JP2014096236A - 二次電池用活物質、二次電池用電極、二次電池、電池パック、電動車両、電力貯蔵システム、電動工具および電子機器 - Google Patents
二次電池用活物質、二次電池用電極、二次電池、電池パック、電動車両、電力貯蔵システム、電動工具および電子機器 Download PDFInfo
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- JP2014096236A JP2014096236A JP2012245995A JP2012245995A JP2014096236A JP 2014096236 A JP2014096236 A JP 2014096236A JP 2012245995 A JP2012245995 A JP 2012245995A JP 2012245995 A JP2012245995 A JP 2012245995A JP 2014096236 A JP2014096236 A JP 2014096236A
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- Prior art keywords
- secondary battery
- negative electrode
- composite oxide
- lithium
- active material
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Images
Classifications
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- 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
- H01M4/485—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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- B60L1/00—Supplying electric power to auxiliary equipment of vehicles
- B60L1/02—Supplying electric power to auxiliary equipment of vehicles to electric heating circuits
- B60L1/04—Supplying electric power to auxiliary equipment of vehicles to electric heating circuits fed by the power supply line
- B60L1/06—Supplying electric power to auxiliary equipment of vehicles to electric heating circuits fed by the power supply line using only one supply
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Abstract
【解決手段】二次電池は、正極および負極と共に電解液を備え、その負極は、下記の式(1)で表されるリチウム複合酸化物を含む。
Liw Znx Sny Mz O4 ・・・(1)
(MはCo、Mg、Ni、Ca、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。w〜zは0.3≦w≦1、0.3≦x≦1、0.8≦y≦1.2および(w+x+y+z)=3を満たす。)
【選択図】図1
Description
(MはCo、Mg、Ni、Ca、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。w〜zは0.3≦w≦1、0.3≦x≦1、0.8≦y≦1.2および(w+x+y+z)=3を満たす。)
1.二次電池用活物質
2.二次電池用活物質の適用例
2−1.二次電池用電極および二次電池(円筒型のリチウムイオン二次電池)
2−2.二次電池用電極および二次電池(ラミネートフィルム型のリチウムイオン二次電池)
3.二次電池の用途
3−1.電池パック
3−2.電動車両
3−3.電力貯蔵システム
3−4.電動工具
本技術の一実施形態の二次電池用活物質(以下、単に「活物質」ともいう。)は、二次電池の電極に用いられるものであり、その二次電池は、例えば、リチウムイオン二次電池などである。ただし、ここで説明する活物質は、正極に用いられてもよいし、負極に用いられてもよい。
活物質は、リチウム複合酸化物のいずれか1種類または2種類以上を含んでおり、そのリチウム複合酸化物は、下記の式(1)で表される組成を有している。
