JP2002063906A - Flat nonaqueous electrolyte secondary battery - Google Patents
Flat nonaqueous electrolyte secondary batteryInfo
- Publication number
- JP2002063906A JP2002063906A JP2000246927A JP2000246927A JP2002063906A JP 2002063906 A JP2002063906 A JP 2002063906A JP 2000246927 A JP2000246927 A JP 2000246927A JP 2000246927 A JP2000246927 A JP 2000246927A JP 2002063906 A JP2002063906 A JP 2002063906A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- stainless steel
- negative electrode
- secondary battery
- electrolyte secondary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 31
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 62
- 239000010935 stainless steel Substances 0.000 claims abstract description 36
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 35
- 239000011733 molybdenum Substances 0.000 claims abstract description 35
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 32
- 239000011651 chromium Substances 0.000 claims abstract description 32
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 32
- 239000010955 niobium Substances 0.000 claims abstract description 32
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010936 titanium Substances 0.000 claims abstract description 32
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000007774 positive electrode material Substances 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 18
- 239000013543 active substance Substances 0.000 abstract description 18
- 238000003860 storage Methods 0.000 abstract description 13
- 230000007774 longterm Effects 0.000 abstract description 7
- 229910000859 α-Fe Inorganic materials 0.000 abstract description 5
- 239000000470 constituent Substances 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract 2
- 238000002844 melting Methods 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 229910052759 nickel Inorganic materials 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000007747 plating Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- -1 MnO 2 or V 2 O 5 Chemical class 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920003026 Acene Polymers 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011302 mesophase pitch Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Sealing Battery Cases Or Jackets (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
- Connection Of Batteries Or Terminals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、扁平形非水電解質
二次電池に係わり、特にその正極部材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flat non-aqueous electrolyte secondary battery, and more particularly to a positive electrode member thereof.
【０００２】[0002]
【従来の技術】正極作用物質にＭｎＯ2やＶ2Ｏ5などの
金属酸化物、あるいはフッ化黒鉛などの無機化合物、あ
るいはポリアニリンやポリアセン構造体などの有機化合
物を用い、負極に金属リチウム、あるいはリチウム合
金、あるいはポリアセン構造体などの有機化合物、ある
いはリチウムを吸蔵、放出可能な炭素質材料、あるいは
チタン酸リチウムやリチウム含有珪素酸化物のような酸
化物を用い、電解質にプロピレンカーボネート、エチレ
ンカーボネート、ブチレンカーボネート、ジエチルカー
ボネート、ジメチルカーボネート、メチルエチルカーボ
ネート、ジメトキシエタン、γ−ブチロラクトンなどの
非水溶媒にＬｉＣｌＯ4，ＬｉＰＦ6，ＬｉＢＦ4，Ｌｉ
ＣＦ3ＳＯ3，ＬｉＮ（ＣＦ3ＳＯ2）2，ＬｉＮ（Ｃ2Ｆ5
ＳＯ2）2などの支持塩を溶解した非水電解質を用いた扁
平形非水電解質二次電池は既に商品化されており、放電
電流が数〜数十μＡ程度の軽負荷で放電を行われるＳＲ
ＡＭやＲＴＣのバックアップ用電源や電池交換不要腕時
計の主電源といった用途に用いられている。 2. Description of the Related Art A metal oxide such as MnO 2 or V 2 O 5 , an inorganic compound such as fluorinated graphite, or an organic compound such as polyaniline or a polyacene structure is used as a positive electrode active material. Lithium alloy, or an organic compound such as a polyacene structure, or a carbonaceous material capable of occluding and releasing lithium, or an oxide such as lithium titanate or lithium-containing silicon oxide, and propylene carbonate, ethylene carbonate as an electrolyte, LiClO 4 , LiPF 6 , LiBF 4 , Li in a non-aqueous solvent such as butylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, dimethoxyethane, and γ-butyrolactone
CF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5
A flat non-aqueous electrolyte secondary battery using a non-aqueous electrolyte in which a supporting salt such as SO 2 ) 2 is dissolved has already been commercialized, and discharge is performed with a light load having a discharge current of about several to several tens μA. SR
It is used for applications such as backup power supplies for AM and RTC and main power supplies for wristwatches that do not require battery replacement.
【０００３】一方、携帯電話やＰＤＡなどの小型情報端
末を中心に使用機器の小型化が加速しており、主電源で
ある二次電池についてもさらなる小型化が望まれてい
る。しかし、従来の正極作用物質にコバルト酸リチウム
含有酸化物、負極に炭素質材料を用いたリチウムイオン
二次電池などの高電圧を有する電池では、長期保存中に
正極部材に含まれる物質が電解液中に溶解し、イオンと
なった物質は負極表面に析出する。その結果、内部抵抗
の上昇を招き、電池性能を劣化させていた。On the other hand, the miniaturization of equipment used has been accelerated, especially for small information terminals such as mobile phones and PDAs, and further miniaturization of secondary batteries as a main power source is desired. However, in conventional batteries having a high voltage, such as a lithium ion secondary battery using a lithium cobalt oxide-containing oxide as the positive electrode active substance and a carbonaceous material as the negative electrode, the substance contained in the positive electrode member during the long-term storage contains the electrolyte solution. The substance dissolved and ionized is deposited on the negative electrode surface. As a result, the internal resistance is increased, and the battery performance is deteriorated.
【０００４】このような電池性能の劣化を防止するた
め、正極作用物質以上に貴の電位を有する金属材料が望
ましいとされ、これまでにクロム、モリブデンを含むフ
ェライト系ステンレス鋼（特開昭６３−１２４３５８号
公報）、クロム、モリブデンを含むオーステナイト系ス
テンレス鋼（特開平６−１１１８４９号公報）、及びク
ロム添加量を増加したモリブデンを含むフェライト系ス
テンレス鋼（特開平２−１２６５５４号公報）などが提
案されているが、電池電圧が４Ｖ以上の非水電解質電池
においては、これらのステンレス鋼を用いても、長期保
存中の正極部材の溶解は完全に防止できるものではなか
った。In order to prevent such deterioration in battery performance, it is considered desirable to use a metal material having a noble potential higher than that of the positive electrode active material. Ferrite stainless steels containing chromium and molybdenum (Japanese Patent Application Laid-Open No. 124358), an austenitic stainless steel containing chromium and molybdenum (Japanese Patent Application Laid-Open No. 6-111849), and a ferritic stainless steel containing molybdenum with an increased amount of chromium added (Japanese Patent Application Laid-Open No. 2-126554). However, in a non-aqueous electrolyte battery having a battery voltage of 4 V or more, even if these stainless steels are used, the dissolution of the positive electrode member during long-term storage cannot be completely prevented.
【０００５】更に、クロムの添加量を増量することで耐
食性の向上は図れるが、鋼材が硬くなり、加工性の悪化
を招いてしまい、長期保存における耐漏液性が損なわれ
るという不具合があった。[0005] Further, although corrosion resistance can be improved by increasing the amount of chromium added, the steel material is hardened, and the workability is deteriorated, and the liquid leakage resistance during long-term storage is impaired.
