JP2594034B2 - Non-aqueous electrolyte battery - Google Patents
Non-aqueous electrolyte batteryInfo
- Publication number
- JP2594034B2 JP2594034B2 JP60205560A JP20556085A JP2594034B2 JP 2594034 B2 JP2594034 B2 JP 2594034B2 JP 60205560 A JP60205560 A JP 60205560A JP 20556085 A JP20556085 A JP 20556085A JP 2594034 B2 JP2594034 B2 JP 2594034B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- stainless steel
- battery
- aqueous electrolyte
- electrolyte battery
- 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.)
- Expired - Lifetime
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000011149 active material Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 239000000470 constituent Substances 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 101150000971 SUS3 gene Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/669—Steels
-
- 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
- H01M50/116—Primary casings; Jackets or wrappings 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
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明はリチウムを活物質とする負極と、金属の酸化
物、ハロゲン化物などを活物質とする正極と、非水電解
液とを備えた電池に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Industrial application field The present invention comprises a negative electrode using lithium as an active material, a positive electrode using metal oxide, halide or the like as an active material, and a non-aqueous electrolyte. Battery.
（ロ）従来の技術 この種電池の缶材料としてはニッケル含有量が約３〜
20重量％の所謂オーステナイト系ステンレス鋼が一般に
用いられているが、電池の保存中に特に正極に電気接続
された正極缶はその構成部材が電解液中に溶解し負極上
に析出して内部抵抗を増大させ、又極端な場合には穴あ
き現象を生じることがある。この原因はステンレス鋼に
含まれるニッケル量に依存すると考えられニッケル量が
大なるほど顕著であった。(B) Conventional technology A nickel material having a nickel content of about 3 to
The so-called austenitic stainless steel of 20% by weight is generally used. However, during storage of the battery, especially in the positive electrode can electrically connected to the positive electrode, the constituent members dissolve in the electrolytic solution and precipitate on the negative electrode to cause an internal resistance. And, in extreme cases, a perforation phenomenon may occur. The cause was considered to depend on the amount of nickel contained in the stainless steel, and became more remarkable as the amount of nickel increased.
そこで、例えば特公昭55−15067号公報に開示されて
いるように正極缶構成部材としてニッケルをほとんど含
まず応力下での割れ感受性の少ないフェライト系ステン
レス鋼を用いることが提案されたが、この場合にも高温
で長期間保存すると構成部材の溶解現象が認められた。Therefore, for example, as disclosed in Japanese Patent Publication No. 55-15067, it has been proposed to use a ferritic stainless steel containing almost no nickel and having a low susceptibility to cracking under stress as a constituent member of a positive electrode can. Also, when stored at a high temperature for a long time, a dissolution phenomenon of the constituent members was observed.
さて、この種電池は従来の銀電池、アルカリ電池に比
して自己放電が小さいため長期間の使用に耐えうるもの
であり、そのため最近では使用機器側のエレクトロニク
スの発展と相俟って微小電流による長期に亘る放電特性
の安定性が求められるようになってきた。ここで述べる
微小電流とは高々数μＡであるがこのような微小電流放
電下において長期間安定した放電特性を得るためには電
池自身の高信頼性が要求される。This type of battery has a lower self-discharge than conventional silver batteries and alkaline batteries, and thus can withstand long-term use. Therefore, the stability of discharge characteristics over a long period of time has been required. The minute current described here is at most several μA, but in order to obtain long-term stable discharge characteristics under such minute current discharge, high reliability of the battery itself is required.
（ハ）発明が解決しようとする問題点 本発明は高温での長期保存においても正極缶構成部材
の溶解（腐蝕）を抑制しうる非水電解液電池を提供する
ことを目的とする。(C) Problems to be Solved by the Invention It is an object of the present invention to provide a nonaqueous electrolyte battery capable of suppressing dissolution (corrosion) of a positive electrode can constituent member even during long-term storage at a high temperature.
（ニ）問題点を解決するための手段 本発明は、リチウムを活物質とする負極を備えた非水
電解液電池において、正極缶構成部材として硅素を1.2
〜5.0重量％含有するフェライト系ステンレス鋼を用い
ることを特徴とする。(D) Means for Solving the Problems The present invention relates to a nonaqueous electrolyte battery provided with a negative electrode using lithium as an active material.
