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JP5211022B2 - リチウムイオン二次電池 - Google Patents

リチウムイオン二次電池 Download PDF

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JP5211022B2
JP5211022B2 JP2009270962A JP2009270962A JP5211022B2 JP 5211022 B2 JP5211022 B2 JP 5211022B2 JP 2009270962 A JP2009270962 A JP 2009270962A JP 2009270962 A JP2009270962 A JP 2009270962A JP 5211022 B2 JP5211022 B2 JP 5211022B2
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battery
heat
lithium ion
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ion secondary
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JP2011113895A (ja
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和雄 高橋
秀和 藤村
宏 高橋
吉美 矢内
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Hitachi Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • H01M10/0587Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/60Heating or cooling; Temperature control
    • H01M10/61Types of temperature control
    • H01M10/613Cooling or keeping cold
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/60Heating or cooling; Temperature control
    • H01M10/65Means for temperature control structurally associated with the cells
    • H01M10/654Means for temperature control structurally associated with the cells located inside the innermost case of the cells, e.g. mandrels, electrodes or electrolytes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
    • H01M50/414Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417Polyolefins
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491Porosity
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50Current conducting connections for cells or batteries
    • H01M50/528Fixed electrical connections, i.e. not intended for disconnection
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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Description

本発明は、リチウムイオン二次電池に関するものであり、特に、電池の内部で発生した熱を効率よく放熱できるリチウムイオン二次電池に関するものである。
リチウムイオン二次電池は、鉛電池やニッケル水素電池などに比べて、起電力およびエネルギー密度が高く、しかも充放電効率も優れていることから、携帯用の小型電池から車載用や電力貯蔵用などの大型電池まで、幅広い用途が期待されている。
しかし、充放電時の電池反応や電池の内部抵抗で発熱することが知られており、特に、出力の大きな電池では電池の内部が高温となり、この状態が長く続くと寿命の低下や劣化を生じて、所定の出力が取れなくなる問題があった。
このような問題を解決するため、以下に示すような電池の内部を冷却する手段が提案されている。
特許文献1では、電池容器(缶)のほぼ中心のセンターピンに電池の外まで伸びたヒートパイプを挿入し、電池の内部で発生した熱を電池の外部に放出する構造が提案されている。