【０００６】[0006]
【発明が解決しようとする課題】本発明は上記問題に対
処するためになされたものであって、長期保存中におけ
る正極部材の溶解が防止でき、かつ貯蔵特性の優れた扁
平形非水電解質二次電池を提供することを目的とするも
のである。SUMMARY OF THE INVENTION The present invention has been made to address the above-mentioned problems, and it is an object of the present invention to provide a flat non-aqueous electrolyte which can prevent dissolution of a positive electrode member during long-term storage and has excellent storage characteristics. It is intended to provide a secondary battery.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
に、本発明の請求項１は、負極端子を兼ねる金属製の負
極ケースと、正極端子を兼ねる金属製の正極ケースが、
絶縁ガスケットを介し嵌合され、さらに前記正極ケース
または負極ケースが加締め加工により加締められた封口
構造を有し、その内部に帯状の正極及び負極の間にセパ
レータが位置するように捲回或いは積層された発電要素
と非水電解質を内包した扁平形非水電解質二次電池、特
に正極作用物質にコバルト酸リチウム含有酸化物、負極
に炭素質材料を用いたリチウムイオン二次電池などの高
電圧を有する扁平形非水電解質二次電池において、正極
端子を兼ねる正極ケースに或いは直接正極作用物質と接
する金属製部品の構成部材として、クロム２８．５０〜
３２．００％、モリブデン１．５０〜２．５０％を含む
フェライト系ステンレス鋼にニオブ０．１〜０．３％、
チタン０．１〜０．３％、アルミニウム０．０５〜０．
１５％を更に含ませたステンレス鋼を使用することを特
徴とする。Means for Solving the Problems In order to achieve the above object, a first aspect of the present invention provides a metal negative electrode case also serving as a negative electrode terminal and a metal positive electrode case also serving as a positive electrode terminal.
Fitted via an insulating gasket, and further has a sealing structure in which the positive electrode case or the negative electrode case is crimped by crimping, and wound or wound so that a separator is positioned between the band-shaped positive electrode and the negative electrode inside. High voltage such as flat non-aqueous electrolyte secondary batteries containing stacked power generating elements and non-aqueous electrolytes, especially lithium ion secondary batteries using lithium cobaltate-containing oxides for the positive electrode active substance and carbonaceous materials for the negative electrode In a flat non-aqueous electrolyte secondary battery having a chromium content of chromium 28.50 or less, as a constituent member of a metal part that is in direct contact with a positive electrode active substance or a positive electrode case also serving as a positive electrode terminal,
Niobium 0.1-0.3% in ferritic stainless steel containing 32.00%, molybdenum 1.50-2.50%,
Titanium 0.1-0.3%, aluminum 0.05-0.
It is characterized by using stainless steel further containing 15%.
【０００８】請求項１の発明によれば、クロム２８．５
０〜３２．００％、モリブデン１．５０〜２．５０％を
含むフェライト系ステンレス鋼にニオブ０．１〜０．３
％、チタン０．１〜０．３％、アルミニウム０．０５〜
０．１５％を複合添加することにより、これまでのモリ
ブデンを含むフェライト系ステンレス鋼、又はモリブデ
ンを含むオーステナイト系ステンレス鋼に対し高い孔食
電位が得られるため、４Ｖを超える高い電圧を有する非
水電解質電池においても、長期保存中の正極部材の溶解
を防止することが可能となった。According to the invention of claim 1, chromium 28.5
Niobium 0.1-0.3 in ferritic stainless steel containing 0-32.00% and 1.50-2.50% molybdenum.
%, Titanium 0.1-0.3%, aluminum 0.05-
By adding 0.15% in combination, a high pitting potential can be obtained with respect to the conventional ferritic stainless steel containing molybdenum or the austenitic stainless steel containing molybdenum. Also in the electrolyte battery, the dissolution of the positive electrode member during long-term storage can be prevented.
【０００９】また、本発明の請求項２は、負極端子を兼
ねる金属製の負極ケースと、正極端子を兼ねる金属製の
正極ケースが、絶縁ガスケットを介し嵌合され、さらに
前記正極ケースまたは負極ケースが加締め加工により加
締められた封口構造を有し、その内部に帯状の正極及び
負極の間にセパレータが位置するように捲回或いは積層
された発電要素と非水電解質を内包した扁平形非水電解
質二次電池、特に正極作用物質にコバルト酸リチウム、
負極に炭素質材料を用いたリチウムイオン二次電池など
の高電圧を有する扁平形非水電解質二次電池において、
正極端子を兼ねる正極ケースに或いは直接正極作用物質
と接する金属製部品の構成部材として、クロム２０．０
０〜２３．００％、モリブデン１．５０〜２．５０％を
含むフェライト系ステンレス鋼にニオブ０．８〜０．９
％、チタン０．０５〜０．１５％、銅０．２０〜０．３
０％を更に含ませたステンレス鋼を使用することを特徴
とする。A second aspect of the present invention is directed to a second aspect of the present invention, wherein a metal negative electrode case also serving as a negative electrode terminal and a metal positive electrode case also serving as a positive electrode terminal are fitted via an insulating gasket. Has a sealing structure swaged by swaging, and a flat non-aqueous electrolyte containing a non-aqueous electrolyte and a power generating element wound or laminated such that a separator is positioned between a strip-shaped positive electrode and a negative electrode inside the sealed structure. Water electrolyte secondary batteries, especially lithium cobalt oxide as the positive electrode active substance,
In a flat nonaqueous electrolyte secondary battery having a high voltage such as a lithium ion secondary battery using a carbonaceous material for the negative electrode,
As a component of a metal part which is in contact with a positive electrode case also serving as a positive electrode terminal or directly in contact with a positive electrode active material, chromium 20.0
Niobium 0.8 to 0.9 in ferritic stainless steel containing 0 to 23.00% and molybdenum 1.50 to 2.50%.
%, Titanium 0.05-0.15%, copper 0.20-0.3
It is characterized by using stainless steel further containing 0%.
【００１０】請求項２の発明によれば、クロム２０．０
０〜２３．００％、モリブデン１．５０〜２．５０％を
含むフェライト系ステンレス鋼にニオブ０．８〜０．９
％、チタン０．０５〜０．１５％、銅０．２０〜０．３
０％を複合添加することにより、これまでのモリブデン
を含むフェライト系ステンレス鋼、又はモリブデンを含
むオーステナイト系ステンレス鋼に対し加工性を損なう
ことなく高い孔食電位が得られるため、４Ｖを超える高
い電圧を有する非水電解質電池においても、長期保存中
の正極部材の溶解を防止でき貯蔵特性の優れた扁平形非
水電解質二次電池を提供することが可能となった。According to the invention of claim 2, chromium 20.0
Niobium 0.8 to 0.9 in ferritic stainless steel containing 0 to 23.00% and molybdenum 1.50 to 2.50%.
%, Titanium 0.05-0.15%, copper 0.20-0.3
By adding 0% in combination, a high pitting potential can be obtained without impairing the workability of the conventional ferritic stainless steel containing molybdenum or austenitic stainless steel containing molybdenum, so that a high voltage exceeding 4 V is obtained. Thus, it has become possible to provide a flat nonaqueous electrolyte secondary battery having excellent storage characteristics by preventing the dissolution of the positive electrode member during long-term storage.
