JP6187676B2 - 非水電解質二次電池 - Google Patents
非水電解質二次電池 Download PDFInfo
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- JP6187676B2 JP6187676B2 JP2016512670A JP2016512670A JP6187676B2 JP 6187676 B2 JP6187676 B2 JP 6187676B2 JP 2016512670 A JP2016512670 A JP 2016512670A JP 2016512670 A JP2016512670 A JP 2016512670A JP 6187676 B2 JP6187676 B2 JP 6187676B2
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Classifications
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- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/651—Means for temperature control structurally associated with the cells characterised by parameters specified by a numeric value or mathematical formula, e.g. ratios, sizes or concentrations
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y—GENERAL 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Y—GENERAL 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
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Description
(1)電池の直流抵抗[Ω]を電池の面方向の熱抵抗[(m・K)/W]で除した値が0.055以上である;
(2)電池の直流抵抗[Ω]を電池熱容量[J/K]で除した値が3.080×10−6以上である;
(3)電池の容量[Ah]を電池の面方向の熱抵抗[(m・K)/W]で除した値が880以上である;
(4)電池の容量[Ah]を電池熱容量[J/K]で除した値が0.05000以上である。
まず、本発明の非水電解質二次電池の全体構造について、図面を用いて説明する。図1は、本発明の一実施形態であるリチウムイオン二次電池の概要を模式的に表した断面概略図である。なお、本明細書においては、図1に示す扁平型(積層型)の双極型でないリチウムイオン二次電池を例に挙げて詳細に説明するが、本発明の技術的範囲はかような形態のみに制限されない。
図1は、扁平型(積層型)の双極型ではないリチウムイオン二次電池(以下、単に「積層型電池」ともいう)の基本構成を模式的に表した断面概略図である。図1に示すように、本実施形態のリチウムイオン二次電池10は、実際に充放電反応が進行する略矩形の発電要素21が、外装体である電池外装材29の内部に封止された構造を有する。ここで、発電要素21は、正極と、セパレータ17と、負極とを積層した構成を有している。なお、セパレータ17は、非水電解質(例えば、液体電解質)を内蔵している。正極は、正極集電体12の両面に正極活物質層15が配置された構造を有する。負極は、負極集電体11の両面に負極活物質層13が配置された構造を有する。具体的には、1つの正極活物質層15とこれに隣接する負極活物質層13とが、セパレータ17を介して対向するようにして、負極、電解質層および正極がこの順に積層されている。これにより、隣接する正極、電解質層および負極は、1つの単電池層19を構成する。したがって、図1に示すリチウムイオン二次電池10は、単電池層19が複数積層されることで、電気的に並列接続されてなる構成を有するとも言える。
正極は、集電体の表面に正極活物質を含む正極活物質層が形成されてなる。正極は、負極とともにリチウムイオンの授受により電気エネルギーを生み出す機能を有する。
集電体は導電性材料から構成され、その一方の面または両面に正極活物質層が配置される。集電体を構成する材料に特に制限はなく、例えば、金属や、導電性高分子材料または非導電性高分子材料に導電性フィラーが添加された導電性を有する樹脂が採用されうる。
