JP3138040B2 - Flat lithium secondary battery - Google Patents
Flat lithium secondary batteryInfo
- Publication number
- JP3138040B2 JP3138040B2 JP04003194A JP319492A JP3138040B2 JP 3138040 B2 JP3138040 B2 JP 3138040B2 JP 04003194 A JP04003194 A JP 04003194A JP 319492 A JP319492 A JP 319492A JP 3138040 B2 JP3138040 B2 JP 3138040B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- lithium secondary
- secondary battery
- flat
- metal sheet
- 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 - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Secondary Cells (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、コイン形あるいはボ
タン形などの偏平形の電池ケースに密封されたリチウム
二次電池に関し、特に、例えば４Ｖほどの電圧の高い偏
平形リチウム二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery sealed in a flat battery case such as a coin type or a button type, and more particularly to a flat type lithium secondary battery having a high voltage of, for example, about 4V.
【０００２】[0002]
【従来の技術】例えば、リチウムアルミニウム合金を負
極とし、ＬｉＣｏＯ2 などを正極とする非水電解液電池
のように、４Ｖを超えるような高い電圧のリチウム二次
電池が開発されている。この種の４Ｖ系のリチウム二次
電池はコイン形あるいはボタン形の電池形態で提供され
ることが多い。 2. Description of the Related Art For example, lithium secondary batteries having a high voltage exceeding 4 V, such as a nonaqueous electrolyte battery having a lithium aluminum alloy as a negative electrode and LiCoO 2 or the like as a positive electrode, have been developed. This type of 4V lithium secondary battery is often provided in the form of a coin or button.
【０００３】[0003]
【発明が解決しようとする課題】良く知られているよう
に、コイン形あるいはボタン形の電池は、正極缶の内周
に封口ガスケットを介して負極缶を組み合わせることで
構成される偏平形の電池ケース内に、偏平な正極とセパ
レータと負極とが電解液とともに積層されて密封されて
いる。正極缶および負極缶はステンレスにより構成され
るのが普通である。この構造で前述した４Ｖ系のリチウ
ム二次電池を製作した場合、非水電解液と接しているス
テンレス製正極缶の内面が徐々に腐食するという問題が
あった。つまり、電池電圧が高いため正極缶の電解液と
接する面でステンレス金属のアノード溶解反応が起き、
正極缶内面が徐々に腐食する。この腐食により正極缶と
正極集電体（金属ネット）との接触性が低下し、電池の
内部抵抗が増加する。また正極缶の腐食により電解液中
に溶け出した金属によって電解液の性能が劣化する。As is well known, a coin-shaped or button-shaped battery is a flat battery which is formed by combining an inner periphery of a positive electrode can with a negative electrode can through a sealing gasket. In the case, a flat positive electrode, a separator and a negative electrode are laminated and sealed together with an electrolytic solution. Usually, the positive electrode can and the negative electrode can are made of stainless steel. When the above-described 4V-based lithium secondary battery is manufactured with this structure, there is a problem that the inner surface of the stainless steel positive electrode can in contact with the nonaqueous electrolyte gradually corrodes. In other words, since the battery voltage is high, the anode dissolution reaction of stainless metal occurs on the surface of the positive electrode can that comes into contact with the electrolyte,
The inner surface of the positive electrode can gradually corrodes. This corrosion reduces the contact between the positive electrode can and the positive electrode current collector (metal net), and increases the internal resistance of the battery. In addition, the performance of the electrolytic solution is deteriorated by the metal dissolved in the electrolytic solution due to corrosion of the positive electrode can.
【０００４】そこで金、白金、チタンなどの腐食しにく
い金属で正極缶を構成すれば前記の問題は解消するが、
これはコストの面でまったく現実的ではない。また、ス
テンレス製正極缶の内面を耐食性金属でメッキするとい
う対策も考えられるが、メッキ層にピンホールなどの欠
陥があるとそこから腐食が進むので、欠陥のない高品質
のメッキを施す必要があり、品質管理やコストの面で問
題がある。The above problem can be solved by constructing the positive electrode can with a metal which is hardly corroded, such as gold, platinum and titanium.
This is far from realistic in terms of cost. It is also conceivable to plate the inner surface of the stainless steel positive electrode can with a corrosion-resistant metal.However, if there is a defect such as a pinhole in the plating layer, corrosion will proceed from there. There is a problem in quality control and cost.
【０００５】この発明は前述した従来の問題点に鑑みな
されたもので、その目的は、低コストで簡単に実施する
ことのできる対策により正極缶の内面の腐食を確実に防
止することにある。The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to reliably prevent corrosion of the inner surface of a positive electrode can by means of a measure that can be easily implemented at low cost.
