JPS63232266A - Alkaline dry battery - Google Patents
Alkaline dry batteryInfo
- Publication number
- JPS63232266A JPS63232266A JP62067235A JP6723587A JPS63232266A JP S63232266 A JPS63232266 A JP S63232266A JP 62067235 A JP62067235 A JP 62067235A JP 6723587 A JP6723587 A JP 6723587A JP S63232266 A JPS63232266 A JP S63232266A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- manganese dioxide
- graphite
- particle size
- alkaline dry
- 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 72
- 239000002245 particle Substances 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 27
- 239000010439 graphite Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims description 27
- 238000000465 moulding Methods 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 230000007423 decrease Effects 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はアルカリ乾電池に関し、特に正極体を構成する
正極合剤を改良したアルカリ乾電池に係わるものである
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an alkaline dry battery, and particularly to an alkaline dry battery in which the positive electrode mixture constituting the positive electrode body is improved.
［従来の技術］
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高負荷放電性能が優れている
ため、携帯用再生録音機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。[Prior art] Alkaline batteries have superior continuous discharge and high-load discharge performance compared to manganese batteries using zinc chloride electrolyte, and are therefore used as power sources for portable playback recorders and camera flashlights. ing.
ところで、アルカリ乾電池に使用される正極活物質とし
ての二酸化マンガンは、従来より平均粒径が３０μｍで
、粒度分布は９０％以上が７４μｍ以下のものが用いら
れてきた。これは、二酸化マンガンの粒径を小さくする
ことにより単位重量当りの表面積を大きくできるため、
導電剤と共に構成される正極体の反応面積を大きくでき
、ひいては大電流を取出すことができるからである。従
って、これらの粒径を持つ二酸化マンガンを用いる場合
、二酸化マンガンのままでは導電性が低いため、黒鉛を
混合した正極合剤が用いられている。かかる黒鉛の粒径
については、特開昭５４−２８４２６号公報に酸化銀を
正極活物質に用いる正極合剤の導電剤として平均粒径ｌ
Ｏ〜５０μｍの黒鉛が開示されている。By the way, manganese dioxide as a positive electrode active material used in alkaline dry batteries has conventionally been used with an average particle size of 30 μm and a particle size distribution in which 90% or more is 74 μm or less. This is because by reducing the particle size of manganese dioxide, the surface area per unit weight can be increased.
This is because the reaction area of the positive electrode body configured together with the conductive agent can be increased, and as a result, a large current can be extracted. Therefore, when manganese dioxide having these particle sizes is used, a positive electrode mixture containing graphite is used because manganese dioxide as it is has low conductivity. Regarding the particle size of graphite, Japanese Patent Application Laid-Open No. 54-28426 describes the average particle size l as a conductive agent of a positive electrode mixture using silver oxide as a positive electrode active material.
Graphite of 0 to 50 μm is disclosed.
［発明が解決しようとする問題点コ
上記二酸化マンガン及び黒鉛からなる正極体は、次のよ
うな方法により製作され、電池の金属缶に収納される。[Problems to be Solved by the Invention] The positive electrode body made of manganese dioxide and graphite is manufactured by the following method and housed in a metal can of a battery.
