JPH01279566A - Alkaline dry battery - Google Patents
Alkaline dry batteryInfo
- Publication number
- JPH01279566A JPH01279566A JP63109306A JP10930688A JPH01279566A JP H01279566 A JPH01279566 A JP H01279566A JP 63109306 A JP63109306 A JP 63109306A JP 10930688 A JP10930688 A JP 10930688A JP H01279566 A JPH01279566 A JP H01279566A
- Authority
- JP
- Japan
- Prior art keywords
- manganese dioxide
- mix
- chemically treated
- positive electrode
- negative
- 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
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000007774 positive electrode material Substances 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 abstract description 18
- 239000002184 metal Substances 0.000 abstract description 18
- 238000007789 sealing Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 14
- 241000862632 Soja Species 0.000 description 8
- 230000003746 surface roughness Effects 0.000 description 8
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- -1 potassium Chemical class 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- 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
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野コ 本発明は、アルカリ乾電池に関する。[Detailed description of the invention] [Industrial application fields] The present invention relates to an alkaline dry battery.
［従来の技術及び課題］
アルカリ乾電池は、塩化亜鉛電解液を用いたマンガン乾
電池に比べて連続放電及び重負荷放電性能が優れている
ため、携帯用再生装置やカメラのフラッシュライトの電
源等として利用されている。[Conventional technology and issues] Alkaline batteries have better continuous discharge and heavy load discharge performance than manganese batteries using zinc chloride electrolyte, so they are used as power sources for portable playback devices and camera flashlights. has been done.
ところで、上記アルカリ乾電池の正極活物質としては従
来より優れた放電性能と高密度を有する電解二酸化マン
ガンが多く用いられていた。しかしながら、かかる電解
二酸化マンガンは、硫酸マンガンの電解により得られ、
その電解に長時間を要しかつ多くの電力を消費するため
、製造コストが高くなるという問題があった。Incidentally, electrolytic manganese dioxide, which has superior discharge performance and high density, has been widely used as the positive electrode active material of the above-mentioned alkaline dry batteries. However, such electrolytic manganese dioxide is obtained by electrolysis of manganese sulfate,
Since the electrolysis takes a long time and consumes a lot of power, there is a problem in that the manufacturing cost is high.
このようなことから、前記電解二酸化マンガンより製造
コストの低い化学合成二酸化マンガンや天然二酸化マン
ガンを正極活物質として用いることが試みられている。For this reason, attempts have been made to use chemically synthesized manganese dioxide or natural manganese dioxide, which are lower in production cost than the electrolytic manganese dioxide, as positive electrode active materials.
しかしながら、これら化学合成二酸化マンガン等を正極
活物質として用いた電池は重負荷放電特性等が良好では
ながった。However, batteries using chemically synthesized manganese dioxide or the like as a positive electrode active material did not have good heavy load discharge characteristics.
そこで、優れた放電性能を有しがっ電解二酸化マンガン
より低コストで得られる活性化化学処理二酸化マンガン
をアルカリ乾電池の正極活物質して用いることが検討さ
れている。この活性化化学処理二酸化マンガンは、下記
式（１）に示すように天然二酸化マンガンを粉砕し高温
で加熱焙燻することによりＭ ｎ ２０３を形成し、こ
のＭｎ２Ｏ３を下記式（２）に示すように硫酸で処理し
、その後中和処理等を行なうことによって得られるもの
である。Therefore, it is being considered to use activated chemically treated manganese dioxide, which has excellent discharge performance and is obtained at a lower cost than electrolytic manganese dioxide, as a positive electrode active material for alkaline dry batteries. This activated chemically treated manganese dioxide is produced by crushing natural manganese dioxide and roasting it at high temperature to form Mn203 as shown in the following formula (1), and converting this Mn2O3 into Mn2O3 as shown in the following formula (2). It is obtained by treating with sulfuric acid, followed by neutralization.
２Ｍｎ０２−Ｍｎ２ ｏ、 ＋１／２０２ （１）
Ｍｎ２ ｏ３ ＋Ｈ２Ｓ ０４
ｍＭｎ ０２ ＋Ｍｎ Ｓ ０４ ＋Ｈ２０（２）
しかしながら、かかる活性化化学処理二酸化マンガンを
正極活物質として用いた電池は、電解二酸化マンガンを
正極活物質とした従来の電池に比べて重負荷放電特性等
が必ずしも優れたものではなかった。2Mn02-Mn2 o, +1/202 (1)
Mn2 o3 +H2S 04 mMn 02 +Mn S 04 +H20 (2)
However, batteries using such activated chemically treated manganese dioxide as a positive electrode active material have not necessarily been superior in heavy load discharge characteristics, etc. compared to conventional batteries using electrolytic manganese dioxide as a positive electrode active material.