【００１１】[0011]
【発明の実施の形態】以下、本発明の実施例及び比較例
について詳細に説明する。 （実施例１）図１は本発明の実施例１の断面図である。
以下、本実施例１の電池の製造方法を具体的に説明す
る。まず、ＬｉＣｏＯ2１００質量部に対し導電剤とし
てアセチレンブラック５質量部と黒鉛粉末５質量部を加
え、結着剤としてポリフッ化ビニリデンを５質量部加
え、Ｎ−メチルピロリドンで希釈，混合し、スラリー状
の正極合剤を得た。この正極合剤を、正極集電体である
厚さ０．０２ｍｍのアルミ箔の片面にドクターブレード
法により塗工，乾燥を行い、アルミ箔表面に正極作用物
質含有層２を形成した。以後、正極作用物質の塗膜厚さ
が両面で０．１５ｍｍとなるまで塗工、乾燥を繰り返
し、両面塗工正極を作製した。次に、この電極体の片面
の端から１０ｍｍ部分の作用物質含有層を除去し、アル
ミ層を剥き出しにし通電部とし、幅１５ｍｍ，長さ１２
０ｍｍ，厚さ０．１５ｍｍの長さに切り出した正極板を
作製した。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention and comparative examples will be described in detail. (Embodiment 1) FIG. 1 is a sectional view of Embodiment 1 of the present invention.
Hereinafter, a method for manufacturing the battery of Example 1 will be specifically described. First, to 100 parts by mass of LiCoO 2 , 5 parts by mass of acetylene black and 5 parts by mass of graphite powder were added as conductive agents, 5 parts by mass of polyvinylidene fluoride was added as a binder, and the mixture was diluted and mixed with N-methylpyrrolidone. A positive electrode mixture was obtained. This positive electrode mixture was applied to one surface of a 0.02 mm thick aluminum foil serving as a positive electrode current collector by a doctor blade method and dried to form a positive electrode active substance-containing layer 2 on the surface of the aluminum foil. Thereafter, coating and drying were repeated until the coating film thickness of the positive electrode active substance reached 0.15 mm on both sides, to produce a double-side coated positive electrode. Next, the active substance-containing layer of 10 mm from the end of one side of the electrode body was removed, and the aluminum layer was exposed to form a current-carrying part. The width was 15 mm and the length was 12 mm.
A positive electrode plate cut to a length of 0 mm and a thickness of 0.15 mm was prepared.
【００１２】次に、黒鉛化メソフェーズピッチ炭素繊維
粉末１００質量部に結着剤としてスチレンブタジエンゴ
ム（ＳＢＲ）とカルボキシメチルセルロース（ＣＭＣ）
をそれぞれ２．５質量部を添加し、イオン交換水で希
釈，混合し、スラリー状の負極合剤を得た。得られた負
極合剤を負極集電体である厚さ０．０２ｍｍの銅箔に作
用物質含有層４の厚さが０．１５ｍｍとなるように正極
の場合と同様に塗工、乾燥を繰り返し実施し、両面塗工
負極を作製した。この電極体の片面の端から１０ｍｍ部
分の作用物質含有層を除去し、銅層を剥き出しにし通電
部とし、幅１５ｍｍ，長さ１２０ｍｍ，厚さ０．１５ｍ
ｍの長さに切り出した負極板を作製した。Next, styrene-butadiene rubber (SBR) and carboxymethylcellulose (CMC) were used as binders in 100 parts by mass of the graphitized mesophase pitch carbon fiber powder.
Was added and diluted with ion-exchanged water and mixed to obtain a slurry-like negative electrode mixture. The obtained negative electrode mixture is repeatedly applied and dried on a 0.02 mm-thick copper foil as a negative electrode current collector in the same manner as in the case of the positive electrode so that the active substance-containing layer 4 has a thickness of 0.15 mm. This was performed to produce a double-sided coated negative electrode. A 10 mm portion of the active substance-containing layer was removed from one end of the electrode body, and the copper layer was exposed to serve as a current-carrying part. The width was 15 mm, the length was 120 mm, and the thickness was 0.15 m.
A negative electrode plate cut out to a length of m was prepared.
【００１３】次に、正負極通電部面を外周巻き終わり側
とし、これら正極と負極の間に厚さ２５μｍのポリエチ
レン微多孔膜からなるセパレータ３を介させて渦巻状に
捲回し、扁平形電池の扁平面に対し水平方向に正負極対
向部を持つように一定方向に捲回電極の中心部の空間が
なくなるまで加圧した。Next, the surface of the current-carrying portion of the positive and negative electrodes is set to the end side of the outer periphery, and spirally wound between the positive electrode and the negative electrode with a separator 3 made of a microporous polyethylene film having a thickness of 25 μm interposed therebetween. Pressure was applied in a certain direction so that the space at the center of the wound electrode was exhausted so as to have the positive and negative electrode facing portions in the horizontal direction with respect to the flat surface of.
【００１４】作製した電極群を８５℃で１２ｈ乾燥した
後、絶縁ガスケット６を一体化した負極金属ケース５の
内底面に電極群の片面塗工負極板の未塗工側が接するよ
うに配置し、エチレンカーボネートとメチルエチルカー
ボネートを体積比１：１の割合で混合した溶媒に支持塩
としてＬｉＰＦ6を１ｍｏｌ／ｌの割合で溶解せしめた
非水電解質を注液し、さらに電極群の片面塗工正極板の
未塗工側に接するようにクロム２８．５０〜３２．００
％、モリブデン１．５０〜２．５０％を含むフェライト
系ステンレス鋼材にニオブ０．２０％、チタン０．２０
％、アルミニウム０．１０％を複合添加し製作されたス
テンレス鋼板にニッケルめっきを電池外壁となる面に施
しプレス加工した正極ケース１を嵌合し、上下反転後、
正極ケースに加締め加工を実施し、封口し、厚さ３ｍ
ｍ，直径φ２４．５ｍｍの実施例１の扁平形非水電解質
二次電池を作製した。After drying the produced electrode group at 85 ° C. for 12 hours, the electrode group is placed such that the uncoated side of the one-side coated negative electrode plate of the electrode group is in contact with the inner bottom surface of the negative electrode metal case 5 in which the insulating gasket 6 is integrated. A non-aqueous electrolyte obtained by dissolving LiPF 6 at a ratio of 1 mol / l as a supporting salt in a solvent in which ethylene carbonate and methyl ethyl carbonate are mixed at a volume ratio of 1: 1 is injected, and a single-sided positive electrode of the electrode group is further added. Chromium 28.50-32.00 so that it contacts the uncoated side of the plate
%, Molybdenum ferrite stainless steel containing 1.50-2.50%, niobium 0.20%, titanium 0.20%
%, Aluminum and 0.10% of aluminum, and a positive electrode case 1 pressed with nickel plating applied to a surface serving as an outer wall of a battery on a stainless steel plate manufactured by adding nickel and then turned upside down.
The positive electrode case is crimped, sealed, and 3m thick
m, a flat non-aqueous electrolyte secondary battery of Example 1 having a diameter of 24.5 mm was produced.
【００１５】（実施例２）正極ケースとして、クロム２
８．５０〜３２．００％、モリブデン１．５０〜２．５
０％を含むフェライト系ステンレス鋼材にニオブ０．１
０％、チタン０．１０％、アルミニウム０．０５％を複
合添加し作製されたステンレス鋼板にニッケルめっきを
電池外壁となる面に施しプレス加工をしたものを使用し
た以外は実施例１と同様の電池を作製し実施例２とし
た。Example 2 Chromium 2 was used as a positive electrode case.
8.50-32.00%, molybdenum 1.50-2.5
Niobium 0.1 in ferritic stainless steel containing 0%
0%, 0.10% of titanium, and 0.05% of aluminum were added in the same manner as in Example 1 except that a stainless steel plate produced by adding nickel was applied to the surface serving as the outer wall of the battery and pressed. A battery was manufactured to be Example 2.