(MはCo、Mg、Ni、Ca、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。w〜zは0.3≦w≦1、0.3≦x≦1、0.8≦y≦1.2および(w+x+y+z)=3を満たす。)
リチウム複合酸化物の具体的な組成は、式(1)に示した条件を満たしていれば、特に限定されない。
(XはCa、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。a〜gは0.3≦a≦1、0≦b≦1、0≦c≦1、0.3≦d≦1、0≦e≦1、0.8≦f≦1.2、0≦g≦0.05、(a+b+c+d+e+f+g)=3および(c+d+g)≦1.3を満たす。)
(a〜fは0.3≦a≦1、0≦b≦1、0≦c≦1、0.3≦d≦1、0≦e≦1、0.8≦f≦1.2、(a+b+c+d+e+f)=3および(c+d)≦1.3を満たす。)
活物質の組成を調べるためには、各種の元素分析法を用いてリチウム複合酸化物を分析することで、構成元素の種類およびモル比w〜z,a〜gの値を特定すればよい。この元素分析法は、例えば、X線回折(XRD)法、飛行時間型二次イオン質量分析(TOF−SIMS)法、高周波誘導結合プラズマ(ICP)発光分光分析法、ラマン分光分析法およびエネルギー分散X線分光法(EDX)などのいずれか1種類または2種類以上である。
この活物質は、例えば、以下の手順により製造される。
この活物質によれば、リチウム複合酸化物が式(1)に示した組成を有している。この場合には、上記したように、リチウム複合酸化物がスピネル型の結晶構造を有すると共に、充放電電位が十分に低下するため、高いエネルギー密度が得られると共に、充放電時におけるリチウム金属の意図しない析出も抑制される。よって、活物質を用いた二次電池では、高い電池容量が得られると共に、リチウム金属の析出に起因する発火などの不具合が生じにくくなる。よって、容量特性と安全性とを両立させることができる。
次に、上記した二次電池用活物質の適用例について説明する。この二次電池用活物質は、以下のようにして二次電池用電極および二次電池に用いられる。
図1および図2は、二次電池の断面構成を表しており、図2では、図1に示した巻回電極体20の一部を拡大している。ここでは、例えば、二次電池用電極を負極22に適用している。
ここで説明する二次電池は、電極反応物質であるリチウム(リチウムイオン)の吸蔵放出により負極22の容量が得られるリチウムイオン二次電池であり、いわゆる円筒型である。
正極21は、図2に示したように、正極集電体21Aの片面または両面に正極活物質層21Bを有している。正極集電体21Aは、例えば、アルミニウム、ニッケルおよびステンレスなどの導電性材料のいずれか1種類または2種類以上により形成されている。
(MはCo、Mn、Fe、Al、V、Sn、Mg、Ti、Sr、Ca、Zr、Mo、Tc、Ru、Ta、W、Re、Yb、Cu、Zn、Ba、B、Cr、Si、Ga、P、SbおよびNbのうちの少なくとも1種である。zは0.005<z<0.5を満たす。)
二次電池用電極である負極22は、図2に示したように、負極集電体22Aの片面または両面に負極活物質層22Bを有している。
セパレータ23は、正極21と負極22とを隔離することで、両極の接触に起因する電流の短絡を防止しながらリチウムイオンを通過させるものである。このセパレータ23は、例えば、合成樹脂およびセラミックなどの多孔質膜であり、2種類以上の多孔質膜が積層された積層膜でもよい。合成樹脂は、例えば、ポリテトラフルオロエチレン、ポリプロピレンおよびポリエチレンなどである。
セパレータ23には、液状の電解質である電解液が含浸されている。この電解液は、溶媒および電解質塩を含んでおり、さらに添加剤などの他の材料のいずれか1種類または2種類以上を含んでいてもよい。
この二次電池は、例えば、以下のように動作する。充電時には、正極21から放出されたリチウムイオンが電解液を介して負極22に吸蔵される。一方、放電時には、負極22から放出されたリチウムイオンが電解液を介して正極21に吸蔵される。
この二次電池は、例えば、以下の手順により製造される。
この円筒型の二次電池によれば、負極22の負極活物質層22Bが負極活物質として上記した二次電池用活物質を含んでいる。この場合には、上記したように、高いエネルギー密度が得られるため、高い電池容量が得られると共に、充放電時におけるリチウム金属の意図しない析出が抑制されるため、安全性も確保される。よって、容量特性と安全性とを両立させることができる。これ以外の作用および効果は、二次電池用活物質と同様である。
図3は、他の二次電池の分解斜視構成を表しており、図4は、図3に示した巻回電極体30のIV−IV線に沿った断面を拡大している。ただし、図3では、巻回電極体30と2枚の外装部材40とを離間させた状態を示している。ここでは、例えば、二次電池用電極を負極34に適用している。以下では、既に説明した円筒型の二次電池の構成要素を随時引用する。