本発明は、上記従来の問題点を解決するためになされた
もので、電解二酸化マンガンに匹敵する重負荷放電特性
を有し、かつ該電解二酸化マンガンより低コストの正極
活物質を備えたアルカリ乾電池を提供しようとするもの
である。The present invention has been made to solve the above conventional problems, and is an alkaline dry battery equipped with a positive electrode active material that has heavy load discharge characteristics comparable to electrolytic manganese dioxide and is lower in cost than electrolytic manganese dioxide. This is what we are trying to provide.
［課題を解決するための手段］
本発明は、表面積が３０〜５５ｍ ／ ９でかつ総社容
積が０．０６〜０．１２ｃＨ３／ ９のγ型結晶を主成
分とする活性化化学処理二酸化マンガンを正極活物質と
して用いたことを特徴とするアルカリ乾電池である。[Means for Solving the Problems] The present invention uses activated chemically treated manganese dioxide whose main component is γ-type crystals with a surface area of 30 to 55 m/9 and a Soja volume of 0.06 to 0.12 cH3/9. This is an alkaline dry battery characterized by its use as a positive electrode active material.
上記活性化化学処理二酸化マンガンの総社容積の値は、
例えば前記活性化化学処理二酸化マンガンの試料を１５
０℃に加熱し１５分間窒素を通気して表面付若水を除去
した後、窒素吸着法により測定し、表面積はＢＥＴ法に
より１１Ｊｌｊ定する。なお、総社容積は半径が８人〜
４００人の孔の総量である。The value of Soja volume of the above activated chemically treated manganese dioxide is:
For example, a sample of the activated chemically treated manganese dioxide
After heating to 0° C. and bubbling nitrogen for 15 minutes to remove surface water, the sample is measured by the nitrogen adsorption method, and the surface area is determined to be 11 Jlj by the BET method. In addition, the radius of Soja volume is 8 people ~
This is the total amount of holes for 400 people.
かかる表面積及び総社容積を限定した理由は、表面積が
３０尻／ｇ未満でありかつ総社容積が０．０６（１’
／ ｇ未満であると、該二酸化マンガンが高密度となっ
て導電材との接触面積が減少すると共に、電解液の吸収
が悪くなって該二酸化マンガン中でのプロトンの拡散等
が不良となるためである。一方、表面積が５５ｍ ／
ｇを越えかつ総社容積が０．１２ｃＩＩ３／ ｇを越え
ると、二酸化マンガンが嵩ぼって正極合剤での二酸化マ
ンガンの充填量が減少するためである。The reason for limiting the surface area and soja volume is that the surface area is less than 30 butts/g and the soja volume is 0.06 (1'
If it is less than /g, the manganese dioxide becomes dense and the contact area with the conductive material decreases, and the absorption of the electrolyte becomes poor, resulting in poor diffusion of protons in the manganese dioxide. It is. On the other hand, the surface area is 55m/
This is because if the total volume exceeds 0.12 cII3/g, the manganese dioxide becomes bulky and the amount of manganese dioxide filled in the positive electrode mixture decreases.
上記活性化化学処理二酸化マンガンは、例えば天然二酸
化マンガンを粉砕、焙燻して三二酸化マンガンとし、こ
の三二酸化マンガンを更に微粉砕して加熱された硫酸等
の鉱酸中に混合することにより二酸化マンガンに変化さ
せ、この二酸化マンガンを中和、乾燥する工程において
、前記鉱酸の処理等を調節することにより製造される０
また・この方法においてアルカリ金属、特にカリウムを
除去した天然二酸化マンガンを用いることにより活性度
の高い前記γ型結晶を主成分とする活性化化学二酸化マ
ンガンが得られる。かかるγ型結晶は１活性化化学処理
二酸化マンガン中に５０重量％以上含むことが望ましい
。The activated chemically treated manganese dioxide can be produced by, for example, pulverizing and roasting natural manganese dioxide to produce manganese sesquioxide, and then finely pulverizing this manganese sesquioxide and mixing it in a heated mineral acid such as sulfuric acid. In the process of converting the manganese dioxide into
Furthermore, in this method, by using natural manganese dioxide from which alkali metals, particularly potassium, have been removed, activated chemical manganese dioxide containing the highly active γ-type crystals as a main component can be obtained. It is desirable that such γ-type crystals be contained in an amount of 50% by weight or more in one activation chemically treated manganese dioxide.