【００１６】（実施例３）正極ケースとして、クロム２
８．５０〜３２．００％、モリブデン１．５０〜２．５
０％を含むフェライト系ステンレス鋼材にニオブ０．３
０％、チタン０．３０％、アルミニウム０．１５％を複
合添加し作製されたステンレス鋼板にニッケルめっきを
電池外壁となる面に施しプレス加工をしたものを使用し
た以外は実施例１と同様の電池を作製し実施例３とし
た。(Example 3) Chromium 2 was used as a positive electrode case.
8.50-32.00%, molybdenum 1.50-2.5
0.3% niobium in ferritic stainless steel containing 0%
0%, 0.30% of titanium, and 0.15% of aluminum were added in the same manner as in Example 1 except that a stainless steel plate prepared by applying nickel plating to a surface serving as an outer wall of a battery and pressing was used. A battery was manufactured to be Example 3.
【００１７】（比較例１）正極ケースとして、クロム２
８．５０〜３２．００％、モリブデン１．５０〜２．５
０％を含むフェライト系ステンレス鋼材にニオブ０．０
５％、チタン０．０５％、アルミニウム０．０２５％を
複合添加し作製されたステンレス鋼板にニッケルめっき
を電池外壁となる面に施しプレス加工をしたものを使用
した以外は実施例１と同様の電池を作製し比較例１とし
た。Comparative Example 1 Chromium 2 was used as a positive electrode case.
8.50-32.00%, molybdenum 1.50-2.5
Niobium 0.0% in ferritic stainless steel containing 0%
Same as Example 1 except that a stainless steel plate prepared by adding 5%, 0.05% of titanium, and 0.025% of aluminum was subjected to nickel plating on the surface serving as the outer wall of the battery and pressed. A battery was manufactured and the battery was used as Comparative Example 1.
【００１８】（比較例２）正極ケースとして、クロム２
８．５０〜３２．００％、モリブデン１．５０〜２．５
０％を含むフェライト系ステンレス鋼材にニオブ０．４
０％、チタン０．４０％、アルミニウム０．２０％を複
合添加し作製されたステンレス鋼板にニッケルめっきを
電池外壁となる面に施しプレス加工をしたものを使用し
た以外は実施例１と同様の電池を作製し比較例２とし
た。Comparative Example 2 Chromium 2 was used as a positive electrode case.
8.50-32.00%, molybdenum 1.50-2.5
Niobium 0.4 in ferritic stainless steel containing 0%
0%, 0.40% of titanium, and 0.20% of aluminum are added in the same manner as in Example 1 except that a stainless steel plate prepared by adding nickel to the surface serving as the outer wall of the battery and pressing is used. A battery was prepared and the battery was used as Comparative Example 2.
【００１９】（比較例３）正極ケースとして、クロム２
８．５０〜３２．００％、モリブデン１．５０〜２．５
０％添加し作製されたステンレス鋼板にニッケルめっき
を電池外壁となる面に施しプレス加工をしたものを使用
した以外は実施例１と同様の電池を作製し比較例３とし
た。なお、このステンレス鋼はＪＩＳ ＳＵＳ４４７Ｊ
１と同等品である。Comparative Example 3 Chromium 2 was used as a positive electrode case.
8.50-32.00%, molybdenum 1.50-2.5
A battery was manufactured in the same manner as in Example 1 except that a stainless steel plate produced by adding 0% was subjected to nickel plating on the surface serving as an outer wall of the battery and pressed, and Comparative Example 3 was produced. This stainless steel is JIS SUS447J
It is equivalent to 1.
【００２０】（比較例４）正極ケースとして、フェライ
ト系ステンレス鋼材にクロム１７．００〜２０．００
％、モリブデン１．７５〜２．５０％添加し作製された
ステンレス鋼板にニッケルめっきを電池外壁となる面に
施しプレス加工したものを使用した以外は実施例１と同
様の電池を作製し比較例４とした。(Comparative Example 4) As a positive electrode case, chromium 17.0 to 20.00 was added to ferritic stainless steel.
% And molybdenum 1.75 to 2.50% were added, and a nickel-plated stainless steel plate was applied to a surface to be an outer wall of the battery and pressed to produce a battery similar to that in Example 1 and a comparative example. And 4.
【００２１】（比較例５）正極ケースとして、オーステ
ナイト系ステンレス鋼材にクロム１６．００〜１８．０
０％、モリブデン２．００〜３．００％添加し作製され
たステンレス鋼板にニッケルめっきを電池外壁となる面
に施しプレス加工をしたものを使用した以外は実施例１
と同様の電池を作製し比較例５とした。なお、このステ
ンレス鋼はＪＩＳ ＳＵＳ３１６と同等品であり、ま
た、本発明における実施例及び比較例に使用したステン
レス鋼板の化学成分を表１に示す。(Comparative Example 5) As a positive electrode case, chromium 16.0 to 18.0 was added to austenitic stainless steel.
Example 1 except that a stainless steel plate prepared by adding 0% and 2.00 to 3.00% of molybdenum was subjected to nickel plating on the surface to be the outer wall of the battery and pressed.
A battery similar to that of Example 1 was produced, and Comparative Example 5 was obtained. This stainless steel is equivalent to JIS SUS316, and Table 1 shows the chemical components of the stainless steel sheet used in the examples and comparative examples of the present invention.
【００２２】[0022]
【表１】 [Table 1]
【００２３】以上の実施例１〜３及び比較例１〜５の電
池を各１０００個作製し、４．２Ｖ，３ｍＡの定電流定
電圧で４８時間初充電を行った後に、６０℃Ｄｒｙの環
境下で４．４Ｖの定電圧を印加した状態で各５０個ずつ
２０日間保存したものの正極ケースの孔食を拡大鏡にて
確認した。表２に孔食の発生数量を示す。After 1000 batteries of each of Examples 1 to 3 and Comparative Examples 1 to 5 were prepared and initially charged at a constant current and a constant voltage of 4.2 V and 3 mA for 48 hours, an environment of 60 ° C. Dry was performed. Under the condition that a constant voltage of 4.4 V was applied below, 50 pieces of each were stored for 20 days, but the pitting corrosion of the positive electrode case was confirmed with a magnifying glass. Table 2 shows the number of pits generated.
【００２４】[0024]
【表２】 [Table 2]
【００２５】表２より、実施例１から３のフェライト系
ステンレス鋼材にニオブ０．１０〜０．３０％以上、チ
タン０．１０〜０．３０％以上、アルミニウム０．０５
〜０．１５％以上複合添加したものからは孔食は発生し
ていない。しかし、比較例１のニオブ０．０５重量部、
チタン０．０５％、アルミニウム０．０２５％と添加量
の少ないものからは孔食が認められた。又、その他クロ
ム、モリブデンを添加している比較例３から５について
も孔食が認められている。As shown in Table 2, the ferritic stainless steels of Examples 1 to 3 contained 0.10 to 0.30% or more of niobium, 0.10 to 0.30% or more of titanium, and 0.05% of aluminum.
No pitting corrosion occurred from the composite addition of 0.15% or more. However, 0.05 parts by weight of niobium of Comparative Example 1,
Pitting was recognized from the small addition amounts of titanium 0.05% and aluminum 0.025%. In addition, pitting corrosion was also observed in Comparative Examples 3 to 5 in which chromium and molybdenum were added.
