JP2006164862A - Alkaline battery - Google Patents
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- JP2006164862A JP2006164862A JP2004357621A JP2004357621A JP2006164862A JP 2006164862 A JP2006164862 A JP 2006164862A JP 2004357621 A JP2004357621 A JP 2004357621A JP 2004357621 A JP2004357621 A JP 2004357621A JP 2006164862 A JP2006164862 A JP 2006164862A
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000003349 gelling agent Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- DEIVNMVWRDMSMJ-UHFFFAOYSA-N hydrogen peroxide;oxotitanium Chemical compound OO.[Ti]=O DEIVNMVWRDMSMJ-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000004972 metal peroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、二酸化マンガンを活物質とする正極およびアルカリ電解液を具備するアルカリ電池に関するものである。 The present invention relates to an alkaline battery including a positive electrode using manganese dioxide as an active material and an alkaline electrolyte.
近年、アルカリマンガン電池などの一次電池の用途は拡大され、例えばデジタルスチルカメラのように強負荷放電性能を要求する用途が増えて来ている。このような市場のニーズに対しては、例えば特許文献１のように、正極用添加剤としてアナターゼ形の酸化チタンまたは酸化チタンを主体とする複合酸化物を使用することにより、正極の反応効率を上げ、強負荷放電性能を向上させる方法が提案されている。 In recent years, applications of primary batteries such as alkaline manganese batteries have been expanded, and applications requiring high load discharge performance, such as digital still cameras, have increased. For such market needs, for example, as in Patent Document 1, anatase-type titanium oxide or a composite oxide mainly composed of titanium oxide is used as a positive electrode additive, thereby improving the reaction efficiency of the positive electrode. And a method for improving the heavy load discharge performance has been proposed.
また、例えば特許文献２のように、正極用添加剤としてＴｉxＳｉ(1-x)Ｏ2（式中、０．５≦ｘ＜１）で表されるチタンケイ素複合酸化物やＴｉＯ（ＯＨ）2を使用することにより、軽負荷放電特性の低下を抑制する方法も提案されている。
上記のような従来の正極添加剤を使ったアルカリ電池においては、強負荷放電特性は向上するものの、軽負荷放電特性が低下してしまうという問題がある。アルカリ電池は、従来のマンガン電池のように、時計など低負荷で使われることもある汎用電池であるため、軽負荷放電特性が低下してしまうことは非常に不都合である。 In the alkaline battery using the conventional positive electrode additive as described above, although the heavy load discharge characteristic is improved, there is a problem that the light load discharge characteristic is deteriorated. Since the alkaline battery is a general-purpose battery that is sometimes used at a low load such as a watch like a conventional manganese battery, it is very inconvenient that the light-load discharge characteristics deteriorate.
上記課題を解決するため、本発明のアルカリ電池は、二酸化マンガンを活物質とする正極、負極およびアルカリ電解液を具備し、前記正極が、窒化チタン（ＴｉＮ）及び三酸化二コバルト（Ｃｏ2Ｏ3）よりなる群から選ばれた少なくとも一種の添加剤を含むことを特徴とする。
ここで、正極は、前記添加剤を、二酸化マンガン１００重量部あたり０．０５〜５重量部含むことが好ましい。
To solve the above problem, an alkaline battery of the present invention, the positive electrode of manganese dioxide as an active material, comprising a negative electrode and an alkaline electrolyte, wherein the positive electrode, a titanium nitride (TiN) and trioxide cobalt (Co 2 O 3 ) It contains at least one additive selected from the group consisting of:
Here, the positive electrode preferably contains 0.05 to 5 parts by weight of the additive per 100 parts by weight of manganese dioxide.
窒化チタン及び三酸化二コバルトは、正極合剤内の導電性を向上するとともに、電解液の浸透性の向上に寄与し、強負荷放電時の分極を低減する。これによって、強負荷放電特性のみならず低負荷放電特性をも向上する。 Titanium nitride and dicobalt trioxide improve the conductivity in the positive electrode mixture, contribute to improving the permeability of the electrolytic solution, and reduce polarization during heavy load discharge. This improves not only the heavy load discharge characteristics but also the low load discharge characteristics.
本発明によれば、強負荷放電特性に優れ、なおかつ軽負荷放電特性が従来のアルカリ電池よりも向上したアルカリ電池を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the alkaline battery which was excellent in the heavy load discharge characteristic and also improved the light load discharge characteristic rather than the conventional alkaline battery can be provided.