［作用］
本発明に使用する正極活物質は、表面積が３０〜５５ｍ
／ＳｉＥの範囲でかつ総社容積が０．０６〜０．１２ｃ
１１３／ ９の範囲のγ形結晶を主成分とする活性化化
学処理二酸化マンガンからなり、従来の電解二酸化マン
ガンと同様な活性度を有するため、放電時において二酸
化マンガン結晶内へのプロトンの拡散と電子の移動とが
良好になされる。また、前記活性化化学処理二酸化マン
ガンは天然二酸化マンガンの化学処理により得られるた
め、電解二酸化マンガンに比べて低コストで得ることが
できる。従って、電解二酸化マンガンに匹敵する重負荷
放電特性を有し、かつ低コストのアルカリ乾電池を得る
ことができる。[Function] The positive electrode active material used in the present invention has a surface area of 30 to 55 m
/SiE range and Soja volume is 0.06 to 0.12c
It is made of activated chemically treated manganese dioxide whose main component is γ-form crystals in the range of 113/9, and has the same activity as conventional electrolytic manganese dioxide, so it prevents the diffusion of protons into the manganese dioxide crystals during discharge. Good electron movement is achieved. Further, since the activated chemically treated manganese dioxide is obtained by chemically treating natural manganese dioxide, it can be obtained at a lower cost than electrolytic manganese dioxide. Therefore, it is possible to obtain a low-cost alkaline dry battery that has heavy load discharge characteristics comparable to electrolytic manganese dioxide.
［実施例］
以下、本発明をＪＩＳ規格ＬＲ６形（単３形）アルカリ
乾電池に適用した例について第１図を参照にして詳細に
説明する。[Example] Hereinafter, an example in which the present invention is applied to a JIS standard LR6 type (AA size) alkaline dry battery will be described in detail with reference to FIG.
実施例１
図中の１は正極端子を兼ねる有底円筒形の金属缶である
。この金属缶１内には、円筒状に加圧成形した正極合剤
２が充填されている。なお、前記正極合剤２は金属缶１
に対する接触性を高めるために金属缶１への充填後にお
いて例えば３ｔｏｎ／ｃｉの圧力で再加圧される。前記
正極合剤２は、後述する方法により得られる活性化化学
処理二酸化マンガン９０重量部と鱗片状黒鉛１０重量部
に６％の水酸化カリウムのアルカリ電解液を３重量部加
え攪拌混合し、これを３ｔｏｎ／ ｃｄの圧力で中空円
筒状に加圧成形したものである。また、前記円筒状の正
極合剤２の中空部にはアセタール化ポリビニルアルコー
ル繊維の不織布からなる有底円筒状のセパレータ３を介
してゲル状負極合剤４が充填されている。このゲル状負
極合剤４は、ポリアクリル酸ソーダを主成分とする水酸
化カリウム電解液に負極活物質であるアマルガム化した
亜鉛粉末を分散させた構成になっている。このゲル状負
極合剤４内には、真鍮源の負極集電棒５がその上端部を
該負極合剤４より突出するように挿着されている。この
負極集電棒５の突出部外周面及び前記金属缶ｌの上部内
周面には二重環状のポリアミド樹脂からなる絶縁ガスケ
ット６が介在されている。また、前記ガスケット６の二
重環状部の間にはリング状の金属板７が配置され、かつ
該金属板７には負極端子を兼ねる帽子形の金属封口板８
が前記集電棒５の頭部に当接するように配置されている
。そして、前記金属缶ｌの開口縁を内方に屈曲させるこ
とにより前記ガスケット６及び金属封口板８で金属缶ｌ
内を密閉口している。Example 1 Reference numeral 1 in the figure is a cylindrical metal can with a bottom that also serves as a positive electrode terminal. This metal can 1 is filled with a positive electrode mixture 2 which is press-formed into a cylindrical shape. Note that the positive electrode mixture 2 is in the metal can 1.
