JPH0410365A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH0410365A JPH0410365A JP2112023A JP11202390A JPH0410365A JP H0410365 A JPH0410365 A JP H0410365A JP 2112023 A JP2112023 A JP 2112023A JP 11202390 A JP11202390 A JP 11202390A JP H0410365 A JPH0410365 A JP H0410365A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- stainless steel
- lithium
- secondary battery
- lithium 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.)
- Pending
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 24
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 22
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 239000011733 molybdenum Substances 0.000 claims abstract description 15
- 229920000767 polyaniline Polymers 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 15
- 239000011651 chromium Substances 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 5
- 229910000733 Li alloy Inorganic materials 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- 239000005486 organic electrolyte Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 18
- 239000010935 stainless steel Substances 0.000 abstract description 5
- 229910001566 austenite Inorganic materials 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- -1 polyvirol Polymers 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- 229910000927 Ge alloy Inorganic materials 0.000 description 1
- 229910012219 LiPFa Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- BZHNHDOWFCBZNK-UHFFFAOYSA-N antimony lithium Chemical compound [Li].[Sb] BZHNHDOWFCBZNK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JYPVGDJNZGAXBB-UHFFFAOYSA-N bismuth lithium Chemical compound [Li].[Bi] JYPVGDJNZGAXBB-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- YFKPABFAJKUPTN-UHFFFAOYSA-N germanium lithium Chemical compound [Li].[Ge] YFKPABFAJKUPTN-UHFFFAOYSA-N 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- KUJOABUXCGVGIY-UHFFFAOYSA-N lithium zinc Chemical compound [Li].[Zn] KUJOABUXCGVGIY-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000323 polyazulene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はリチウム二次電池に係わり、さらに詳しくは、
正極缶または正極缶と正極集電体との耐腐食性を高めた
リチウム二次電池に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a lithium secondary battery, and more specifically,
The present invention relates to a lithium secondary battery in which the corrosion resistance of a positive electrode can or a positive electrode can and a positive electrode current collector is improved.
〔従来の技術］
従来のリチウム二次電池においては、正極缶や正極集電
体に５ＵＳ３０４．５ＵＳ３１６などのオーステナイト
系ステンレス鋼や５ＵＳ４３０系のフェライト系ステン
レス鋼が用いられていた（例えば、特開昭６（］−６６
１号公報特開昭６２−９１５２９号公報）。[Prior art] In conventional lithium secondary batteries, austenitic stainless steels such as 5US304.5US316 and ferritic stainless steels such as 5US430 were used for positive electrode cans and positive electrode current collectors (for example, 6(]-66
No. 1 (Japanese Patent Application Laid-Open No. 62-91529).
しかしながら、正極活物質として高電圧化が可能なポリ
アニリンなどを用い、高電圧、高容量化を目的として充
電終止電圧を高くしたり、充放電を繰り返すと、ステン
レス鋼で作製された正極缶や正極集電体表面の酸化物保
護膜が正極活物質の強力な酸化力などによって損傷を受
けて、孔食腐食が生しる。However, if polyaniline, which can be used for high voltages, is used as a positive electrode active material, and if the end-of-charge voltage is increased for the purpose of high voltage and high capacity, or if charging and discharging are repeated, the positive electrode can or cathode made of stainless steel The oxide protective film on the surface of the current collector is damaged by the strong oxidizing power of the positive electrode active material, resulting in pitting corrosion.
そして、この孔食腐食が進行すると、負極表面にステン
レス鋼成分が析出して内部短絡の発生や自己放電を促進
して、開路電圧を低下させたり、充放電容量を減少させ
る。As this pitting corrosion progresses, stainless steel components precipitate on the surface of the negative electrode, promoting the occurrence of internal short circuits and self-discharge, lowering the open circuit voltage and reducing the charge/discharge capacity.
