JP2012018792A - 固体電解質材料およびリチウム電池 - Google Patents
固体電解質材料およびリチウム電池 Download PDFInfo
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Abstract
【解決手段】本発明は、Li、La、Zr、Al、SiおよびOを有し、ガーネット型構造を有し、焼結体であることを特徴とする固体電解質材料を提供することにより、上記課題を解決する。
【選択図】図1
Description
まず、本発明の固体電解質材料について説明する。本発明の固体電解質材料は、Li、La、Zr、Al、SiおよびOを有し、ガーネット型構造を有し、焼結体であることを特徴とするものである。
次に、本発明のリチウム電池について説明する。本発明のリチウム電池は、正極活物質を含有する正極活物質層と、負極活物質を含有する負極活物質層と、上記正極活物質層および上記負極活物質層の間に形成された固体電解質層とを有するリチウム電池であって、上記固体電解質層が、上述した固体電解質材料を含有することを特徴とするものである。
以下、本発明のリチウム電池について、構成ごとに説明する。
まず、本発明における固体電解質層について説明する。本発明における固体電解質層は、上述した固体電解質材料を含有するものである。固体電解質層の厚さの範囲は、上述した固体電解質材料の厚さの範囲と同様であることが好ましい。また、本発明における固体電解質層は、上述した固体電解質材料のみからなるものであっても良く、他の固体電解質材料をさらに含有するものであっても良い。
次に、本発明における正極活物質層について説明する。本発明における正極活物質層は、少なくとも正極活物質を含有する層であり、必要に応じて、導電化材、固体電解質材料および結着材の少なくとも一つを含有していても良い。正極活物質としては、例えばLiCoO2、LiMnO2、Li2NiMn3O8、LiVO2、LiCrO2、LiFePO4、LiCoPO4、LiNiO2、LiNi1/3Co1/3Mn1/3O2等を挙げることができる。
次に、本発明における負極活物質層について説明する。本発明における負極活物質層は、少なくとも負極活物質を含有する層であり、必要に応じて、導電化材、固体電解質材料および結着材の少なくとも一つを含有していても良い。負極活物質としては、例えば金属活物質およびカーボン活物質を挙げることができる。金属活物質としては、例えばIn、Al、SiおよびSn等を挙げることができる。一方、カーボン活物質としては、例えばメソカーボンマイクロビーズ(MCMB)、高配向性グラファイト(HOPG)、ハードカーボン、ソフトカーボン等を挙げることができる。
本発明のリチウム電池は、上述した固体電解質層、正極活物質層および負極活物質層を少なくとも有するものである。さらに通常は、正極活物質層の集電を行う正極集電体、および負極活物質層の集電を行う負極集電体を有する。正極集電体の材料としては、例えばSUS、アルミニウム、ニッケル、鉄、チタンおよびカーボン等を挙げることができ、中でもSUSが好ましい。一方、負極集電体の材料としては、例えばSUS、銅、ニッケルおよびカーボン等を挙げることができ、中でもSUSが好ましい。また、正極集電体および負極集電体の厚さや形状等については、リチウム電池の用途等に応じて適宜選択することが好ましい。また、本発明に用いられる電池ケースには、一般的なリチウム電池の電池ケースを用いることができる。電池ケースとしては、例えばSUS製電池ケース等を挙げることができる。
本発明のリチウム電池は、一次電池であっても良く、二次電池であっても良いが、中でも二次電池であることが好ましい。繰り返し充放電でき、例えば車載用電池として有用だからである。本発明のリチウム電池の形状としては、例えば、コイン型、ラミネート型、円筒型および角型等を挙げることができる。また、本発明のリチウム電池の製造方法は、上述したリチウム電池を得ることができる方法であれば特に限定されるものではなく、一般的なリチウム電池の製造方法と同様の方法を用いることができる。例えば、正極活物質層を構成する材料、固体電解質層を構成する材料、および負極活物質層を構成する材料を順次プレスすることにより、発電要素を作製し、この発電要素を電池ケースの内部に収納し、電池ケースをかしめる方法等を挙げることができる。
出発原料として、Li源(LiOH・H2O)、La源(La2O3)、Zr源(ZrO2)、Al源(Al2O3)、Si源(SiO2)を用意した。次に、Li源、La源、Zr源、Al源、Si源を所定の量添加し混合した。これにより原料組成物を得た。
Al源およびSi源の量を下記表1のように変更したこと以外は、実施例1と同様にして、固体電解質材料を得た。
Al源およびSi源を用いなかったこと以外は、実施例1と同様にして、固体電解質材料を得た。
(緻密性評価)
実施例1〜5および比較例1で得られた固体電解質材料の緻密性を評価した。まず、固体電解質材料の乾燥重量を測定し、次に、固体電解質材料の実寸法から体積を算出し、乾燥重量を体積で除することにより、焼結密度(g/cm3)を算出した。また、その焼結密度と、理論密度とから相対密度である焼結密度(%)を算出した。なお、上記理論密度には、AlおよびSiを有しないLi7La3Zr2O12の理論密度(5.115g/cm3)を用いた。得られた結果を表1および図2に示す。
実施例1〜5および比較例1で得られた固体電解質材料に対して、CuKα線を用いたX線回折(XRD)測定を行った。その結果を図3に示す。図3に示されるように、実施例1〜5および比較例1では、ほぼ同じピークが確認されたことから、固体電解質材料に含まれるSiは、バルクの結晶構造には影響を与えず、粒界の界面に作用していることが示唆された。
実施例1〜5および比較例1で得られた固体電解質材料に対して、交流インピーダンス法によるLiイオン伝導度(室温)の測定を行った。測定には、ソーラトロン社製インピーダンス/ゲインフェーズアナライザー1260を用い、測定条件は、印加電圧10mV、測定周波数域3.2MHz〜10Hzまたは32MHz〜10Hzとした。その結果を表2および図4に示す。
2 … 負極活物質層
3 … 固体電解質層
4 … 正極集電体
5 … 負極集電体
6 … 電池ケース
10 … リチウム電池
Claims (5)
- Li、La、Zr、Al、SiおよびOを有し、ガーネット型構造を有し、焼結体であることを特徴とする固体電解質材料。
- 前記Li、前記Laおよび前記Zrの割合が、モル基準で、Li:La:Zr=7:3:2であることを特徴とする請求項1に記載の固体電解質材料。
- Liイオン伝導度が2.0×10−4S/cm以上であることを特徴とする請求項1または請求項2に記載の固体電解質材料。
- 前記Siの含有量(重量%)に対する、前記Alの含有量(重量%)の割合(Al/Si)が、4.6〜11.9の範囲内であることを特徴とする請求項1から請求項3までのいずれかの請求項に記載の固体電解質材料。
- 正極活物質を含有する正極活物質層と、負極活物質を含有する負極活物質層と、前記正極活物質層および前記負極活物質層の間に形成された固体電解質層とを有するリチウム電池であって、
前記固体電解質層が、請求項1から請求項4までのいずれかの請求項に記載の固体電解質材料を含有することを特徴とするリチウム電池。
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