また、特許文献2では、外部端子を含む電流経路を冷却する手段を設けることが開示されており、冷却手段として気体や液体が提案され、また、電気やガス等をエネルギー源とした冷却装置を用いることが提案されている。
さらに、特許文献3では、電極の捲回領域にある軸芯の一部に軸芯の比熱より大きな比熱を有する有機系の接着剤からなる熱吸収部を設け、電池が発熱した際に熱吸収部と軸芯との両方から熱を回収して放熱させることが提案されている。
特開2000−260474号公報 特開2002−352863号公報 特開2007−311374号公報
しかしながら、電池容器(缶)のほぼ中心にヒートパイプを挿入し、外部から内部に冷却媒体を循環させた場合、高い冷却効果が得られるものの、電池ごとに冷却媒体の強制循環ラインが必要となる。また、複数の電池を集合化してシステムを構築する場合、電池の配置上で制約を受けるというおそれがある。
また、伝熱経路となる電流経路を直接冷却することは、冷却効率が高く、かつ電池の体積効率の面でも優れているが、放熱部分が電池の電極端子に限られるため、強制冷却が必要である。また、電極端子に直接冷却作用を施すため静電作用により、浮遊する微細粒子が付着し易くなり、電極端子が腐食する可能性がある。
さらに、軸芯よりも比熱の大きな熱吸収部を設けることは、一定時間後の電池の内部の温度上昇を緩和するためには有効であるが、出力変動の大きな使用環境や急峻な充放電を繰り返すような使用環境では、吸熱の応答性が悪く、適切な温度に維持管理できない可能性がある。
そこで、本発明の目的は、電池の構造を大幅に変えることなく、電池の内部で発生した熱を効率良く電池缶に伝え、温度に起因する電池特性の劣化を防止したリチウムイオン二次電池を提供することである。
本発明の一実施形態であるリチウムイオン二次電池は、リチウムイオンが出入り可能な正極板とリチウムイオンが出入り可能な負極板とを、電気的に分離する多孔質のセパレータを介して渦状に巻く捲回体を、電池缶に挿入して形成するリチウムイオン電池である。
そして、電池缶の内部であって、電池缶と接する様に放熱板を設けることを特徴とする。
また、捲回体の中心に、放熱板と同様の材料からなる軸芯を有することが好ましい。
また、軸芯と放熱板との間に、軸芯及び放熱板と同様の材料からなる負極集電リングを有することが好ましい。
また、軸芯が負極集電リングに接する面積よりも、放熱板が負極集電リングに接する面積のほうが大きいことが好ましい。
また、このリチウムイオン二次電池は、電池缶とパッキンを介して接合する電池蓋と、電池蓋に正極接合部材を介して電気的に接合する正極集電リングと、を有することを特徴とする。
そして、正極集電リングと軸芯とに接合する接続リングを有することが好ましい。
これにより、本発明は、電池の構造を大幅に変えることなく、電池の内部で発生した熱を効率良く電池缶に伝え、温度に起因する電池特性の劣化を防止したリチウムイオン二次電池を提供することができる。
円筒型のリチウムイオン二次電池の摸式断面図。 角型のリチウムイオン二次電池の摸式図。
リチウムイオン二次電池には、用途に応じて、コイン型,円筒型,角型,ラミネート型など様々な形態がある。
本発明は、正極板と負極板とを、セパレータを介して渦状に巻く捲回体を用いたリチウムイオン二次電池であり、円筒型や角型のリチウムイオン二次電池に適用可能である。
以下、実施例1では円筒型のリチウムイオン二次電池を、実施例2では角型のリチウムイオン二次電池を例にとって詳細に説明する。
図1は、実施例1による円筒型のリチウムイオン二次電池の摸式断面図である。
この実施例におけるリチウムイオン二次電池1は、電池缶2と電池蓋3とで構成された空間内部に、捲回体4が組み込まれており、充放電中に、この捲回体4で発生した熱を電池缶2に伝えて外部に放熱できるような構成となっている。
なお、捲回体4は、リチウムイオンが出入り可能な正極板とリチウムイオンが出入り可能な負極板とを、電気的に分離する多孔質のセパレータを介して渦状に巻いたものである。
このように正極電極と負極電極とがセパレータを介してスパイラル状に捲回した捲回体4は、中心に軸芯5が組み込まれている。
捲回体4の負極電極からは、電池缶2の底部側に多数の負極タブ6が出ており、この多数の負極タブ6は、軸芯5に接合された負極集電リング7の外周に接合されている。負極集電リング7は、電池缶2の底部に設けた放熱板8に接合されている。
捲回体4の正極電極からは、電池蓋3側に多数の正極タブ9が出ており、この多数の正極タブ9は、正極集電リング10の周囲に接合されている。正極集電リング10は、電気絶縁性の接続リング12を介して、軸芯5に固定されている。
また、正極集電リング10は、正極接続部材11で外部正極端子を兼ねた電池蓋3に接続されている。
これらの構成部材について、さらに詳しく説明する。
電池缶2は、表面がニッケルメッキされたスチール製である。この電池缶2の底部には、予め銅製の放熱板8を取り付ける。放熱板8は、電池缶2の底部と、電池缶2の側面部の一部に接するように円筒状に製作して挿入し、内部からローラで拡管して、電池缶2と密着させ固定する。
なお、電池缶2の側面部の一部に接する放熱板8は、構造上の観点から、捲回体4の設置位置より低く形成される。
