JPH0666143B2 - Heating agent for thermal batteries - Google Patents
Heating agent for thermal batteriesInfo
- Publication number
- JPH0666143B2 JPH0666143B2 JP59223407A JP22340784A JPH0666143B2 JP H0666143 B2 JPH0666143 B2 JP H0666143B2 JP 59223407 A JP59223407 A JP 59223407A JP 22340784 A JP22340784 A JP 22340784A JP H0666143 B2 JPH0666143 B2 JP H0666143B2
- Authority
- JP
- Japan
- Prior art keywords
- heating agent
- iron powder
- battery
- kclo
- powder
- 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.)
- Expired - Lifetime
Links
- 238000010438 heat treatment Methods 0.000 title claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 4
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 4
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004880 explosion Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid 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
- H01M6/30—Deferred-action cells
- H01M6/36—Deferred-action cells containing electrolyte and made operational by physical means, e.g. thermal cells
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、電池内部で加熱剤を燃焼させて発電要素を活
性化させる熱電池に関するもので、さらに詳しくは、鉄
粉と過塩素酸カリウム粉を用いる加熱剤の特性向上を図
るものである。Description: TECHNICAL FIELD The present invention relates to a thermal battery in which a heating agent is burned inside a battery to activate a power generation element, and more specifically, iron powder and potassium perchlorate powder are used. It is intended to improve the characteristics of the heating agent used.
従来例の構成とその問題点 熱電池は、常温では固体で不活性状態にあるが、高温に
加熱されると活性化して良好なイオン伝導体となる溶融
塩を電池の電解質として用いる一次電池で、通常、使用
の簡便化を図るために電池内部に加熱剤を内蔵させて、
使用時に加熱剤を燃焼させたときの高熱で溶融塩電解質
を溶かし、電池を活性化させる電池である。Conventional configuration and problems The thermal battery is a solid battery that is inactive at room temperature, but is a primary battery that uses a molten salt that is activated when heated to a high temperature and becomes a good ion conductor as the electrolyte of the battery. Normally, a heating agent is built into the battery to simplify the use,
It is a battery in which the molten salt electrolyte is melted by the high heat generated when the heating agent is burned during use to activate the battery.
従って、発電要素とともに発熱源としての加熱剤も電池
特性に与える影響にきわめて大きい。熱電池の加熱剤と
して用いるには、密閉容器中で燃焼すること、ガス発生
が小さいこと、成形強度が強いこと、燃焼速度が早いこ
と等々、多くの制限された条件を満たす必要がある。こ
れらの条件を満たして実用化されている加熱剤の種類は
多くない。例えば還元剤−酸化剤系の化学式で表わす
と、Zr−BaCrO4，Zr−（PbCrO4＋KMnO4），Fe−KClO4な
どである。一般にはこれらの物質をベースとして若干の
混ぜものを加えるので「系」という表現をした方がよい
と思われる。Therefore, the heating agent as a heat source as well as the power generation element has a great influence on the battery characteristics. To be used as a heating agent for a thermal battery, it is necessary to satisfy many restricted conditions such as combustion in a closed container, small gas generation, high molding strength, and high burning rate. There are not many types of heating agents that satisfy these conditions and are in practical use. For example the reducing agent - is represented by the chemical formula of the oxidant-based, Zr-BaCrO 4, Zr- ( PbCrO 4 + KMnO 4), and the like Fe-KClO 4. In general, it is better to use the term "system" because some mixtures are added based on these substances.
本発明は前記のFe−KClO4系加熱剤のFe粉末に関して改
良を行なおうとするものであるが、従来の熱電池用鉄粉
としては各種鉄粉の中で電解鉄の微粉砕品がよいとされ
ている。これは還元鉄粉，噴霧鉄粉，カーボニル鉄粉な
どと比べて純度が高く、平均粒径３０〜４０μ程度のも
のも市販されているので入手し易いこと、加熱剤として
の性質もこれらの中では良好であるなどの理由からであ
った。The present invention is to improve the Fe powder of the above Fe-KClO 4 type heating agent, but as the iron powder for the conventional thermal battery, finely crushed electrolytic iron among various iron powders is preferable. It is said that. This is higher in purity than reduced iron powder, atomized iron powder, carbonyl iron powder, etc., and it is easy to obtain because it has an average particle size of about 30 to 40 μm, and the property as a heating agent is also among these. It was because it was good.
