515444 A JP 2018515444A JP 2018515444 A JP2018515444 A JP 2018515444A JP 2018530113 A JP2018530113 A JP 2018530113A
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Classifications
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- 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
-
- 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
- H01M4/139—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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/139—Processes of manufacture
-
- 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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- 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
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- 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
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Abstract
Description
本出願は2016年3月24日付韓国特許出願第2016−0035562号及び2017年3月23日付韓国特許出願第2017−0036956号に基づく優先権の利益を主張し、当該韓国特許出願の文献に開示された全ての内容は本明細書の一部として含まれる。
Li1+aNixCoyMnzMwO2 化学式(4)
前記化学式(4)において、MはAl、Cu、Fe、V、Cr、Ti、Zr、Zn、Ta、Nb、Mg、B、W及びMoからなる群より選択されるいずれか一つまたは二つ以上の元素を含むものであってよく、a、x、y、z及びwはそれぞれ独立的に当該元素等の原子分率であって、−0.5≦a≦0.5、0≦x≦1、0<y≦1、0≦z≦1、0≦w≦1及び0<x+y+z≦1であってよい。
N−メチルピロリドン(NMP)溶媒中に導電材として下記表1に記載されたカーボンブラック(SSA=135m2/g、OAN=220ml/100g)、及び分散剤として下記表2に記載された部分水素化ニトリルゴムを添加して下記表3に記載された組成比で混合した後、下記のような条件でビーズミリング工程を行って導電材分散液を製造した。
ローター直径:150mm
ローター速度:1000rpm
ローター周速:7.9m/s
ビーズ直径:1.25mm
ビーズ充填率:80重量%
吐出速度:1kg/min
下記表1から3に記載された配合で各構成成分等を用い、また導電材分散液の製造のためのビーズミリング工程時に吐出速度を0.5kg/minで行うことを除いては、前記実施例1と同じ方法で実施して正極形成用組成物を製造した。
下記表1から3に記載された配合で各構成成分等を用い、また導電材分散液の製造のためのビーズミリング工程時に吐出速度を1.2kg/minで行うことを除いては、前記実施例1と同じ方法で実施して正極形成用組成物を製造した。
下記表1から3に記載された配合で各構成成分等を用い、また導電材分散液の製造のためのビーズミリング工程時に吐出速度を2kg/minで行うことを除いては、前記実施例1と同じ方法で実施して正極形成用組成物を製造した。
下記表1から3に記載された配合で各構成成分等を用い、また導電材分散液の製造のためのビーズミリング工程時に吐出速度を0.3kg/minで行うことを除いては、前記実施例1と同じ方法で実施して正極形成用組成物を製造した。
下記表1から3に記載された配合で各構成成分等を用いることを除いては、前記実施例1と同じ方法で実施して正極形成用組成物を製造した。
下記表1から3に記載された配合で各構成成分等を用いるが、分散剤としてポリビニルアルコール(PVA)を用いることを除いては、前記実施例1と同じ方法で実施して正極形成用組成物を製造した。
前記実施例1〜3及び比較例1〜4で製造した正極形成用組成物をそれぞれアルミニウムホイルの一面にコーティングし、乾燥及び圧延した後、一定の大きさでパンチングして正極を製造した。
前記実施例1〜3及び比較例1〜4で製造した正極形成用組成物に対して、導電材の粒度分布を測定した。
前記実施例1〜3及び比較例1〜4で製造した正極形成用組成物を用いて、前記製造例により製造した電池に対して抵抗特性を評価した。
前記実施例1〜3及び比較例1〜4で製造した正極形成用組成物を用いて製造した電池に対して、レート特性を評価した。
前記実施例1から3、及び比較例1〜4で製造した正極形成用組成物を用いて製造した電池に対して、高温での容量維持率を評価した。
〔1〕 二次電池の正極形成用組成物であって、
正極活物質、導電材、及び分散剤を含んでなり、