まず、従来技術で示した平均粒径３０μｍで粒度分布が
９０９６以上で７４μｍ以下の小さい粒径の二酸化マン
ガンを正極活物質とし、これに平均粒径２０μｍの黒鉛
を該二酸化マンガンに対し８〜１２重量％混合させ、こ
れに結着剤としてポリエチレン、ポリスチロールの粉末
又は水溶性高分子のポリアクリル酸塩及び水溶性無機化
合物の水酸化アルカリ（例えば水酸化カリウム）を添加
し、攪拌混合して正極合剤を調製する。つづいて、該正
極合剤を成形密度を向上させるために顆粒にした後、円
筒状に加圧成形して正極体とし、これを金属缶内に挿入
し、ひきつづきパンチにより正極体を再加圧して該正極
体と金属缶体との接触を高める方法か採用されている。First, manganese dioxide with an average particle size of 30 μm and a particle size distribution of 9096 or more and 74 μm or less as shown in the prior art is used as a positive electrode active material, and graphite with an average particle size of 20 μm is added to this as a positive electrode active material. % by weight, and add polyethylene, polystyrene powder or water-soluble polymer polyacrylate as a binder, and a water-soluble inorganic compound alkali hydroxide (e.g. potassium hydroxide), and stir and mix. Prepare a positive electrode mixture. Next, the positive electrode mixture is granulated to improve the molding density, and then pressure-molded into a cylindrical shape to form a positive electrode body. This is inserted into a metal can, and the positive electrode body is then re-pressurized using a punch. A method of increasing the contact between the positive electrode body and the metal can is adopted.
しかしながら、前述した加圧成形に際して二酸化マンガ
ンの平均粒径が３０μｍと小さいため、攪拌時又は顆粒
時に二酸化マンガン粒周辺に取込まれる空気が脱気され
ずに、そのまま正極合剤に保持された状態で正極か製作
される。その結果、二酸化マンガンの平均粒径を小さく
することによって、単位重量当りの表面積の増大、放電
容量の向上効果を図ることができるものの、反面、正極
体内に空気が残留し易くなり、前記放電容量の向上効果
が半減されてしまうという問題があった。However, because the average particle size of manganese dioxide is as small as 30 μm during the above-mentioned pressure molding, the air that is taken in around the manganese dioxide particles during stirring or granulation is not degassed and remains in the positive electrode mixture. The positive electrode is manufactured by As a result, by reducing the average particle size of manganese dioxide, it is possible to increase the surface area per unit weight and improve the discharge capacity, but on the other hand, air tends to remain in the positive electrode body, which increases the discharge capacity. There was a problem in that the improvement effect was halved.
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、正極体内に残留する空気量を減少させ、放電容
量を向−ヒさせ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-mentioned conventional problems, and aims to provide an alkaline dry battery with increased discharge capacity by reducing the amount of air remaining in the positive electrode body.
［問題点を解決するための手段］
本発明は、二酸化マンガンを正極活物質とし、黒鉛を導
電剤として配合される正極合剤を加圧成形した正極体と
、亜鉛からなる負極活物質とを備えたアルカリ乾電池に
おいて、前記二酸化マンガンとして平均粒径が８０〜３
００μｍのものを、前記黒鉛として平均粒径が０．５〜
１０μｍのものを夫々用いる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 includes a positive electrode body formed by pressure molding a positive electrode mixture containing manganese dioxide as a positive electrode active material and graphite as a conductive agent, and a negative electrode active material made of zinc. In the alkaline dry battery equipped with the above-mentioned manganese dioxide, the average particle size is 80 to 3.
00 μm is used as the graphite with an average particle size of 0.5 to 0.00 μm.
These alkaline dry batteries are characterized by using 10 μm cells.
上記二酸化マンガンの平均粒径を限定した理由は、その
粒径を８０μｍ未満にすると正極合剤の加圧成形時での
脱気を効果的に行なえず、かといってその粒径が３００
μｍを越えると充分な脱気を行なえるものの、二酸化マ
ンガンの表面積が低減されて放電反応の低下するからで
ある。The reason for limiting the average particle size of manganese dioxide is that if the particle size is less than 80 μm, degassing cannot be performed effectively during pressure molding of the positive electrode mixture.
This is because if the diameter exceeds .mu.m, sufficient deaeration can be achieved, but the surface area of manganese dioxide is reduced and the discharge reaction is reduced.
上記黒鉛の平均粒径を限定した理由は、その粒径が０．
５μｍ未満になっても、１０μｍを越えても正極体の成
形作業性が悪化するからである。The reason for limiting the average particle size of the graphite is that the particle size is 0.