しかしながら、従来の鉄粉を用いたFe−KClO4系加熱剤
を使用した場合、電池電圧の立上がり時間（最大電圧の
７０％に到達す時間）は１秒よりも早く立上がらせるこ
とは不可能であったので、１秒よりも早い立上がり時間
を要求される場合には、例えばZr−BaCrO4系加熱剤を用
いざるを得なかった。このために電池の品番や用途によ
っては加熱剤をZr−BaCrO4系，Zr−（PbCrO4＋KMnO4）
系，Fe−KClO4系と変えねばならないので必然的に煩雑
になること、性質的におとなしく、燃焼残査が良好な電
導性を有する性質が生されないことなどの欠点があっ
た。However, when using a conventional Fe-KClO 4 type heating agent using iron powder, the rise time of the battery voltage (the time to reach 70% of the maximum voltage) cannot be raised faster than 1 second. Therefore, when a rise time that is shorter than 1 second is required, for example, a Zr—BaCrO 4 type heating agent must be used. For this reason, heating agents such as Zr-BaCrO 4 system, Zr- (PbCrO 4 + KMnO 4 ) may be used depending on the battery product number and application.
However, it had to be changed from the Fe-KClO 4 system to the system, so that it was inevitably complicated, and the properties were mild, and the combustion residue did not have the property of good electrical conductivity.
発明の目的 本発明は、上記の欠点を除去するために鉄粉の性質を改
良し、かつ上記鉄粉と過塩素酸カリウム粉末との組成比
を限定した混合物を使用して、電池電圧の立上がり時間
の短縮を図ることを目的とする。OBJECT OF THE INVENTION The present invention improves the properties of iron powder in order to eliminate the above-mentioned drawbacks, and uses a mixture having a limited composition ratio of the iron powder and potassium perchlorate powder to raise the battery voltage. The purpose is to reduce the time.
発明の構成 本発明は、上記の目的を達成するため、オキシ水酸化鉄
（FeO(OH)）を水素ガス雰囲気中で加熱還元して調製し
た還元鉄粉に、KClO4粉末を加え、その組成比を９０：
１０から７５：２５の範囲に規制した混合物を加圧成型
してFe−KClO4系加熱剤としたことを特徴とする。In order to achieve the above-mentioned object, the present invention has a composition in which KClO 4 powder is added to reduced iron powder prepared by heating and reducing iron oxyhydroxide (FeO (OH)) in a hydrogen gas atmosphere. Ratio 90:
The mixture was regulated to 10 to a range of 75:25 to pressure molding is characterized in that the Fe-KClO 4 based heating agent.
実施例の説明 以下、本発明の実施例を説明する。Description of Examples Examples of the present invention will be described below.
第１図は、本発明の鉄粉を用いた加熱剤の製造フローチ
ャートである。FIG. 1 is a manufacturing flowchart of a heating agent using the iron powder of the present invention.
第１図によって工程を順に説明する。The steps will be described in order with reference to FIG.
まず原材料であるFeO(OH)を約１kg鉄製バットにとり、
Ｈ２ガスを一定量流しながら水素還元炉を昇温し、FeO
(OH)を炉内に送りこむ。炉内温度を４４０℃以上に保ち
３０〜９０分間保持すると、FeO(OH)はＨ２ガスと結合
してFeとH2Oになって還元される。引続きＨ２ガスを流
しながら冷却し、完全に常温となったら取出す。First, take FeO (OH), which is the raw material, in an iron bat of about 1 kg,
While flowing a certain amount of H 2 gas, the temperature of the hydrogen reduction furnace was raised and FeO was added.
Send (OH) into the furnace. When the temperature in the furnace is kept at 440 ° C. or higher and kept for 30 to 90 minutes, FeO (OH) is combined with H 2 gas to become Fe and H 2 O, and is reduced. Then, it is cooled while flowing H 2 gas and taken out when the temperature is completely normal.
