JP6505561B2 - 電池用活物質、非水電解質電池及び電池パック - Google Patents
電池用活物質、非水電解質電池及び電池パック Download PDFInfo
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- JP6505561B2 JP6505561B2 JP2015182915A JP2015182915A JP6505561B2 JP 6505561 B2 JP6505561 B2 JP 6505561B2 JP 2015182915 A JP2015182915 A JP 2015182915A JP 2015182915 A JP2015182915 A JP 2015182915A JP 6505561 B2 JP6505561 B2 JP 6505561B2
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- Prior art keywords
- battery
- active material
- negative electrode
- lithium
- aqueous electrolyte
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- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
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- 230000035945 sensitivity Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
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Classifications
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- B60L58/00—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles
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Description
第1の実施形態によると、単斜晶型の結晶構造を有する複合酸化物を含む電池用活物質が提供される。この複合酸化物は、一般式LixM14-yTi10-zM22+zO27+δで表される。ここで、M1は、Na、K、Csより選択される少なくとも1種類の元素である。M2は、Zr, Sn, V, Nb, Ta, Mo, W, Fe, Co, Mn, Ni, Alからなる群より選択される少なくとも1種類の元素である。xは0≦x<18の範囲内にある。yは0<y<4の範囲内にある。zは0<z<4の範囲内にある。δは−0.3≦δ≦0.3の範囲内にある。
第1の実施形態に係る電池用活物質が含む複合酸化物のBET比表面積は特に制限されないが、5m2/g以上200m2/g未満であることが好ましい。より好ましくは、5m2/g以上30m2/g以下である。
第1の実施形態に係る電池用活物質は、以下に説明するように合成することが好ましい。具体的には、固相反応法によって出発化合物を合成し、この出発化合物に対しプロトン交換を行って前駆体を生成する。その後、前駆体に対し熱処理をして脱水することで合成できる。
活物質の粉末X線回折測定は、次のように行う。
電池用活物質の組成は、例えば、誘導結合プラズマ(Inductively Coupled Plasma:ICP)発光分光法を用いて分析することができる。この際、各元素の存在比は、使用する分析装置の感度に依存する。従って、例えば、第1の実施形態に係る一例の電池用活物質の組成をICP発光分光法を用いて分析した際、先に説明した元素比から測定装置の誤差分だけ数値が逸脱することがある。しかしながら、分析装置の誤差範囲で測定結果が上記のように逸脱したとしても、第1の実施形態に係る一例の電池用活物質は先に説明した効果を十分に発揮することができる。
第2の実施形態によると、非水電解質電池が提供される。この非水電解質電池は、第1の実施形態に係る電池用活物質を含む負極と、正極と、非水電解質とを含む。
負極は、集電体と、負極層(負極活物質含有層)とを含むことができる。負極層は、集電体の片面又は両面に形成され得る。負極層は、負極活物質と、任意に導電剤及び結着剤とを含むことができる。
正極は、集電体と、正極層(正極活物質含有層)とを含むことができる。正極層は、集電体の片面若しくは両面に形成され得る。正極層は、正極活物質と、任意に導電剤及び結着剤を含むことができる。
非水電解質は、例えば、電解質を有機溶媒に溶解することにより調製される液状非水電解質、又は、液状電解質と高分子材料とを複合化したゲル状非水電解質であってよい。
セパレータは、例えば、ポリエチレン、ポリプロピレン、セルロース、若しくはポリフッ化ビニリデン(polyvinylidene fluoride; PVdF)を含む多孔質フィルム、又は合成樹脂製不織布から形成されてよい。中でも、ポリエチレン又はポリプロピレンから形成された多孔質フィルムは、一定温度において溶融し、電流を遮断することが可能であるため、安全性を向上できる。