本発明のアルカリ電池は、負極と、アルカリ電解液と、二酸化マンガンおよび黒鉛粉末を含む正極とを具備し、前記正極が、窒化チタン及び三酸化二コバルトよりなる群から選ばれた少なくとも一種を含むことを特徴とする。
負極は、亜鉛を主成分とする合金粉末を用い、ゲル化剤によりゲル亜鉛負極を形成したものが好ましい。しかし、アルカリ水溶液中で卑な電位を示し、放電可能かつ安定な金属であればよく、その金属に防食性、安定性のために他の金属や有機または無機の添加剤を添加したものであってもよい。
電解液は、水酸化カリウムを主成分とするアルカリ水溶液であることが好ましい。水酸化ナトリウムや水酸化リチウム、水酸化カルシウムを含んでもよい。
The alkaline battery of the present invention includes a negative electrode, an alkaline electrolyte, and a positive electrode including manganese dioxide and graphite powder, and the positive electrode includes at least one selected from the group consisting of titanium nitride and dicobalt trioxide. It is characterized by that.
The negative electrode is preferably an alloy powder containing zinc as a main component and a gel zinc negative electrode formed by a gelling agent. However, any metal that shows a base potential in an aqueous alkaline solution and can be discharged and is stable and has other metals and organic or inorganic additives added to the metal for corrosion resistance and stability. May be.
The electrolytic solution is preferably an alkaline aqueous solution mainly composed of potassium hydroxide. Sodium hydroxide, lithium hydroxide, or calcium hydroxide may be included.
正極の活物質は、二酸化マンガンを主成分として用いることが好ましい。例えば、オキシ水酸化ニッケルなどの他の金属過酸化物、金属酸化物、または金属水酸化物を少量もしくは主成分として含んでもよい。正極の導電剤としては、黒鉛粉末を用いることが好ましい。他の炭素系導電剤などを含んでもよい。 The positive electrode active material is preferably made of manganese dioxide as a main component. For example, other metal peroxides such as nickel oxyhydroxide, metal oxides, or metal hydroxides may be contained in a small amount or as a main component. As the conductive agent for the positive electrode, it is preferable to use graphite powder. Other carbon-based conductive agents may be included.
正極と負極との間には、セパレータとしては耐アルカリ性の合成樹脂などの不織布を介在することが好ましい。その他多孔膜など電解液を透過するものを用いてもよい。
電池の外装には、通常、鉄にメッキを施した円筒形ケースを用いた電池が一般的であるが、材質は合成樹脂でもよく、形状も規定するものではない。
It is preferable to interpose a nonwoven fabric such as an alkali-resistant synthetic resin as a separator between the positive electrode and the negative electrode. In addition, you may use what permeate | transmits electrolyte solution, such as a porous film.
Generally, a battery using a cylindrical case in which iron is plated is generally used as the battery exterior. However, the material may be a synthetic resin, and the shape is not specified.
正極は、前記添加剤を二酸化マンガン１００重量部あたり０．０５〜５重量部含むことが好ましい。添加量が０．０５重量部より少ないと、強負荷放電及び軽負荷放電特性の向上が不十分であり、５重量部より多い場合、正極活物質などの充填量が減ってしまうために強負荷放電及び軽負荷放電特性が低下してしまう。これは、添加剤粒子が主たる活物質である二酸化マンガンよりも嵩高いために、一定圧力下で、一定体積となるように成形された正極合剤においては、合剤総量が少なくなるためと考えられる。ただし、添加剤量が二酸化マンガン１００重量部あたり０．０５〜５重量部の範囲であれば、二酸化マンガンの粒子と添加剤粒子がうまく混ざり合うため、正極活物質の充填量が減ることはない。 The positive electrode preferably contains 0.05 to 5 parts by weight of the additive per 100 parts by weight of manganese dioxide. If the addition amount is less than 0.05 parts by weight, the improvement of the heavy load and light load discharge characteristics is insufficient, and if it is more than 5 parts by weight, the filling amount of the positive electrode active material and the like decreases, resulting in a heavy load. Discharge and light load discharge characteristics deteriorate. This is because the additive particles are bulkier than manganese dioxide, which is the main active material, and therefore the total amount of the mixture is reduced in the positive electrode mixture formed to have a constant volume under a constant pressure. It is done. However, if the amount of the additive is in the range of 0.05 to 5 parts by weight per 100 parts by weight of manganese dioxide, the manganese dioxide particles and the additive particles are mixed well, so the filling amount of the positive electrode active material does not decrease. .