This is because the molding workability of the positive electrode body deteriorates even if the thickness is less than 5 μm or exceeds 10 μm.
上記正極合剤の二酸化マンガンと黒鉛との配合重量比は
、９２：８〜８５：１５の範囲にすることが好ましい。The weight ratio of manganese dioxide and graphite in the positive electrode mixture is preferably in the range of 92:8 to 85:15.
この理由は、一方の成分である黒鉛の比率が８未満にな
ると、正極体の導電率が低下し、かといって黒鉛の比率
か１５を越えると黒鉛の比重か小さいために正極合剤の
単位体積当りに占める黒鉛の体積が多くなり、二酸化マ
ンガンの配合量が低減されて放電容量が低下する恐れが
あるからである。The reason for this is that when the ratio of graphite, one of the components, is less than 8, the conductivity of the positive electrode decreases, but when the ratio of graphite exceeds 15, the specific gravity of graphite is small, so the unit of the positive electrode mixture This is because the volume of graphite per volume increases, and the amount of manganese dioxide blended is reduced, which may lead to a decrease in discharge capacity.
［作用］
本発明によれば、正極合剤の一成分として平均粒径が８
０〜３００μｍと粗い二酸化マンガンを用いることによ
って、正極合剤として単位体積当りの二酸化マンガンの
実質重量が増加し、しかも表面積が減少するため、攪拌
時や顆粒時に二酸化マンガン周辺に取込まれた空気を成
形時の圧力により容易に脱気できる。従って、かかる二
酸化マンガンと平均粒径を０．５〜１０μｍの規定した
黒鉛とが配合された正極合剤を加圧成形することによっ
て、反応面積の高い正極体を容易に製作でき、放電容量
の高い乾電池を得ることができる。[Function] According to the present invention, as one component of the positive electrode mixture, the average particle size is 8.
By using coarse manganese dioxide with a diameter of 0 to 300 μm, the actual weight of manganese dioxide per unit volume as a positive electrode mixture increases, and the surface area decreases. can be easily degassed by the pressure during molding. Therefore, by press-molding a positive electrode mixture containing manganese dioxide and graphite with a defined average particle size of 0.5 to 10 μm, a positive electrode body with a high reaction area can be easily produced, and the discharge capacity can be increased. You can get high quality batteries.
［発、明の実施例コ
以下、本発明をＪ Ｉ ５−ＬＲ６（単３形）アルカリ
乾電池に適用した例について図面を参照して詳細に説明
する。[Embodiments of the Invention] Hereinafter, an example in which the present invention is applied to a JI5-LR6 (AA size) alkaline battery will be described in detail with reference to the drawings.
実施例１ 図中の１は、正極端子を兼ねる金属缶である。Example 1 1 in the figure is a metal can that also serves as a positive electrode terminal.
この色属缶１内には、円筒状に加圧成形した正極体２が
充填されており、かつ該正極体２には金属缶１に対する
接触性を高めるために例えば３ｔｏｎ／ｉの圧力で再加
圧される。前記正極体２は、平均粒径８０μｍの二酸化
マンガン９２重量部と平均粒径０．５μｍの黒鉛８重量
部にＯ％苛性カリのアルカリ電解液を３重量部加えて攪
拌混合して正極合剤を調製し、これを３ｔｏｎ／ＣＩｊ
の圧力で中空円筒状に加圧成形したものである。This colored metal can 1 is filled with a positive electrode body 2 which is press-molded into a cylindrical shape, and the positive electrode body 2 is refilled at a pressure of, for example, 3 tons/i to improve contact with the metal can 1. Pressurized. The positive electrode body 2 was prepared by adding 3 parts by weight of an alkaline electrolyte of 0% caustic potash to 92 parts by weight of manganese dioxide having an average particle size of 80 μm and 8 parts by weight of graphite having an average particle size of 0.5 μm, and stirring and mixing the mixture to form a positive electrode mixture. 3ton/CIj
It is press-molded into a hollow cylindrical shape at a pressure of .