したがって、本発明は、上記従来のリチウム二次電池が
持っていた正極缶や正極集電体が充放電の繰り返しなど
によって孔食腐食が生し、内部短絡の発生や自己放電を
促進するという問題点を解決し、正極缶や正極集電体の
耐腐食性を高めて、開路電圧の低下や充放電容量の低下
が少ないリチウム二次電池を提供することを目的とする
。Therefore, the present invention solves the problem that pitting corrosion occurs in the positive electrode can and positive electrode current collector of the conventional lithium secondary battery due to repeated charging and discharging, which promotes internal short circuits and self-discharge. It is an object of the present invention to provide a lithium secondary battery in which the corrosion resistance of the positive electrode can and the positive electrode current collector is improved, and the decrease in open circuit voltage and charge/discharge capacity is minimized.
本発明は、正極缶または正極缶と正極集電体にクロムを
２８．５〜３２．０重量％、モリブデンを１．５〜２．
５重量％含有するフェライト系ステンレス鋼を使用する
ことによって、上記目的を達成したものである。In the present invention, the positive electrode can or the positive electrode can and the positive electrode current collector contain 28.5 to 32.0% by weight of chromium and 1.5 to 2.0% by weight of molybdenum.
The above object was achieved by using ferritic stainless steel containing 5% by weight.
上記のフェライト系ステンレス鋼は、クロム含有量が２
８，５〜３２．０重量％と高く （ちなみに、ＳＵＳ
４３０系のフェライト系ステンレス鋼ではクロム含有量
が１６〜１８重量％、オーステナイト系ステンレス網で
はクロム含有量が１６〜２０重量％）、シかもモリブデ
ンを１．５〜２．５重量％含有しているので、ステンレ
ス綱表面に形成される酸化物保護膜が強化され、耐腐食
性が優れている。特にモリブデンは孔食腐食の発生防止
に効果があり、充放電の繰り返しなどによって孔食腐食
が発生するのが防止される。したがって、上記クロムを
２８．５〜３２．０重量％、モリブデンを１．５〜２．
５重量％含有するフェライト系ステンレス鋼を正極缶や
正極集電体に使用することによって、孔食腐食に基づく
内部短絡の発生や自己放電の促進が防止され、開路電圧
の低下や充放電容量の低下が防止される。The above ferritic stainless steel has a chromium content of 2
As high as 8.5 to 32.0% by weight (by the way, SUS
430 series ferritic stainless steel has a chromium content of 16 to 18% by weight, austenitic stainless steel has a chromium content of 16 to 20% by weight), and it also contains molybdenum of 1.5 to 2.5% by weight. As a result, the oxide protective film formed on the surface of the stainless steel is strengthened and has excellent corrosion resistance. Molybdenum is particularly effective in preventing pitting corrosion, and prevents pitting corrosion from occurring due to repeated charging and discharging. Therefore, the chromium content is 28.5 to 32.0% by weight, and the molybdenum content is 1.5 to 2.0% by weight.
By using ferritic stainless steel containing 5% by weight for the positive electrode can and positive electrode current collector, the occurrence of internal short circuits due to pitting corrosion and the promotion of self-discharge are prevented, reducing open circuit voltage and charging/discharging capacity. Deterioration is prevented.
また、フェライト系ステンレス鋼であるため、ニッケル
をほとんど含まないので、５Ｏ３３０４などのオーステ
ナイト系ステンレス鋼を正極缶や正極集電体に使用した
場合のようなニッケルに基づ（低電圧下での腐食が生じ
ない。In addition, since it is a ferritic stainless steel, it contains almost no nickel, so if an austenitic stainless steel such as 5O3304 is used for the positive electrode can or positive electrode current collector, nickel-based (corrosion under low voltage) does not occur.