本発明は、強負荷放電特性に優れ、かつ軽負荷放電特性が従来のアルカリ電池よりも向上したアルカリ電池を提供することができる。
以下、本発明の実施の形態を説明する。
INDUSTRIAL APPLICABILITY The present invention can provide an alkaline battery that is excellent in heavy load discharge characteristics and has improved light load discharge characteristics over conventional alkaline batteries.
Embodiments of the present invention will be described below.
実施の形態１
Ａｌを３０ｐｐｍ、Ｂｉを２００ｐｐｍ、Ｉｎを４００ｐｐｍ含む亜鉛合金と４０重量％のＫＯＨ水溶液からなる電解液とを混合、攪拌してゲル状亜鉛を作製する。一方、電解二酸化マンガンと黒鉛粉末を重量比９：１の割合で混合し、さらに、二酸化マンガン１００重量部あたり１重量部のＴｉＮを加え、成形して正極合剤を作製する。これらの負極および正極に、アルカリ電解液および合成樹脂の不織布からなるセパレータを組み合わせて正極ケース内に収め、密閉してアルカリ電池を作製する。
Embodiment 1
A zinc alloy containing 30 ppm of Al, 200 ppm of Bi, and 400 ppm of In and an electrolytic solution composed of 40 wt% KOH aqueous solution is mixed and stirred to produce gelled zinc. On the other hand, electrolytic manganese dioxide and graphite powder are mixed at a weight ratio of 9: 1, and 1 part by weight of TiN is further added per 100 parts by weight of manganese dioxide, followed by forming a positive electrode mixture. These negative electrode and positive electrode are combined with a separator made of a non-woven fabric of an alkaline electrolyte and a synthetic resin, and are placed in a positive electrode case and sealed to produce an alkaline battery.
実施の形態２
電解二酸化マンガンと黒鉛粉末とを重量比９：１の割合で混合し、さらに二酸化マンガン１００重量部あたり１重量部のＣｏ2Ｏ3を加え、成形して正極合剤を作製する。この他は実施の形態１と同様にしてアルカリ電池を作製する。
Electrolytic manganese dioxide and graphite powder are mixed at a weight ratio of 9: 1, and 1 part by weight of Co 2 O 3 is further added per 100 parts by weight of manganese dioxide, followed by molding to prepare a positive electrode mixture. Otherwise, the alkaline battery is fabricated in the same manner as in the first embodiment.
以下、本発明のより具体的な実施例について説明するが、本発明はこれらのみに限定されるものではない。
本発明の実施例において作製したアルカリ電池の一部を断面にした正面図を図１に示す。図１において、電池ケース１の内部には、短筒状のペレット形状に成形された正極合剤２、セパレータ４およびゲル状負極３が収容されている。電池ケース１は、内面にニッケルメッキが施された鋼のケースなどを用いることができる。電池ケース１の内面には、複数個の正極合剤２が密着した状態で収容されている。正極合剤２のさらに内側にはセパレータ４が配され、さらにその内側にゲル状負極３が充填されている。
Hereinafter, although the more concrete Example of this invention is described, this invention is not limited only to these.
FIG. 1 is a front view showing a cross section of a part of an alkaline battery produced in an example of the present invention. In FIG. 1, a
正極合剤２はつぎのようにして作製した。まず、二酸化マンガンと黒鉛とアルカリ電解液とを重量比９０：１０：３の割合で混合し、得られた混合物を充分に撹拌した後、フレーク状に圧縮成形した。ついで、フレーク状の正極合剤を粉砕して顆粒状の正極合剤とし、これを篩によって分級し、１０〜１００メッシュのものを中空円筒形に加圧成形してペレット状の正極合剤２を得た。この正極合剤２個を電池ケース１内に挿入し、加圧治具によって正極合剤２を再成形して、電池ケース１の内壁に密着させた。実施例のいずれの正極についても成形圧力は同じ条件で作製し、この時成形された正極合剤の高さが同じになるように各実施例の正極合剤量を調整した。
The
上記のようにして電池ケース１内に配置された正極合剤２の中央に、有底円筒形のセパレータ４を配置し、セパレータ４内へ所定量のアルカリ電解液を注入した。所定時間経過後、アルカリ電解液とゲル化剤と亜鉛合金粉末とからなるゲル状負極３をセパレータ４内へ充填した。
A bottomed cylindrical separator 4 was placed in the center of the
ゲル状負極３としては、ゲル化剤であるポリアクリル酸ナトリウム１重量部、水酸化カリウムの４０重量％水溶液３３重量部および亜鉛粉末６６重量部からなるゲルを用いた。また、セパレータ４は、ポリビニルアルコール繊維とレーヨン繊維を主体として混抄した不織布を用いた。 As the gelled negative electrode 3, a gel composed of 1 part by weight of sodium polyacrylate as a gelling agent, 33 parts by weight of a 40% by weight aqueous solution of potassium hydroxide and 66 parts by weight of zinc powder was used. Moreover, the separator 4 used the nonwoven fabric which mixed and mixed mainly the polyvinyl alcohol fiber and the rayon fiber.