【００２６】このことから、４Ｖを上回る高電圧の非水
電解質電池では、クロム、モリブデンを添加したステン
レス鋼材では孔食電位が正極作用物質の電位より低くな
ることから、正極部材中の物質が電解液中に溶解し孔食
が発生し、ニオブ、チタン、アルミニウムの添加量が少
量であることでも、孔食が発生する。From this fact, in a non-aqueous electrolyte battery having a high voltage exceeding 4 V, the pitting potential of a stainless steel material to which chromium and molybdenum is added becomes lower than the potential of the positive electrode active substance. It dissolves in the liquid and causes pitting, and pitting occurs even with a small amount of niobium, titanium and aluminum added.
【００２７】又、比較例２のニオブ０．４％、チタン
０．４％、アルミニウム０．２％と添加量が多いものに
ついても少数ではあるが孔食の発生が認められた。これ
は、チタン、アルミニウムの添加量を多くしたことによ
り、介在物及び析出物等が分離生成するため、耐孔食性
を劣化させている。In the comparative example 2, niobium was 0.4%, titanium was 0.4%, and aluminum was 0.2%. This is because inclusions and precipitates and the like are separated and generated by increasing the addition amount of titanium and aluminum, thereby deteriorating pitting corrosion resistance.
【００２８】したがって、クロム２８．５０〜３２．０
０％、モリブデン１．５０〜２．５０％を含むフェライ
ト系ステンレス鋼材に添加するニオブ、チタン、アルミ
ニウム添加量はニオブ０．１０〜０．３０％、チタン
０．１０〜０．３０％、アルミニウム０．０５〜０．１
５％が望ましく、これらを複合添加したステンレス鋼材
を正極部材として用いることで、貯蔵特性に優れた扁平
形非水電解質二次電池を提供することができる。Therefore, chromium 28.50-32.0
Niobium, titanium, and aluminum added to a ferritic stainless steel material containing 0% and 1.50 to 2.50% of molybdenum are 0.10 to 0.30% of niobium, 0.10 to 0.30% of titanium, and aluminum. 0.05-0.1
5% is desirable, and a flat nonaqueous electrolyte secondary battery having excellent storage characteristics can be provided by using a stainless steel material to which these are added in combination as a positive electrode member.
【００２９】なお、本実施例では正極及び負極をその間
のセパレータが位置するよう捲回された発電要素を用い
たが、この他にも正極及び負極がセパレータを介して多
層積層された発電要素又は正極及び負極がタブレット状
に成形されたセパレータを介し積層された発電要素を用
いても、同様の効果が得られた。In this embodiment, the power generating element in which the positive electrode and the negative electrode are wound so that the separator is located therebetween is used. The same effect was obtained by using a power generation element in which the positive electrode and the negative electrode were laminated via a tablet-shaped separator.
【００３０】（実施例４）次に、本実施例４の電池の製
造方法を具体的に説明する。まず、ＬｉＣｏＯ2１００
質量部に対し導電剤としてアセチレンブラック５質量部
と黒鉛粉末５質量部を加え、結着剤としてポリフッ化ビ
ニリデンを５質量部加え、Ｎ−メチルピロリドンで希
釈，混合し、スラリー状の正極合剤を得た。(Embodiment 4) Next, a method for manufacturing the battery of Embodiment 4 will be specifically described. First, LiCoO 2 100
5 parts by weight of acetylene black and 5 parts by weight of graphite powder are added to the parts by weight of the conductive agent, and 5 parts by weight of polyvinylidene fluoride are added as a binder, and the mixture is diluted and mixed with N-methylpyrrolidone. I got
【００３１】次にこの正極合剤を、正極集電体である厚
さ０．０２ｍｍのアルミ箔の片面にドクターブレード法
により塗工，乾燥を行い、アルミ箔表面に正極作用物質
含有層２ａを形成した。Next, this positive electrode mixture is applied to one surface of a 0.02 mm thick aluminum foil serving as a positive electrode current collector by a doctor blade method and dried, and a positive electrode active substance-containing layer 2a is formed on the aluminum foil surface. Formed.
【００３２】以後、正極作用物質含有層の塗膜厚さが両
面で０．１５ｍｍとなるまで塗工，乾燥を繰り返し、両
面塗工正極を作製した。次に、この電極体の片面の端か
ら１０ｍｍ部分の作用物質含有層を除去し、アルミ層を
剥き出しにし通電部とし、幅１５ｍｍ，長さ１２０ｍ
ｍ，厚さ０．１５ｍｍの長さに切り出した正極板を作製
した。Thereafter, coating and drying were repeated until the coating thickness of the positive electrode active substance-containing layer reached 0.15 mm on both sides, thereby producing a double-side coated positive electrode. Next, a 10 mm portion of the active substance-containing layer was removed from one end of the electrode body, and the aluminum layer was exposed to form a current-carrying part. The width was 15 mm and the length was 120 m.
m, and a positive electrode plate cut out to a length of 0.15 mm was prepared.
【００３３】次に黒鉛化メソフェーズピッチ炭素繊維粉
末１００質量部に結着剤としてスチレンブタジエンゴム
（ＳＢＲ）とカルボキシメチルセルロース（ＣＭＣ）を
それぞれ２．５質量部添加し、イオン交換水で希釈，混
合し、スラリー状の負極合剤を得た。得られた負極合剤
を負極集電体である厚さ０．０２ｍｍの銅箔に作用物質
含有層４の厚さが０．１５ｍｍとなるように正極の場合
と同様に塗工、乾燥を繰り返し実施し、両面塗工負極を
作製した。Next, 2.5 parts by mass of styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) were added as binders to 100 parts by mass of the graphitized mesophase pitch carbon fiber powder, and the mixture was diluted and mixed with ion-exchanged water. Thus, a slurry-like negative electrode mixture was obtained. The obtained negative electrode mixture is repeatedly applied and dried on a 0.02 mm-thick copper foil as a negative electrode current collector in the same manner as in the case of the positive electrode so that the active substance-containing layer 4 has a thickness of 0.15 mm. This was performed to produce a double-sided coated negative electrode.
【００３４】次に、この電極体の片面の端から１０ｍｍ
部分の作用物質含有層を除去し、銅層を剥き出しにし通
電部とし、幅１５ｍｍ，長さ１２０ｍｍ，厚さ０．１５
ｍｍの長さに切り出した負極板を作製した。Next, 10 mm from one end of the electrode body
A part of the active substance-containing layer was removed, and the copper layer was exposed to form a current-carrying part. The width was 15 mm, the length was 120 mm, and the thickness was 0.15.
A negative electrode plate cut to a length of 1 mm was prepared.
【００３５】次に、正負極通電部面を外周巻き終わり側
とし、これら正極と負極の間に厚さ２５μｍのポリエチ
レン微多孔膜からなるセパレータ３を介させて渦巻状に
捲回し、扁平形電池の扁平面に対し水平方向に正負極対
向部を持つように一定方向に捲回電極の中心部の空間が
なくなるまで加圧した。Next, the surface of the current-carrying part of the positive and negative electrodes was set to the outer peripheral winding end side, and spirally wound between the positive electrode and the negative electrode with a separator 3 made of a 25 μm-thick polyethylene microporous film interposed therebetween to form a flat battery. Pressure was applied in a certain direction so that the space at the center of the wound electrode was exhausted so as to have the positive and negative electrode facing portions in the horizontal direction with respect to the flat surface of.