本形態において、正極活物質層は、リチウム−ニッケル−マンガン−コバルト複合酸化物(以下、「NMC複合酸化物」とも称する)を必須に含み、必要に応じて他の正極活物質を含みうる。
負極は、集電体の表面に負極活物質層が形成されてなる。負極は、正極とともにリチウムイオンの授受により電気エネルギーを生み出す機能を有する。
負極に用いられうる集電体は、正極に用いられうる集電体と同様であるため、ここでは説明を省略する。
負極活物質層は負極活物質を含み、必要に応じて、導電助剤、バインダー、電解質(ポリマーマトリックス、イオン伝導性ポリマー、電解液など)、イオン伝導性を高めるためのリチウム塩などのその他の添加剤をさらに含む。導電助剤、バインダー、電解質(ポリマーマトリックス、イオン伝導性ポリマー、電解液など)、イオン伝導性を高めるためのリチウム塩などのその他の添加剤については、上記正極活物質層の欄で述べたものと同様である。
セパレータは、電解質を保持して正極と負極との間のリチウムイオン伝導性を確保する機能、および正極と負極との間の隔壁としての機能を有する。
十分な電池特性が得られるものであればよく、特に制限されるべきものではない。さらに、不織布セパレータの厚さは、電解質層と同じであればよく、好ましくは5〜200μmであり、特に好ましくは10〜100μmである。
集電板(25、27)を構成する材料は、特に制限されず、リチウムイオン二次電池用の集電板として従来用いられている公知の高導電性材料が用いられうる。集電板の構成材料としては、例えば、アルミニウム、銅、チタン、ニッケル、ステンレス鋼(SUS)、これらの合金等の金属材料が好ましい。軽量、耐食性、高導電性の観点から、より好ましくはアルミニウム、銅であり、特に好ましくはアルミニウムである。なお、正極集電板27と負極集電板25とでは、同一の材料が用いられてもよいし、異なる材料が用いられてもよい。
また、図示は省略するが、集電体11と集電板(25、27)との間を正極リードや負極リードを介して電気的に接続してもよい。正極および負極リードの構成材料としては、公知のリチウムイオン二次電池において用いられる材料が同様に採用されうる。なお、外装から取り出された部分は、周辺機器や配線などに接触して漏電したりして製品(例えば、自動車部品、特に電子機器等)に影響を与えないように、耐熱絶縁性の熱収縮チューブなどにより被覆することが好ましい。
外装材としては、従来公知の金属缶ケースやラミネートフィルムを用いることができるが、高出力化や冷却性能に優れ、EV、HEV用の大型機器用電池に好適に利用することができるという観点から、ラミネートフィルムが望ましい。また、外部から掛かる発電要素への群圧を容易に調整することができ、所望の電解液層厚みへと調整容易であることから、外装体はアルミニウムを含むラミネートフィルムがより好ましい。ラミネートフィルムは、例えば、ポリプロピレン、アルミニウム、ナイロンがこの順に積層されてなる3層構造として構成されうる。このようなラミネートフィルムを用いることにより、外装材の開封、容量回復材の添加、外装材の再封止を容易に行うことができる。
図2は、非水電解質二次電池の代表的な実施形態である扁平なリチウムイオン二次電池の外観を表した斜視図である。このリチウムイオン二次電池のように、本発明における好ましい実施形態によれば、アルミニウムを含むラミネートフィルムからなる電池外装体に前記発電要素が封入されてなる構成を有する扁平積層型ラミネート電池が提供される。
一般的な電気自動車では、一回の充電による走行距離(航続距離)は100kmが市場要求である。かような航続距離を考慮すると、電池の体積エネルギー密度は157Wh/L以上であることが好ましく、かつ定格容量は20Wh以上であることが好ましい。
本形態の非水電解質二次電池は、下記条件(1)〜(4)の少なくとも1つを満たすことを特徴とする。
組電池は、電池を複数個接続して構成した物である。詳しくは、電池を少なくとも2つ以上用いて、直列化あるいは並列化あるいはその両方で構成されるものである。直列、並列化することで容量および電圧を自由に調節することが可能になる。
本発明の非水電解質二次電池は、長期使用しても放電容量が維持され、サイクル特性が良好である。さらに、体積エネルギー密度が高い。電気自動車やハイブリッド電気自動車や燃料電池車やハイブリッド燃料電池自動車などの車両用途においては、電気・携帯電子機器用途と比較して、高容量、大型化が求められるとともに、長寿命化が必要となる。したがって、上記非水電解質二次電池は、車両用の電源として、例えば、車両駆動用電源や補助電源に好適に利用することができる。
