JP2010027616A - 非水電解液二次電池および非水電解液二次電池の充電制御システムおよびこれを用いた機器 - Google Patents
非水電解液二次電池および非水電解液二次電池の充電制御システムおよびこれを用いた機器 Download PDFInfo
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- JP2010027616A JP2010027616A JP2009229435A JP2009229435A JP2010027616A JP 2010027616 A JP2010027616 A JP 2010027616A JP 2009229435 A JP2009229435 A JP 2009229435A JP 2009229435 A JP2009229435 A JP 2009229435A JP 2010027616 A JP2010027616 A JP 2010027616A
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- battery
- electrolyte secondary
- secondary battery
- nonaqueous electrolyte
- negative electrode
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/574—Devices or arrangements for the interruption of current
- H01M50/581—Devices or arrangements for the interruption of current in response to temperature
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/574—Devices or arrangements for the interruption of current
- H01M50/583—Devices or arrangements for the interruption of current in response to current, e.g. fuses
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2200/00—Safety devices for primary or secondary batteries
- H01M2200/10—Temperature sensitive devices
- H01M2200/106—PTC
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Abstract
【解決手段】 再充電可能な正極と負極と非水電解液とを用いる非水電解液二次電池において、半経験的分子軌道計算法でハミルトニアンにPM3法を用いて計算したHOMOエネルギー(最高占有軌道エネルギー)が−8.5eV〜−11.0eVであり、且つLUMOエネルギー(最低空軌道エネルギー)が−0.135eV〜3.5eVである有機化合物を電解液添加剤と非水溶媒との合計に対して0.1〜20重量%の範囲において添加した電池および充電制御システムを構成したものである。
【選択図】 図3
Description
アルキル基(二重結合を含んでもよい)
1,2位で環を形成してもよい(環中にヘテロ原子を含んでもよい
)
アリール基
シクロヘキサン(環中にヘテロ原子を含んでもよい)
アミノ基(アリール基をもってもよい))
例えばこの様な芳香族化合物の具体例としてはヘキサフェニルベンゼン、フェニルシクロヘキサン、1,3,5−トリフェニルベンゼン、p−テルフェニル、ドデカヒドロトリフェニレン、1−フェニルピペラジン、ジビニルベンゼン、ジシクロヘキシルベンゼンなどが挙げられる。
アルキル基(二重結合を含んでもよい)
アルキル基(エステル結合を含んでもよい)
アルキル基(脂環式化合物を含んでもよい)
アルコキシル基
アリール基(R1,R2もしくはR3,R4で環を形成してもよい)
シクロヘキサン(環中にヘテロ原子を含んでもよい))
このような不飽和脂肪酸化合物としてはビニルシクロヘキサン、t−ブチルビニルエーテル、メタクリル酸メチルモノマー、cis−スチルベン、メチレンシクロヘキサン、テトラフェニルエチレン、2,3−ジメチル−1,3−ブタジエンが挙げられる。
アルキル基
アリールアルキル基
アリール基
ナフチル基)
このようなアミン類化合物としては例えばトリベンジルアミン、N−フェニル−ジベンジルアミンが挙げられる。
電気化学的耐酸化性とHOMOエネルギーの関係を調査した結果、HOMOエネルギーが−8.5eV〜−11.0eVであるときに通常電池が使用される電位領域では安定で、且つ過充電になった場合に効率的に酸化電解重合することがわかった。従って、本発明における添加剤としての有機化合物はHOMOエネルギーが−8.5eV〜−11.0eVであることが望ましい。
ミスタ(PTC)もしくは温度ヒューズであることを備えた非水電解液二次電池の充電制御システムとする事により、より信頼性の高い二次電池システムを提供することが出来る。
フルオロエチレン共重合体、エチレン−テトラフルオロエチレン共重合体(ETFE樹脂)、ポリクロロトリフルオロエチレン(PCTFE)、フッ化ビニリデン−ペンタフルオロプロピレン共重合体、プロピレン−テトラフルオロエチレン共重合体、エチレン−クロロトリフルオロエチレン共重合体(ECTFE)、フッ化ビニリデン−ヘキサフルオロプロピレン−テトラフルオロエチレン共重合体、フッ化ビニリデン−パーフルオロメチルビニルエーテル−テトラフルオロエチレン共重合体を挙げる事ができる。特に、この中で最も好ましいのはポリフッ化ビニリデン(PVDF)、ポリテトラフルオロエチレン(PTFE)である。
層や、合剤層の機械的保護や化学的保護の目的で導入する保護層などを有してもよい。この下塗り層や保護層は、結着剤や導電剤粒子、導電性を持たない粒子などを含む事ができる。
特に金型プレス法やカレンダープレス法が好ましい。プレス圧は、特に限定されないが、0.2〜3t/cm2が好ましい。カレンダープレス法のプレス速度は、0.1〜50m/分が好ましい。プレス温度は、室温〜200℃が好ましい。負極シートに対する正極シートの幅の比率は、0.9〜1.1が好ましい。特に、0.95〜1.0が好ましい。正極活物質と負極材料の含有量比は、化合物種類や合剤処方により異なるため、限定できないが、容量、サイクル性、安全性の観点で最適な値に設定できる。