上記のクロムを２８．５〜３２，０重量％、モリブデン
を１．５〜２．５重量％を含有したフェライト系ステン
レス鋼の具体例としては、例えばＳ Ｕ Ｓ ４４７Ｊ
１などが挙げられる。A specific example of the above-mentioned ferritic stainless steel containing 28.5 to 32.0% by weight of chromium and 1.5 to 2.5% by weight of molybdenum is, for example, SUS 447J.
1 etc.
本発明において、正極缶または正極缶と正極集電体に使
用するフェライト系ステンレス鋼のクロム含有量を２８
．５〜３２．０重量％、モリブデン含を量を１．５〜２
．５重置％に特定しているのは、次の理由によるもので
ある。In the present invention, the chromium content of the ferritic stainless steel used for the positive electrode can or the positive electrode can and the positive electrode current collector is 28%.
．． 5-32.0% by weight, molybdenum content 1.5-2
．． The reason for specifying 5 overlapping percentages is as follows.
すなわち、クロム含有量が２８．５重量％より少ない場
合は、耐腐食性が低下し、クロム含有量が３２．０重置
％より多くなると、加工性が悪くなるからである。また
、モリブデンの含有量が１．５１量％より少ない場合は
、耐腐食性が低下し、モリブデンの含有量が２．５重置
％より多（なると、加工性が悪くなるとともに、コスト
高になるからである。That is, if the chromium content is less than 28.5% by weight, the corrosion resistance will decrease, and if the chromium content is more than 32.0% by weight, the workability will deteriorate. In addition, if the molybdenum content is less than 1.51% by weight, corrosion resistance will decrease, and if the molybdenum content is more than 2.5% by weight, processability will deteriorate and costs will increase. Because it will be.
負極にはリチウムまたはリチウム合金が用いられる。上
記リチウム合金としては、例えぼりチウム−アルミニウ
ム合金、リチウム−錫合金、リチウム−亜鉛合金、リチ
ウム−鉛合金、リチウムビスマス合金、リチウム−ケイ
素合金、リチウムアンチモン合金、リチウム−マグネシ
ウム合金、リチウム−インジウム合金、リチウム−ガリ
ウム合金、リチウム−ゲルマニウム合金、リチウムガリ
ウム−インジウム合金などが挙げられる。また、それら
のリチウム合金にさらに他の金属を少量添加したものも
負極に用いることができる。Lithium or a lithium alloy is used for the negative electrode. Examples of the above lithium alloys include lithium-aluminum alloy, lithium-tin alloy, lithium-zinc alloy, lithium-lead alloy, lithium-bismuth alloy, lithium-silicon alloy, lithium-antimony alloy, lithium-magnesium alloy, and lithium-indium alloy. , lithium-gallium alloy, lithium-germanium alloy, lithium gallium-indium alloy, and the like. Moreover, those lithium alloys to which small amounts of other metals are added can also be used for negative electrodes.
電解液は、リチウム二次電池に通常使用されている有機
電解液をいずれも使用することができる。As the electrolyte, any organic electrolyte commonly used in lithium secondary batteries can be used.
電解液を例示すると、例えば１，２−ジメトキシエタン
、１，２−ジェトキシエタン、エチレンカーボネート、
プロピレンカーボネート、γ−ブチロラクトン、テトラ
ヒドロフラン、１．３−ジオキソラン、４−メチル−１
，３−ジオキソランなどの有機溶媒の単独または２種以
上の混合溶媒に、例えばＬｉｃ＋ｏ４ 、ＬｉＰＦａ
、ＬｉＡｓＦ６、Ｌｉ５ｂＦ、、ＬｉＢＦ４、ＬｉＣＦ
ｚ ＳＯ３、ＬｉＢ （Ｃ，ＨＳ）４などの溶質の１種
または２種以上を溶解させることによって調製した有機
電解液が挙げられる。Examples of electrolytes include 1,2-dimethoxyethane, 1,2-jethoxyethane, ethylene carbonate,
Propylene carbonate, γ-butyrolactone, tetrahydrofuran, 1,3-dioxolane, 4-methyl-1
, 3-dioxolane or a mixture of two or more organic solvents, for example, Lic+o4, LiPFa.