【００３６】作製した電極群を８５℃で１２ｈ乾燥した
後、絶縁ガスケット６を一体化した負極金属ケース５の
内底面に電極群の片面塗工負極板の未塗工側が接するよ
うに配置し、エチレンカーボネートとメチルエチルカー
ボネートを体積比１：１の割合で混合した溶媒に支持塩
としてＬｉＰＦ6を１ｍｏｌ／ｌの割合で溶解せしめた
非水電解質を注液し、さらに電極群の片面塗工正極板の
未塗工側に接するようにクロム２０．００〜２３．００
％、モリブデン１．５０〜２．５０％を含むフェライト
系ステンレス鋼にニオブ０．８５％、チタン０．１％、
銅０．２５％を更に複合添加し作製されたステンレス鋼
板にニッケルめっきを電池外壁となる面に施しプレス加
工をした正極ケース１を嵌合し、上下反転後、正極ケー
スに加締め加工を実施し、封口し、厚さ３ｍｍ，直径φ
２４．５ｍｍの実施例４の扁平形非水電解質二次電池を
作製した。After the produced electrode group was dried at 85 ° C. for 12 hours, the electrode group was placed such that the uncoated side of the single-side coated negative electrode plate of the electrode group was in contact with the inner bottom surface of the negative electrode metal case 5 with the insulating gasket 6 integrated therewith. A non-aqueous electrolyte obtained by dissolving LiPF 6 at a ratio of 1 mol / l as a supporting salt in a solvent in which ethylene carbonate and methyl ethyl carbonate are mixed at a volume ratio of 1: 1 is injected, and a single-sided positive electrode of the electrode group is further added. Chromium 20.00-23.00 so as to contact the uncoated side of the plate
%, Molybdenum ferrite stainless steel containing 1.50-2.50%, niobium 0.85%, titanium 0.1%,
A stainless steel plate prepared by further adding 0.25% of copper is nickel-plated on the surface to be the outer wall of the battery, and the pressed positive electrode case 1 is fitted thereto. After turning upside down, the positive electrode case is crimped. And seal, thickness 3mm, diameter φ
A 24.5 mm flat nonaqueous electrolyte secondary battery of Example 4 was produced.
【００３７】（実施例５）正極ケースとして、クロム２
０．００〜２３．００％、モリブデン１．５０〜２．５
０％を含むフェライト系ステンレス鋼材にニオブ０．８
０％、チタン０．０５％、銅０．２０％を複合添加し作
製されたステンレス鋼板にニッケルめっきを電池外壁と
なる面に施しプレス加工をしたものを使用した以外は実
施例４と同様の電池を作製し実施例５とした。(Example 5) Chromium 2 was used as the positive electrode case.
0.00-23.00%, molybdenum 1.50-2.5
Niobium 0.8 in ferritic stainless steel containing 0%
0%, 0.05% of titanium, and 0.20% of copper were added in the same manner as in Example 4 except that a stainless steel plate prepared by adding nickel to the surface serving as the outer wall of the battery and pressing was used. A battery was manufactured to be Example 5.
【００３８】（実施例６）正極ケースとして、クロム２
０．００〜２３．００％、モリブデン１．５０〜２．５
０％を含むフェライト系ステンレス鋼材にニオブ０．９
０％、チタン０．１５％、銅０．３０％を複合添加し作
製されたステンレス鋼板にニッケルめっきを電池外壁と
なる面に施しプレス加工をしたものを使用した以外は実
施例４と同様の電池を作製し実施例６とした。Example 6 Chromium 2 was used as the positive electrode case.
0.00-23.00%, molybdenum 1.50-2.5
Niobium 0.9 in ferritic stainless steel containing 0%
0%, 0.15% of titanium, and 0.30% of copper were added in the same manner as in Example 4 except that a stainless steel plate prepared by adding nickel to the surface serving as the outer wall of the battery and pressing was used. A battery was manufactured to be Example 6.
【００３９】（比較例６）正極ケースとして、クロム２
０．００〜２３．００％、モリブデン１．５０〜２．５
０％を含むフェライト系ステンレス鋼材にニオブ０．７
５％、チタン０．０３％、銅０．１５％を複合添加し作
製されたステンレス鋼板にニッケルめっきを電池外壁と
なる面に施しプレス加工をしたものを使用した以外は実
施例４と同様の電池を作製し比較例６とした。(Comparative Example 6) Chromium 2 was used as a positive electrode case.
0.00-23.00%, molybdenum 1.50-2.5
Niobium 0.7 in ferritic stainless steel containing 0%
Same as Example 4 except that a stainless steel plate prepared by adding 5%, 0.03% of titanium, and 0.15% of copper was subjected to nickel plating on the surface to be the outer wall of the battery and pressed. A battery was fabricated and Comparative Example 6 was made.
【００４０】（比較例７）正極ケースとして、クロム２
０．００〜２３．００％、モリブデン１．５０〜２．５
０％を含むフェライト系ステンレス鋼材にニオブ０．９
５％、チタン０．２０％、銅０．３５％を複合添加し作
製されたステンレス鋼板にニッケルめっきを電池外壁と
なる面に施しプレス加工をしたものを使用した以外は実
施例４と同様の電池を作製し比較例７とした。(Comparative Example 7) Chromium 2 was used as the positive electrode case.
0.00-23.00%, molybdenum 1.50-2.5
Niobium 0.9 in ferritic stainless steel containing 0%
Same as Example 4 except that a stainless steel plate prepared by adding 5%, 0.20% of titanium, and 0.35% of copper was subjected to nickel plating on the surface serving as the battery outer wall and pressed. A battery was fabricated and Comparative Example 7 was made.
【００４１】（比較例８）正極ケースとして、フェライ
ト系ステンレス鋼材にクロム１７．００〜２０．００
％、モリブデン１．７５〜２．５０％添加し作製された
ステンレス鋼板にニッケルめっきを電池外壁となる面に
施しプレス加工をしたものを使用した以外は実施例４と
同様の電池を作製し比較例８とした。なお、このステン
レス鋼はＪＩＳ ＳＵＳ４４４と同等品である。(Comparative Example 8) As a positive electrode case, chromium 17.0 to 20.00 was added to ferritic stainless steel.
% And molybdenum 1.75 to 2.50% were added, and the same battery as in Example 4 was used except that a stainless steel plate prepared by applying nickel plating to the surface serving as the battery outer wall and pressing was used. Example 8 was used. This stainless steel is equivalent to JIS SUS444.
【００４２】（比較例９）正極ケースとして、オーステ
ナイト系ステンレス鋼材にクロム１６．００〜１８．０
０％、モリブデン２．００〜３．００％添加し作製され
たステンレス鋼板にニッケルめっきを電池外壁となる面
に施しプレス加工をしたものを使用した以外は実施例４
と同様の電池を作製し比較例９とした。なお、このステ
ンレス鋼はＪＩＳ ＳＵＳ３１６と同等品である。(Comparative Example 9) As a positive electrode case, chromium 16.00 to 18.0 was added to austenitic stainless steel.
Example 4 except that a stainless steel plate prepared by adding 0% and 2.00 to 3.00% of molybdenum was nickel-plated on the surface to be the outer wall of the battery and pressed.
A battery similar to that of Example 1 was produced, and Comparative Example 9 was obtained. This stainless steel is equivalent to JIS SUS316.
【００４３】本発明における実施例及び比較例に使用し
たステンレス鋼板の化学成分を表３に示す。Table 3 shows the chemical components of the stainless steel sheets used in the examples and comparative examples in the present invention.