外装部材としては、例えば厚さが0.5mm以下であるラミネートフィルム又は厚さが1mm以下である金属製容器を用いることができる。ラミネートフィルムの厚さは、0.2mm以下であることがより好ましい。金属製容器は、厚さが0.5mm以下であることがより好ましく、厚さが0.2mm以下であることがさらに好ましい。
正極端子は、例えば、リチウムイオン金属に対する電位が3V以上5V以下の範囲における電気的安定性と導電性とを有する材料から形成されることができる。具体的には、正極端子は、アルミニウム、又はMg、Ti、Zn、Mn、Fe、Cu、Si等の元素を含むアルミニウム合金から形成される。正極端子は、正極集電体との接触抵抗を低減するために、正極集電体と同様の材料から形成されることが好ましい。
第3の実施形態によると、電池パックが提供される。この電池パックは、第2の実施形態に係る非水電解質電池を具備する。
以下、実施例に基づいて上記実施形態をさらに詳細に説明する。なお、合成した単斜晶型複合酸化物の結晶相の同定及び結晶構造の推定は、Cu−Kα線を用いた粉末X線回折法によって行った。また、生成物の組成をICP法により分析し、目的物が得られていることを確認した。
<実施例1〜12>
実施例1〜12では、第1の実施形態の製造方法の手順にならって、実施例1〜12の生成物を合成した。
比較例1及び2では、目的化合物を得るために、出発原料として、表1に示した市販の酸化物や炭酸塩試薬を(Liソース、M1ソース、Tiソース)、同じく表1に示したモル比を満たし且つ合計の重量が50gとなるように準備した。次に、以上のようにして準備した出発原料を混合し、この混合物をボールミル用メノウ製ポッド(容積300ml)に投入した。このポッドに直径がそれぞれ10mm及び5mmであるメノウ製ボールを1:1の数量で、ポッド容積の1/3となるように入れた。その後、このポッドにエタノールを50ml入れ、120rpmで60分間湿式混合を行って混合物を得た。このような湿式混合により原料が均一に混合されるため、目的とする結晶相の単相を得ることができる。
実施例1〜12の生成物及び比較例1及び2の組成を、先に説明したICP法により分析した。その結果を以下の表2に示す。
実施例1〜12の生成物及び比較例1及び2の生成物について、先に説明した手順で粉末X線回折測定を行った。生成物の粒度分布を揃えて、上記粉末X線回折法の結果をリートベルト法によって解析した結果、実施例1〜12で得られた生成物は、図2に示す空間群C2/mまたはCmの対称性を有する単斜晶型化合物であることが分かった。また、それぞれの結晶中に構造水(結晶水)を含んでいないことを調べるため、室温から600℃の範囲で示差熱重量測定を行った。その結果、脱水による重量変化が生じないことから、結晶水を含んでいないことを確認した。それぞれの生成物の空間群、格子定数、単位格子体積等の解析結果を、以下の表3にまとめて記載する。
上記実施例及び比較例で得られた各生成物について、以下の手順で電気化学測定を行った。なお、以下では実施例1の生成物を用いた例を説明するが、他の実施例及び比較例の各生成物についても、実施例1の生成物と同様に電気化学測定を行った。
Claims (7)
- 一般式LixM14-yTi10-zM22+zO27+δで表され、式中、M1は、Na、K、Csのうち少なくとも1つを含み、M2は、Zr, Sn, V, Nb, Ta, Mo, W, Fe, Co, Mn, Ni, Alのうち少なくとも1つを含む複合酸化物であって、0≦x<18、0<y<4、0<z<4、-0.3≦δ≦0.3を満たす複合酸化物を含む電池用活物質。
- 前記複合酸化物は、空間群C2、Cm、C2/mのうち少なくとも1つに属する単斜晶型の結晶構造を有し、a軸、b軸、c軸の格子定数がそれぞれ、16.0Å≦a≦21.0Å、3.5Å≦b≦4.5Å、8.0Å≦c≦13.0Åを満たす請求項1に記載の電池用活物質。
- 前記複合酸化物において、M2に含まれる元素の価数の合計が+5価より大きい請求項1に記載の電池用活物質。
- 前記複合酸化物は、一般式LixNa4-yTi10-zM22+zO27+δで表され、式中、M2はNb, Ta, Mo, Fe, Alのうち少なくとも1種を含み、0≦x<18、0<y<4、0<z<4、-0.3≦δ≦0.3を満たす請求項1〜3の何れか1項に記載の電池用活物質。
- 請求項1〜4の何れか1項に記載の電池用活物質を含む負極と、
正極と、
非水電解質と、
を含む非水電解質電池。 - 請求項5に記載の非水電解質電池を含む電池パック。
- 前記非水電解質電池を複数具備し、前記複数の非水電解質電池が電気的に直列及び/又は並列に接続されていることを特徴とする、請求項6に記載の電池パック。
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CN201610813990.XA CN106887582B (zh) | 2015-09-16 | 2016-09-09 | 活性物质、非水电解质电池、电池包及车辆 |
US15/262,242 US10020504B2 (en) | 2015-09-16 | 2016-09-12 | Active material, nonaqueous electrolyte battery, battery pack, and vehicle |
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