(電池の作製)
厚さ120μmの高分子−金属複合ラミネートフィルムからなる電池外装材をその周辺部を熱融着にて接合し、熱融着部のうち一辺の2箇所から厚さ100μm、幅80mmの正極端子リード、負極端子リードを取り出す構造とした扁平型電池を作製した(図1)。
正極のバインダー、導電助剤の混合比率を4:4(質量比)として正極を作製し、正極以外は、実施例1と同様の方法で電池を作製した。
正極のバインダー、導電助剤の混合比率を4:3(質量比)として正極を作製し、正極以外は、実施例1と同様の方法で電池を作製した。
上限電圧を4.15Vとして、電流制御により1C相当の電流で充電し、続いて電圧制御により4.15Vに2時間保持した。その後下限電圧を2.5Vとして、電流制御により1C相当の電流で放電し、続いて0.2C相当の電流で放電した。
上記の電池の容量の測定の放電後、容量の50%に相当する容量(SOC50%)を、電流制御により1C相当の電流で充電した。充電後の電圧をV1とした。続いて電流制御により1C相当の電流で20秒間放電した。放電後の電圧をV2とした。
(1)比熱の測定
断熱容器内の熱媒体(フロリナート)に電池を浸漬し,熱媒体を20Wで加熱した。投入電力量と,電池および熱媒体の温度上昇傾向から,電池の比熱を算出した。電池の比熱は次式で表せる。
厚さ方向の熱抵抗値は、電池をホットプレートで40℃、55℃、70℃に加熱し、温度の経時変化を3次元熱伝導方程式で再現することで、フィッティングパラメータとして熱伝導率を求めた。熱伝導率の逆数を熱抵抗値として算出した。
面方向の熱抵抗値は、電池の短辺の端をヒーター2つで挟み、ヒーター温度を40℃、55℃、70℃の3水準で加熱して、ラミネートセルの温度上昇を測定した。厚さ方向の熱抵抗値測定と同様、温度の経時変化を3次元熱伝導方程式で再現し、フィッティングパラメータとして熱伝導率を求め、熱抵抗値を算出した。
雰囲気温度45℃において、上限電圧を4.15V、下限電圧を2.5Vとして、1C相当の充放電を750サイクルまで繰り返した。
11 負極集電体、
12 正極集電体、
13 負極活物質層、
15 正極活物質層、
17 セパレータ、
19 単電池層、
21、57 発電要素、
25 負極集電板、
27 正極集電板、
29、52 電池外装材、
58 正極タブ、
59 負極タブ。
Claims (4)
- 集電体の表面に、リチウム−ニッケル−マンガン−コバルト複合酸化物を含む正極活物質層が形成されてなる正極と、
電解質層と、
負極と、
が積層されてなる発電要素を有し、
下記条件(1)〜(6)を全て満たす、非水電解質二次電池;
(1)電池の直流抵抗[Ω]を電池の面方向の熱抵抗[(m・K)/W]で除した値が0.055以上である;
(2)電池の直流抵抗[Ω]を電池熱容量[J/K]で除した値が3.080×10−6以上である;
(3)電池の容量[Ah]を電池の面方向の熱抵抗[(m・K)/W]で除した値が880以上である;
(4)電池の容量[Ah]を電池熱容量[J/K]で除した値が0.05000以上である;
(5):電池の直流抵抗[Ω]を電池の厚さ方向の熱抵抗[(m・K)/W]で除した値が0.0008以上である;
(6):電池の容量[Ah]を電池の厚さ方向の熱抵抗[(m・K)/W]で除した値が13以上である。 - SOC30〜50%の全範囲において、上記条件(1)および(2)の少なくとも1つを満たす、請求項1に記載の非水電解質二次電池。
- 定格容量に対する電池面積(電池外装体まで含めた電池の投影面積)の比の値が5cm2/Ah以上であり、かつ、定格容量が3Ah以上である、請求項1または2に記載の非水電解質二次電池。
- 矩形状の前記正極活物質層の縦横比として定義される前記正極のアスペクト比は、1〜3である、請求項1〜3のいずれか1項に記載の非水電解質二次電池。
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US20170033418A1 (en) | 2017-02-02 |
JPWO2015156155A1 (ja) | 2017-04-13 |
CN106170884A (zh) | 2016-11-30 |
EP3131150A1 (en) | 2017-02-15 |
CN106170884B (zh) | 2017-09-19 |
WO2015156155A1 (ja) | 2015-10-15 |
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