JP5838934B2 - 非水電解質二次電池用正極活物質の製造方法 - Google Patents
非水電解質二次電池用正極活物質の製造方法 Download PDFInfo
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- JP5838934B2 JP5838934B2 JP2012190411A JP2012190411A JP5838934B2 JP 5838934 B2 JP5838934 B2 JP 5838934B2 JP 2012190411 A JP2012190411 A JP 2012190411A JP 2012190411 A JP2012190411 A JP 2012190411A JP 5838934 B2 JP5838934 B2 JP 5838934B2
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Classifications
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- H—ELECTRICITY
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Description
ポリアニオン系正極活物質は、XO4四面体が安定しているが故に、Li拡散速度や電子導電性が低いことがその課題として知られている。
そして、この問題に対して、特許文献2〜3には、正極活物質の微粒子化や活物質表面へのカーボンコートを施すことが提案されている。
本発明の製造方法による非水電解質二次電池用正極活物質は、細孔径分布曲線を図示したときに示されるグラフが連なった構成となっている。この構成は、細孔分布を測定される正極活物質表面の細孔が、シェル部にコア部が露出する様な大きな細孔が無いことを示す。すなわち、本発明による正極活物質は、コア部がシェル部にコーティングされた構成となり、コア部を構成する無機(複合)酸化物の表面に酸化物が形成されないという効果を発揮する。すなわち、コア部の無機(複合)酸化物の表面に酸化物が形成されることで生じる不具合が生じなくなっている。
具体的には、本発明による正極活物質は、コア部とシェル部とを備えたコアシェル構造を有している。そして、この構成の正極活物質は、表面に細孔を有している。表面の細孔には、シェル部を形成するカーボン自身に開口した微細な細孔と、シェル部が形成されないことによる粗大な細孔(微細な細孔よりも孔径が大きな細孔)と、の二種類の細孔がある。粗大な細孔は、シェル部が形成されないことによる細孔であり、コア部が露出した構成となる。つまり、粗大な細孔が形成されていると、露出したコア部の無機(複合)酸化物の表面が露出し、酸化物が形成される。
本発明による正極活物質は、細孔分布を測定して、横軸を細孔径とし、縦軸をlog微分細孔容積としたときの細孔径分布曲線を求めたときに、得られた曲線が連なっているものとなっている。このことは、実質的には、上記の微細な細孔のみが測定される状態を示し、コア部がシェル部に完全にコーティングされていることを示す。コア部がシェル部に完全にコーティングされていることは、コア部の無機(複合)酸化物の表面が露出しないことを示し、コア部の無機(複合)酸化物の表面に酸化物が形成されないことを示す。
対して、細孔径分布を測定したときに、不連続な細孔径分布曲線が得られる場合には、得られた不連続なピークは、上記の微細な細孔と粗大な細孔のそれぞれの細孔の孔径に対応する。このような構成では、上記の通り、酸化物が生成される。
本発明の製造方法により製造される非水電解質二次電池用正極活物質(以下、本発明の非水電解質二次電池用正極活物質と称する)は、ポリアニオン構造の無機酸化物,炭素複合されたポリアニオン構造の無機複合酸化物のうち無機複合酸化物を有するコア部と、コア部をコーティングするカーボンを有するシェル部と、を備えたコアシェル構造の非水電解質二次電池用正極活物質であって、横軸を細孔径とし縦軸をlog微分細孔容積としたときの細孔径分布曲線が連なっている。
本発明の非水電解質二次電池用正極活物質の製造方法は、炭素複合されたポリアニオン構造の無機複合酸化物を有するコア部と、コア部をコーティングするカーボンを有するシェル部と、を備えたコアシェル構造の非水電解質二次電池用正極活物質の製造方法であって、カーボン原料の存在下で水熱合成法で無機複合酸化物を生成する工程と、生成した無機複合酸化物を、pHが2〜4に調整される有機酸水溶液で、D50が5〜15μmとなるように湿式解砕する工程と、解砕体を不活性雰囲気下で焼成する工程と、を有する。
酸化物生成工程で生成される無機(複合)酸化物は、カーボンよりなるシェル部が形成されていてもよい。
有機酸水溶液を構成する有機酸は、特に限定されるものではない。