また、前記円筒状の正極体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。このデル状負極合剤４は、ポリアクリル酸ソーダ
を含む苛性カリ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。図中の５
は、真鍮製の負極集電棒であり、該負極集電棒５の一端
側は前記ゲル状負極合剤４内に挿入されており、かつ他
端は金属封口板６に接続されている。前記金属缶ｌと前
記金属封口板６の間には、ポリアミド樹脂からなる絶縁
ガスケット７か介在されており、該金属缶１の開口縁を
内方に屈曲させることにより該ガスケット７及び金属封
口板６で金属缶１内を密封口している。Further, the hollow portion of the cylindrical positive electrode body 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 delta-shaped negative electrode mixture 4 has a structure in which amalgamated zinc powder, which is a negative electrode active material, is dispersed in a caustic potassium electrolyte containing sodium polyacrylate. 5 in the diagram
is a negative electrode current collector rod made of brass; one end side of the negative electrode current collector rod 5 is inserted into the gel-like negative electrode mixture 4, and the other end is connected to the metal sealing plate 6. An insulating gasket 7 made of polyamide resin is interposed between the metal can 1 and the metal sealing plate 6, and by bending the opening edge of the metal can 1 inward, the gasket 7 and the metal sealing plate are separated. At 6, the inside of the metal can 1 is sealed.
実施例２〜９
下記表に示す組成の正極合剤から実施例１と同様な方法
で製作した正極合剤を用いた以外、実施例１と同構成の
アルカリ乾電池を組立てた。Examples 2 to 9 Alkaline dry batteries having the same configuration as in Example 1 were assembled, except that a positive electrode mixture prepared in the same manner as in Example 1 from a positive electrode mixture having the composition shown in the table below was used.
しかして、本実施例１〜９で用いた正極合剤を加圧成形
した後、別に用意した金属缶の内径に等しい金型に挿入
し、３ｔｏｎ／Ｃ７ｊで再加圧し、ひきつづき金型から
取出した正極体に水溶液を浸透させて加圧成形により取
込まれた空気を置換し、２０°Ｃの温度で正極体に置換
された水分量を、空気含有量として測定した。その結果
を同表に併記した。After the positive electrode mixture used in Examples 1 to 9 was press-molded, it was inserted into a mold that was equal to the inner diameter of a separately prepared metal can, re-pressurized at 3 tons/C7j, and then removed from the mold. An aqueous solution was permeated into the positive electrode body to replace the air taken in by pressure molding, and the amount of water displaced into the positive electrode body at a temperature of 20°C was measured as the air content. The results are also listed in the same table.
また、本実施例１〜９のアルカリ乾電池を２０°Ｃの室
温で負荷抵抗１０Ω、終止電圧０．９Ｖまでの放電持続
時間を測定した。その結果を電池１０個当りの平均値と
して同表に併記した。なお、表中には従来のアルカリ乾
電池を従来例とし、平均粒径が本発明の範囲から外れる
二酸化マンガン及び黒鉛からなる正極合剤を成形した正
極体を有するアルカリ乾電池を比較例１〜８として併記
した。Further, the discharge duration of the alkaline dry batteries of Examples 1 to 9 at a room temperature of 20° C. with a load resistance of 10Ω and a final voltage of 0.9V was measured. The results are also shown in the same table as an average value per 10 batteries. In addition, in the table, conventional alkaline dry batteries are shown as conventional examples, and alkaline dry batteries having positive electrode bodies formed from positive electrode mixtures made of manganese dioxide and graphite whose average particle size is outside the range of the present invention are shown as Comparative Examples 1 to 8. Also listed.
