JP5720026B2 - 電池外装用積層体および二次電池 - Google Patents
電池外装用積層体および二次電池 Download PDFInfo
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- JP5720026B2 JP5720026B2 JP2011025081A JP2011025081A JP5720026B2 JP 5720026 B2 JP5720026 B2 JP 5720026B2 JP 2011025081 A JP2011025081 A JP 2011025081A JP 2011025081 A JP2011025081 A JP 2011025081A JP 5720026 B2 JP5720026 B2 JP 5720026B2
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- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229940098424 potassium pyrophosphate Drugs 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
-
- 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
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
-
- 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
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/121—Organic material
-
- 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
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
-
- 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
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/122—Composite material consisting of a mixture of organic and inorganic materials
-
- 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
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
- H01M50/1245—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure characterised by the external coating on the casing
-
- 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
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
- H01M50/126—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers
- H01M50/129—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
-
- 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
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/131—Primary casings, jackets or wrappings of a single cell or a single battery characterised by physical properties, e.g. gas-permeability or size
- H01M50/133—Thickness
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Description
[1]第1の面および第2の面を有するステンレス鋼板と;前記ステンレス鋼板の第1の面に形成された、カルボキシル基含有樹脂、オキサゾリン基含有樹脂および塩基性リン酸化合物を含有する樹脂組成物の硬化物からなる有機無機複合処理層と;前記有機無機複合処理層の表面に形成された、厚みが10〜100μmの熱融着性ポリオレフィン系樹脂層とを有する、電池外装用積層体。