前記導電材は、前記正極形成用組成物の総重量に対して0.1重量%から2重量%の量で、比表面積が130m2/g以上であり、オイル吸収量が220ml/100g以上である炭素系物質を含んでなるものであり、
前記分散剤は、前記導電材に導入されて導電材−分散剤複合体を形成させるものであり、
前記導電材−分散剤複合体は、粒度分布のD50が0.8μmから1.2μmであるものである、二次電池の正極形成用組成物。
〔2〕 前記導電材−分散剤複合体は、粒度分布のD90が2.0μmから5.0μmであるものである、〔1〕に記載の二次電池の正極形成用組成物。
〔3〕 前記炭素系物質は、1次粒子が組立てられてなる(1次粒子を造粒し又は凝集してなる)2次粒子であるものである、〔1〕又は〔2〕に記載の二次電池の正極形成用組成物。
〔4〕 前記炭素系物質は、カーボンブラックである、〔1〕〜〔3〕の何れか一項に記載の二次電池の正極形成用組成物。
〔5〕 前記分散剤は、ゴムの総重量に対して水素化された共役ジエン由来構造の繰り返し単位を20重量%から50重量%で含んだ部分水素化ニトリルゴムを含んでなるものである、〔1〕〜〔4〕の何れか一項に記載の二次電池の正極形成用組成物。
〔6〕 前記部分水素化ニトリルゴムは、α,β−不飽和ニトリル由来構造の繰り返し単位をゴムの総重量に対して20重量%から50重量%で含んだものである、〔5〕に記載の二次電池の正極形成用組成物。
〔7〕 前記部分水素化ニトリルゴムは、
下記化学式(1)の構造の繰り返し単位、
下記化学式(2)の構造の繰り返し単位、
下記化学式(3)の構造の繰り返し単位、及び
α,β−不飽和カルボン酸のエステル由来構造単位、を含んだアクリロニトリル−ブタジエンゴムであり、
前記アクリロニトリル−ブタジエンゴムは、下記化学式(3)の構造の繰り返し単位をゴムの総重量に対して20重量%から50重量%で含んでなるものである、〔5〕又は〔6〕に記載の二次電池の正極形成用組成物。
〔8〕 前記部分水素化ニトリルゴムは、重量平均分子量が10,000g/molから700,000g/molであるものである、〔5〕〜〔7〕の何れか一項に記載の二次電池の正極形成用組成物。
〔9〕 前記分散剤は、前記導電材100重量部に対して10重量部から50重量部で含んでなるものである、〔1〕〜〔8〕の何れか一項に記載の二次電池の正極形成用組成物。
〔10〕 〔1〕〜〔9〕の何れか一項に記載の二次電池の正極形成用組成物の製造方法であって、
溶媒中で導電材及び分散剤を混合した混合物をミリングして導電材分散液を準備する段階、及び
前記導電材分散液に正極活物質を添加して混合する段階を含んでなり、
前記導電材は、前記正極形成用組成物の総重量に対して0.1重量%から2重量%の量で、比表面積が130m2/g以上であり、オイル吸収量が220ml/100g以上である炭素系物質を含んでなり、
前記導電材分散液は、前記分散剤が導電材に導入された導電材−分散剤複合体を含んでなり、
前記導電材−分散剤複合体は、粒度分布のD50が0.8μmから1.2μmであるものである、製造方法。
〔11〕 前記ミリングは、直径が0.5mmから2mmであるビーズミルを導電材分散液の総重量に対して50重量%から90重量%の充填率で充填して行うものである、〔10〕に記載の製造方法。
〔12〕 前記ミリングは、前記混合物を6m/sから12m/sの周速で回転させて行うものである、〔10〕又は〔11〕に記載の製造方法。
〔13〕 前記ミリングは、前記混合物を0.5kg/minから1.5kg/minの吐出速度で吐出させて行うものである、〔10〕〜〔12〕の何れか一項に記載の製造方法。
〔14〕 〔1〕〜〔9〕の何れか一項に記載の正極形成用組成物を用いて製造された、二次電池用正極。
〔15〕 〔14〕に記載の正極を備えてなる、リチウム二次電池。
前記課題を解決するために、本発明の一実施形態によれば、正極活物質、導電材、及び分散剤を含み、前記導電材は、比表面積が130m2/g以上であり、オイル吸収量が220ml/100g以上である炭素系物質を正極形成用組成物の総重量に対して0.1重量%から2重量%で含み、前記分散剤は前記導電材に導入されて導電材−分散剤複合体を形成し、前記導電材−分散剤複合体は、粒度分布のD50が0.8μmから1.2μmであるものである二次電池の正極形成用組成物を提供する。
Claims (15)
- 二次電池の正極形成用組成物であって、
正極活物質、導電材、及び分散剤を含んでなり、
前記導電材は、前記正極形成用組成物の総重量に対して0.1重量%から2重量%の量で、比表面積が130m2/g以上であり、オイル吸収量が220ml/100g以上である炭素系物質を含んでなるものであり、
前記分散剤は、前記導電材に導入されて導電材−分散剤複合体を形成させるものであり、
前記導電材−分散剤複合体は、粒度分布のD50が0.8μmから1.2μmであるものである、二次電池の正極形成用組成物。 - 前記導電材−分散剤複合体は、粒度分布のD90が2.0μmから5.0μmであるものである、請求項1に記載の二次電池の正極形成用組成物。
- 前記炭素系物質は、1次粒子が組立てられてなる2次粒子であるものである、請求項1に記載の二次電池の正極形成用組成物。
- 前記炭素系物質は、カーボンブラックである、請求項1に記載の二次電池の正極形成用組成物。
- 前記分散剤は、ゴムの総重量に対して水素化された共役ジエン由来構造の繰り返し単位を20重量%から50重量%で含んだ部分水素化ニトリルゴムを含んでなるものである、請求項1に記載の二次電池の正極形成用組成物。