, LiAsF6, Li5bF, , LiBF4, LiCF
Examples include organic electrolytes prepared by dissolving one or more solutes such as zSO3 and LiB(C,HS)4.
正極活物質としては、例えばポリアニリン、ポリビロー
ル、ポリチオフェン、ポリフェニレン、ポリアズレン、
ポリアセチレンなどのポリマー活物質、リチウム塩と二
酸化マンガンとを焼成して得られるリチウムマンガン複
合酸化物、ＬｉＣ。Examples of positive electrode active materials include polyaniline, polyvirol, polythiophene, polyphenylene, polyazulene,
LiC, a lithium manganese composite oxide obtained by firing a polymer active material such as polyacetylene, lithium salt, and manganese dioxide.
Ｏｚ 、Ｃｒｉ Ｏｓ 、Ｖｚ Ｏｓなどが用いられる
。Oz, CriOs, VzOs, etc. are used.
特にポリアニリンは、高電圧化が可能であり、充放電効
率が良く、自己放電が少ないので、本発明において好適
に使用される。In particular, polyaniline is preferably used in the present invention because it can be used at a high voltage, has good charge/discharge efficiency, and has little self-discharge.
つぎに実施例を挙げて本発明をさらに詳細に説明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例１
蒸留水１５０ａｉｉ中に、アニリン１０ｇと４２重量％
ＨＢＦ、水溶液６７．１ｇを加え、フラスコ中で攪拌混
合しながら、二酸化マンガン１０．３ ｇを約１時間か
けて徐々に添加した。二酸化マンガンの添加後、さらに
１時間攪拌を続けてアニリンの重合を行った。Example 1 10 g of aniline and 42% by weight in 150 aii of distilled water
67.1 g of an aqueous solution of HBF was added, and while stirring and mixing in the flask, 10.3 g of manganese dioxide was gradually added over about 1 hour. After the addition of manganese dioxide, stirring was continued for an additional hour to polymerize aniline.
重合終了後、反応液を濾過し、重合生成物を２５０ｄの
蒸留水で１回、２５０社のアセトンで４回、洗浄と濾過
を繰り返した後、１００’Ｃで５時間真空乾燥を行って
、ポリアニリン粉末９．２ｇを得た。After the polymerization was completed, the reaction solution was filtered, and the polymerized product was washed and filtered once with 250 d of distilled water and 4 times with 250 acetone, and then vacuum dried at 100'C for 5 hours. 9.2 g of polyaniline powder was obtained.
得られたポリアニリン粉末５０ｍｇを金型に充填して１
．Ｏｔｏｎ／ｃｆｌｌの圧力で加圧成形し、直径１５Ｉ
ＩＩＩＩ＋、厚さ０．３５閣のペレット状の成形体を作
製した。50 mg of the obtained polyaniline powder was filled into a mold and 1
．． Pressure molded at Oton/cfll pressure, diameter 15I
A pellet-shaped molded product having a thickness of 0.35 mm was produced.
このポリアニリン成形体を正極として用い、第１図に示
す構造のリチウム二次電池を作製した。Using this polyaniline molded body as a positive electrode, a lithium secondary battery having the structure shown in FIG. 1 was produced.
