JPS59175570A - Cylindrical type nonaqueous electrolyte battery - Google Patents
Cylindrical type nonaqueous electrolyte batteryInfo
- Publication number
- JPS59175570A JPS59175570A JP58049427A JP4942783A JPS59175570A JP S59175570 A JPS59175570 A JP S59175570A JP 58049427 A JP58049427 A JP 58049427A JP 4942783 A JP4942783 A JP 4942783A JP S59175570 A JPS59175570 A JP S59175570A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- activated alumina
- nonaqueous electrolyte
- electrode group
- prevented
- 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
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、金属リチウムを負極活物質とし、非水電解液
を用いた円筒形非水電解液電池に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a cylindrical nonaqueous electrolyte battery using metallic lithium as a negative electrode active material and a nonaqueous electrolyte.
この種の電池は、負極活物質である金属リチウムが、水
分と反応するのを防止するため、電解液として１００
ｐｐｍ程度に脱水された非水電解液を使用するようＫし
ている。しかし脱水工程や電池への注液時に水分が混入
して水分量が数百ｐｐｍに上昇しやすく、この場合電池
保存中に水分が金属リチウムと反応してガス発生や電池
性能が劣化する問題がある。This type of battery uses 100% electrolyte as an electrolyte to prevent metal lithium, which is the negative electrode active material, from reacting with moisture.
It is recommended to use a non-aqueous electrolyte that has been dehydrated to about ppm. However, water tends to get mixed in during the dehydration process or when pouring into the battery, and the water content can easily rise to several hundred ppm. In this case, the water may react with metallic lithium during battery storage, causing gas generation and deterioration of battery performance. be.
この改善として、渦巻状に巻回した電極群の中央部巻芯
跡にモレキュラーシーブ（示性式％式％
提案されている（特公昭５４−１２６０８号）。As an improvement on this, a molecular sieve has been proposed (Japanese Patent Publication No. 12608/1983) for forming a core trace in the center of a spirally wound electrode group.
この電池によれば、モレキュラーシーブにより非水電解
液中の水分濃度を下げ、金属リチウムと水分との反応を
防止することができる。According to this battery, the molecular sieve can lower the water concentration in the nonaqueous electrolyte and prevent reaction between metallic lithium and water.
しかしモレキュラーシープは、多量のナトリウムイオン
を溶出し、これが負極活物質である金属リチウムの表面
に析出してしまう。このため閉路電圧が低下したシ、内
部抵抗が上昇したシする問題がある。また金属リチウム
表面にナトリウムが析出すれば下式に示すように描量の
リチウムがイオンとなって溶は出し、それだけ容量が劣
化する。However, molecular sheep elutes a large amount of sodium ions, which are deposited on the surface of metallic lithium, which is the negative electrode active material. Therefore, there are problems in that the closed circuit voltage decreases and the internal resistance increases. Furthermore, if sodium precipitates on the surface of metallic lithium, a certain amount of lithium becomes ions and dissolves, as shown in the equation below, and the capacity deteriorates accordingly.
Ｎａ′１′−１−Ｌ ｉ−＋Ｎａ↓＋Ｌ１＋更にナトリ
ウムの析出が進み、樹枝状となるとセパレータを突き抜
は内部短絡を起こす欠点ｉｘある。Na'1'-1-L i-+Na↓+L1+ Further, the precipitation of sodium progresses, and when it becomes dendritic, it has the disadvantage of causing an internal short circuit if it pierces the separator.
本発明は、この問題に鑑みナトリウムの溶出がほとんど
ない脱水剤を使用することにより、容量劣化を防ぐこと
ができる円筒形非水電解液電池を得ることを目的とする
。 ″
すなわち本発明は渦巻状に巻回した電極群の巻芯防空間
部に、モレキュラーシー′と同等な水分吸着能力を持ち
しかもナトリウムイオンの溶出のほとんど々い活性アル
ミナを充填することとを特徴とする。In view of this problem, the present invention aims to provide a cylindrical nonaqueous electrolyte battery that can prevent capacity deterioration by using a dehydrating agent that hardly releases sodium. '' In other words, the present invention is characterized in that the core space of the spirally wound electrode group is filled with activated alumina, which has a moisture adsorption capacity equivalent to that of molecular sea, and which elutes almost no sodium ions. shall be.