上記表から明らかなように、従来例の正極体の空気含有
ごは０．５２ｃｃ、放電持続時間は１２．５ｈｒである
のに対し、本実施例１〜９で用いた正極体は空気含有量
が０．２６〜０．３０ｃｃと低く、かつ該正極組込んだ
アルカリ乾電池の放電持続時間は１３，８〜１４６ｈ「
と長いことがわかる。なお、二酸化マンガンと黒鉛の配
合重合比を９２＝８〜８５：１５の範囲とすることが、
正極体を加圧成形時のパンチ抜は時の力に耐える硬さに
でき、欠は等を防止する上でａ効であった。As is clear from the above table, the air content of the conventional positive electrode body was 0.52 cc and the discharge duration was 12.5 hr, whereas the positive electrode bodies used in Examples 1 to 9 had an air content of 0.52 cc and a discharge duration of 12.5 hr. is as low as 0.26 to 0.30cc, and the discharge duration of the alkaline dry battery incorporating the positive electrode is 13.8 to 146 hours.
You can see that it is long. In addition, setting the blending polymerization ratio of manganese dioxide and graphite in the range of 92=8 to 85:15,
Punching during pressure molding of the positive electrode body made it hard enough to withstand the force of time, and was effective in preventing chips and the like.
一方、平均粒径が本発明の範囲から外れる７０μｍの二
酸化マンガンを配合して正極体とした比較例１．２では
、空気含有量が増加して放電持続時間が１２．２ｈｒ、
１２．３ｈｒと低くなる。また、平均粒径が本発明の範
囲から外れる４００μｍの二酸化マンガンを配合して正
極体とした比較例３．４では、空気ｃｓ Ｑ ＭＬが低
減されるものの、表面積が小さくなり過ぎて同様に放電
時間が１１．７ｈｒ、 １１．６ｈｒと低下する。On the other hand, in Comparative Example 1.2 in which the positive electrode was made by blending manganese dioxide with an average particle size of 70 μm outside the range of the present invention, the air content increased and the discharge duration was 12.2 hr.
It will be as low as 12.3hr. In addition, in Comparative Example 3.4, in which the positive electrode was made by blending manganese dioxide with an average particle size of 400 μm outside the range of the present invention, although the air cs Q ML was reduced, the surface area became too small and the discharge was similarly reduced. The time decreases to 11.7hr and 11.6hr.
更に、二酸化マンガンの平均粒径が８０〜３００ｕｍで
あるが、平均粒径か本発明から外れる黒鉛を用い、かつ
二酸化マンガンと黒鉛の比を９３ニア、ｇ４：１８とし
て比較例５〜８のアルカリ乾電池においては、比較例５
．６では空気量Ｎ ｘが本実施例と変らないが、二酸化
マンガンの比率が９３と増加した分だけ黒鉛の平均粒径
を小さくするため、正極体の導電性が低下して電池内部
抵抗が増大し、放電持続時間が低下する。また、比較例
６．８は黒鉛配合量が増加するため、二酸化マンガンの
量が減少して放電持続時間が低下する。このことから、
二酸化マンガンと黒鉛の配合重量比が９２；８〜８５：
１５の範囲が好ましいことがわかる。Furthermore, the average particle size of manganese dioxide is 80 to 300 um, but using graphite whose average particle size is out of the scope of the present invention, and using a ratio of manganese dioxide and graphite of 93 nia and g4:18, the alkali of Comparative Examples 5 to 8 For dry batteries, Comparative Example 5
．． In case of No. 6, the air amount N However, the discharge duration decreases. Furthermore, in Comparative Examples 6 and 8, since the blended amount of graphite increases, the amount of manganese dioxide decreases and the discharge duration decreases. From this,
The blending weight ratio of manganese dioxide and graphite is 92; 8 to 85:
It can be seen that the range of 15 is preferable.