After filling the metal can 1, the metal can is re-pressurized at a pressure of, for example, 3 tons/ci to improve contact with the metal can. The positive electrode mixture 2 was prepared by adding 3 parts by weight of an alkaline electrolyte of 6% potassium hydroxide to 90 parts by weight of activated chemically treated manganese dioxide obtained by the method described below and 10 parts by weight of flaky graphite, and mixing the mixture with stirring. It is press-molded into a hollow cylindrical shape at a pressure of 3 tons/cd. Further, the hollow portion of the cylindrical positive electrode mixture 2 is filled with a gelled negative electrode mixture 4 via a bottomed cylindrical separator 3 made of a nonwoven fabric of acetalized polyvinyl alcohol fibers. This gelled negative electrode mixture 4 has a structure in which amalgamated zinc powder, which is a negative electrode active material, is dispersed in a potassium hydroxide electrolyte containing sodium polyacrylate as a main component. A negative electrode current collector rod 5 made of brass is inserted into the gelled negative electrode mixture 4 so that its upper end protrudes beyond the negative electrode mixture 4 . A double annular insulating gasket 6 made of polyamide resin is interposed on the outer circumferential surface of the protrusion of the negative electrode current collector rod 5 and on the inner circumferential surface of the upper part of the metal can 1. Further, a ring-shaped metal plate 7 is disposed between the double annular portions of the gasket 6, and a cap-shaped metal sealing plate 8 that also serves as a negative electrode terminal is attached to the metal plate 7.
is arranged so as to come into contact with the head of the current collector rod 5. Then, by bending the opening edge of the metal can l inward, the gasket 6 and the metal sealing plate 8 close the metal can l.
The inside is sealed.
前記活性化化学処理二酸化マンガンは、次のようにして
製造される。まず、Ｍ ｎ ０２８０％、５ｉ０２４％
、ｌ；’ｅ２０３５％及びその他の不純物１１９６の組
成からなる天然二酸化マンガン鉱石を粗粉砕し、カリウ
ムを除去した後この粉砕物を８５０℃の雰囲気下で１時
間焙焼してＭｎ２０Ｂを調製する。つづいて、このＭｎ
２Ｏ３を１５０ｐ以下に微粉砕し、ＩＭ−硫酸溶液中で
１時間酸処理を行なうことにより前記Ｍｎ２Ｏ３をＭ
ｎ Ｏ２に化学変化させる。次いで、このＭ ｎ Ｏ３
を中和処理し、乾燥、圧縮した後、所定の粒度に調製す
ることにより活性化化学処理二酸化マンガンを製造する
。得られた活性化化学処理二酸化マンガンは、ＢＥＴ表
面積が３１ｉ／’ｊで、前述した窒素吸着法による総孔
容積が０．０６２ ｄｌｇのγ型結晶ヲ７０％、残りが
α型結晶の組成を有するものである。The activated chemically treated manganese dioxide is produced as follows. First, M n 0280%, 5i024%
A natural manganese dioxide ore having a composition of 35%, l;'e2, and 1196% of other impurities is coarsely ground, potassium is removed, and the ground product is roasted in an atmosphere of 850° C. for 1 hour to prepare Mn20B. Next, this Mn
The Mn2O3 is converted into Mn2O3 by pulverizing 2O3 to 150p or less and acid-treating it in an IM-sulfuric acid solution for 1 hour.
Chemically changed to n O2. Then, this M n O3
Activated chemically treated manganese dioxide is produced by neutralizing, drying, compressing, and adjusting to a predetermined particle size. The obtained activated chemically treated manganese dioxide has a BET surface area of 31i/'j, a total pore volume of 0.062 dlg by the nitrogen adsorption method described above, and has a composition of 70% γ-type crystals and the remainder α-type crystals. It is something that you have.
実施例２
表面績が３５ｍ／ｇ、総孔容積が０．１００ ａｘ３／
ｇのγ型結晶を７０％で残部がα型結晶である活性化
化学処理二酸化マンガンを正極活物質として用いた以外
、実施例１と同様な構造のアルカリ乾電池を組立てた。Example 2 Surface roughness is 35 m/g, total pore volume is 0.100 ax3/
An alkaline dry battery having the same structure as in Example 1 was assembled, except that activated chemically treated manganese dioxide containing 70% gamma type crystals and the remainder α type crystals was used as the positive electrode active material.