以下本発明を図面を参照して説明する。The present invention will be explained below with reference to the drawings.
第１図は本発明に係る円筒形非水電解液電池の半裁図で
ある。この電池は、負極端子を兼ねる電池容器Ｚ内に渦
巻状に巻回さｉ″ｌ−た電極群２を収容し、この電極群
２の中央に形成されだ巻芯防空間部に活性アルミナ３を
充填してシト水電解液を注液し、電池容器１の開口部に
封口板４を介して正極端子５を取付け、封口している。FIG. 1 is a half-cut diagram of a cylindrical non-aqueous electrolyte battery according to the present invention. This battery houses a spirally wound electrode group 2 in a battery container Z which also serves as a negative electrode terminal, and an activated alumina 3 The battery container 1 is filled with aqueous electrolyte, and a positive electrode terminal 5 is attached to the opening of the battery container 1 via a sealing plate 4 to seal it.
なお図中６，７はそれぞれ絶縁板である。Note that 6 and 7 in the figure are insulating plates, respectively.
この電池において、電極群２は、二酸化マンガン、酸化
銀などの酸化物、フッ化炭素、フッ化銅などのフッ化物
を主成分とした帯状正極８と、金購リチウムからなる帯
状負極９とをポリプロピレン等の不織布からなるセ・ぐ
レータ１０を介して渦巻状（ｃ巻回して構成されている
。非水電解液は、グロビレンカーボネート、ジメトキシ
エタン、γ−ブチルラクトン等の非水溶媒に過塩素酸リ
チウム、ホウフッ化リチウム等の予め脱水した無機塩を
溶解した電解液である。In this battery, the electrode group 2 includes a strip-shaped positive electrode 8 mainly composed of oxides such as manganese dioxide and silver oxide, and fluorides such as carbon fluoride and copper fluoride, and a strip-shaped negative electrode 9 made of lithium gold. The non-aqueous electrolyte is formed into a spiral (c-wound) via a separator 10 made of a non-woven fabric such as polypropylene. This is an electrolytic solution in which pre-dehydrated inorganic salts such as lithium chlorate and lithium fluoroborate are dissolved.
しかして巻芯防空間部に充填する活性アルミナ３は、充
分に乾燥させて活性度を高くすることが好ましい。捷た
、活性アルミナ３のうち水に浸漬された時浸漬した液が
酸性または中性を示すものは、ナトリウムイオン溶出量
がよシ少なく、好適である。このことは以下に示す実躾
により明らかとなった。Therefore, it is preferable that the activated alumina 3 filled in the core space is sufficiently dried to increase its activity. Among the splintered activated aluminas 3, those whose immersion liquid is acidic or neutral when immersed in water are preferable because they elute a small amount of sodium ions. This was made clear through the training shown below.
実施例
酸性、中性及び塩基性を示す各種活性アルミナ４ｆを、
電解液（ｆロビレンカーゼネイト。Examples Various types of activated alumina 4f exhibiting acidity, neutrality and basicity,
Electrolyte (f Robylene Casenate.
ジメトキシエタンを１＝１の体積比に混合し、この混合
液に１モルの過塩素酸１ノチウムを溶解した電解液）
１０ ｍｌに浸け、１０日間室温で放置した後、電解液
のナトリウムイオン量を調べだ。その結果を第１表に示
す。An electrolytic solution in which dimethoxyethane is mixed at a volume ratio of 1=1 and 1 mole of notium perchlorate is dissolved in this mixture)
After soaking in 10 ml of electrolyte and leaving it at room temperature for 10 days, the amount of sodium ions in the electrolyte was determined. The results are shown in Table 1.
また比較のためモレキュラーシーブ４ｆについても同じ
組成の電解液に浸け、ナト１ノウムイオン量を調べた。For comparison, molecular sieve 4f was also immersed in an electrolytic solution having the same composition, and the amount of sodium ions was investigated.
その結果を第１表に併＝己する。The results are included in Table 1.