- 前記部分水素化ニトリルゴムは、α,β−不飽和ニトリル由来構造の繰り返し単位をゴムの総重量に対して20重量%から50重量%で含んだものである、請求項5に記載の二次電池の正極形成用組成物。
- 前記部分水素化ニトリルゴムは、
下記化学式(1)の構造の繰り返し単位、
下記化学式(2)の構造の繰り返し単位、
下記化学式(3)の構造の繰り返し単位、及び
α,β−不飽和カルボン酸のエステル由来構造単位、を含んだアクリロニトリル−ブタジエンゴムであり、
前記アクリロニトリル−ブタジエンゴムは、下記化学式(3)の構造の繰り返し単位をゴムの総重量に対して20重量%から50重量%で含んでなるものである、請求項5に記載の二次電池の正極形成用組成物。
- 前記部分水素化ニトリルゴムは、重量平均分子量が10,000g/molから700,000g/molであるものである、請求項5に記載の二次電池の正極形成用組成物。
- 前記分散剤は、前記導電材100重量部に対して10重量部から50重量部で含んでなるものである、請求項1に記載の二次電池の正極形成用組成物。
- 請求項1に記載の二次電池の正極形成用組成物の製造方法であって、
溶媒中で導電材及び分散剤を混合した混合物をミリングして導電材分散液を準備する段階、及び
前記導電材分散液に正極活物質を添加して混合する段階を含んでなり、
前記導電材は、前記正極形成用組成物の総重量に対して0.1重量%から2重量%の量で、比表面積が130m2/g以上であり、オイル吸収量が220ml/100g以上である炭素系物質を含んでなり、
前記導電材分散液は、前記分散剤が導電材に導入された導電材−分散剤複合体を含んでなり、
前記導電材−分散剤複合体は、粒度分布のD50が0.8μmから1.2μmであるものである、製造方法。 - 前記ミリングは、直径が0.5mmから2mmであるビーズミルを導電材分散液の総重量に対して50重量%から90重量%の充填率で充填して行うものである、請求項10に記載の製造方法。
- 前記ミリングは、前記混合物を6m/sから12m/sの周速で回転させて行うものである、請求項10に記載の製造方法。
- 前記ミリングは、前記混合物を0.5kg/minから1.5kg/minの吐出速度で吐出させて行うものである、請求項10に記載の製造方法。
- 請求項1に記載の正極形成用組成物を用いて製造された、二次電池用正極。
- 請求項14に記載の正極を備えてなる、リチウム二次電池。
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KR20160035562 | 2016-03-24 | ||
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KR1020170036956A KR102143953B1 (ko) | 2016-03-24 | 2017-03-23 | 이차전지의 양극 형성용 조성물 및 이를 이용하여 제조한 이차전지용 양극 및 이차전지 |
KR10-2017-0036956 | 2017-03-23 | ||
PCT/KR2017/003219 WO2017164701A1 (ko) | 2016-03-24 | 2017-03-24 | 이차전지의 양극 형성용 조성물 및 이를 이용하여 제조한 이차전지용 양극 및 이차전지 |
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WO2020218211A1 (ja) * | 2019-04-26 | 2020-10-29 | デンカ株式会社 | カーボンブラックを含有するスラリー、電極ペースト、電極の製造方法、及び二次電池の製造方法 |
JP2021072240A (ja) * | 2019-11-01 | 2021-05-06 | 東洋インキScホールディングス株式会社 | 分散剤の製造方法、該分散剤を用いた導電材分散体、合材スラリーおよび非水電解質二次電池の製造方法 |
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WO2023027191A1 (ja) * | 2021-08-27 | 2023-03-02 | 御国色素株式会社 | 導電材複合粒子の提供方法 |
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EP3331072A4 (en) | 2018-06-06 |
CN107949940B (zh) | 2021-02-02 |
JP6636141B2 (ja) | 2020-01-29 |
US10741829B2 (en) | 2020-08-11 |
CN107949940A (zh) | 2018-04-20 |
EP3331072B1 (en) | 2019-08-28 |
KR102143953B1 (ko) | 2020-08-12 |
US20180233734A1 (en) | 2018-08-16 |
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KR20170113212A (ko) | 2017-10-12 |
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