実施例３
表面績が４２尻／ｇ、総孔容積が０．０９００３／９の
γ型結晶を７０％で残部がα型結晶である活性化化学処
理二酸化マンガンを正極活物質として用いた以外、実施
例１と同様な構造のアルカリ乾電池を組立てた。Example 3 An activated chemically treated manganese dioxide having a surface roughness of 42 butts/g and a total pore volume of 0.09003/9, 70% of which was γ-type crystals and the remainder of which was α-type crystals, was used as the positive electrode active material. An alkaline dry battery having the same structure as in Example 1 was assembled.
実施例４
表面績が５０ｍ ／ ｇ、総孔容積が０．１１０ Ｃｌ
ｌｌ３／ ｇのγ型結晶を７０９６で残部がα型結晶で
ある活性化化学処理二酸化マンガンを正極活物質として
用いた以外、実施例１と同様な構造のアルカリ乾電池を
組立てた。Example 4 Surface roughness is 50 m/g, total pore volume is 0.110 Cl
An alkaline dry battery having the same structure as in Example 1 was assembled, except that activated chemically treated manganese dioxide containing 7096 γ-type crystals of 113/g and the remainder α-type crystals was used as the positive electrode active material.
実施例５
表面績が５５７Ｉｌ／ｇ、総孔容積が０．０６０ ｃＩ
Ｉ３／ ９のγ型結晶を７０％で残部がα型結晶である
活性化化学処理二酸化マンガンを正極活物質として用い
た以外、実施例１と同様な構造のアルカリ乾電池を組立
てた。Example 5 Surface roughness is 557 Il/g, total pore volume is 0.060 cI
An alkaline dry cell having the same structure as in Example 1 was assembled, except that activated chemically treated manganese dioxide containing 70% I3/9 γ-type crystals and the remainder α-type crystals was used as the positive electrode active material.
参照例１
表面績が４０７７ｉ／ｇ、総孔容積が０．０４１α３／
ｇのγ型結晶を７０％で残部がα型結晶である活性化化
学処理二酸化マンガンを正極活物質として用いた以外、
実施例１と同様な構造のアルカリ乾電池を組立てた。Reference example 1 Surface roughness is 4077i/g, total pore volume is 0.041α3/
Other than using activated chemically treated manganese dioxide with 70% gamma type crystals and the remainder α type crystals as the positive electrode active material,
An alkaline dry battery having the same structure as in Example 1 was assembled.
参照例２
表面績が４２７７ｉ／ｇ、総孔容積が０゜１４０ｃ１１
３／ｇのγ型結晶を７０％で残部がα型結晶である活性
化化学処理二酸化マンガンを正極活物質として用いた以
外、実施例１と同様な構造のアルカリ乾電池を組立てた
。Reference example 2 Surface roughness is 4277i/g, total pore volume is 0°140c11
An alkaline dry cell having the same structure as in Example 1 was assembled, except that activated chemically treated manganese dioxide having 70% γ-type crystals and the remainder α-type crystals was used as the positive electrode active material.
参照例３
表面績が６５７１ｉ／ｇ、総孔容積が０．１８０α３／
ｇのγ型結晶を７０％で残部がα型結晶である活性化化
学処理二酸化マンガンを正極活物質として用いた以外、
実施例１と同様な構造のアルカリ乾電池を組立てた。Reference example 3 Surface roughness is 6571i/g, total pore volume is 0.180α3/
Other than using activated chemically treated manganese dioxide with 70% gamma type crystals and the remainder α type crystals as the positive electrode active material,
An alkaline dry battery having the same structure as in Example 1 was assembled.
比較例
表面績が３８７７１／ ９、総孔容積が０．０５４ ａ
ｔｔ３／ ９の電解二酸化マンガンを正極活物質として
用いた以外、実施例１と同様な構造のアルカリ乾電池を
組立てた。Comparative example surface roughness is 38771/9, total pore volume is 0.054a
An alkaline dry battery having the same structure as in Example 1 was assembled except that electrolytic manganese dioxide of TT3/9 was used as the positive electrode active material.
しかして、本実施例１〜５及び参照例１〜３及び比較例
の電池夫々について、２Ω抵抗による連続放電を行ない
、０．９Ｖの放電電圧になるまでの放電持続時間を測定
する重負荷放電特性試験を行なった。その結果を下記第
１表に示す。Therefore, for each of the batteries of Examples 1 to 5, Reference Examples 1 to 3, and Comparative Example, continuous discharge was performed using a 2Ω resistance, and heavy load discharge was performed to measure the discharge duration until the discharge voltage reached 0.9V. Characteristic tests were conducted. The results are shown in Table 1 below.