【００４４】[0044]
【表３】 [Table 3]
【００４５】以上の実施例４〜６及び比較例６〜９の電
池を各１０００個作製し、４．２Ｖ，３ｍＡの定電流定
電圧で４８時間初充電を行った後に、室温にて４．４Ｖ
の定電圧を印加した状態で各５０個ずつ６ヶ月間保存し
たものの正極ケースの孔食を拡大鏡にて確認した。又、
４５℃−９３％の環境下で各２００個ずつ１００日間保
存し、拡大鏡にて漏液の確認を行った。表４に孔食及び
漏液の発生数量を示す。Each of the above-described batteries of Examples 4 to 6 and Comparative Examples 6 to 9 was manufactured in a quantity of 1,000, and initially charged at a constant current and a constant voltage of 4.2 V and 3 mA for 48 hours. 4V
Although 50 pieces of each were stored for 6 months with the constant voltage applied, the pitting corrosion of the positive electrode case was confirmed with a magnifying glass. or,
200 pieces of each were stored for 100 days in an environment of 45 ° C. and 93%, and leakage was confirmed with a magnifying glass. Table 4 shows the number of pits and leaks generated.
【００４６】[0046]
【表４】 [Table 4]
【００４７】表４より、実施例４から実施例６のフェラ
イト系ステンレス鋼材にニオブ０．８０〜０．９０％、
チタン０．０５〜０．１５％、銅０．２０〜０．３０％
を複合添加したものからは孔食は発生していない。しか
し、比較例６のニオブ０．７５％、チタン０．０３％、
銅０．１５％を添加した添加量の少ないものからは孔食
が認められた。As shown in Table 4, the ferritic stainless steels of Examples 4 to 6 contain 0.80 to 0.90% niobium.
Titanium 0.05-0.15%, copper 0.20-0.30%
No pitting occurred from the composite addition of. However, niobium 0.75%, titanium 0.03% of Comparative Example 6,
Pitting was observed from a small addition amount of 0.15% copper.
【００４８】また、比較例７のニオブ０．９５％、チタ
ン０．２０％、銅０．３５％を添加した添加量の多いも
のからは、孔食及び漏液が認められた。その他クロム、
モリブデンを添加している比較例８から比較例９につい
ても孔食が認められており、特に比較例８からは漏液も
認められた。In Comparative Example 7, pitting corrosion and liquid leakage were observed in the case of adding a large amount of niobium 0.95%, titanium 0.20% and copper 0.35%. Other chrome,
Pitting corrosion was also observed in Comparative Examples 8 to 9 in which molybdenum was added, and in particular, liquid leakage was also observed in Comparative Example 8.
【００４９】このことから、４Ｖを上回る高電圧の非水
電解質電池では、クロム、モリブデンを添加したステン
レス鋼材では孔食電位が正極作用物質の電位より低くな
ることから、正極部材中の物質が電解液中に溶解し孔食
が発生し、ニオブ、チタン、銅を添加することでステン
レス鋼材の孔食電位が正極作用物質の電位より高くなる
ため、孔食の発生を防止できる。しかし、ニオブ、チタ
ン、銅の添加量が少ないと、ステンレス鋼の孔食電位が
正極作用物質の電位に対し十分ではないため、孔食が発
生する。From this, in a non-aqueous electrolyte battery having a high voltage exceeding 4 V, the pitting potential of a stainless steel material to which chromium and molybdenum is added becomes lower than the potential of the positive electrode active material, and the material in the positive electrode member is not electrolyzed. The pitting corrosion is caused by dissolving in the liquid, and the pitting potential of the stainless steel material becomes higher than the potential of the positive electrode active substance by adding niobium, titanium, and copper, so that pitting corrosion can be prevented. However, when the addition amount of niobium, titanium, or copper is small, pitting corrosion occurs because the pitting potential of stainless steel is not sufficient with respect to the potential of the positive electrode active substance.
【００５０】又、ニオブ、チタン、銅の添加寮を多くす
るとステンレス鋼材中に含まれる添加物の介在物及び析
出物等が分離生成し易くなるため耐孔食性を劣化させ、
更にニオブの影響によりフェライトの形成が促進され鋼
材が硬くなり、加工が困難となる。Further, if the addition of niobium, titanium and copper is increased, inclusions and precipitates of the additives contained in the stainless steel material are easily separated and formed, so that the pitting corrosion resistance is deteriorated,
Further, the formation of ferrite is promoted by the influence of niobium, the steel material becomes hard, and the working becomes difficult.
【００５１】したがって、クロム２０．００〜２３．０
０％、モリブデン１．５０〜２．５０％を含むフェライ
ト系ステンレス鋼材に添加するニオブ、チタン、銅の添
加量はニオブ０．８０〜０．９０％、チタン０．０５〜
０．１５％、銅０．２０〜０．３０％が望ましく、これ
らを複合添加したフェライト系ステンレス鋼材を正極部
材として用いることで、貯蔵特性に優れた扁平形非水電
解質二次電池を提供することができる。Therefore, the chromium content is 20.00 to 23.0.
The amount of niobium, titanium and copper added to the ferritic stainless steel material containing 0% and 1.50 to 2.50% of molybdenum is 0.80 to 0.90% of niobium and 0.05 to 0.05% of titanium.
0.15% and 0.20 to 0.30% of copper are desirable, and a flat nonaqueous electrolyte secondary battery having excellent storage characteristics is provided by using a ferritic stainless steel material to which these are added in combination as a positive electrode member. be able to.
【００５２】なお、本実施例では正極及び負極をその間
のセパレータが位置するよう捲回された発電要素を用い
たが、この他にも正極及び負極がセパレータを介して多
層積層された発電要素又は正極及び負極がタブレット状
に成形されたセパレータを介し積層された発電要素を用
いても、同様の効果が得られた。In this embodiment, the power generating element in which the positive electrode and the negative electrode are wound so that the separator is located therebetween is used. The same effect was obtained by using a power generation element in which the positive electrode and the negative electrode were laminated via a tablet-shaped separator.
【００５３】[0053]
【発明の効果】以上説明したように、本発明によれば、
複合添加したステンレス鋼材を正極部材として用いるこ
とで、貯蔵特性に優れた扁平形非水電解質二次電池を提
供することができる。As described above, according to the present invention,
By using the composite-added stainless steel material as the positive electrode member, a flat nonaqueous electrolyte secondary battery having excellent storage characteristics can be provided.
【図１】本発明の実施例１の断面図。FIG. 1 is a sectional view of a first embodiment of the present invention.
１…正極ケース、２…正極作用物質含有層（塗工電
極）、３…セパレータ、４…負極作用物質含有層（塗工
電極）、５…負極ケース、６…絶縁ガスケット。DESCRIPTION OF SYMBOLS 1 ... Positive electrode case, 2 ... Positive active material containing layer (coated electrode), 3 ... Separator, 4 ... Negative active material containing layer (coated electrode), 5 ... Negative case, 6 ... Insulating gasket.