【０００６】[0006]
【課題を解決するための手段】そこでこの発明では、偏
平形リチウム二次電池において正極缶の内底面と正極と
の間に正極缶より分解電圧の高い金属材料からなる腐食
防止用の金属シートを介在し、この金属シートの周縁端
部を正極缶と封口ガスケットとの間に挾み込むようにし
た。Therefore, according to the present invention, in a flat lithium secondary battery, a metal sheet for preventing corrosion made of a metal material having a higher decomposition voltage than the positive electrode can is provided between the inner bottom surface of the positive electrode can and the positive electrode. Intervening, the peripheral edge of this metal sheet
The portion was sandwiched between the positive electrode can and the sealing gasket.
【０００７】[0007]
【作用】前記正極缶の内底面が前記腐食防止用の金属シ
ートによってカバーされ、その金属シートの表面側に正
極や非水電解液が存在することになる。正極缶の内底面
は直接電解液に接しないし、正極缶と金属シートとの界
面に電解液がしみこんできても有効な電界はかからない
ので、腐食反応は起きない。The inner bottom surface of the positive electrode can is covered with the metal sheet for preventing corrosion, and the positive electrode and the non-aqueous electrolyte are present on the surface side of the metal sheet. The inner bottom surface of the positive electrode can is not in direct contact with the electrolytic solution, and no effective electric field is applied even if the electrolytic solution permeates the interface between the positive electrode can and the metal sheet, so that no corrosion reaction occurs.
【０００８】[0008]
【実施例】この発明を適用したＣＲ２０２５（外径２０
mm、総高２．５mm）のリチウム二次電池について図１に
従って説明する。これの基本的な構成は従来とほぼ同様
で、正極缶１の内周に封口ガスケット６を介して負極缶
５を組み合わせることで構成されるコイン形電池ケース
内に、偏平な正極２とセパレータ３と負極とが非水電解
液とともに積層されて密封されている。正極缶１と負極
缶５は共にステンレス（ＳＵＳ４４４）製である。DESCRIPTION OF THE PREFERRED EMBODIMENTS CR2025 (outer diameter 20) to which the present invention is applied
mm, a total height of 2.5 mm) will be described with reference to FIG. The basic configuration of this is almost the same as the conventional one, and a flat positive electrode 2 and a separator 3 are placed in a coin-shaped battery case formed by combining the negative electrode can 5 with the inner periphery of the positive electrode can 1 via a sealing gasket 6. And the negative electrode are laminated and sealed together with the non-aqueous electrolyte. Both the positive electrode can 1 and the negative electrode can 5 are made of stainless steel (SUS444).
【０００９】負極４はリチウムアルミニウム合金の直径
１４mmの円板からなり、負極缶５の内面中央にニッケル
集電体（図示省略）を介して圧着されている。セパレー
タ３はポリプロピレン不織布とポリプロピレンの微孔性
シートからなる。電解液は、プロピレンカーボネイトと
ジメトキシエタンの同量の混合液１リットルに対して１
モルの割合で過塩素酸リチウムを溶解させた非水電解液
を用いる。The negative electrode 4 is made of a disc having a diameter of 14 mm and made of a lithium aluminum alloy, and is pressed to the center of the inner surface of the negative electrode can 5 via a nickel current collector (not shown). The separator 3 is made of a polypropylene nonwoven fabric and a polypropylene microporous sheet. The electrolytic solution is 1 liter per 1 liter of a mixed solution of the same amount of propylene carbonate and dimethoxyethane.
A non-aqueous electrolyte in which lithium perchlorate is dissolved in a molar ratio is used.
【００１０】この実施例では正極缶１の腐食防止用金属
シートとして厚さ０．０３mmのチタンシート７を用いて
いる。チタンシート７は正極缶１の内径とほぼ等しい直
径の円形に裁断され、正極缶１の内底面にスポット溶接
されている。また、このチタンシート７の上に正極集電
体としてのチタンネット８がスポット溶接され、その上
に直径１５mm、重量５００mgの円形の正極２が圧着され
ている。正極２は次のように製作される。Ｌｉ2 ＣＯ3
とＣｏＣＯ3 とをＬｉ：Ｃｏのモル比が１：１となるよ
うに混合したものを６５０℃で１２時間焼成し、さらに
９００℃で１２時間焼成する。これを粉砕し平均粒径５
〜２０μｍの粉末とした。これとアセチレンブラックお
よびテフロンが重量比で６：１：１となるように混練
し、２５メッシュのふるいに通した。これを５００mg秤
量し、直径１５mmの円板形の正極２に成形する。In this embodiment, a 0.03 mm thick titanium sheet 7 is used as a metal sheet for preventing corrosion of the positive electrode can 1. The titanium sheet 7 is cut into a circle having a diameter substantially equal to the inner diameter of the positive electrode can 1 and spot-welded to the inner bottom surface of the positive electrode can 1. Further, a titanium net 8 as a positive electrode current collector is spot-welded on the titanium sheet 7, and a circular positive electrode 2 having a diameter of 15 mm and a weight of 500 mg is crimped thereon. The positive electrode 2 is manufactured as follows. Li 2 CO 3
And CoCO 3 mixed at a molar ratio of Li: Co of 1: 1 are fired at 650 ° C. for 12 hours, and further fired at 900 ° C. for 12 hours. This is crushed and the average particle size is 5
２０20 μm powder. This was kneaded with acetylene black and Teflon in a weight ratio of 6: 1: 1, and passed through a 25-mesh sieve. 500 mg of this is weighed and formed into a disk-shaped positive electrode 2 having a diameter of 15 mm.