It is characterized by using a ferritic stainless steel containing up to 5.0% by weight.
（ホ）作用 本発明によれば、詳細な機構については明らかではな
いが、フェライト系ステンレス鋼に含有させた硅素が非
水電解液中において粒界腐蝕感受性を低下させる効果が
あり正極缶構成部材の腐蝕の発生を抑制しうる。尚、硅
素の効果は含有量が1.2〜5.0重量％の時に顕著である。(E) Action According to the present invention, although the detailed mechanism is not clear, the silicon contained in the ferritic stainless steel has the effect of lowering the intergranular corrosion susceptibility in the non-aqueous electrolyte and has a positive electrode can component. Corrosion can be suppressed. The effect of silicon is remarkable when the content is 1.2 to 5.0% by weight.
（ヘ）実施例 以下本発明の一実施例を図面に基づき説明するに、第
１図において（１）はリチウム圧延板を所定形状に打抜
いた負極であってオーステナイト系ステンレス鋼（SUS3
04）よりなる負極缶（２）の内面に固着せる負極集電体
（３）に圧着されている。（４）は活物質としての二酸
化マンガンに、導電剤としてのカーボン粉末及び結着剤
としてのフッ素樹脂粉末を85:10:5の重量比で混合し、
この混合物を成型して得た正極であって、本発明の要旨
とする正極缶（５）の内面に固着せる正極集電体（６）
に圧接されている。(F) Embodiment One embodiment of the present invention will be described below with reference to the drawings. In FIG. 1, (1) is a negative electrode obtained by stamping a lithium rolled plate into a predetermined shape, and is an austenitic stainless steel (SUS3
04), which is crimped to a negative electrode current collector (3) fixed to the inner surface of a negative electrode can (2). (4) mixing manganese dioxide as an active material with carbon powder as a conductive agent and fluororesin powder as a binder in a weight ratio of 85: 10: 5,
A positive electrode obtained by molding the mixture, wherein the positive electrode current collector (6) is fixed to the inner surface of the positive electrode can (5) according to the present invention.
Is pressed against.
ここで正極缶（５）は鉄80重量％、クロム18重量％、
ニッケル０重量％及び硅素２重量％の組成からなるフェ
ライト系ステンレス鋼で構成されている。Here, the positive electrode can (5) is composed of 80% by weight of iron, 18% by weight of chromium,
It is composed of a ferritic stainless steel having a composition of 0% by weight of nickel and 2% by weight of silicon.
尚、（７）は非水電解液を含浸せるセパレータ、
（８）は絶縁パッキングである。(7) is a separator impregnated with a non-aqueous electrolyte,
(8) is an insulating packing.
下表は各種正極缶を用いた電池を60℃において３ケ月
保存後、周波数1KHZで測定した内部インピーダンスを比
較したものであり、（Ａ）は本発明電池、（Ｂ）は硅素
をほとんど含まないフェライト系ステンレス鋼（SUS43
0）を正極缶に用いた第１の比較電池、（Ｃ）はオース
テナイト系ステンレス鋼（SUS304）を正極缶に用いた第
２の比較電池の場合を夫々示す。The following table compares the internal impedance measured at a frequency of 1 KHZ after storing batteries using various positive electrode cans at 60 ° C. for 3 months, (A) the battery of the present invention, and (B) almost no silicon. Ferritic stainless steel (SUS43
0) shows a first comparative battery using a positive electrode can, and (C) shows a second comparative battery using austenitic stainless steel (SUS304) for a positive electrode can.
上表より本発明電池によると高温、保存後の内部イン
ピーダンスは低く、且バラツキも小さいことがわかる。
尚、測定後の各電池の正極缶を走査型電子顕微鏡で観察
したところ比較電池（Ｂ）（Ｃ）の正極缶では腐蝕が見
られたが、本発明電池（Ａ）の正極缶では腐蝕現象は認
められなかった。 From the above table, it can be seen that according to the battery of the present invention, the internal impedance after storage at high temperature is low and the dispersion is small.
In addition, when the positive electrode can of each battery after the measurement was observed with a scanning electron microscope, corrosion was observed in the positive electrode can of the comparative batteries (B) and (C), but the corrosion phenomenon was observed in the positive electrode can of the battery (A) of the present invention. Was not found.