ここで説明する二次電池は、いわゆるラミネートフィルム型のリチウムイオン二次電池であり、例えば、図3に示したように、フィルム状の外装部材40の内部に巻回電極体30が収納されている。この巻回電極体30は、例えば、セパレータ35および電解質層36を介して正極33と負極34とが積層されてから巻回されたものである。正極33には正極リード31が取り付けられていると共に、負極34には負極リード32が取り付けられている。巻回電極体30の最外周部は、保護テープ37により保護されている。
電解質層36は、高分子化合物により電解液が保持されたものであり、いわゆるゲル状の電解質である。高いイオン伝導率(例えば、室温で1mS/cm以上)が得られると共に、電解液の漏液が防止されるからである。この電解質層36は、さらに添加剤などの他の材料を含んでいてもよい。
この二次電池は、例えば、以下のように動作する。充電時には、正極33から放出されたリチウムイオンが電解質層36を介して負極34に吸蔵される。一方、放電時には、負極34から放出されたリチウムイオンが電解質層36を介して正極33に吸蔵される。
ゲル状の電解質層36を備えた二次電池は、例えば、以下の3種類の手順により製造される。
このラミネートフィルム型の二次電池によれば、負極34の負極活物質層34Bが負極活物質として上記した二次電池用活物質を含んでいるので、円筒型の場合と同様の理由により、容量特性と安全性とを両立させることができる。これ以外の作用および効果は、円筒型の場合と同様である。
次に、上記した二次電池の適用例について説明する。
図5は、電池パックのブロック構成を表している。この電池パックは、例えば、筐体60の内部に、制御部61と、電源62と、スイッチ部63と、電流測定部64と、温度検出部65と、電圧検出部66と、スイッチ制御部67と、メモリ68と、温度検出素子69と、電流検出抵抗70と、正極端子71および負極端子72とを備えている。なお、筐体60は、例えば、プラスチック材料などにより形成されている。
図6は、電動車両の一例であるハイブリッド自動車のブロック構成を表している。この電動車両は、例えば、金属製の筐体73の内部に、制御部74と、エンジン75と、電源76と、駆動用のモータ77と、差動装置78と、発電機79と、トランスミッション80およびクラッチ81と、インバータ82,83と、各種センサ84とを備えている。この他、電動車両は、例えば、差動装置78およびトランスミッション80に接続された前輪用駆動軸85および前輪86と、後輪用駆動軸87および後輪88とを備えている。
図7は、電力貯蔵システムのブロック構成を表している。この電力貯蔵システムは、例えば、一般住宅および商業用ビルなどの家屋89の内部に、制御部90と、電源91と、スマートメータ92と、パワーハブ93とを備えている。
図8は、電動工具のブロック構成を表している。この電動工具は、例えば、電動ドリルであり、プラスチック材料などにより形成された工具本体98の内部に、制御部99と、電源100とを備えている。この工具本体98には、例えば、可動部であるドリル部101が稼働(回転)可能に取り付けられている。
[負極活物質の合成]
最初に、負極活物質として、式(3)に示した組成を有するリチウム複合酸化物(Lia Cob Mgc Znd Nie Snf O4 )を合成した。
以下の手順により、図9に示した試験用の二次電池(コイン型のリチウムイオン二次電池)を作製した。
二次電池の電池特性として容量特性および安全性を調べたところ、表1および表2に示した結果が得られた。
負極活物質として、式(2)に示したリチウム複合酸化物(Lia Cob Mgc Znd Nie Snf Xg O4 )を用いたことを除き、実験例11と同様の手順により二次電池を作製すると共に容量特性を調べたところ、表3に示した結果が得られた。なお、リチウム複合酸化物を合成する場合には、原料として、酸化カルシウム(CaO)および酸化アルミニウム(Al2 O3 )などの各種酸化物(他の元素Xの酸化物)を用いた。ICP発光分光分析法を用いたリチウム複合酸化物の組成(モル比a〜g)の分析結果は、表3に示した通りである。
(1)
正極および負極と共に電解液を備え、
前記負極は、下記の式(1)で表されるリチウム複合酸化物を含む、
二次電池。
Liw Znx Sny Mz O4 ・・・(1)
(MはCo、Mg、Ni、Ca、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。w〜zは0.3≦w≦1、0.3≦x≦1、0.8≦y≦1.2および(w+x+y+z)=3を満たす。)
(2)
前記リチウム複合酸化物は、下記の式(2)で表される、
上記(1)に記載の二次電池。
Lia Cob Mgc Znd Nie Snf Xg O4 ・・・(2)