続いて、負極集電子６をゲル状負極３の中央に差し込んだ。なお、負極集電子６には、ガスケット５および負極端子を兼ねる底板７を一体化させた。そして、電池ケース１の開口端部を、ガスケット５の端部を介して、底板７の周縁部にかしめつけ、電池ケース１の開口部を封口した。最後に、外装ラベル８で電池ケース１の外表面を被覆して、アルカリ電池を得た。
Subsequently, the negative electrode
《実施例１》
二酸化マンガンと黒鉛粉末とを重量比９：１の割合で混合し、これにＴｉＮを二酸化マンガン１００重量部あたり１．０重量部添加して正極合剤を作製した。この正極合剤を用いて図１に示す構造を有するアルカリ電池を作製した。
Example 1
Manganese dioxide and graphite powder were mixed at a weight ratio of 9: 1, and 1.0 part by weight of TiN was added to 100 parts by weight of manganese dioxide to prepare a positive electrode mixture. Using this positive electrode mixture, an alkaline battery having the structure shown in FIG. 1 was produced.
《実施例２》
ＴｉＮの代わりにＣｏ2Ｏ3を添加した正極合剤を用いた以外は実施例１と同様にしてアルカリ電池を作製した。
Example 2
An alkaline battery was fabricated in the same manner as in Example 1 except that a positive electrode mixture to which Co 2 O 3 was added instead of TiN was used.
《比較例１》
二酸化マンガンと黒鉛粉末との混合物（重量比９：１）を正極合剤に用いた以外は実施例１と同様にしてアルカリ電池を作製した。
<< Comparative Example 1 >>
An alkaline battery was produced in the same manner as in Example 1 except that a mixture of manganese dioxide and graphite powder (weight ratio 9: 1) was used as the positive electrode mixture.
《比較例２》
ＴｉＮの代わりにアナターゼ型ＴｉＯ2を添加した正極合剤を用いた以外は実施例１と同様にしてアルカリ電池を作製した。
<< Comparative Example 2 >>
An alkaline battery was produced in the same manner as in Example 1 except that a positive electrode mixture in which anatase TiO 2 was added instead of TiN was used.
《比較例３》
ＴｉＮの代わりにＴｉＯ（ＯＨ）2を添加した正極合剤を用いた以外は実施例１と同様にしてアルカリ電池を作製した。
<< Comparative Example 3 >>
An alkaline battery was produced in the same manner as in Example 1 except that a positive electrode mixture to which TiO (OH) 2 was added instead of TiN was used.
《比較例４》
ＴｉＮの代わりにＴｉ0.95Ｓｉ0.05Ｏ2で表されるチタンケイ素複合酸化物を添加した正極合剤を用いた以外は実施例１と同様にしてアルカリ電池を作製した。
<< Comparative Example 4 >>
An alkaline battery was fabricated in the same manner as in Example 1 except that a positive electrode mixture to which a titanium silicon composite oxide represented by Ti 0.95 Si 0.05 O 2 was added instead of TiN was used.
電池の強負荷放電特性を評価するために、初度（作製直後、室温で１週間放置後）の電池１０個を、１Ωの負荷、終止電圧０．９Ｖで連続放電させ、そのときの放電時間を測定し、その平均値を求めた。添加剤を添加しなかったアルカリ電池（比較例１）の結果を基準である１００とし、強負荷放電特性を指数で表した。また、軽負荷放電特性は、３９Ωの負荷、終止電圧０．９Ｖで連続放電させ、そのときの放電時間を測定し、その平均値を求めた。これらの結果を表１に示した。 In order to evaluate the heavy load discharge characteristics of the battery, 10 batteries at the first time (immediately after fabrication and after standing for 1 week at room temperature) were continuously discharged at a load of 1Ω and a final voltage of 0.9 V, and the discharge time at that time was determined. The average value was measured. The result of the alkaline battery (Comparative Example 1) to which no additive was added was taken as 100 as a reference, and the heavy load discharge characteristics were expressed as an index. The light load discharge characteristics were obtained by continuously discharging at a load of 39Ω and a final voltage of 0.9 V, measuring the discharge time at that time, and obtaining the average value. These results are shown in Table 1.