【００１１】以上のようにして製作したリチウム二次電
池を４．１Ｖで充電した後、温度６０℃の雰囲気中で保
存し、その内部抵抗の経時変化を測定した。その結果は
図２に示すように、内部抵抗はほとんど変化せず低いレ
ベルに保たれていた。これに対し、チタンシートを用い
ずに、他の構成は前記と同様にして製作した従来の電池
について同じ試験をしたところ、その内部抵抗は図２に
示すように保存日数とともに増大した。これは正極缶１
の腐食によるものと考えられる。The lithium secondary battery manufactured as described above was charged at 4.1 V, stored in an atmosphere at a temperature of 60 ° C., and its internal resistance was measured over time. As a result, as shown in FIG. 2, the internal resistance hardly changed and was kept at a low level. On the other hand, when the same test was performed on a conventional battery manufactured in the same manner as described above without using the titanium sheet, the internal resistance increased with the storage days as shown in FIG. This is the positive electrode can 1
It is thought to be due to corrosion of the steel.
【００１２】次にこの発明の他の実施態様について説明
する。前記の腐蝕防止用金属シートとしてはチタンシー
トに限定されず、厚さ０．１mm以下のアルミニウムシー
トも好適な材料である。また、チタンシートあるいはア
ルミニウムシートに０．１μｍ程度の厚さの金メッキを
施したものを腐蝕防止用のシートとして用いても良い。
金メッキを施したシートを用いる場合は、その導電性が
高いので、チタンネットなどの正極集電体は不必要とな
る。さらに、腐蝕防止用金属シートと封口ガスケットと
の接合界面にシール剤（変性ポリエチレン製のドーナツ
形シートやホットスタンプ接着剤など）を介在させるこ
とで、この部分のシール性が向上し、電解液のまわり込
みや減少を防止することができる。なお、腐蝕防止用金
属シートを正極缶に溶接する必要性は必ずしもない。Next, another embodiment of the present invention will be described. The metal sheet for corrosion prevention is not limited to a titanium sheet, and an aluminum sheet having a thickness of 0.1 mm or less is also a preferable material. Further, a titanium sheet or an aluminum sheet plated with gold having a thickness of about 0.1 μm may be used as a sheet for preventing corrosion.
When a gold-plated sheet is used, its conductivity is high, so that a positive electrode current collector such as a titanium net is unnecessary. In addition, by interposing a sealant (such as a modified polyethylene donut-shaped sheet or a hot stamp adhesive) at the joint interface between the metal sheet for corrosion prevention and the sealing gasket, the sealability of this portion is improved, and It is possible to prevent wraparound and decrease. It is not always necessary to weld the metal sheet for corrosion prevention to the positive electrode can.
【００１３】[0013]
【発明の効果】以上詳細に説明したように、この発明で
は、耐食性の金属材料からなるシートを正極缶の内底面
に敷くように配設し、その上に正極合剤を配置して電解
液を注液するという簡単で安価に実施できる対策によ
り、正極缶の内底面が直接電解液に触れるのを防ぎ、正
極缶がアノード溶解反応によって腐食するのを防止する
ことができる。従って正極缶の腐食による性能低下（内
部抵抗の増大）を簡単に防止することができる。As described [Effect Invention above in detail, in the present invention, it arranged so as lay sheet made of corrosion-resistant metallic material on the inner bottom surface of the positive electrode can, the electrolyte by placing the positive electrode mixture thereon Of the positive electrode can is prevented from directly contacting the electrolytic solution, and the positive electrode can is prevented from being corroded by the anode dissolution reaction. Therefore, performance degradation (increase in internal resistance) due to corrosion of the positive electrode can can be easily prevented.
【図１】この発明の一実施例による偏平形リチウム二次
電池の断面図である。FIG. 1 is a cross-sectional view of a flat lithium secondary battery according to one embodiment of the present invention.
【図２】この発明によるリチウム二次電池と従来のリチ
ウム二次電池との内部抵抗の経時変化を比較して示すグ
ラフである。FIG. 2 is a graph showing a change over time in internal resistance of a lithium secondary battery according to the present invention and a conventional lithium secondary battery.