第１図において、（１）は上記ポリアニリン成形体から
なる正極で、（２）は正極缶であり、この正極缶（２）
はクロムを３０重量％、モリブデンを２．０５重量％含
有するフェライト系ステンレス鋼である５ＵＳ４４７Ｊ
１で作製されている。（３）は負極であり、この負極（
３）は厚さ０．２ｇｍ、直径１５閣のリチウム板からな
り、オーステナイト系ステンレス鋼である５ＵＳ３０４
製の負極缶（４）の内面にあらかしめスポット溶接して
おいた５ＵＳ３０４製の負極集電体（５）に圧着されて
いる。（６）はセパレータで、このセパレータ（６）は
微孔性ポリプロピレンフィルムとポリプロピレン不織布
とを積重してなるものであり、（７）はポリプロピレン
製の環状ガスケットである。そして、この電池の電解液
としては、プロピレンカーボネートと１．２−ジメトキ
シエタンとの容量比１：１の混合溶媒に乾燥処理したＬ
ｉＢＦａを２ｅＡｏｌ／ｆｆｉ溶解した有機電解液が使
用されている。In FIG. 1, (1) is a positive electrode made of the above-mentioned polyaniline molded body, and (2) is a positive electrode can.
5US447J is a ferritic stainless steel containing 30% by weight of chromium and 2.05% by weight of molybdenum.
It is made with 1. (3) is a negative electrode, and this negative electrode (
3) consists of a lithium plate with a thickness of 0.2 gm and a diameter of 15 cm, and is made of 5US304 austenitic stainless steel.
It is crimped to a negative electrode current collector (5) made of 5US304, which has been pre-spot welded to the inner surface of a negative electrode can (4) made of aluminum. (6) is a separator, and this separator (6) is made by stacking a microporous polypropylene film and a polypropylene nonwoven fabric, and (7) is an annular gasket made of polypropylene. The electrolyte for this battery is L, which has been dried and mixed with a mixed solvent of propylene carbonate and 1,2-dimethoxyethane in a volume ratio of 1:1.
An organic electrolyte in which 2eAol/ffi of iBFa is dissolved is used.
実施例２
本実施例２のリチウム二次電池は、第２図に示すように
、正極（１）の一方の端部に正極集電体（８）を配設し
たものである。Example 2 As shown in FIG. 2, the lithium secondary battery of Example 2 has a positive electrode current collector (8) disposed at one end of the positive electrode (1).
上記正極集電体（８）は、クロムを３０重量％、モリブ
デンを２．０５重量％含有するフェライト系ステンレス
鋼であるＳ Ｕ Ｓ ４４７Ｊ１製の網からなるもので
、正極（１）の正極缶（２）の底部と接する側に配置さ
れている。The positive electrode current collector (8) is made of a mesh made of SUS 447J1, which is a ferritic stainless steel containing 30% by weight of chromium and 2.05% by weight of molybdenum. (2) It is arranged on the side that contacts the bottom part.
正極缶（２）は、実施例１と同様に、クロムを３０重量
％、モリブデンを２．０５重量％含有するフェライト系
ステンレス鋼であるＳ Ｕ Ｓ ４４７Ｊ１によって作
製されたものであり、また、負極（３）、負極缶（４）
、負極集電体（５）、セパレータ（６）、ガスケット（
７）なども、実施例１の場合と同様の構成のものである
。As in Example 1, the positive electrode can (2) was made of SUS 447J1, which is a ferritic stainless steel containing 30% by weight of chromium and 2.05% by weight of molybdenum. (3), negative electrode can (4)
, negative electrode current collector (5), separator (6), gasket (
7) etc. also have the same configuration as in the first embodiment.
比較例１
正極缶（２）をクロムを１８重量％含有するフェライト
系ステンレス鋼製である５ＵＳ４３０製のものに変えた
ほかは、実施例１と同様のリチウム二次電池を作製した
。Comparative Example 1 A lithium secondary battery was produced in the same manner as in Example 1, except that the positive electrode can (2) was changed to one made of 5US430, which is a ferritic stainless steel containing 18% by weight of chromium.
比較例２
正極缶（２）をオーステナイト系ステンレス鋼である５
ＵＳ３０４製のものに変えたほかは、実施例１と同様に
してリチウム二次電池を作製した。Comparative Example 2 The positive electrode can (2) was made of austenitic stainless steel.
A lithium secondary battery was produced in the same manner as in Example 1, except that the battery was changed to one made of US304.