表１から、正極合剤にＴｉＮまたはＣｏ2Ｏ3を添加した実施例１および２の電池は、それらを添加しなかった比較例１の電池よりも強負荷放電特性が向上しており、また、軽負荷放電特性も比較例１〜４の電池よりも高い。一方、比較例２〜４の電池は、比較例１に比べ、強強負荷放電特性は向上しているが、軽負荷放電特性は若干低下するかほぼ同じである。
以上の結果から、本発明によれば、強負荷放電特性及び軽負荷放電特性に優れたアルカリ電池が得られることがわかる。
From Table 1, the batteries of Examples 1 and 2 in which TiN or Co 2 O 3 was added to the positive electrode mixture had improved heavy load discharge characteristics as compared with the battery of Comparative Example 1 in which they were not added, The light load discharge characteristics are also higher than those of the batteries of Comparative Examples 1 to 4. On the other hand, the batteries of Comparative Examples 2 to 4 have improved strong and heavy load discharge characteristics as compared with Comparative Example 1, but the light load discharge characteristics are slightly reduced or substantially the same.
From the above results, it can be seen that according to the present invention, an alkaline battery excellent in heavy load discharge characteristics and light load discharge characteristics can be obtained.
上記実施例では、二酸化マンガンと黒鉛粉末の混合物（重量比９：１）に添加する添加剤量を二酸化マンガン１００重量部あたり１．０重量部とした。次に、表２に示す範囲で添加剤量を変化させて試験を行った。その結果を表２に示す。 In the above example, the amount of additive added to the mixture of manganese dioxide and graphite powder (weight ratio 9: 1) was 1.0 part by weight per 100 parts by weight of manganese dioxide. Next, the test was performed by changing the amount of the additive within the range shown in Table 2. The results are shown in Table 2.
表２から明らかなように、本発明のいずれの添加剤も添加量が二酸化マンガン１００重量部あたり０．０５〜５重量部の範囲で効果が得られた。また、ＴｉＮ、Ｃｏ2Ｏ3のどちらか一方のみを正極に添加した場合の実施例を示したが、これら両者を混合して使用した場合にも効果があり、その場合は、両者の添加量の和が二酸化マンガン１００重量部あたり０．０５〜５重量部の範囲で効果が認められた。 As can be seen from Table 2, the effect was obtained when any additive of the present invention was added in an amount of 0.05 to 5 parts by weight per 100 parts by weight of manganese dioxide. Further, TiN, although either the Co 2 O 3 only shows an embodiment of adding to the positive electrode, is also effective when used as a mixture of both of them, in which case the amount of both In the range of 0.05 to 5 parts by weight per 100 parts by weight of manganese dioxide.
本発明によれば、強負荷放電特性及び軽負荷放電特性に優れたアルカリ電池を提供することができる。したがって、本発明は市場のニーズに合ったアルカリ一次電池に有用である。 ADVANTAGE OF THE INVENTION According to this invention, the alkaline battery excellent in the heavy load discharge characteristic and the light load discharge characteristic can be provided. Therefore, the present invention is useful for alkaline primary batteries that meet market needs.
１ 電池ケース
２ 正極合剤
３ ゲル状負極
４ セパレータ
５ ガスケット
６ 負極集電子
７ 底板
８ 外装ラベル
DESCRIPTION OF SYMBOLS 1
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| JP2004357621A JP2006164862A (en) | 2004-12-10 | 2004-12-10 | Alkaline battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004357621A JP2006164862A (en) | 2004-12-10 | 2004-12-10 | Alkaline battery |
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| JP2006164862A true JP2006164862A (en) | 2006-06-22 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008218105A (en) * | 2007-03-01 | 2008-09-18 | Matsushita Electric Ind Co Ltd | Active material for alkaline dry cell and method of manufacturing the same, and battery using the same |
| WO2014097511A1 (en) * | 2012-12-20 | 2014-06-26 | パナソニック株式会社 | Alkaline cell |
-
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- 2004-12-10 JP JP2004357621A patent/JP2006164862A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008218105A (en) * | 2007-03-01 | 2008-09-18 | Matsushita Electric Ind Co Ltd | Active material for alkaline dry cell and method of manufacturing the same, and battery using the same |
| WO2014097511A1 (en) * | 2012-12-20 | 2014-06-26 | パナソニック株式会社 | Alkaline cell |
| JP5568185B1 (en) * | 2012-12-20 | 2014-08-06 | パナソニック株式会社 | Alkaline battery |
| US9337485B2 (en) | 2012-12-20 | 2016-05-10 | Panasonic Intellectual Property Management Co., Ltd. | Alkaline battery |
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