また、軸芯5が負極集電リング7に接する面積よりも、放熱板8が負極集電リング7に接する面積のほうが大きくし、放熱板8と軸芯5と負極集電リング7とは同様の材料とする。
捲回体4の正極電極は、短冊型のアルミニウム箔の両面に正極活物質であるリチウム遷移金属複合酸化物を塗工して製作する。
捲回体4の負極電極は、短冊型の銅箔の両面に負極活物質である炭素材を塗工して製作する。
これら正極活物質および負極活物質は、単体では塗工できないため、バインダであるポリフッ化ビニリデン(PVDF)と、分散溶媒であるN−メチル−2−ピロリドン(NMP)を加えてスラリー化して塗工する。
活物質を塗工後、乾燥してプレス機で所定の密度にプレスして電極とする。
セパレータは、ポリプロピレン/ポリエチレン/ポリプロピレンの3層構造で空孔率が45%の微孔性フィルムを用いる。
中空の軸芯5は、銅製で、負極タブ6が形成される側を、捲回体4の長さより長くし、正極タブ9が形成される側を捲回体4の長さより短くする。
軸芯5の負極側は、銅製の負極集電リング7の中央部と接合して負極集電リング7を固定する。負極集電リング7の周囲には、複数の負極タブ6を超音波溶接機により溶接する。
一方、軸芯5の正極側には、ポリプロピレン製の接続リング12を固定し、接続リング12にアルミニウム製の正極集電リング10を固定する。
組み上げた捲回体4を放熱板8の付いた電池缶2に挿入して接合した後、正極集電リング10と電池蓋3とは、アルミニウム箔を複数枚重ねて作成した正極接続部材11を介して接続される。
電池蓋3は、内圧上昇の異常時に開裂するアルミニウム製の開裂弁の機能を有し、捲回体4の正極側と正極接続部材11を介して接続され、外部正極端子を兼ねている。
電池缶2と電池蓋3は、電気絶縁性のパッキン(ガスケット)14を介して、内部に電解液13を充填して接続され、電池缶2をかしめ機でかしめて密封する。
次に、実施例1のリチウムイオン二次電池1について、その作用等を説明する。
充放電操作における電池の内部の発熱は、電池の内部抵抗による発熱と、過充電等の電池の異常時に生じる電解液と活物質との化学反応による発熱とがある。
一般的に、電池の内部抵抗による発熱の場合では、放熱特性の悪い電池の中心部分が高温となる。
一方、化学反応による発熱の場合では、反応を生じている部位で発熱するため高温となる部位が偏在する。
これらの発熱を効率良く放熱するためには、伝熱面積を大きく取る方法、および、強制冷却で温度差を大きくする方法が有効である。
本実施例は、放熱手段として伝熱面積を大きく取るように構成にしたものであり、電池の中心部の発熱を熱伝導性の良好な銅製の軸芯5に伝え、この軸芯5に伝わった熱を伝熱面積の大きな負極集電リング7に伝え、この負極集電リング7に伝わった熱をさらに伝熱面積の大きな放熱板8に伝え、この放熱板8と接する面の電池缶2から放熱できるようにした点に特徴を有する。
また、リチウムイオン二次電池1の使用環境により、電池缶2の自然冷却が取れないことが想定される場合には、放熱板8と接して電池缶2の部分を強制冷却することにより、電池全体の冷却が可能となる。
実施例1では、円筒型のリチウムイオン二次電池1を例示したが、本発明は電池形状に制限されるものではなく、捲回型であれば、角形、その他の多角形の電池にも適用可能である。
図2は、実施例2による角型のリチウムイオン二次電池を例にとって詳細に説明する。
この実施例における角型のリチウムイオン二次電池は、捲回体4を横に配置したもので、負極が図の左側で、正極が図の右側に相当する。
本実施例で使用する捲回体4は、正極電極と負極電極とをセパレータを介してスパイラル状に捲回したものであり、中心に楕円状の軸芯を組み込んだものである。
捲回体4の負極側は、軸芯に負極集電リング7を取り付け、この負極集電リング7に放熱板8を取り付ける。
放熱板8は、角型の電池容器22の内側の側面に接するように製作する。
軸芯,負極集電リング7および放熱板8の材質は、熱伝導性の良好な銅とした。
負極集電リング7と負極端子24との間は、銅製で剛体の負極接続部材21を用いて電池蓋3に接続した。
一方、捲回体4の正極側は、アルミニウム製の正極集電リング10の内側に電気絶縁性の接続リング12を組み込み、軸芯と接続する。
接続リング12は、正極集電リング10より長めに形成し、角型の電池容器22と接触しても短絡しないようにする。
正極集電リング10と正極端子23との間は、アルミニウム箔を複数枚重ねて可撓性のある正極接続部材11で接続する。
電池蓋3に設けた正極端子23は、ガスケット14を介して取り付けられ、電気絶縁する。電池蓋3と一体化した放熱板8がついた捲回体4を電解液の入った角型の電池容器22に挿入して電池蓋3の周囲をシールして角型リチウムイオン電池に仕上げる。
次に、実施例2の角型のリチウムイオン二次電池について、その作用等を説明する。
本実施例の角型のリチウムイオン二次電池では、捲回体4の中心に組み込んだ軸芯で充放電時に発生した熱を、負極集電リング7を介して放熱板8に伝え、角型の電池容器22から効率よく放熱できる。
また、捲回体4の負極側を軸芯,負極集電リングおよび放熱板で、正極側を電気絶縁性の接続リング12で支持しているために、振動や衝撃に強い電池構造となっている。
以上、実施例1及び実施例2とから、本発明の目的を達成するためのポイントは次の通りである。
