JPH0644968A - Battery - Google Patents
BatteryInfo
- Publication number
- JPH0644968A JPH0644968A JP19695492A JP19695492A JPH0644968A JP H0644968 A JPH0644968 A JP H0644968A JP 19695492 A JP19695492 A JP 19695492A JP 19695492 A JP19695492 A JP 19695492A JP H0644968 A JPH0644968 A JP H0644968A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- aluminum
- negative electrode
- alloy
- aluminum alloy
- 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
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
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アルミニウム又はアル
ミニウム合金を主体とした負極を有する電池に関し、特
に負極の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a battery having a negative electrode mainly composed of aluminum or an aluminum alloy, and more particularly to improvement of the negative electrode.
【０００２】[0002]
【従来の技術】アルミニウム，亜鉛，鉄等の金属を負極
活物質として使用する電池としては、金属−空気電池等
が挙げられる。この金属−空気電池は、正極活物質とし
て空気中の酸素が、電解液として水酸化ナトリウム水溶
液が用いられており、一般にエネルギー密度が高いのが
特長である。これら金属−空気電池は充電の仕方によっ
て、以下の二つに大別される。即ち、通常の二次電池と
同様電気的に充電する型と，放電によって消費された負
極を新しい負極に取り替える機械的充電型（メカニカル
チャージ方式）とに大別される。特に、アルミニウムを
負極活物質として使用するアルミニウム−空気電池は、
アルミニウム負極の放電生成物の電解還元による再生が
むずかしいため、後者の型のみが検討対象とされてき
た。この場合、アルミニウム負極の過電圧の低減，及び
利用率の向上を図るため、アルミニウムに少量のＩｎ，
Ｍｎ，Ｇａ，Ｍｇ等の金属元素を添加させたアルミニウ
ム合金が使用されることもある。2. Description of the Related Art As a battery using a metal such as aluminum, zinc or iron as a negative electrode active material, there is a metal-air battery. This metal-air battery uses oxygen in the air as a positive electrode active material and an aqueous sodium hydroxide solution as an electrolytic solution, and is generally characterized by high energy density. These metal-air batteries are roughly classified into the following two types depending on the charging method. That is, it is roughly classified into an electrically charged type similar to a normal secondary battery and a mechanically charged type (mechanical charge type) in which a negative electrode consumed by discharging is replaced with a new negative electrode. In particular, an aluminum-air battery using aluminum as the negative electrode active material,
Since the regeneration of the discharge product of the aluminum negative electrode by electrolytic reduction is difficult, only the latter type has been considered. In this case, in order to reduce the overvoltage of the aluminum negative electrode and improve the utilization rate, a small amount of In,
An aluminum alloy to which a metal element such as Mn, Ga or Mg is added may be used.
【０００３】[0003]
【発明が解決しようとする課題】ところが、上記アルミ
ニウム−空気電池等の負極として用いられるアルミニウ
ム合金（又はアルミニウム）は、合金中にイオン半径の
異なる金属が混入されている等の理由によって、結晶が
歪んでいる。したがって、結晶が歪んでいる分だけ空気
中の酸素によって酸化（腐食）されやすく、これを負極
として使用する電池は保存特性が悪いという課題を有し
ていた。However, the aluminum alloy (or aluminum) used as the negative electrode of the aluminum-air battery or the like has a crystallized state because of the fact that the alloys are mixed with metals having different ionic radii. It is distorted. Therefore, there is a problem that the crystal is distorted and is easily oxidized (corroded) by oxygen in the air, and a battery using this as a negative electrode has poor storage characteristics.
【０００４】本発明は上記課題に鑑み、アルミニウム合
金等の腐食を抑制しつつ、保存特性に優れた電池を提供
することを目的とする。In view of the above problems, it is an object of the present invention to provide a battery having excellent storage characteristics while suppressing the corrosion of aluminum alloys and the like.
【０００５】[0005]
【課題を解決するための手段】本発明は上記課題を解決
するため、正極と，負極と，両極間に介在せしめた電解
液とから成る電池において、上記負極は、結晶性が良好
なアルミニウム又はアルミニウム合金から成ることを特
徴とする。また、上記結晶性が良好なアルミニウム又は
アルミニウム合金は、不均一歪の値が0.０１２以下であ
ることを特徴とする。In order to solve the above-mentioned problems, the present invention provides a battery comprising a positive electrode, a negative electrode, and an electrolytic solution interposed between both electrodes, wherein the negative electrode is made of aluminum or aluminum having good crystallinity. It is characterized by being made of an aluminum alloy. The aluminum or aluminum alloy having good crystallinity is characterized in that the value of non-uniform strain is 0.012 or less.