上記実施例１〜２の電池および比較例１〜２の電池を５
００μＡで、３．０■、３．３■、３，５■まで充電し
た後、６０°Ｃで２０日間フローティング（各電圧を２
０日間印加し続けること）を行った。The batteries of Examples 1 and 2 and the batteries of Comparative Examples 1 and 2 were
After charging to 3.0■, 3.3■, 3.5■ at 00μA, float at 60°C for 20 days (each voltage is set to 2).
(continued application for 0 days).
フローティング後の電池の開路電圧を測定し、その後、
充を電流、放電電流とも０．５ｍＡで３．３〜２．ＯＶ
の電圧範囲で充放電させ、３サイクル後の放電容量を測
定し、初期放電容量に対する保持率を調べた。その結果
を第１表に示す。Measure the open circuit voltage of the battery after floating, then
Charging current and discharging current are both 0.5 mA and 3.3 to 2. O.V.
The battery was charged and discharged in a voltage range of 3 cycles, and the discharge capacity was measured after 3 cycles to examine the retention rate with respect to the initial discharge capacity. The results are shown in Table 1.
第１表に示すように、実施例１〜２の電池は、いずれの
フローティング電圧においても、開路電圧の低下が少な
く、また比較例１〜２の電池に比べて、放電容量の保持
率が高かった。これは、実施例１〜２の電池では、正極
缶（２）や正極集電体（８）に耐腐食性の優れたＳ Ｕ
Ｓ ４４７Ｊ１を使用しているので、正極缶（２）や
正極集電体（８）が孔食腐食を生しることが少なく、そ
のため、内部短絡の発生が少なく、自己放電の進行が少
なかったためであると考えられる。As shown in Table 1, the batteries of Examples 1 and 2 had less drop in open circuit voltage at any floating voltage, and had a higher discharge capacity retention rate than the batteries of Comparative Examples 1 and 2. Ta. This is because in the batteries of Examples 1 and 2, the positive electrode can (2) and the positive electrode current collector (8) were made of S U with excellent corrosion resistance.
Since S447J1 is used, the positive electrode can (2) and the positive electrode current collector (8) are less prone to pitting corrosion, which results in fewer internal short circuits and less progression of self-discharge. It is thought that.
なお、比較例１〜２の電池を３．５■および３．７■で
フローティングを行った後、分解したところ、セパレー
タ上に黒い析出物がみられた。これは、正極缶の一部が
孔食腐食により電解液中に熔解し、それが負極側に移行
し、負極で還元されて生成したステンレス鋼成分の析出
物であると考えられる。When the batteries of Comparative Examples 1 and 2 were floated at 3.5 and 3.7 square centimeters and then disassembled, black precipitates were observed on the separator. This is considered to be a precipitate of stainless steel components generated by a portion of the positive electrode can being dissolved in the electrolyte due to pitting corrosion, transferred to the negative electrode side, and reduced at the negative electrode.
上記セパレータ上の黒い析出物を蛍光χ線分析で分析し
た結果もそれと一致していた。The results of analyzing the black precipitate on the separator by fluorescent chi-ray analysis were also consistent with this.
これに対し、実施例１〜２の電池では、３．５■および
３．７■でフローティングし、分解したところ、そのよ
うなセパレータ上への黒色物質の析出はまったく認めら
れなかった。On the other hand, in the batteries of Examples 1 and 2, when they were floated and decomposed at 3.5 and 3.7 inches, no black substance was observed to be deposited on the separator.