フロントページの続き (72)発明者 鈴木 正美 東京都品川区南品川三丁目４番10号 東芝 電池株式会社内 Ｆターム(参考） 5H011 AA02 AA17 CC06 DD15 KK02 5H017 AA03 AS06 AS08 AS10 EE04 HH01 5H029 AJ13 AJ15 AK03 AL07 AM03 AM05 AM07 BJ03 CJ03 DJ02 DJ05 EJ01 HJ01 Continuation of front page (72) Inventor Masami Suzuki 3-4-10 Minamishinagawa, Shinagawa-ku, Tokyo Toshiba Battery Corporation F-term (reference) 5H011 AA02 AA17 CC06 DD15 KK02 5H017 AA03 AS06 AS08 AS10 EE04 HH01 5H029 AJ13 AJ15 AK03 AL07 AM03 AM05 AM07 BJ03 CJ03 DJ02 DJ05 EJ01 HJ01
Claims (2)
と、正極端子を兼ねる金属製の正極ケースが、絶縁ガス
ケットを介し嵌合され、さらに前記正極ケースまたは負
極ケースが加締め加工により加締められた封口構造を有
し、その内部に正極及び負極の間にセパレータが位置す
るように配置された発電要素と非水電解質を内包した扁
平形非水電解質二次電池において、正極端子を兼ねる正
極ケースに或いは直接正極作用物質と接する金属製部品
の構成部材として、クロム２８．５０〜３２．００％、
モリブデン１．５０〜２．５０％を含むフェライト系ス
テンレス鋼にニオブ０．１〜０．３％、チタン０．１〜
０．３％、アルミニウム０．０５〜０．１５％を更に含
ませたステンレス鋼を使用することを特徴とする扁平形
非水電解質二次電池。1. A metal negative electrode case also serving as a negative electrode terminal and a metal positive electrode case also serving as a positive electrode terminal are fitted via an insulating gasket, and the positive electrode case or the negative electrode case is caulked by caulking. Positive electrode case also serving as a positive electrode terminal in a flat non-aqueous electrolyte secondary battery including a power generating element and a non-aqueous electrolyte in which a closed structure is provided and a separator is positioned between a positive electrode and a negative electrode inside thereof Or 28.50-32.00% of chromium,
Ferritic stainless steel containing 1.50 to 2.50% molybdenum with 0.1 to 0.3% niobium and 0.1 to 0.1% titanium
A flat non-aqueous electrolyte secondary battery characterized by using stainless steel further containing 0.3% and 0.05 to 0.15% of aluminum.
と、正極端子を兼ねる金属製の正極ケースが、絶縁ガス
ケットを介し嵌合され、さらに前記正極ケースまたは負
極ケースが加締め加工により加締められた封口構造を有
し、その内部に正極及び負極の間にセパレータが位置す
るように配置された発電要素と非水電解質を内包した扁
平形非水電解質二次電池において、正極端子を兼ねる正
極ケースに或いは直接正極作用物質と接する金属製部品
の構成部材として、クロム２０．００〜２３．００％、
モリブデン１．５０〜２．５０％を含むフェライト系ス
テンレス鋼にニオブ０．８〜０．９％、チタン０．０５
〜０．１５％、銅０．２０〜０．３０％を更に含ませた
ステンレス鋼を使用することを特徴とする扁平形非水電
解質二次電池。2. A metal negative electrode case also serving as a negative electrode terminal and a metal positive electrode case also serving as a positive electrode terminal are fitted via an insulating gasket, and the positive electrode case or the negative electrode case is caulked by caulking. Positive electrode case also serving as a positive electrode terminal in a flat non-aqueous electrolyte secondary battery including a power generating element and a non-aqueous electrolyte in which a closed structure is provided and a separator is positioned between a positive electrode and a negative electrode inside thereof Or as a component of a metal part in direct contact with the positive electrode active material, chromium 20.00 to 23.00%,
0.8 to 0.9% niobium and 0.05% titanium in ferritic stainless steel containing 1.50 to 2.50% molybdenum
A flat nonaqueous electrolyte secondary battery characterized by using stainless steel further containing 0.15% to 0.15% and copper 0.20 to 0.30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000246927A JP4877678B2 (en) | 2000-08-16 | 2000-08-16 | Flat non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000246927A JP4877678B2 (en) | 2000-08-16 | 2000-08-16 | Flat non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002063906A true JP2002063906A (en) | 2002-02-28 |
| JP4877678B2 JP4877678B2 (en) | 2012-02-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000246927A Expired - Lifetime JP4877678B2 (en) | 2000-08-16 | 2000-08-16 | Flat non-aqueous electrolyte secondary battery |
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| JP (1) | JP4877678B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006164527A (en) * | 2004-12-02 | 2006-06-22 | Matsushita Electric Ind Co Ltd | Flat type nonaqueous electrolytic solution battery |
| JP2007328978A (en) * | 2006-06-07 | 2007-12-20 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2010033782A (en) * | 2008-07-25 | 2010-02-12 | Nisshin Steel Co Ltd | Collector and negative electrode material for lithium-ion secondary battery |
| WO2012132452A1 (en) * | 2011-03-30 | 2012-10-04 | パナソニック株式会社 | Lithium primary cell |
| US9905369B2 (en) | 2012-05-22 | 2018-02-27 | Gs Yuasa International Ltd. | Energy storage device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6266559A (en) * | 1985-09-18 | 1987-03-26 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery |
| JPS62186467A (en) * | 1986-02-10 | 1987-08-14 | Matsushita Electric Ind Co Ltd | Cylindrical lithium cell |
| JPS62262368A (en) * | 1986-05-08 | 1987-11-14 | Sanyo Electric Co Ltd | Nonaqueous electrolyte cell |
| JPH02126554A (en) * | 1988-11-07 | 1990-05-15 | Toshiba Battery Co Ltd | Nonaqueous solvent secondary cell |
| JPH02236972A (en) * | 1989-03-09 | 1990-09-19 | Hitachi Maxell Ltd | Polyaniline battery |
| JPH0410365A (en) * | 1990-04-26 | 1992-01-14 | Hitachi Maxell Ltd | Lithium secondary battery |
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- 2000-08-16 JP JP2000246927A patent/JP4877678B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6266559A (en) * | 1985-09-18 | 1987-03-26 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery |
| JPS62186467A (en) * | 1986-02-10 | 1987-08-14 | Matsushita Electric Ind Co Ltd | Cylindrical lithium cell |
| JPS62262368A (en) * | 1986-05-08 | 1987-11-14 | Sanyo Electric Co Ltd | Nonaqueous electrolyte cell |
| JPH02126554A (en) * | 1988-11-07 | 1990-05-15 | Toshiba Battery Co Ltd | Nonaqueous solvent secondary cell |
| JPH02236972A (en) * | 1989-03-09 | 1990-09-19 | Hitachi Maxell Ltd | Polyaniline battery |
| JPH0410365A (en) * | 1990-04-26 | 1992-01-14 | Hitachi Maxell Ltd | Lithium secondary battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006164527A (en) * | 2004-12-02 | 2006-06-22 | Matsushita Electric Ind Co Ltd | Flat type nonaqueous electrolytic solution battery |
| JP2007328978A (en) * | 2006-06-07 | 2007-12-20 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2010033782A (en) * | 2008-07-25 | 2010-02-12 | Nisshin Steel Co Ltd | Collector and negative electrode material for lithium-ion secondary battery |
| WO2012132452A1 (en) * | 2011-03-30 | 2012-10-04 | パナソニック株式会社 | Lithium primary cell |
| JP5583270B2 (en) * | 2011-03-30 | 2014-09-03 | パナソニック株式会社 | Lithium primary battery |
| US9905369B2 (en) | 2012-05-22 | 2018-02-27 | Gs Yuasa International Ltd. | Energy storage device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4877678B2 (en) | 2012-02-15 |
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