【０００６】[0006]
【作用】上記構成の如く、結晶性が良好なアルミニウム
又はアルミニウム合金を負極として使用した電池は、保
存特性が向上する。この理由は明らかではないが、アル
ミニウム又はアルミニウム合金の結晶性が良好であれ
ば、結晶の歪みが少ないため、アルミニウム等が腐食さ
れにくくなるからであると思われる。As described above, a battery using aluminum or aluminum alloy having good crystallinity as a negative electrode has improved storage characteristics. The reason for this is not clear, but it is considered that if the crystallinity of aluminum or an aluminum alloy is good, the distortion of the crystal is small and the aluminum or the like is less likely to be corroded.
【０００７】また、アルミニウム合金等の不均一歪につ
いて検討した結果、不均一歪の値が0.０１２以下であれ
ば、上記と同様の理由により保存特性が向上する。Further, as a result of studying the non-uniform strain of an aluminum alloy or the like, if the value of the non-uniform strain is 0.012 or less, the storage characteristics are improved for the same reason as above.
【０００８】[0008]
〔実施例１〕図１は本発明の一実施例に係る扁平型非水
電解液電池の断面図であり、ステンレススチールから成
る負極外装缶１の内底面にはＡｌ−Ｇａ合金から成る負
極２が圧着されている。上記負極外装缶１の周端はポリ
オレフィン製の絶縁パッキング３の内部に固定されてお
り、この絶縁パッキング３の外周にはステンレススチー
ルから成る正極外装缶４が固定されている。この正極外
装缶４の内底面には電解二酸化マンガンを活物質とする
正極５が固定されており、この正極５と前記負極２との
間には、ポリプロピレン製不織布より成り電解液が含浸
されたセパレータ６が介挿されている。前記電解液に
は、0.５Ｍ ＡｌＣｌ3 を含むＭＦＡ（ｎ−メチルホル
ムアミド）を用いている。尚、本電池の寸法は直径２0.
０mm，厚み2.５mmである。[Example 1] Fig. 1 is a cross-sectional view of a flat type non-aqueous electrolyte battery according to an example of the present invention. A negative electrode outer can 1 made of stainless steel has a negative electrode 2 made of an Al-Ga alloy on the inner bottom surface thereof. Is crimped. A peripheral end of the negative electrode outer can 1 is fixed inside an insulating packing 3 made of polyolefin, and a positive electrode outer can 4 made of stainless steel is fixed to the outer periphery of the insulating packing 3. A positive electrode 5 having electrolytic manganese dioxide as an active material is fixed to the inner bottom surface of the positive electrode case 4, and an electrolytic solution made of polypropylene nonwoven fabric is impregnated between the positive electrode 5 and the negative electrode 2. The separator 6 is inserted. MFA (n-methylformamide) containing 0.5 M AlCl 3 is used as the electrolytic solution. The size of this battery is 20.
The thickness is 0 mm and the thickness is 2.5 mm.
【０００９】ここで、上記正極５を以下のようにして作
製した。電解二酸化マンガン９０重量％に、導電剤とし
て黒鉛５重量％，及び結着剤としてフッ素樹脂粉末５重
量％を加えて混合した後、この混合物を加圧成型して、
直径１5.０mm，厚み1.５mmの成型体を得た。この成型体
を２５０℃〜３５０℃の温度で熱処理して正極５とし
た。Here, the positive electrode 5 was manufactured as follows. To 90% by weight of electrolytic manganese dioxide, 5% by weight of graphite as a conductive agent and 5% by weight of fluororesin powder as a binder were added and mixed, and then the mixture was pressure-molded,
A molded body having a diameter of 15.0 mm and a thickness of 1.5 mm was obtained. This molded body was heat-treated at a temperature of 250 ° C to 350 ° C to obtain a positive electrode 5.
【００１０】一方、上記負極２は以下のようにして作製
した。先ず、既知の方法にて製造された１重量％のガリ
ウムを含むアルミニウム合金を、アルゴン不活性雰囲気
のアーク溶解炉内で溶解した後、冷却した。続いて、こ
のＡｌ−Ｇａ合金を所定の寸法に切断して、直径１2.０
mm，厚み0.５mmの負極２を作製した。On the other hand, the negative electrode 2 was manufactured as follows. First, an aluminum alloy containing 1% by weight of gallium manufactured by a known method was melted in an arc melting furnace in an argon inert atmosphere, and then cooled. Then, this Al-Ga alloy is cut into a predetermined size to have a diameter of 12.0.