以上説明したように、本発明では、正極缶または正極缶
と正極集電体にクロムを２８．５〜３２．０重量％、モ
リブデンを１．５〜２．５重量％含有するフェライト系
ステンレス綱を用いることによって、正極缶や正極集電
体の耐腐食性を高め、内部短絡の発生や自己放電の進行
を防止して、充放電の繰り返しなどに伴う開路電圧の低
下や放電容量の低下が少ないリチウム二次電池を提供す
ることができた。As explained above, in the present invention, the positive electrode can or the positive electrode can and the positive electrode current collector are made of ferritic stainless steel containing 28.5 to 32.0% by weight of chromium and 1.5 to 2.5% by weight of molybdenum. By using this, the corrosion resistance of the cathode can and cathode current collector is increased, preventing the occurrence of internal short circuits and the progression of self-discharge, and reducing the drop in open circuit voltage and discharge capacity due to repeated charging and discharging. We were able to provide fewer lithium secondary batteries.
第１図は本発明の実施例１のリチウム二次電池を示す断
面図であり、第２図は本発明の実施例２のリチウム二次
電池を示す断面図である。
（１）・・・正極、 （２）・・・正極缶、 （３）・
・・負極、（４）・・・負極缶、（６）・・・セパレー
タ、（８）・・・正極集電体FIG. 1 is a cross-sectional view showing a lithium secondary battery according to Example 1 of the present invention, and FIG. 2 is a cross-sectional view showing a lithium secondary battery according to Example 2 of the present invention. (1)...Positive electrode, (2)...Positive electrode can, (3)...
... Negative electrode, (4) ... Negative electrode can, (6) ... Separator, (8) ... Positive electrode current collector
Claims (2)
液に有機電解液を用いたリチウム二次電池において、 正極缶または正極缶と正極集電体にクロムを２８．５〜
３２．０重量％、モリブデンを１．５〜２．５重量％含
有するフェライト系ステンレス鋼を使用したことを特徴
とするリチウム二次電池。(1) In a lithium secondary battery that uses lithium or a lithium alloy for the negative electrode and an organic electrolyte for the electrolyte, the positive electrode can or the positive electrode can and the positive electrode current collector contain 28.5 to 28.5% chromium.
A lithium secondary battery characterized by using ferritic stainless steel containing 32.0% by weight and 1.5 to 2.5% by weight of molybdenum.
１記載のリチウム二次電池。(2) The lithium secondary battery according to claim 1, wherein polyaniline is used as the positive electrode active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2112023A JPH0410365A (en) | 1990-04-26 | 1990-04-26 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2112023A JPH0410365A (en) | 1990-04-26 | 1990-04-26 | Lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0410365A true JPH0410365A (en) | 1992-01-14 |
Family
ID=14576058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2112023A Pending JPH0410365A (en) | 1990-04-26 | 1990-04-26 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0410365A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0599654A1 (en) * | 1992-11-26 | 1994-06-01 | Seiko Electronic Components Ltd. | Non-aqueous electrolyte electrochemical cell |
| JP2002063906A (en) * | 2000-08-16 | 2002-02-28 | Toshiba Battery Co Ltd | Flat nonaqueous electrolyte secondary battery |
| JP2015518278A (en) * | 2012-04-13 | 2015-06-25 | ポリジュール・インコーポレイテッドＰｏｌｙＪｏｕｌｅ，Ｉｎｃ． | Devices and methods comprising polyacetylene |
-
1990
- 1990-04-26 JP JP2112023A patent/JPH0410365A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0599654A1 (en) * | 1992-11-26 | 1994-06-01 | Seiko Electronic Components Ltd. | Non-aqueous electrolyte electrochemical cell |
| US5478670A (en) * | 1992-11-26 | 1995-12-26 | Seiko Electronic Components, Ltd. | Non-aqueous electrolyte electrochemical cell comprising high Ni austenitic stainless steel positive electrode case |
| JP2002063906A (en) * | 2000-08-16 | 2002-02-28 | Toshiba Battery Co Ltd | Flat nonaqueous electrolyte secondary battery |
| JP2015518278A (en) * | 2012-04-13 | 2015-06-25 | ポリジュール・インコーポレイテッドＰｏｌｙＪｏｕｌｅ，Ｉｎｃ． | Devices and methods comprising polyacetylene |
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