正極板と負極板とをセパレータを介して、渦状または楕円渦巻状に巻いて作成する捲回型のリチウムイオン二次電池で関するものであり、捲回の中心軸から電池缶の放熱部に至る経路に熱伝導材を配置するものである。
そして、その熱伝導材の伝熱面積を、電池缶の中心軸から電池缶に負極側に至るほど大きく形成するものである。これにより、放熱効率を高めることができる。
また、電池缶に接する放熱部が、負極側の端子面と、電池缶の側面とで形成されていることである。これにより、放熱効果を高めることが可能となる。
更には、電池缶と接する放熱部に、電池缶の側面から強制的に冷却する冷却手段を設けてもよい。
そして、これら実施例の特徴は、軸芯を単に電池缶に接するように構成するのではなく、放熱板を用いたことにある。
つまり、内部の熱を外部に効率よく放熱するには、軸芯から放熱面まで熱を伝え、この放熱面と雰囲気との温度差を大きくする必要がある。熱を伝える条件として、伝熱面積を大きくすることが有効であるが、材質固有の熱伝導率も重要である。
電池缶には所定の強度が必要であり、現状、スチール(鉄基)缶あるいはアルミニウム缶が使用されている。電池缶の底部を厚く形成し、放熱板を兼ねさせることも考えられるが、こうするためには電池缶と放熱板とを同一材質とする必要がある。この場合、室温近傍での熱伝導率は、鉄を基準にするとアルミニウムは約2.8倍、さらに銅であれば約4.7倍の大きな値となる。
しかしながら、熱伝導率の大きな銅を電池缶として用いると強度が低くなり、所定の強度を達成するため、電池缶を厚く形成した場合には、重量エネルギー密度の低下をまねくおそれがある。
しがって、これら実施例では、電池缶とは別の材料で放熱板を形成する必要がある。
このように、電池缶と放熱板との材質を変え、役割分担をする。すなわち、電池缶は薄板のスチール製として強度を確保し、放熱板や軸芯には銅を用いて、放熱を良好にすることができ、電池の内部の温度を適正に保つことによって、寿命劣化や電池特性の低下を防止できる。
以上のように、これら実施例であれば、複数の電池を集合化してシステムを構築する場合であっても、電池の配置上、制約を受けることがない。
また、電極端子を直接冷却する必要がないため、電極端子の腐食や、導電性の付着物が絶縁部分に付着し、電気的な短絡を生じることがない。
また、出力変動の大きな使用環境や、急峻な充放電を繰り返すような使用環境でも、吸熱の応答性がよく、適切な温度に維持管理できる。
つまり、これら実施例では、電池の構造を大幅に変えることなく、電池の内部で発生した熱を効率良く電池缶に伝え、放熱面積を大きく取り、温度に起因する電池特性の劣化を防止して長寿命化を図ることができる。また、充放電中の電池温度の上昇も抑えて長寿命化を図ることができる。
これら本実施例によれば、捲回中心軸から電池缶の放熱部に至る熱伝導材が配置され、その熱伝導材の伝熱面積が電池缶の放熱部に至るほど大きく形成されていることから、電池の内部で発生した熱を電池缶に効率良く伝え、放熱部である電池缶から外部に熱を放散できる。
また、これら実施例によれば、外部冷却手段を付加する場合、放熱板の取付け位置に特定して冷却可能であり、かつ導電性付着物による腐食や短絡を防止できる。
また、これら実施例によれば、充放電時に生じる捲回体の温度上昇を適切な範囲に抑えられるため、温度上昇に起因する電池特性の劣化防止ができる。
さらに、過充電等の電池異常時に生じる電解液と活物質との化学反応で発生した熱に対しても電池缶の放熱部から放熱できるため電池を健全に維持できる。
本発明は、リチウムイオン二次電池に関するものであり、特に、車載用や電力貯蔵用などの大型電池に利用可能性が大きい。
1 リチウムイオン二次電池
2 電池缶
3 電池蓋
4 捲回体
5 軸芯
6 負極タブ
7 負極集電リング
8 放熱板
9 正極タブ
10 正極集電リング
11 正極接続部材
12 接続リング
13 電解液
14 パッキン(ガスケット)
21 負極接続部材
22 角型の電池容器

Claims (4)

  1. リチウムイオンが出入り可能な正極板とリチウムイオンが出入り可能な負極板とを、電気的に分離する多孔質のセパレータを介して渦状に巻く捲回体を、電池缶に挿入して形成する捲回型のリチウムイオン二次電池において、前記電池缶の内部であって、前記電池缶と接する様に放熱板を設け、
    前記捲回体の中心に、前記放熱板と同様の材料からなる軸芯を有し、
    前記軸芯と前記放熱板との間に、前記軸芯及び前記放熱板と同様の材料からなる負極集電リングを有することを特徴とするリチウムイオン二次電池。
  2. 請求項1において、
    前記軸芯が前記負極集電リングに接する面積よりも、前記放熱板が前記負極集電リング
    に接する面積のほうが大きいことを特徴とするリチウムイオン二次電池。
  3. 請求項1において、
    前記電池缶とパッキンを介して接合する電池蓋と、前記電池蓋に正極接合部材を介して電気的に接合する正極集電リングと、を有することを特徴とするリチウムイオン二次電池。
  4. 請求項3において、
    前記正極集電リングと前記軸芯とに接合する接続リングを有することを特徴とするリチ
    ウムイオン二次電池。
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