[2]前記有機無機複合処理層は、前記硬化物の樹脂成分を5〜800mg/m2含有し、かつ前記硬化物のリン成分をリン換算で0.1〜100mg/m2含有する、[1]に記載の電池外装用積層体。
[3]前記樹脂組成物における、前記カルボキシル基含有樹脂および前記オキサゾリン基含有樹脂の合計量に対する前記オキサゾリン基含有樹脂の割合は、2.0〜50.0質量%の範囲内である、[1]または[2]に記載の電池外装用積層体。
[4]前記カルボキシル基含有樹脂の酸価は、樹脂固形分換算で300mgKOH/g以上である、[1]〜[3]のいずれか一項に記載の電池外装用積層体。
[5]前記樹脂組成物は、塩基性ジルコニウム化合物をさらに含有し;前記有機無機複合処理層は、前記硬化物のジルコニウム成分をジルコニウム換算で0.5〜60mg/m2含有する[1]〜[4]のいずれか一項に記載の電池外装用積層体。
[6]前記有機無機複合処理層と前記熱融着性ポリオレフィン系樹脂層との間に、厚みが10〜100μmの酸変性ポリオレフィン系樹脂層をさらに有する、[1]に記載の電池外装用積層体。
[7]前記ステンレス鋼板の板厚は、20〜400μmの範囲内である、[1]に記載の電池外装用積層体。
[8]前記ステンレス鋼板の第2の面に形成された樹脂層をさらに有する、[1]に記載の電池外装用積層体。
[9][1]に記載の電池外装用積層体の成形品を熱融着して形成されたケースを有する二次電池。
本発明の電池外装用積層体は、ステンレス鋼板と、有機無機複合処理層と、熱融着性ポリオレフィン系樹脂層とを含む積層体である。有機無機複合処理層は、ステンレス鋼板の表面に形成されている。熱融着性ポリオレフィン系樹脂層は、有機無機複合処理層の表面に直接接合されているか、または酸変性ポリオレフィン系樹脂を介して有機無機複合処理層の表面に接合されている。本明細書では、ステンレス鋼板の表面のうち、有機無機複合処理層および熱融着性ポリオレフィン系樹脂層が形成されている面を「第1の面」といい、反対側の面を「第2の面」という。本発明の電池外装用積層体を二次電池に適用した場合、第1の面は内面(電解質側の面)となり、第2の面は外面(外界側の面)となる。
ステンレス鋼板を構成するステンレス鋼の鋼種は、オーステナイト系、フェライト系、マルテンサイト系など特に限定されない。鋼種の例には、SUS304、SUS430、SUS316などが含まれる。また、ステンレス鋼板の表面仕上げの種類も、特に限定されない。表面仕上げの種類の例には、BA、2B、2D、No.4、HLなどが含まれる。
有機無機複合処理層は、ステンレス鋼板の第1の面に形成されている。有機無機複合処理層は、ステンレス鋼板と熱融着性ポリオレフィン系樹脂層(または酸変性ポリオレフィン系樹脂層)とを強固に密着させて、電解質の劣化または加水分解により発生するフッ酸によるステンレス鋼板の劣化を防ぐ機能を担う。
カルボキシル基含有樹脂(A)は、オキサゾリン基含有樹脂(B)と共に三次元網目構造の硬化物を形成し、ステンレス鋼板と熱融着性ポリオレフィン系樹脂層(または酸変性ポリオレフィン系樹脂層)との密着性を向上させる。
オキサゾリン基含有樹脂(B)は、カルボキシル基含有樹脂(A)と共に三次元網目構造の硬化物を形成し、ステンレス鋼板と熱融着性ポリオレフィン系樹脂層(または酸変性ポリオレフィン系樹脂層)との密着性を向上させる。
塩基性リン酸化合物(C)は、ステンレス鋼板と強固に結合または付着して無機処理層を形成する。また、塩基性リン酸化合物(C)は、樹脂(A)が有するカルボキシル基と樹脂(B)が有するオキサゾリン基との反応触媒としても機能し、カルボキシル基含有樹脂(A)、オキサゾリン基含有樹脂(B)および塩基性リン酸化合物(C)の3成分に由来する高架橋密度の耐薬品性に優れた有機無機複合処理層を形成するために必須の成分である。
塩基性ジルコニウム化合物(D)は、樹脂間を金属架橋することで、有機無機複合処理層の造膜性、バリア性および熱融着性ポリオレフィン系樹脂層(または酸変性ポリオレフィン系樹脂層)に対する密着性をより向上させる。また、有機無機複合処理層を形成する際に塗布する樹脂組成物(有機無機処理液)に塩基性ジルコニウム化合物を添加した場合、ジルコニウム同士が酸素を介して結合して高分子量化するため、有機無機複合処理層のバリア性がさらに向上する。さらに、塩基性ジルコニウム化合物(D)は、塩基性リン酸化合物(C)と反応することで不溶性のリン酸ジルコニウム塩を形成して、有機無機複合処理層のバリア性をさらに向上させる。