A negative electrode 2 having a thickness of 0.5 mm and a thickness of 0.5 mm was prepared.
【００１１】このようにして作製した電池を以下、（Ａ
1 ）電池と称する。 〔実施例２〜４〕Ａｌ−Ｇａ合金の代わりに、Ａｌ−Ｓ
ｎ合金，Ａｌ−Ｃａ合金，及びＡｌ−Ｚｎ合金をそれぞ
れ用いる他は、上記実施例１と同様にして電池を作製し
た。このようにして作製した電池を以下、それぞれ（Ａ
2 ）電池〜（Ａ4 ）電池と称する。 〔実施例５〕Ａｌ−Ｇａ合金の代わりにＡｌ−Ｃｕ合金
を用い、且つ、アニール処理を施する他は、上記実施例
１と同様にして電池を作製した。The battery thus produced is described below in (A
1 ) Called battery. [Examples 2 to 4] Instead of Al-Ga alloy, Al-S
A battery was manufactured in the same manner as in Example 1 except that the n alloy, the Al-Ca alloy, and the Al-Zn alloy were used. The batteries produced in this way are respectively described below (A
2 ) Battery to (A 4 ) battery. [Example 5] A battery was produced in the same manner as in Example 1 except that an Al-Cu alloy was used instead of the Al-Ga alloy and annealing treatment was performed.
【００１２】このようにして作製した電池を以下、（Ａ
5 ）電池と称する。 〔比較例〕Ａｌ−Ｇａ合金の代わりに、Ａｌ−Ｃｕ合金
を用る他は、上記実施例１と同様にして電池を作製し
た。このようにして作製した電池を以下、（Ｘ）電池と
称する。 〔実験１〕上記本発明の（Ａ1 ）電池〜（Ａ4 ）電池，
及び比較例の（Ｘ）電池を用いて、Ｈａｌｌ法による不
均一歪の値，及び３か月後の容量保存率を調べたので、
その結果を表１，及び図２に示す。また、本発明の（Ａ
3 ）電池，及び比較例の（Ｘ）電池については、１か月
後，２か月後，３か月後の容量保存率を調べたので、そ
の結果を図３に示す。尚、容量保存率は放置温度６０
℃，電流0.０２５Ｃ，電池電圧1.０Ｖまで容量を確認
し、Ａｌ合金は１０％アノード溶解後使用した。ここ
で、不均一歪とは、以下のように定義される。 ・不均一歪の定義 ラウエカメラ等でデバイ環を測定した際、このデバイ環
がブロードになるという現象の原因の一つであって、下
記数１により定義される。The battery thus produced is described below in (A
5 ) Called battery. [Comparative Example] A battery was produced in the same manner as in Example 1 except that an Al-Cu alloy was used instead of the Al-Ga alloy. The battery thus manufactured is hereinafter referred to as (X) battery. [Experiment 1] (A 1 ) battery to (A 4 ) battery of the present invention,
Using the (X) battery of Comparative Example, the value of the non-uniform strain by the Hall method and the capacity storage rate after 3 months were examined.
The results are shown in Table 1 and FIG. In addition, (A of the present invention
3 ) With respect to the battery and the battery (X) of the comparative example, the capacity preservation rates after 1 month, 2 months and 3 months were examined, and the results are shown in FIG. In addition, the capacity preservation rate is 60
The capacity was confirmed up to ℃, current 0.025C, battery voltage 1.0V. Al alloy was used after 10% anodic dissolution. Here, the non-uniform strain is defined as follows. -Definition of non-uniform strain This is one of the causes of the phenomenon that the Debye ring becomes broad when the Debye ring is measured with a Laue camera or the like, and is defined by the following mathematical formula 1.
【００１３】[0013]
【数１】 [Equation 1]
【００１４】η：不均一歪 λ：測定Ｘ線波長 β：積分幅 θ：回折線のブラッグ角 ε：結晶格子の平均の大きさΗ: non-uniform strain λ: measured X-ray wavelength β: integral width θ: Bragg angle of diffraction line ε: average size of crystal lattice
【００１５】[0015]
【表１】 [Table 1]
【００１６】表１，及び図２から明らかなように、本発
明の（Ａ1 ）電池〜（Ａ4 ）電池は比較例の（Ｘ）電池
に比べて、いずれも容量保存率が向上していることが認
められる。これは、本発明の（Ａ1 ）電池〜（Ａ5 ）電
池は不均一歪の値がいずれも0.０１２０以下であること
から、結晶性が良好であるためと思われる。また、図３
から明らかなように、比較例の（Ｘ）電池は１か月放置
後から急激に容量保存率が減少し、３か月放置後には約
５０％にまで容量保存率が減少するのに対し、本発明の
（Ａ3 ）電池は３か月放置後でも殆ど容量保存率が減少
していないことが認められる。As can be seen from Table 1 and FIG. 2, the batteries (A 1 ) to (A 4 ) of the present invention each have a higher capacity storage ratio than the battery (X) of the comparative example. It is recognized that It is considered that this is because the (A 1 ) battery to (A 5 ) battery of the present invention each have a nonuniform strain value of 0.0120 or less, and therefore have good crystallinity. Also, FIG.
As is clear from the comparison, the (X) battery of the comparative example shows a rapid decrease in the capacity retention rate after being left for 1 month, and a capacity retention rate of about 50% after being left for 3 months. It can be seen that the (A 3 ) battery of the present invention has almost no decrease in capacity storage ratio even after being left for 3 months.
【００１７】尚、Ａｌ−Ｇａ合金，Ａｌ−Ｓｎ合金，Ａ
ｌ−Ｃａ合金，及びＡｌ−Ｚｎ合金はいずれもアニール
処理を施していないが、アニール処理を施すことにより
本発明の（Ａ1 ）電池〜（Ａ4 ）電池の容量保存率は更
に向上するものと思われる。 〔実験２〕上記本発明の（Ａ5 ）電池，及び比較例の
（Ｘ）電池を用いて、Ｈａｌｌ法による不均一歪の値，
及び１か月後，２か月後，３か月後の容量保存率を調べ
たので、その結果を表２，及び図４に示す。尚、不均一
歪の値，及び容量保存率は上記実験１と同様の条件で測
定した。Al-Ga alloy, Al-Sn alloy, A
Neither the l-Ca alloy nor the Al-Zn alloy has been subjected to annealing treatment, but by subjecting it to annealing treatment, the capacity preservation ratios of the (A 1 ) battery to (A 4 ) battery of the present invention are further improved. I think that the. [Experiment 2] Using the (A 5 ) battery of the present invention and the (X) battery of the comparative example, the value of the non-uniform strain by the Hall method,
The capacity preservation rates after 1 month, 2 months and 3 months were examined, and the results are shown in Table 2 and FIG. The value of the non-uniform strain and the capacity retention rate were measured under the same conditions as in Experiment 1 above.
【００１８】[0018]
【表２】 [Table 2]
【００１９】図４から明らかなように、本発明の
（Ａ5 ）電池は比較例の（Ｘ）電池に比べて、容量保存
率が向上していることが認められる。これは、表２から
も明らかなように、アニール処理を施すことによって不
均一歪みの値が小さくなることから、本発明の（Ａ5 ）
電池は比較例の（Ｘ）電池に比べて合金の結晶性が良好
であるためと思われる。As is apparent from FIG. 4, the capacity preservation ratio of the (A 5 ) battery of the present invention is improved as compared with the battery of the comparative example (X). This is because, as is clear from Table 2, the value of the non-uniform strain is reduced by performing the annealing treatment, and therefore (A 5 ) of the present invention is used.
It is considered that the battery has better crystallinity of the alloy than the battery (X) of the comparative example.
【００２０】〔その他の事項〕 上記実施例においては、第２金属元素として、Ｇ
ａ，Ｓｎ，Ｃａ，Ｚｎ，Ｃｕ等を添加したが、本発明は
何らこれに限定されるものではなく、例えば、Ｉｎ等を
添加することも勿論可能である。 また、第２金属元素（Ｇａ，Ｓｎ，Ｃａ，Ｃｕ，Ｚ
ｎ等）の添加量はいずれも１重量％であるが、本発明は
何らこれに限定されるものではない。[Other Matters] In the above embodiment, the second metal element is G
Although a, Sn, Ca, Zn, Cu and the like are added, the present invention is not limited to this, and it is of course possible to add In or the like. In addition, the second metal element (Ga, Sn, Ca, Cu, Z
The addition amount of (n, etc.) is 1% by weight, but the present invention is not limited thereto.