［発明の効果］
以上詳述した如く、本発明によれば正極体内に残留する
空気量を減少させて正極活物質の反応面積を増大でき、
ひいては放電容量等の放電特性の優れたアルカリ乾電池
を提供できる。[Effects of the Invention] As detailed above, according to the present invention, the amount of air remaining in the cathode body can be reduced and the reaction area of the cathode active material can be increased.
Furthermore, it is possible to provide an alkaline dry battery with excellent discharge characteristics such as discharge capacity.
図面は、本発明の一実施例を示すアルカリ乾電池の断面
図である。
１・・・金属缶、２・・・正極体、４・・・ゲル状負極
合剤、５・・・負極集電棒。The drawing is a sectional view of an alkaline dry battery showing one embodiment of the present invention. DESCRIPTION OF SYMBOLS 1... Metal can, 2... Positive electrode body, 4... Gel-like negative electrode mixture, 5... Negative electrode current collector rod.
Claims (2)
剤として配合される正極合剤を加圧成形した正極体と、
亜鉛からなる負極活物質とを備えたアルカリ乾電池にお
いて、前記二酸化マンガンとして平均粒径が８０〜３０
０μｍのものを、前記黒鉛として平均粒径が０．５〜１
０μｍのものを夫々用いることを特徴とするアルカリ乾
電池。(1) A positive electrode body formed by pressure molding a positive electrode mixture containing manganese dioxide as a positive electrode active material and graphite as a conductive agent;
In an alkaline dry battery equipped with a negative electrode active material made of zinc, the manganese dioxide has an average particle size of 80 to 30
0 μm is used as the graphite with an average particle size of 0.5 to 1.
An alkaline dry battery characterized by using a 0 μm battery.
比が９２：８〜８５：１５の範囲であることを特徴とす
る特許請求の範囲第１項記載のアルカリ乾電池。(2) The alkaline dry battery according to claim 1, wherein the weight ratio of manganese dioxide and graphite in the positive electrode mixture is in the range of 92:8 to 85:15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62067235A JPS63232266A (en) | 1987-03-20 | 1987-03-20 | Alkaline dry battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62067235A JPS63232266A (en) | 1987-03-20 | 1987-03-20 | Alkaline dry battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63232266A true JPS63232266A (en) | 1988-09-28 |
Family
ID=13339050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62067235A Pending JPS63232266A (en) | 1987-03-20 | 1987-03-20 | Alkaline dry battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63232266A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07142060A (en) * | 1993-11-16 | 1995-06-02 | Fuji Elelctrochem Co Ltd | Alkaline-manganese battery |
| US5482798A (en) * | 1994-03-28 | 1996-01-09 | Matsushita Electric Industrial Co., Ltd. | Alkaline manganese battery |
| US6828064B1 (en) | 1998-01-07 | 2004-12-07 | Eveready Battery Company, Inc. | Alkaline cell having a cathode incorporating enhanced graphite |
| US6833217B2 (en) | 1997-12-31 | 2004-12-21 | Duracell Inc. | Battery cathode |
| JP2016162646A (en) * | 2015-03-03 | 2016-09-05 | セイコーインスツル株式会社 | Flat alkaline primary battery and method of manufacturing the same |
-
1987
- 1987-03-20 JP JP62067235A patent/JPS63232266A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07142060A (en) * | 1993-11-16 | 1995-06-02 | Fuji Elelctrochem Co Ltd | Alkaline-manganese battery |
| US5482798A (en) * | 1994-03-28 | 1996-01-09 | Matsushita Electric Industrial Co., Ltd. | Alkaline manganese battery |
| US6833217B2 (en) | 1997-12-31 | 2004-12-21 | Duracell Inc. | Battery cathode |
| US6828064B1 (en) | 1998-01-07 | 2004-12-07 | Eveready Battery Company, Inc. | Alkaline cell having a cathode incorporating enhanced graphite |
| JP2016162646A (en) * | 2015-03-03 | 2016-09-05 | セイコーインスツル株式会社 | Flat alkaline primary battery and method of manufacturing the same |
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