前述の通り、熱融着性ポリオレフィン系樹脂層は、ステンレス鋼板の第1の面に形成された有機無機複合処理層に直接接合されているか、または有機無機複合処理層の上に形成された後述の酸変性ポリオレフィン系樹脂を介して有機無機複合処理層に接合されている。熱融着性ポリオレフィン系樹脂層は、電池内部を外気から遮断して密封系にする機能を担う。すなわち、本発明の積層体を用いて電池を製造する際に、一方の積層体の熱融着性ポリオレフィン系樹脂層を他方の積層体の熱融着性ポリオレフィン系樹脂層または金属製電極と熱融着させることにより、電池内部を外気から遮断するとともに、電解液の液漏れを防止する。特に外気の水蒸気ガスが電池内部に侵入した場合、電解液中の電解質が加水分解を受けてフッ酸が生成することから、二次電池自体が劣化するばかりでなく、ステンレス鋼板が腐食してしまうおそれもあり、熱融着性ポリオレフィン系樹脂層は、電解液に対するステンレス鋼板の耐腐食性を向上させる機能も担っている。
本発明の積層体は、ステンレス鋼板の第1の面に形成された有機無機複合処理層と熱融着性ポリオレフィン系樹脂層との間に、酸変性ポリオレフィン系樹脂層を有していてもよい。酸変性ポリオレフィン系樹脂層は、有機無機複合処理層とポリオレフィン系樹脂層との密着性をより向上させる。
本発明の積層体は、ステンレス鋼板の第2の面側に樹脂層(以下「外層樹脂層」ともいう)を有していてもよい。外層樹脂層は、電池外装用材に求められる加工性、意匠性、耐突き刺し性、絶縁性などを向上させうる。
本発明の積層体は、二次電池の外装材(ケース)として好適に使用されうる。二次電池の形状は、直方体の角筒形状や円筒形状など、特に限定されない。二次電池の種類も、リチウムイオン電池、リチウムポリマー電池、ニッケル水素電池、ニッケルカドミウム電池など、特に限定されない。
Claims (9)
- 第1の面および第2の面を有するステンレス鋼板と、
前記ステンレス鋼板の第1の面に直接形成された、カルボキシル基含有樹脂、オキサゾリン基含有樹脂および塩基性リン酸化合物を含有する樹脂組成物の硬化物からなる有機無機複合処理層と、
前記有機無機複合処理層の表面に形成された、厚みが10〜100μmの熱融着性ポリオレフィン系樹脂層と、
を有し、
前記カルボキシル基含有樹脂は、カルボキシル基含有エチレン性不飽和モノマー、またはカルボキシル基含有エチレン性不飽和モノマーと他のエチレン性不飽和モノマーとの組み合わせを重合させた、複数のカルボキシル基を有する重合体であり、
前記オキサゾリン基含有樹脂は、主鎖がアクリル骨格であり、かつ複数のオキサゾリン基を有する、
電池外装用積層体。 - 前記有機無機複合処理層は、前記硬化物の樹脂成分を5〜800mg/m2含有し、かつ前記硬化物のリン成分をリン換算で0.1〜100mg/m2含有する、請求項1に記載の電池外装用積層体。
- 前記樹脂組成物における、前記カルボキシル基含有樹脂および前記オキサゾリン基含有樹脂の合計量に対する前記オキサゾリン基含有樹脂の割合は、2.0〜50.0質量%の範囲内である、請求項1または請求項2に記載の電池外装用積層体。
- 前記カルボキシル基含有樹脂の酸価は、樹脂固形分換算で300mgKOH/g以上である、請求項1〜3のいずれか一項に記載の電池外装用積層体。
- 前記樹脂組成物は、塩基性ジルコニウム化合物をさらに含有し、
前記有機無機複合処理層は、前記硬化物のジルコニウム成分をジルコニウム換算で0.5〜60mg/m2含有する、
請求項1〜4のいずれか一項に記載の電池外装用積層体。 - 前記有機無機複合処理層と前記熱融着性ポリオレフィン系樹脂層との間に、厚みが10〜100μmの酸変性ポリオレフィン系樹脂層をさらに有する、請求項1に記載の電池外装用積層体。
- 前記ステンレス鋼板の板厚は、20〜400μmの範囲内である、請求項1に記載の電池外装用積層体。
- 前記ステンレス鋼板の第2の面に形成された樹脂層をさらに有する、請求項1に記載の電池外装用積層体。
- 請求項1に記載の電池外装用積層体の成形品を熱融着して形成されたケースを有する二次電池。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011025081A JP5720026B2 (ja) | 2011-02-08 | 2011-02-08 | 電池外装用積層体および二次電池 |
PCT/JP2012/000431 WO2012108134A1 (ja) | 2011-02-08 | 2012-01-24 | 電池外装用積層体および二次電池 |
KR1020137019571A KR101854487B1 (ko) | 2011-02-08 | 2012-01-24 | 전지 외장용 적층체 및 2차 전지 |
CN201280007768.0A CN103348504B (zh) | 2011-02-08 | 2012-01-24 | 电池外壳用层叠体和二次电池 |
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