なお活性アルミナの酸性、中性、塩基性というのは、そ
の活性アルミナを蒸留水に浸漬した時、浸漬しだ液がそ
れぞれ酸性、中性、塩基性を示すものをいう。Note that the acidity, neutrality, and basicity of activated alumina mean that when the activated alumina is immersed in distilled water, the immersion liquid exhibits acidity, neutrality, and basicity, respectively.
第 １ 表
上表から活性アルミナは、ナトリウムイオンの溶出量が
ほとんどなく、とくに酸性及び中性のものが好適である
ことがわかる。From Table 1, it can be seen that activated alumina has almost no elution of sodium ions, and acidic and neutral activated alumina are particularly suitable.
なお活性アルミナ３は多孔質で、電解液が入シ込むため
、電解液が少なくなる問題はない。Note that since the activated alumina 3 is porous and the electrolyte infiltrates therein, there is no problem of the electrolyte becoming insufficient.
次に本発明の実施例につき説明する。Next, examples of the present invention will be described.
実施例１
正極活物質として二酸化マンガン、負極活物質としてリ
チウム、電解液としてノロピレンカーボネートとジメト
キシエタンを１：１の体積比で混合した混合液に過塩素
酸リチウムを１モル溶解させたものを使用し、巻芯防空
間部によく乾燥させた酸性の活性アルミナを充填して、
径１６．５個、高さ３３Ｍの″２ＡＡ型電池（本発明電
池Ａ）を作製した。Example 1 One mole of lithium perchlorate was dissolved in a mixture of manganese dioxide as a positive electrode active material, lithium as a negative electrode active material, and nolopyrene carbonate and dimethoxyethane as an electrolyte in a volume ratio of 1:1. Fill the core space with well-dried acidic activated alumina.
2AA type batteries (battery A of the present invention) having a diameter of 16.5 and a height of 33M were produced.
またこれと比較するために他の条件を同じとして巻芯防
空間部にモレキュラーシーブ４Ａを充填した電池Ｂ及び
巻芯防空間部になにも充填しない電池Ｃを作製した。In addition, in order to compare with this, a battery B in which the core space prevention part was filled with molecular sieve 4A and a battery C in which the core space prevention part was not filled with anything were prepared under the same conditions.
このようにして得られた電池Ａ−Ｃにつき、製造直後に
６００の抵抗を負荷して連続放電曲線を調べた。その結
果を第２図に曲線Ａ−Ｃで示す。Immediately after manufacture, a resistance of 600 Ω was applied to the batteries A-C thus obtained, and the continuous discharge curves were examined. The results are shown in FIG. 2 by curves A-C.
第２図から本発明に係る電池及びモレキュラーシープを
充填した比較電池は、いずれも放電特性が良好で、電池
容量が大きいことがわかる。From FIG. 2, it can be seen that both the battery according to the present invention and the comparative battery filled with molecular sheep have good discharge characteristics and large battery capacities.
実施例２
実施例１と同じ構造の電池Ａ−Ｃを作製し、４５℃で２
ケ月間保存後、６０Ωの抵抗を負荷した。その放電特性
を第３図に曲線Ａ−Ｃで示す。Example 2 Batteries A-C having the same structure as Example 1 were manufactured and heated at 45°C for 2 hours.
After storage for several months, a resistance of 60Ω was loaded. The discharge characteristics are shown in FIG. 3 by curve A-C.
第３図から明らかなように、比較電池Ｃでは、電池製造
時に入った水分と保存中に正極合剤から溶出する水分に
より電池容量の低下が顕著に表われている。また比較電
池Ｂでは保存中にナトリウムがリチウム表面に析出する
だめ端子電圧が下がり、電池容量も減少（，２ている。As is clear from FIG. 3, in Comparative Battery C, the battery capacity was significantly reduced due to moisture introduced during battery manufacture and moisture eluted from the positive electrode mixture during storage. In addition, in comparative battery B, sodium precipitates on the lithium surface during storage, so the terminal voltage decreases and the battery capacity also decreases (.2).