１ 正極缶 ２ 正極 ３ セパレータ ４ 負極 ５ 負極缶 ６ 封口ガスケット ７ チタンシート ８ チンネット DESCRIPTION OF SYMBOLS 1 Positive electrode can 2 Positive electrode 3 Separator 4 Negative electrode 5 Negative electrode can 6 Sealing gasket 7 Titanium sheet 8 Tin net
───────────────────────────────────────────────────── フロントページの続き (72)発明者 名倉 秀哲 東京都港区新橋５丁目36番11号 富士電 気化学株式会社内 (72)発明者 小川 琢司 東京都港区新橋５丁目36番11号 富士電 気化学株式会社内 (56)参考文献 特開 平５−174873（ＪＰ，Ａ) 特開 昭50−73137（ＪＰ，Ａ) 特開 昭58−137971（ＪＰ，Ａ) 特開 昭63−108662（ＪＰ，Ａ) 実開 昭59−144877（ＪＰ，Ｕ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 10/40 H01M 2/02 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hidenori Nakura 5-36-11 Shimbashi, Minato-ku, Tokyo Inside Fuji Electric Chemical Co., Ltd. (72) Inventor Takuji Ogawa 5-36-11 Shimbashi, Minato-ku, Tokyo (56) References JP-A-5-174873 (JP, A) JP-A-50-73137 (JP, A) JP-A-58-137971 (JP, A) JP-A-63-173 108662 (JP, A) Actually open sho 59-144877 (JP, U) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 10/40 H01M 2/02
Claims (6)
負極缶を組み合わせることで構成される偏平形の電池ケ
ース内に偏平な正極とセパレータと負極とが非水電解液
ともに積層されて密封された偏平形リチウム二次電池で
あって、前記正極缶の内底面と前記正極との間に前記正
極缶より分解電圧の高い金属材料からなる腐蝕防止用の
金属シートが介在され、この金属シートの周縁端部が前
記正極缶と前記封口ガスケットとの間に挾み込まれてい
ることを特徴とする偏平形リチウム二次電池。1. A flat cathode case, a separator and a negative electrode are laminated together with a non-aqueous electrolyte in a flat battery case formed by combining an anode can with an inner periphery of a cathode can via a sealing gasket and sealed. A flat lithium secondary battery, wherein a metal sheet for preventing corrosion made of a metal material having a decomposition voltage higher than that of the positive electrode can is interposed between the inner bottom surface of the positive electrode can and the positive electrode. Characterized in that a peripheral edge of the flat lithium secondary battery is sandwiched between the positive electrode can and the sealing gasket.
０．１mm以下のチタンシートを用いたことを特徴とする
請求項１に記載の偏平形リチウム二次電池。2. The flat lithium secondary battery according to claim 1, wherein a titanium sheet having a thickness of 0.1 mm or less is used as the corrosion preventing metal sheet.
０．１mm以下のアルミニウムシートを用いたことを特徴
とする請求項１に記載の偏平形リチウム二次電池。3. The flat lithium secondary battery according to claim 1, wherein an aluminum sheet having a thickness of 0.1 mm or less is used as the corrosion preventing metal sheet.
またはアルミニウムシートに厚さ０．１μｍ程度の金メ
ッキを施したものを用いたことを特徴とする請求項１に
記載の偏平形リチウム二次電池。4. The flat lithium secondary battery according to claim 1, wherein the metal sheet for corrosion prevention is a titanium or aluminum sheet plated with gold having a thickness of about 0.1 μm.
の内底面に溶接したことを特徴とする請求項１に記載の
偏平形リチウム二次電池。5. The flat lithium secondary battery according to claim 1, wherein the corrosion preventing metal sheet is welded to an inner bottom surface of the positive electrode can.
スケットとの接合界面にシール剤を介在させたことを特
徴とする請求項１に記載の偏平形リチウム二次電池。6. The flat lithium secondary battery according to claim 1, wherein a sealant is interposed at a joint interface between the corrosion preventing metal sheet and the sealing gasket.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04003194A JP3138040B2 (en) | 1992-01-10 | 1992-01-10 | Flat lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04003194A JP3138040B2 (en) | 1992-01-10 | 1992-01-10 | Flat lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05190207A JPH05190207A (en) | 1993-07-30 |
| JP3138040B2 true JP3138040B2 (en) | 2001-02-26 |
Family
ID=11550607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04003194A Expired - Fee Related JP3138040B2 (en) | 1992-01-10 | 1992-01-10 | Flat lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3138040B2 (en) |
-
1992
- 1992-01-10 JP JP04003194A patent/JP3138040B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05190207A (en) | 1993-07-30 |
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