第２図は正極缶構成部材としてのフェライト系ステン
レスに含有せる硅素の含有量と内部インピーダンスとの
関係を示す。尚、測定方法は硅素の含有量を種々変化さ
せたフェライト系ステンレスを正極缶とせる電池を夫々
５ケづつ作成し、60℃で３ケ月保存した後、周波数1KHZ
で内部インピーダンスを測定した。FIG. 2 shows the relationship between the silicon content and the internal impedance contained in the ferritic stainless steel as a positive electrode can constituent member. The measurement method was as follows. Five batteries were made each with a positive electrode can made of ferritic stainless steel with various changes in the silicon content. After storage at 60 ° C for three months, the frequency was 1 KHZ.
Measured the internal impedance.
第２図から硅素の含有量としては1.2〜5.0重量％の範
囲が特に好ましいことがわかる。FIG. 2 shows that the silicon content is particularly preferably in the range of 1.2 to 5.0% by weight.
（ト）発明の効果 上述した如く、リチウムを活物質とする負極を備えた
非水電解液電池において、正極缶構成部材として硅素を
1.2〜5.0重量％含有せるフェライト系ステンレス鋼を用
いることにより、正極缶の腐蝕が抑制され保存特性に優
れた非水電解液電池を得ることができるものであり、そ
の工業的価値は極めて大である。(G) Effect of the Invention As described above, in a nonaqueous electrolyte battery provided with a negative electrode using lithium as an active material, silicon is used as a positive electrode can constituent member.
By using a ferritic stainless steel containing 1.2 to 5.0% by weight, it is possible to obtain a nonaqueous electrolyte battery excellent in storage characteristics by suppressing corrosion of the positive electrode can, and its industrial value is extremely large. is there.
第１図は本発明電池の半断面図、第２図は正極缶を構成
するフェライト系ステンレス鋼の硅素の含有量と内部イ
ンピーダンスとの関係を示す図である。 （１）…負極、（２）…負極缶、（４）…正極、（５）
…正極缶、（７）…セパレータ、（８）…絶縁パッキン
グ。FIG. 1 is a half sectional view of the battery of the present invention, and FIG. 2 is a diagram showing the relationship between the silicon content and the internal impedance of the ferritic stainless steel constituting the positive electrode can. (1): negative electrode, (2) negative electrode can, (4) positive electrode, (5)
... positive electrode can, (7) ... separator, (8) ... insulating packing.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−66559（ＪＰ，Ａ) 特開 昭62−41753（ＪＰ，Ａ) 特開 昭58−158856（ＪＰ，Ａ) 特公 昭59−19984（ＪＰ，Ｂ２) ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-66559 (JP, A) JP-A-62-41753 (JP, A) JP-A-58-158856 (JP, A) 19984 (JP, B2)
Claims (1)
液と、正極とを備え、正極缶構成部材として硅素を1.2
〜5.0重量％含有するフェライト系ステンレス鋼を用い
ることを特徴とする非水電解液電池。1. A negative electrode comprising lithium as an active material, a non-aqueous electrolyte, and a positive electrode.
A nonaqueous electrolyte battery using a ferritic stainless steel containing up to 5.0% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60205560A JP2594034B2 (en) | 1985-09-18 | 1985-09-18 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60205560A JP2594034B2 (en) | 1985-09-18 | 1985-09-18 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6266560A JPS6266560A (en) | 1987-03-26 |
| JP2594034B2 true JP2594034B2 (en) | 1997-03-26 |
Family
ID=16508914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60205560A Expired - Lifetime JP2594034B2 (en) | 1985-09-18 | 1985-09-18 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2594034B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017199909A1 (en) | 2016-05-18 | 2017-11-23 | 日本電気株式会社 | Distributed cooperative information processing device, distributed cooperative information processing method, and recording medium |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58158856A (en) * | 1982-03-16 | 1983-09-21 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolytic battery |
| JPS5919984A (en) * | 1982-07-26 | 1984-02-01 | Olympus Optical Co Ltd | Toner cleaning device |
-
1985
- 1985-09-18 JP JP60205560A patent/JP2594034B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6266560A (en) | 1987-03-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |