JPS62226574A - Zinc chloride dry battery - Google Patents
Zinc chloride dry batteryInfo
- Publication number
- JPS62226574A JPS62226574A JP6876986A JP6876986A JPS62226574A JP S62226574 A JPS62226574 A JP S62226574A JP 6876986 A JP6876986 A JP 6876986A JP 6876986 A JP6876986 A JP 6876986A JP S62226574 A JPS62226574 A JP S62226574A
- Authority
- JP
- Japan
- Prior art keywords
- zinc chloride
- positive electrode
- electrolyte
- zinc
- electrode mixture
- 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
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 title claims abstract description 96
- 239000011592 zinc chloride Substances 0.000 title claims abstract description 48
- 235000005074 zinc chloride Nutrition 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 39
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011701 zinc Substances 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 239000008151 electrolyte solution Substances 0.000 claims description 11
- 239000011149 active material Substances 0.000 claims description 3
- 230000002093 peripheral effect Effects 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 230000003247 decreasing effect Effects 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract 1
- 208000028659 discharge Diseases 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000003575 carbonaceous material Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution 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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
- H01M6/08—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with cup-shaped electrodes
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、塩化亜鉛を主成分とする電解液を用いる円
筒形のマンガン乾電池（以下、塩化亜鉛系乾電池と称す
る）の改良に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an improvement in a cylindrical manganese dry battery (hereinafter referred to as a zinc chloride dry battery) that uses an electrolyte containing zinc chloride as a main component.
（従来の技術）
一般的な塩化亜鉛系乾電池は、負極亜鉛缶の内面にセパ
レータを配し、その内部に二酸化マンガンを活物質とす
る正極合剤を充填し、この正極合剤層の中心に正極集電
棒を挿入した内部構造になっている。そして上記セパレ
ータと上記正極合剤に塩化亜鉛を主成分とする電解液が
含まれている。(Prior technology) A typical zinc chloride dry battery has a separator arranged on the inner surface of a negative electrode zinc can, and a positive electrode mixture containing manganese dioxide as an active material is filled inside the separator, and the center of this positive electrode mixture layer is It has an internal structure in which a positive electrode current collector rod is inserted. The separator and the positive electrode mixture contain an electrolytic solution containing zinc chloride as a main component.
ここで正極合剤層の組成は均一であり、約２０％程度の
導電性炭素質が均一に含まれているとともに、約２５％
程度の塩化亜鉛濃度の電解液が均一に含まれている。Here, the composition of the positive electrode mixture layer is uniform, and approximately 20% of conductive carbon is uniformly contained, and approximately 25% of conductive carbon is uniformly contained.
The electrolyte solution with a zinc chloride concentration of about 100% is uniformly contained.
（発明が解決しようとする問題点）
塩化亜鉛系乾電池は、塩化アンモニウム系の旧来のマン
ガン乾電池に比べると急速放電（高負荷放電）や低温で
の放電性能に優れているが、アルカリ電池などと比較し
た場合は、高負荷放電特性が劣り、この面でのより一層
の性能向上が望まれている。(Problems to be solved by the invention) Zinc chloride-based dry batteries are superior in rapid discharge (high-load discharge) and low-temperature discharge performance compared to traditional ammonium chloride-based manganese dry batteries, but they are superior to alkaline batteries, etc. When compared, the high-load discharge characteristics are inferior, and further improvement in performance in this aspect is desired.
従来の塩化亜鉛系乾電池の放電反応を詳しく研究した結
果、特に高負荷連続放電の際に、放電末期には正極合剤
層の塩化亜鉛濃度の著しい減少がみられ、二酸化マンガ
ンや水分の未反応分に比べて塩化亜鉛が不十分な状態と
なり、これによって端子電圧が著しく低下することが分
った。As a result of detailed research on the discharge reaction of conventional zinc chloride-based dry batteries, we found that, especially during high-load continuous discharge, the concentration of zinc chloride in the positive electrode mixture layer decreased significantly at the end of discharge, resulting in unreacted manganese dioxide and water. It was found that the amount of zinc chloride was insufficient compared to the actual amount of zinc chloride, which resulted in a significant drop in terminal voltage.
塩化亜鉛系乾電池の放電反応は水を消費する。The discharge reaction of zinc chloride dry batteries consumes water.
特に放電初期においては水の消費量が多い。このことか
ら正極合剤には水分を多聞に含有させている。しかし放
電未明においては、電解質である塩化亜鉛の」が不足し
、水分は十分にあるという状態になっている。Particularly in the early stages of discharge, water consumption is large. For this reason, the positive electrode mixture contains a large amount of water. However, in the early hours of discharge, there is a shortage of zinc chloride, an electrolyte, and there is sufficient water.
この発明は上述した研究結果に基づいてなされたもので
、その目的は、塩化亜鉛系乾電池の放電性能、特に高負
荷連続放電での放電性能を従来より向上させることにあ
る。This invention was made based on the above-mentioned research results, and its purpose is to improve the discharge performance of zinc chloride dry batteries, especially the discharge performance under high load continuous discharge, compared to the conventional ones.
（問題点を解決するための手段）
そこでこの発明では、正極合剤の負極亜鉛缶に近い外周
側の領域に塩化亜鉛濃度の比較的小さい電解液を含ませ
、正極合剤の正極集電棒に近い中心側の領域に塩化亜鉛
の比較的大きい電解液を含ませた。(Means for Solving the Problems) Therefore, in this invention, an electrolytic solution with a relatively low concentration of zinc chloride is impregnated in the outer circumferential region of the positive electrode mixture near the negative electrode zinc can, and the positive electrode current collector rod of the positive electrode mixture is The region near the center contained a relatively large electrolyte of zinc chloride.
（作 用）
上記正極合剤の外周側の領域は、放電初期において使わ
れる十分な過の水分を供給する。上記正極合剤の中心側
の領域は、放電末期において不足しがちになる塩化亜鉛
を十分に供給する。(Function) The area on the outer circumferential side of the positive electrode mixture supplies sufficient excess water to be used in the initial stage of discharge. The region on the center side of the positive electrode mixture sufficiently supplies zinc chloride, which tends to be insufficient at the end of discharge.
（実施例）
図はこの発明による塩化亜鉛系乾電池の外装前の状態を
示している。１０は有底円筒形の負極亜鉛缶、１２は負
極亜鉛缶１０の内周面および底面に密着配器されたセパ
レータ、１４ａと１４ｂは二酸化マンガンを活物質とす
る正極合剤、１６は中心側の正極合剤１４ｂに挿入され
た炭素棒からなる正極集電棒、１８は正極集電棒１６を
中心に突出させて負極亜鉛缶１０の上端開口部を塞ぐ封
口ガスケットである。(Example) The figure shows the state of the zinc chloride dry battery according to the present invention before being packaged. 10 is a cylindrical negative electrode zinc can with a bottom, 12 is a separator closely arranged on the inner peripheral surface and bottom surface of the negative electrode zinc can 10, 14a and 14b are positive electrode mixtures containing manganese dioxide as an active material, and 16 is a center side A positive electrode current collector rod 18 made of a carbon rod inserted into the positive electrode mixture 14b is a sealing gasket that protrudes from the positive electrode current collector rod 16 and closes the upper end opening of the negative electrode zinc can 10.
セパレータ１２と正極合剤１４ａ、１４ｂには、主電解
質としての塩化亜鉛と少量の塩化アンモニウムとを水に
溶解した電解液が含浸されている。The separator 12 and the positive electrode mixtures 14a and 14b are impregnated with an electrolytic solution in which zinc chloride as a main electrolyte and a small amount of ammonium chloride are dissolved in water.
この電解液の塩化亜鉛濃度については以下に説明する。The zinc chloride concentration of this electrolyte will be explained below.
正極合剤１４ａ、１４ｂは、二酸化マンガンとＩ電性炭
素！！ｊ（アセチレンブラックや黒鉛粉末）と上述の電
解液とを混合して円筒形に加圧成形したものであるが、
この実施例においては、負極亜鉛缶１０に近い外側部分
１４ａの導電性炭素質の含有率を高くするとともに’Ｒ
Ｍ液の塩化亜鉛濃度を小さくし、正極集電棒１６に近い
内側部分１４ｂの導電性炭素質の含有率を低くするとと
もに電解液の塩化亜鉛１１ｉ１度を大きくしている。The positive electrode mixtures 14a and 14b are manganese dioxide and I-electrocarbon! ! j (acetylene black or graphite powder) and the above-mentioned electrolyte are mixed and pressure-molded into a cylindrical shape.
In this embodiment, the content of conductive carbon in the outer portion 14a near the negative electrode zinc can 10 is increased, and 'R
The zinc chloride concentration of the M solution is reduced, the content of conductive carbonaceous material in the inner portion 14b near the positive electrode current collector rod 16 is reduced, and the zinc chloride concentration of the electrolytic solution is increased.
具体的には、外側の正極合剤層１４ａにおいては、二酸
化マンガン１に対して導電性炭素質を１／４とし、また
電解液の塩化亜鉛濃度を２６．４％にしている。一方、
内側の正極合剤層１４ｂにおいては、二酸化マンガン１
に対して導電性炭素質を１／９とし、また電解液の塩化
亜鉛濃度を３３．３％としている。Specifically, in the outer positive electrode mixture layer 14a, the conductive carbonaceous material is set to 1/4 of the manganese dioxide 1, and the zinc chloride concentration of the electrolytic solution is set to 26.4%. on the other hand,
In the inner positive electrode mixture layer 14b, manganese dioxide 1
The conductive carbonaceous material is set to 1/9 of that, and the zinc chloride concentration of the electrolyte is set to 33.3%.
上述した本発明の実施例による単一型電池を本発明品Ａ
とする。これに対して同じ大きさの単一型電池で、正極
合剤層における導電性炭素質が二酸化マンガン１に対し
て１／６と均一で、また２６．４％の塩化亜鉛濃度の電
解液が均一に含まれた乾電池を従来品Ｂとする。The single type battery according to the embodiment of the present invention described above is referred to as the present invention product A.
shall be. On the other hand, in a single battery of the same size, the conductive carbon in the positive electrode mixture layer is uniform at 1/6 to 1 part manganese dioxide, and the electrolyte has a zinc chloride concentration of 26.4%. A dry battery that is uniformly contained is referred to as conventional product B.
本発明品Ａと従来品Ｂとについて、同じ条件で４Ω連続
放電の試験を行なった結果、従来品Ｂの放電時間が１１
４０分であったのに対し、本発明品Ａの放電時間は１３
２０分となり、明らかな性能向上が認められた。As a result of conducting a 4Ω continuous discharge test under the same conditions for product A of the present invention and conventional product B, the discharge time of conventional product B was 11
The discharge time of product A of the present invention was 13 minutes, whereas the discharge time was 40 minutes.
It took 20 minutes, and a clear improvement in performance was observed.
前述したように、放電初期においては反応による水分消
費が多いが、負極亜鉛缶１０に近い正極合剤ＩＥ１４ａ
の電解液の塩化亜鉛濃度が小さいので（その分だけ水分
が多い）、必要な水分は遅滞なく供給され、放電特性は
良好である。As mentioned above, in the early stage of discharge, there is a lot of water consumption due to the reaction, but the positive electrode mixture IE14a, which is close to the negative electrode zinc can 10,
Since the concentration of zinc chloride in the electrolyte is small (and the water content is correspondingly large), the necessary water is supplied without delay, and the discharge characteristics are good.
一方、放電末期において、従来の電池では正極合剤層に
おける塩化亜鉛が不足し、その結果端子電圧が著しく低
下していた。ところが本発明のものにおいては、放電末
期において消費される内側の正極合剤層１４ｂに、塩化
亜鉛濃度の大きい電解液を含ませているので、塩化亜鉛
の不足現象はおきず、二酸化マ、ンガンや水の未反応分
とつりあった量が保たれている。その結果前述のように
放常時間が長くなるのである。On the other hand, at the end of discharge, in conventional batteries, zinc chloride in the positive electrode mixture layer was insufficient, resulting in a significant drop in terminal voltage. However, in the case of the present invention, since the inner positive electrode mixture layer 14b, which is consumed at the end of discharge, contains an electrolytic solution with a high concentration of zinc chloride, there is no shortage of zinc chloride, and no shortage of zinc chloride occurs. The amount is maintained in balance with the unreacted portion of water and water. As a result, the exposure time becomes longer as described above.
なお上記の実施例においては、外側の正極合剤ｆｆ１４
ａの導電性炭素質の比率を大きくしているため、この部
分の抵抗値が小さくなるとともに、この部分に多量の電
解液を保持することができることから合剤内部へのイオ
ン伝導がよくなり、急速放電時の抵抗分極および濃度分
極を小さくするのに大いに効果がある。In the above example, the outer positive electrode mixture ff14
Since the ratio of conductive carbonaceous material in a is increased, the resistance value of this part is reduced, and since a large amount of electrolyte can be held in this part, ion conduction into the mixture is improved, It is highly effective in reducing resistance polarization and concentration polarization during rapid discharge.
また内側の正極合剤層１４ｂの二酸化マンガンの比率を
大きくしているが、この部分の二酸化マンガンは低率放
電で放電深度が高くなった時に有効に活用され、電池容
量を高める効果がある。ただし、二酸化マンガンが多い
と電解液の保持量゛が比較的小さくなる。しかしこの部
分に含まれる電解液の塩化亜鉛濃度が大きいので、必要
な塩化亜鉛の旦を確保できる。Furthermore, the ratio of manganese dioxide in the inner positive electrode mixture layer 14b is increased, and the manganese dioxide in this portion is effectively utilized when the depth of discharge becomes high due to low rate discharge, and has the effect of increasing battery capacity. However, if the amount of manganese dioxide is large, the amount of electrolyte retained will be relatively small. However, since the electrolyte contained in this portion has a high concentration of zinc chloride, the necessary amount of zinc chloride can be secured.
本発明は上述した実施例に限定されるものではなく、正
極合剤における二酸化マンガンと導電性炭素質の比率は
均一とし、°電解液の塩化亜鉛濃度のみを変えるように
してもよい。また上記実施例では正極合剤層を塩化亜Ｋ
） １度の面で外側と内側の二層に分けているが、これ
を三層以上に分けて、段階的に塩化亜鉛濃度を変化させ
てもよい。The present invention is not limited to the embodiments described above, and the ratio of manganese dioxide and conductive carbonaceous material in the positive electrode mixture may be made uniform, and only the zinc chloride concentration of the electrolyte solution may be changed. In addition, in the above embodiment, the positive electrode mixture layer was made of sodium chloride.
) Although one layer is divided into two layers, an outer layer and an inner layer, it is also possible to divide this layer into three or more layers and change the zinc chloride concentration stepwise.
（発明の効果）
以上訂■に説明したように、この発明にあっては、正極
合剤層の外周側で電解液の塩化亜鉛濃度を小さくし、内
周側で大きくするという簡単な改良手段により、この種
の塩化亜鉛系乾電池の放電性能が向上し、特に高負荷連
続放電の際の放電末期にお【プる端子電圧の低下を少な
くし、放電時間を長くすることができる。(Effects of the Invention) As explained in the above section 2, this invention employs a simple improvement method of reducing the zinc chloride concentration of the electrolyte on the outer circumferential side of the positive electrode mixture layer and increasing it on the inner circumferential side. As a result, the discharge performance of this type of zinc chloride dry battery is improved, and in particular, the drop in terminal voltage at the end of discharge during high-load continuous discharge can be reduced, and the discharge time can be lengthened.
図はこの発明の一実施例による塩化亜鉛系乾電池の断面
図である。
１０・・・負極亜鉛缶 １２・・・セパレータ１４
ａ・・・外側の正極合剤層
１４ｂ・・・内側の正極合剤層The figure is a sectional view of a zinc chloride dry battery according to an embodiment of the present invention. 10...Negative electrode zinc can 12...Separator 14
a...Outer positive electrode mixture layer 14b...Inner positive electrode mixture layer
Claims (1)
に二酸化マンガンを活物質とする正極合剤を充填し、こ
の正極合剤層の中心に正極集電棒を挿入した構造で、上
記セパレータと上記正極合剤に塩化亜鉛を主成分とする
電解液を含ませた塩化亜鉛系乾電池において、上記正極
合剤の上記負極亜鉛缶に近い外周側の領域に塩化亜鉛濃
度の比較的小さい電解液を含ませ、上記正極合剤の上記
正極集電棒に近い中心側の領域に塩化亜鉛濃度の比較的
大きい電解液を含ませたことを特徴とする塩化亜鉛系乾
電池。(1) A separator is arranged on the inner surface of a negative electrode zinc can, a positive electrode mixture containing manganese dioxide as an active material is filled inside the separator, and a positive electrode current collector rod is inserted into the center of this positive electrode mixture layer. In a zinc chloride dry battery in which the positive electrode mixture contains an electrolytic solution containing zinc chloride as a main component, an electrolytic solution with a relatively low concentration of zinc chloride is contained in the outer peripheral region of the positive electrode mixture near the negative electrode zinc can. A zinc chloride-based dry battery, characterized in that an electrolytic solution having a relatively high concentration of zinc chloride is contained in a central region of the positive electrode mixture near the positive electrode current collector rod.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61068769A JPH0711964B2 (en) | 1986-03-28 | 1986-03-28 | Zinc chloride battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61068769A JPH0711964B2 (en) | 1986-03-28 | 1986-03-28 | Zinc chloride battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62226574A true JPS62226574A (en) | 1987-10-05 |
| JPH0711964B2 JPH0711964B2 (en) | 1995-02-08 |
Family
ID=13383268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61068769A Expired - Lifetime JPH0711964B2 (en) | 1986-03-28 | 1986-03-28 | Zinc chloride battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0711964B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51136141A (en) * | 1975-05-20 | 1976-11-25 | Matsushita Electric Ind Co Ltd | Dry element battery |
| JPS5220231A (en) * | 1975-08-08 | 1977-02-16 | Toshiba Ray O Vac | Layerrbuilt dry element battery |
-
1986
- 1986-03-28 JP JP61068769A patent/JPH0711964B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51136141A (en) * | 1975-05-20 | 1976-11-25 | Matsushita Electric Ind Co Ltd | Dry element battery |
| JPS5220231A (en) * | 1975-08-08 | 1977-02-16 | Toshiba Ray O Vac | Layerrbuilt dry element battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0711964B2 (en) | 1995-02-08 |
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