第１表
また、上記実施例１〜５、参照例１〜３及び比較例の電
池における正極活物質の表面積と総社容積との関係を、
第２図に示した。なお、図中のＡ〜ｌは夫々実施例１〜
５の電池、参照例１〜３の電池及び比較例の電池に用い
た正極活物質を示している。また、第２図中において点
線で囲まれた領域は、本発明における表面積と総社容積
を満足する部分である。Table 1 also shows the relationship between the surface area of the positive electrode active material and the Soja volume in the batteries of Examples 1 to 5, Reference Examples 1 to 3, and Comparative Example.
It is shown in Figure 2. In addition, A to l in the figure represent Examples 1 to 1, respectively.
The positive electrode active materials used in the batteries of No. 5, the batteries of Reference Examples 1 to 3, and the batteries of Comparative Examples are shown. Furthermore, the area surrounded by dotted lines in FIG. 2 is a portion that satisfies the surface area and total volume in the present invention.
上記第１表から明らかなように、表面積と総社容積の関
係が第２図の点線内にある正極活物質を用いた本実施例
１〜５の電池は、表面積等が第２図の点線内から外れる
参照例１〜３の電池に比べて重負荷放電特性が良好にな
っていることがわかる。また、本実施例１〜５の電池は
電解二酸化マンガンを正極活物質として用いた比較例の
電池に匹敵する重負荷放電特性を示していることがわか
る。As is clear from Table 1 above, the batteries of Examples 1 to 5 using positive electrode active materials whose relationship between surface area and Soja volume is within the dotted line in FIG. It can be seen that the heavy load discharge characteristics are better compared to the batteries of Reference Examples 1 to 3, which deviate from the above. Moreover, it can be seen that the batteries of Examples 1 to 5 exhibit heavy load discharge characteristics comparable to the batteries of comparative examples using electrolytic manganese dioxide as the positive electrode active material.
［発明の効果］
以上詳述したように、本発明によれば電解二酸化マンガ
ンに匹敵する重負荷放電特性を有し、かつ低コストのア
ルカリ乾電池を得ることができる。[Effects of the Invention] As detailed above, according to the present invention, it is possible to obtain a low-cost alkaline dry battery that has heavy load discharge characteristics comparable to electrolytic manganese dioxide.
第１図は本発明の一実施例を示すアルカリ乾電池の断面
図、第２図は正極活物質における表面積と総社容積との
関係を示す線図である。
■・・・金属缶、２・・・正極合剤、３・・・セパレー
タ、４・・・ゲル状負極合剤、５・・・負極集電棒、８
・・・金属封口板。
出願人代理人 弁理士 鈴江武彦
第１図FIG. 1 is a cross-sectional view of an alkaline dry battery showing an embodiment of the present invention, and FIG. 2 is a diagram showing the relationship between the surface area and the total volume of the positive electrode active material. ■... Metal can, 2... Positive electrode mixture, 3... Separator, 4... Gel-like negative electrode mixture, 5... Negative electrode current collector rod, 8
...Metal sealing plate. Applicant's agent Patent attorney Takehiko Suzue Figure 1
Claims (1)
６〜０．１２ｃｍ＾３／ｇのγ型結晶を主成分とする活
性化化学処理二酸化マンガンを正極活物質として用いた
ことを特徴とするアルカリ乾電池。Surface area is 30-55m^2/g and total pore volume is 0.0
An alkaline dry battery characterized in that activated chemically treated manganese dioxide containing γ-type crystals of 6 to 0.12 cm^3/g as a main component is used as a positive electrode active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63109306A JPH01279566A (en) | 1988-05-02 | 1988-05-02 | Alkaline dry battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63109306A JPH01279566A (en) | 1988-05-02 | 1988-05-02 | Alkaline dry battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01279566A true JPH01279566A (en) | 1989-11-09 |
Family
ID=14506853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63109306A Pending JPH01279566A (en) | 1988-05-02 | 1988-05-02 | Alkaline dry battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01279566A (en) |
-
1988
- 1988-05-02 JP JP63109306A patent/JPH01279566A/en active Pending
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