これに対し本発明電池Ａでは、放電面ＩＷＡが第２図の
曲線Ａに示した貯蔵前のものとほとんど変らず、保存に
よる劣化がない。On the other hand, in the battery A of the present invention, the discharge surface IWA is almost the same as that shown by the curve A in FIG. 2 before storage, and there is no deterioration due to storage.
以上説明したように本発明によれは活性アルミナを巻芯
防空間部に充填することにより、電池を保存した場合の
電池性能容量の劣化を防止することができる顕著な効果
を奏する。As explained above, the present invention provides a remarkable effect of preventing deterioration of battery performance and capacity when the battery is stored by filling the core space prevention part with activated alumina.
第１図は本発明の一実施例を示す円筒形非水電解液電池
の半裁図、第２図は製造直後における本発明電池の放電
特性を比較電池の放電特性とともに示す特性図、第３図
は貯蔵した不発明電池の放電特性を比較電池の放電特性
とともに示す特性図である。
ｌ・・・電池容器、２・・・電極群、３・・・活性アル
ミナ、４・・・封口板、５・・・正極端子、６，７・・
・絶縁板、８・・・帯状正極、９・・・帯状負極、１θ
・・・セ・やレータ。
出願人代理人 弁理士 鈴 江 武 彦第１図Figure 1 is a half-cut diagram of a cylindrical non-aqueous electrolyte battery showing an example of the present invention, Figure 2 is a characteristic diagram showing the discharge characteristics of the battery of the present invention immediately after manufacture together with the discharge characteristics of a comparative battery. FIG. 2 is a characteristic diagram showing the discharge characteristics of a stored non-inventive battery together with the discharge characteristics of a comparative battery. l... Battery container, 2... Electrode group, 3... Activated alumina, 4... Sealing plate, 5... Positive electrode terminal, 6, 7...
・Insulating plate, 8... Strip-shaped positive electrode, 9... Strip-shaped negative electrode, 1θ
... Se-yareta. Applicant's agent Patent attorney Takehiko Suzue Figure 1
Claims (2)
／（’レータを介して渦巻状に巻回した電極群と、同電
極群の中央に形成された巻芯跡空間部に充填された活性
アルミナと、非水電解液とを、円筒形容器内に収納した
ことを特徴とする円筒形非水電解液電池。(1) An electrode group in which a band-shaped positive electrode and a band-shaped negative electrode made of metal lithium are spirally wound through a separator, and a core trace space formed in the center of the electrode group is filled. A cylindrical nonaqueous electrolyte battery characterized in that activated alumina and a nonaqueous electrolyte are housed in a cylindrical container.
だは中性を示すものであることを特徴とする特許請求の
範囲第１項記載の円筒形非水電解電池。(2) The cylindrical non-aqueous electrolytic battery according to claim 1, wherein when the activated alumina is immersed in water, the immersion liquid is acidic but neutral.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58049427A JPS59175570A (en) | 1983-03-24 | 1983-03-24 | Cylindrical type nonaqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58049427A JPS59175570A (en) | 1983-03-24 | 1983-03-24 | Cylindrical type nonaqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59175570A true JPS59175570A (en) | 1984-10-04 |
| JPH0349180B2 JPH0349180B2 (en) | 1991-07-26 |
Family
ID=12830793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58049427A Granted JPS59175570A (en) | 1983-03-24 | 1983-03-24 | Cylindrical type nonaqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59175570A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999034471A1 (en) * | 1997-12-26 | 1999-07-08 | Tonen Corporation | Electrolyte for lithium cells and method of producing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5859564A (en) * | 1981-09-15 | 1983-04-08 | ヴアルタ・バツテリ−・アクチエン・ゲゼルシヤフト | Battery |
-
1983
- 1983-03-24 JP JP58049427A patent/JPS59175570A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5859564A (en) * | 1981-09-15 | 1983-04-08 | ヴアルタ・バツテリ−・アクチエン・ゲゼルシヤフト | Battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999034471A1 (en) * | 1997-12-26 | 1999-07-08 | Tonen Corporation | Electrolyte for lithium cells and method of producing the same |
| JP4646399B2 (en) * | 1997-12-26 | 2011-03-09 | 三和油化工業株式会社 | Electrolytic solution for lithium battery and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0349180B2 (en) | 1991-07-26 |
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