(XはCa、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。a〜gは0.3≦a≦1、0≦b≦1、0≦c≦1、0.3≦d≦1、0≦e≦1、0.8≦f≦1.2、0≦g≦0.05、(a+b+c+d+e+f+g)=3および(c+d+g)≦1.3を満たす。)
(3)
前記リチウム複合酸化物は、下記の式(3)で表される、
上記(2)に記載の二次電池。
Lia Cob Mgc Znd Nie Snf O4 ・・・(3)
(a〜fは0.3≦a≦1、0≦b≦1、0≦c≦1、0.3≦d≦1、0≦e≦1、0.8≦f≦1.2、(a+b+c+d+e+f)=3および(c+d)≦1.3を満たす。)
(4)
リチウムイオン二次電池である、
上記(1)ないし(3)のいずれかに記載の二次電池。
(5)
下記の式(1)で表されるリチウム複合酸化物を含む、
二次電池用電極。
Liw Znx Sny Mz O4 ・・・(1)
(MはCo、Mg、Ni、Ca、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。w〜zは0.3≦w≦1、0.3≦x≦1、0.8≦y≦1.2および(w+x+y+z)=3を満たす。)
(6)
下記の式(1)で表されるリチウム複合酸化物を含む、
二次電池用活物質。
Liw Znx Sny Mz O4 ・・・(1)
(MはCo、Mg、Ni、Ca、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。w〜zは0.3≦w≦1、0.3≦x≦1、0.8≦y≦1.2および(w+x+y+z)=3を満たす。)
(7)
上記(1)ないし(4)のいずれかに記載の二次電池と、
その二次電池の使用状態を制御する制御部と、
その制御部の指示に応じて前記二次電池の使用状態を切り換えるスイッチ部と
を備えた、電池パック。
(8)
上記(1)ないし(4)のいずれかに記載の二次電池と、
その二次電池から供給された電力を駆動力に変換する変換部と、
その駆動力に応じて駆動する駆動部と、
前記二次電池の使用状態を制御する制御部と
を備えた、電動車両。
(9)
上記(1)ないし(4)のいずれかに記載の二次電池と、
その二次電池から電力を供給される1または2以上の電気機器と、
前記二次電池からの前記電気機器に対する電力供給を制御する制御部と
を備えた、電力貯蔵システム。
(10)
上記(1)ないし(4)のいずれかに記載の二次電池と、
その二次電池から電力を供給される可動部と
を備えた、電動工具。
(11)
上記(1)ないし(4)のいずれかに記載の二次電池を電力供給源として備えた、電子機器。
Claims (11)
- 正極および負極と共に電解液を備え、
前記負極は、下記の式(1)で表されるリチウム複合酸化物を含む、
二次電池。
Liw Znx Sny Mz O4 ・・・(1)
(MはCo、Mg、Ni、Ca、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。w〜zは0.3≦w≦1、0.3≦x≦1、0.8≦y≦1.2および(w+x+y+z)=3を満たす。) - 前記リチウム複合酸化物は、下記の式(2)で表される、
請求項1記載の二次電池。
Lia Cob Mgc Znd Nie Snf Xg O4 ・・・(2)
(XはCa、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。a〜gは0.3≦a≦1、0≦b≦1、0≦c≦1、0.3≦d≦1、0≦e≦1、0.8≦f≦1.2、0≦g≦0.05、(a+b+c+d+e+f+g)=3および(c+d+g)≦1.3を満たす。) - 前記リチウム複合酸化物は、下記の式(3)で表される、
請求項2記載の二次電池。
Lia Cob Mgc Znd Nie Snf O4 ・・・(3)
(a〜fは0.3≦a≦1、0≦b≦1、0≦c≦1、0.3≦d≦1、0≦e≦1、0.8≦f≦1.2、(a+b+c+d+e+f)=3および(c+d)≦1.3を満たす。) - リチウムイオン二次電池である、
請求項1記載の二次電池。 - 下記の式(1)で表されるリチウム複合酸化物を含む、
二次電池用電極。
Liw Znx Sny Mz O4 ・・・(1)
(MはCo、Mg、Ni、Ca、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。w〜zは0.3≦w≦1、0.3≦x≦1、0.8≦y≦1.2および(w+x+y+z)=3を満たす。) - 下記の式(1)で表されるリチウム複合酸化物を含む、
二次電池用活物質。
Liw Znx Sny Mz O4 ・・・(1)
(MはCo、Mg、Ni、Ca、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。w〜zは0.3≦w≦1、0.3≦x≦1、0.8≦y≦1.2および(w+x+y+z)=3を満たす。) - 二次電池と、