【００２１】[0021]
【発明の効果】以上の本発明によれば、アルミニウム又
はアルミニウム合金の結晶性が良好でであるので、アル
ミニウム等が腐食されにくくなり、電池の保存特性が向
上するといった優れた効果を奏する。As described above, according to the present invention, since the crystallinity of aluminum or aluminum alloy is good, aluminum or the like is less likely to be corroded and the storage characteristics of the battery are improved.
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明の一実施例に係る扁平型非水電解液電池
の断面図である。FIG. 1 is a cross-sectional view of a flat type non-aqueous electrolyte battery according to an embodiment of the present invention.
【図２】本発明の（Ａ1 ）電池〜（Ａ4 ）電池と，比較
例の（Ｘ）電池とにおける３か月後の容量保存率を示す
グラフである。FIG. 2 is a graph showing the capacity preservation ratios of the (A 1 ) battery to (A 4 ) battery of the present invention and the (X) battery of the comparative example after 3 months.
【図３】本発明の（Ａ3 ）電池と，比較例の（Ｘ）電池
とにおける、１か月後，２か月後，３か月後の容量保存
率を示すグラフである。FIG. 3 is a graph showing the capacity preservation ratios of the (A 3 ) battery of the present invention and the (X) battery of the comparative example after 1 month, 2 months, and 3 months.
【図４】本発明の（Ａ5 ）電池と，比較例の（Ｘ）電池
とにおける、１か月後，２か月後，３か月後の容量保存
率を示すグラフである。FIG. 4 is a graph showing the capacity preservation ratios of the (A 5 ) battery of the present invention and the (X) battery of the comparative example after 1 month, 2 months, and 3 months.
２ 負極 ５ 正極 2 Negative electrode 5 Positive electrode
───────────────────────────────────────────────────── フロントページの続き (72)発明者 武江 正夫 守口市京阪本通２丁目18番地 三洋電機株 式会社内 (72)発明者 水瀧 房吾 守口市京阪本通２丁目18番地 三洋電機株 式会社内 (72)発明者 松浦 義典 守口市京阪本通２丁目18番地 三洋電機株 式会社内 (72)発明者 古川 修弘 守口市京阪本通２丁目18番地 三洋電機株 式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Masao Takee, 2-18 Keihan Hondori, Moriguchi City Sanyo Electric Co., Ltd. (72) Inventor, Shugo Mizutaki 2-18, Keihan Hondori, Moriguchi Sanyo Electric Co., Ltd. Inside the ceremony company (72) Inventor Yoshinori Matsuura 2-18 Keihan Hondori, Moriguchi Sanyo Electric Co., Ltd. Inside the formula company (72) Inoue Nobuhiro Furukawa 2-18 Keihan Hondori, Moriguchi Sanyo Electric Co., Ltd.
Claims (2)
た電解液とから成る電池において、 上記負極は、結晶性が良好なアルミニウム又はアルミニ
ウム合金から成ることを特徴とする電池。1. A battery comprising a positive electrode, a negative electrode, and an electrolytic solution interposed between both electrodes, wherein the negative electrode is made of aluminum or an aluminum alloy having good crystallinity.
アルミニウム合金は、不均一歪の値が0.０１２以下であ
ることを特徴とする請求項１記載の電池。2. The battery according to claim 1, wherein the aluminum or aluminum alloy having good crystallinity has a non-uniform strain value of 0.012 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19695492A JPH0644968A (en) | 1992-07-23 | 1992-07-23 | Battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19695492A JPH0644968A (en) | 1992-07-23 | 1992-07-23 | Battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0644968A true JPH0644968A (en) | 1994-02-18 |
Family
ID=16366421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19695492A Pending JPH0644968A (en) | 1992-07-23 | 1992-07-23 | Battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0644968A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3886221A4 (en) * | 2018-11-22 | 2022-08-03 | Sumitomo Chemical Company Limited | Negative-electrode active material for non-aqueous electrolyte secondary cell, negative electrode, cell, and laminate |
-
1992
- 1992-07-23 JP JP19695492A patent/JPH0644968A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3886221A4 (en) * | 2018-11-22 | 2022-08-03 | Sumitomo Chemical Company Limited | Negative-electrode active material for non-aqueous electrolyte secondary cell, negative electrode, cell, and laminate |
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