図1に本実施例で用いた円筒形電池の縦断面図を示す。図において、1は耐有機電解液性のステンレス鋼板を加工した電池ケ−ス、2は安全弁を設けた封口板、3は絶縁パッキングを示す。4は極板群であり、正極および負極がセパレ−タを介して複数回渦巻状に巻回されてケース1内に収納されている。そして上記正極からは正極リ−ド5が引き出されて封口板2に接続され、負極からは負極リ−ド6が引き出されて電池ケ−ス1の底部に接続されている。7は絶縁リングで極板群4の上下部にそれぞれ設けられている。以下正、負極板等について詳しく説明する。
5%を混合した後、カルボキシメチルセルロ−ス水溶液に懸濁させてペ−スト状にした。そしてこの負極合剤ペーストを厚さ0.02mmのCu箔の両面に塗工し、乾燥後圧延して、厚さ0.20mm、幅39mm、長さ420mmの負極板とした。
電解液の添加剤として、(化2)に該当する有機化合物としてt−ブチルビニルエーテル、メタクリル酸メチルモノマー、ビニルシクロヘキサン、2,3−ジメチル−1,3−ブタジエンを用いた以外は(実施例1)と同様に渦巻型の筒型電池を構成した。これを本発明の電池10〜14とした。
電解液の添加剤として、(化3)に該当する有機化合物としてトリベンジルアミン、N−フェニル−ジベンジルアミンを用いた以外は(実施例1)と同様に渦巻型の筒型電池を構成した。これを本発明の電池15,16とした。
電解液の添加剤として二重結合を持つ炭素数15〜60の直鎖型有機化合物に該当する有機化合物としてスクアレンもしくは(E)−β−ファルネセンを用いた以外は(実施例1)と同様に渦巻型の筒型電池を構成した。これを本発明の電池15,16とした。
電解液の添加剤としてトリス(4−メトキシフェニル)ホスフィン、(1R)−(+)−αピネン、ジシクロペンタジエン、ジ(エチレングリコール)ジビニルエーテル、9、10−ジヒドロアントラセン、トリプチセン、[2、2]パラシクロファンを用いた以外は(実施例1)と同様に渦巻型の筒型電池を構成した。これを本発明の電池19〜25とした。
比較例として、電解液の添加剤を加えない電池を(実施例1)と同様に渦巻型の筒型電池を構成した。これを比較の電池(電池26)とした。
比較例として、電解液の添加剤としてビフェニル、チオフェン、3−クロロチオフェンを用いた以外は(実施例1)と同様に渦巻型の筒型電池を構成した。これを比較の電池(電池27〜29)とした。
保存後の電池についても同様の条件で充電、放電を行い保存後の容量回復率(保存後の容量/保存前の容量×100(%))を求めた結果を表1〜6に示す。
2 封口板
3 絶縁パッキング
4 極板群
5 正極リ−ド
6 負極リ−ド
7 絶縁リング
Claims (5)
- リチウム含有複合酸化物を正極活物質とし、リチウムの吸蔵、放出が可能な材料を負極材料とし、セパレータと非水溶媒を含む非水電解液を用い、前記非水電解液中に、半経験的分子軌道計算法でハミルトニアンにPM3法を用いて計算したHOMOエネルギー(最高占有軌道エネルギー)が−8.5eV〜−11.0eVであり、且つLUMOエネルギー(最低空軌道エネルギー)が −0.135eV〜3.5eVである有機化合物を1種類以上含有し、前記有機化合物の総量が前記非水溶媒と前記有機化合物の総量との合計に対して0.1〜20重量%の範囲にある非水電解液二次電池において、
前記セパレータは、80℃以上で閉塞すると共に孔径0.01〜1μmの孔を持つ、厚さ10〜300μmおよび空孔率30〜80%のポリオレフィンフィルムであり、前記有機化合物が、p−テルフェニル、フェニルシクロヘキサン、ドデカヒドロトリフェニレン、ジビニルベンゼン、メタクリル酸メチルモノマー、トリベンジルアミン、N−フェニル−ジベンジルアミン、(1R)−(+)−αピネン、9,10−ジヒドロアントラセンからなる群から選ばれた1種以上である非水電解液二次電池。 - 請求項1に記載の非水電解液二次電池の電池温度の上昇を感知して充電の回路を切断する機能を持つ非水電解液二次電池の充電制御システム。
- 前記電池温度の上昇を感知して充電の回路を切断する機能が、正特性サーミスタ(PTC)もしくは温度ヒューズである請求項2記載の非水電解液二次電池の充電制御システム。
- 前記正特性サーミスタ(PTC)もしくは温度ヒューズの作動温度が60〜120℃の範囲であることを特徴とする請求項3記載の非水電解液二次電池の充電制御システム。
- 請求項1に記載の非水電解液二次電池、もしくは請求項1に記載の非水電解液二次電池と請求項2から4のいずれかに記載の非水電解液二次電池の充電制御システムとを搭載した携帯電話、携帯情報端末機器、カムコーダ、パーソナルコンピュータ、PDA、携帯音響機器、電気自動車、ロードレベリング用電源からなる群から選ばれる機器。
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Also Published As
Publication number | Publication date |
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US20080014496A1 (en) | 2008-01-17 |
KR100721230B1 (ko) | 2007-05-22 |
CN1190864C (zh) | 2005-02-23 |
KR20020020698A (ko) | 2002-03-15 |
EP1215745A1 (en) | 2002-06-19 |
KR20070037749A (ko) | 2007-04-06 |
EP1215745A4 (en) | 2007-11-28 |
CN1349672A (zh) | 2002-05-15 |
JP3633510B2 (ja) | 2005-03-30 |
JP2002050398A (ja) | 2002-02-15 |
JP4411691B2 (ja) | 2010-02-10 |
WO2001003226A1 (fr) | 2001-01-11 |
JP2001015158A (ja) | 2001-01-19 |
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