その二次電池の使用状態を制御する制御部と、
その制御部の指示に応じて前記二次電池の使用状態を切り換えるスイッチ部と
を備え、
前記二次電池は、正極および負極と共に電解液を備え、
前記負極は、下記の式(1)で表されるリチウム複合酸化物を含む、
電池パック。
Liw Znx Sny Mz O4 ・・・(1)
(MはCo、Mg、Ni、Ca、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。w〜zは0.3≦w≦1、0.3≦x≦1、0.8≦y≦1.2および(w+x+y+z)=3を満たす。) - 二次電池と、
その二次電池から供給された電力を駆動力に変換する変換部と、
その駆動力に応じて駆動する駆動部と、
前記二次電池の使用状態を制御する制御部と
を備え、
前記二次電池は、正極および負極と共に電解液を備え、
前記負極は、下記の式(1)で表されるリチウム複合酸化物を含む、
電動車両。
Liw Znx Sny Mz O4 ・・・(1)
(MはCo、Mg、Ni、Ca、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。w〜zは0.3≦w≦1、0.3≦x≦1、0.8≦y≦1.2および(w+x+y+z)=3を満たす。) - 二次電池と、
その二次電池から電力を供給される1または2以上の電気機器と、
前記二次電池からの前記電気機器に対する電力供給を制御する制御部と
を備え、
前記二次電池は、正極および負極と共に電解液を備え、
前記負極は、下記の式(1)で表されるリチウム複合酸化物を含む、
電力貯蔵システム。
Liw Znx Sny Mz O4 ・・・(1)
(MはCo、Mg、Ni、Ca、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。w〜zは0.3≦w≦1、0.3≦x≦1、0.8≦y≦1.2および(w+x+y+z)=3を満たす。) - 二次電池と、
その二次電池から電力を供給される可動部と
を備え、
前記二次電池は、正極および負極と共に電解液を備え、
前記負極は、下記の式(1)で表されるリチウム複合酸化物を含む、
電動工具。
Liw Znx Sny Mz O4 ・・・(1)
(MはCo、Mg、Ni、Ca、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。w〜zは0.3≦w≦1、0.3≦x≦1、0.8≦y≦1.2および(w+x+y+z)=3を満たす。) - 二次電池を電力供給源として備え、
前記二次電池は、正極および負極と共に電解液を備え、
前記負極は、下記の式(1)で表されるリチウム複合酸化物を含む、
電子機器。
Liw Znx Sny Mz O4 ・・・(1)
(MはCo、Mg、Ni、Ca、Al、Ti、V、Cr、Mn、Fe、CuおよびAgのうちの少なくとも1種である。w〜zは0.3≦w≦1、0.3≦x≦1、0.8≦y≦1.2および(w+x+y+z)=3を満たす。)
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- 2013-10-21 US US14/058,993 patent/US9263744B2/en not_active Expired - Fee Related
- 2013-10-31 CN CN201310530711.5A patent/CN103811739B/zh not_active Expired - Fee Related
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JP2020527834A (ja) * | 2017-07-13 | 2020-09-10 | イーコントロールズ エルエルシー | フォークリフト用のモジュール式リチウムイオン電池システム |
JP7203080B2 (ja) | 2017-07-13 | 2023-01-12 | イーコントロールズ エルエルシー | フォークリフト用のモジュール式リチウムイオン電池システム |
Also Published As
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JP5924237B2 (ja) | 2016-05-25 |
CN103811739B (zh) | 2016-05-11 |
CN103811739A (zh) | 2014-05-21 |
US9263744B2 (en) | 2016-02-16 |
US20140129065A1 (en) | 2014-05-08 |
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