この多価カルボン酸としては、分子内に2 以上のカルボキシル基を有するものであればよく、クエン酸,アスコルビン酸,リンゴ酸,乳酸,コハク酸,フマル酸,マレイン酸,フマール酸、マロン酸、アジピン酸、テレフタル酸、イソフタル酸、セバシン酸、ドデカン二酸、ジフェニルエーテル−4,4′−ジカルボン酸、ピリジン−2,6−ジカルボン酸等を、ブタン−1,2,4−トリカルボン酸、シクロヘキサン−1,2,3−トリカルボン酸、ベンゼン−1,2,4−トリカルボン酸、ナフタレン−1,2,4−トリカルボン酸、ブタン−1,2,3,4−テトラカルボン酸、シクロブタン−1,2,3,4−テトラカルボン酸、ベンゼン−1,2,4,5−テトラカルボン酸、3,3′,4,4′− ベンゾフェノンテトラカルボン酸、3,3′,4,4′−ジフェニルエーテルテトラカルボン酸等をあげることができる。
焼成工程における焼成温度は、カーボンよりなるシェル部を形成できる温度であれば限定されるものではない。
焼成工程の焼成時間についても、カーボンよりなるシェル部を形成できる温度であれば限定されるものではない。
非水電解質二次電池(以下、本発明の非水電解質二次電池と称する)は、上記の製造方法で製造されてなる非水電解質二次電池用正極活物質を正極活物質として用いてなる。
LiOH・H2Oを1.5mol,MnSO4・5H2OとFe(NO3)3・9H2OをMnとFeの合計が1mol,(NH4)2HPO4を1mol秤量した。秤量した各原料は、超純水に混合して原料溶液が調製された。
窒素ガス流通下,室温で10分間、混合溶液を攪拌した。
攪拌後、200℃で3時間保持し、水熱合成で無機酸化物前駆体を生成した。
生成した無機酸化物前駆体を遠心分離により粉末洗浄し、濾過後、真空下,80℃で10時間保持して乾燥した。
乾燥後、3%で水素ガスを含有するアルゴンガス雰囲気下,700℃で1時間の熱処理を施した。これにより、コアシェル構造の無機酸化物が生成された。
表1に示した有機酸を用いて有機酸水溶液を調製した。なお、有機酸は、その水溶液のpHが表1に示した値となるように添加された。
本比較例では、各原料溶液から、Li溶液,P溶液,Fe溶液を選択し、CMCを添加することなく、実施例と同様にして無機酸化物を製造した。
製造された無機酸化物は、有機酸を含有しないこと以外は実施例と同様にして解砕、熱処理された。
以上により、本比較例の正極活物質(LiFePO4)が製造された。
解砕処理を行うときに、有機酸を含有しないこと以外は実施例と同様にして、比較例2〜4のコアシェル構造の正極活物質が製造された。
解砕処理を行うときに、有機酸に替えて0.86%CMC水溶液を用いたこと以外は実施例と同様にして、比較例5のコアシェル構造の正極活物質が製造された。
製造された正極活物質の評価として、各実施例及び各比較例の正極活物質の細孔分布を測定した。
各実施例及び各比較例の正極活物質を用いて、コイン型のリチウムイオン二次電池を製造した。
調製された正極活物質粉末と、導電剤であるアセチレンブラックと、バインダであるPVDFとを、85:50:10の質量比となるように秤量し、メノウ乳鉢で混合し、正極活物質ペーストを調製した。
作製されたコイン型電池には、電池容量当たり1/5の電流レート(1/5×C)で、2.0Vから4.5Vの電圧範囲の充放電を施し、そのときの電池容量を測定した。実施例1及び比較例2のコイン型電池の電池容量の測定結果を図3に示した。また、各コイン型電池の電池容量の測定結果を表1に併せて示した。
2:負極 2a:負極集電体 2b:負極活物質
3:電解液
4:正極ケース
5:負極ケース
6:ガスケット
7:セパレータ
10:コイン型電池
Claims (6)
- 炭素複合されたポリアニオン構造の無機複合酸化物を有するコア部と、該コア部をコーティングするカーボンを有するシェル部と、を備えたコアシェル構造の非水電解質二次電池用正極活物質の製造方法であって、
カーボン原料の存在下で水熱合成法で該無機複合酸化物を生成する工程と、
生成した該無機複合酸化物を、pHが2〜4に調整される有機酸水溶液で、D50が5〜15μmとなるように湿式解砕する工程と、
解砕体を不活性雰囲気下で焼成する工程と、
を有することを特徴とする非水電解質二次電池用正極活物質の製造方法。 - 前記有機酸水溶液は、有機酸が水溶性であり、かつ熱負荷時に遷移金属とキレート錯体を形成する請求項1記載の非水電解質二次電池用正極活物質の製造方法。
- 前記有機酸水溶液の有機酸は、カルボキシル基,スルホン基、チオール基、エノール基より選ばれる少なくとも一つの官能基を有する請求項1〜2のいずれかに記載の非水電解質二次電池用正極活物質の製造方法。
- 前記有機酸水溶液の有機酸は、多価カルボン酸である請求項1〜3のいずれかに記載の非水電解質二次電池用正極活物質の製造方法。
- 前記不活性雰囲気下での焼成は、550〜650℃の熱処理である請求項1〜4のいずれかに記載の非水電解質二次電池用正極活物質の製造方法。
- 前記無機複合酸化物は、LixMnyM1−yXO4(M;Co,Ni,Fe,Cu,Cr,Mg,Ca,Zn,Tiより選ばれる一種以上、X;P,As,Si,Moより選ばれる一種以上、0≦x≦1.5、0≦y<1.0)を炭素複合したものである請求項1〜5のいずれかに記載の非水電解質二次電池用正極活物質の製造方法。
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KR102270591B1 (ko) | 2018-06-01 | 2021-06-30 | 주식회사 엘지화학 | 리튬 이차전지용 양극 활물질, 이의 제조방법, 이를 포함하는 리튬 이차전지용 양극 및 리튬 이차전지 |
CN114267876A (zh) * | 2021-12-20 | 2022-04-01 | 上海科技大学 | 一种一体化电极-电解质结构及其制备方法与全固态电池 |
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US5910382A (en) | 1996-04-23 | 1999-06-08 | Board Of Regents, University Of Texas Systems | Cathode materials for secondary (rechargeable) lithium batteries |
CA2270771A1 (fr) | 1999-04-30 | 2000-10-30 | Hydro-Quebec | Nouveaux materiaux d'electrode presentant une conductivite de surface elevee |
CA2320661A1 (fr) | 2000-09-26 | 2002-03-26 | Hydro-Quebec | Nouveau procede de synthese de materiaux limpo4 a structure olivine |
JP4707950B2 (ja) * | 2003-12-26 | 2011-06-22 | 住友大阪セメント株式会社 | リチウム電池用正極活物質の製造方法とリチウム電池用正極活物質及びリチウム電池用電極並びにリチウム電池 |
JP2009032656A (ja) * | 2007-02-28 | 2009-02-12 | Sanyo Electric Co Ltd | リチウム二次電池用活物質の製造方法、リチウム二次電池用電極の製造方法、リチウム二次電池の製造方法、及びリチウム二次電池用活物質の品質モニタリング方法 |
US8187735B2 (en) * | 2007-07-12 | 2012-05-29 | A123 Systems, Inc. | Multifunctional mixed metal olivines for lithium ion batteries |
JP5331419B2 (ja) * | 2007-09-11 | 2013-10-30 | 国立大学法人長岡技術科学大学 | リチウムイオン二次電池用正極材料およびその製造方法 |
JP5470700B2 (ja) * | 2007-12-10 | 2014-04-16 | 住友大阪セメント株式会社 | 電極材料およびその製造方法、並びに、電極および電池 |
JP4963675B2 (ja) | 2008-02-25 | 2012-06-27 | 古河電池株式会社 | リチウム二次電池,その正極活物質およびその製造方法 |
JP5196555B2 (ja) * | 2008-08-06 | 2013-05-15 | 独立行政法人産業技術総合研究所 | 電極材料前駆体の製造方法及び得られた電極材料前駆体を用いる電極材料の製造方法 |
KR100939647B1 (ko) * | 2009-01-22 | 2010-02-03 | 한화석유화학 주식회사 | 전극 활물질인 음이온 부족형 비화학양론 리튬 전이금속 다중산 화합물, 그 제조 방법 및 그를 이용한 전기화학 소자 |
JP5388822B2 (ja) * | 2009-03-13 | 2014-01-15 | Jfeケミカル株式会社 | リン酸鉄リチウムの製造方法 |
KR20120046297A (ko) * | 2009-07-31 | 2012-05-09 | 도요타지도샤가부시키가이샤 | 정극 활물질 및 그 제조 방법 |
CN102009969B (zh) * | 2010-11-10 | 2012-07-25 | 河北力滔电池材料有限公司 | 一种锂离子电池正极材料磷酸铁锂的处理方法 |
CN102610813B (zh) * | 2011-12-31 | 2015-01-07 | 华为技术有限公司 | 一种去除磷酸铁锂中杂质的方法及其电池 |
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JP2014049258A (ja) | 2014-03-17 |
KR20140029301A (ko) | 2014-03-10 |
KR101578973B1 (ko) | 2015-12-18 |
CN103682265A (zh) | 2014-03-26 |
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