次にArガスで不活性状態とした室内に粉砕機を設置し、
前記の還元鉄を微粉砕して４００メッシュの篩をパスさ
せ、加熱剤用鉄粉とする。Next, install a crusher in a room made inert with Ar gas,
The reduced iron is finely pulverized and passed through a sieve of 400 mesh to obtain iron powder for heating agent.
一方、KClO4は試薬一級グレードを用い、強い衝撃を加
えないように微粉砕し、篩分けを行って粒子をそろえ
る。On the other hand, KClO 4 uses a first-grade reagent, which is pulverized so as not to give a strong impact, and sieved to obtain particles.
このようにして得られた鉄粉８５部とKClO4粉末１５部
を調合し、ホモジナイザーで均一に混合する。次に所定
量の前記混合物を秤取し、金型に入れて加圧成形し、金
型より取出して所望形状とした熱電池用加熱剤を得る。85 parts of the iron powder thus obtained and 15 parts of KClO 4 powder are mixed and uniformly mixed with a homogenizer. Next, a predetermined amount of the mixture is weighed, placed in a mold and pressure-molded, and taken out from the mold to obtain a heating agent for a thermal battery having a desired shape.
第２図は、本発明の還元鉄粉と従来の電解鉄粉を用いた
加熱剤における、FeとKClO4との混合組成比と、燃焼時
間との関係を示している。試験片２ｇを内容積一定の圧
力センサーつき密閉容器に入れ、容器内で燃焼させた時
の圧力上昇カーブから燃焼時間を計測する方法で求め
た。FIG. 2 shows the relationship between the burning composition and the composition ratio of Fe and KClO 4 in the heating agent using the reduced iron powder of the present invention and the conventional electrolytic iron powder. 2 g of the test piece was placed in a closed container with a pressure sensor having a constant inner volume, and the combustion time was measured from the pressure rise curve when burning in the container.
図中、Ａは本発明の還元鉄粉を用いた場合、Ｂは従来例
の電解鉄粉を用いた場合である。組成比Fe：KClO4を９
０：１０から７５：２５へと移行させていくと、Ａ，Ｂ
のいずれの場合も燃焼時間は早くなる傾向を示すが、Ａ
はいずれも１秒以内であるのに対し、ＢはKClO4１５％
以下では１秒以上となる。燃焼時のガス圧力，電気伝導
性から最適組成比はFe：KClO4＝８５：１５と考えられ
ること、電池の溶融塩電解質を溶融する時間に0.3秒は
かかることなどから、従来例Ｂでは電池電圧の立上がり
時間を１秒以内にすることができない。一方本発明Ａの
最も長い燃焼時間でも約0.8秒であり、立上がり目標の
１秒以内となる。ここでＦｅとＫＣｌＯ４の混合組成比
において還元鉄粉量を９０％よりさらに大にした場合、
燃焼時間が長くなり目標の１秒を越えてしまい、逆に７
５％より小さくした場合、ＫＣｌＯ４量が多くなり、混
合物の加圧成型時に爆発等の危険性が生じ易く工程上問
題であり、また導電性の点でも鉄粉量減少に伴い劣化す
る等の問題があり、好ましい組成比は９０％から７５％
の範囲であった。In the figure, A is the case where the reduced iron powder of the present invention is used, and B is the case where the electrolytic iron powder of the conventional example is used. Composition ratio Fe: KClO 4 is 9
Moving from 0:10 to 75:25, A and B
In either case, the combustion time tends to be shorter, but
Is less than 1 second, whereas B is KClO 4 15%
Below is 1 second or more. The optimum composition ratio is considered to be Fe: KClO 4 = 85: 15 from the gas pressure during combustion and electrical conductivity, and it takes 0.3 seconds to melt the molten salt electrolyte of the battery. The voltage rise time cannot be set within 1 second. On the other hand, the longest combustion time of Invention A is about 0.8 seconds, which is within 1 second of the rising target. Here, when the amount of reduced iron powder in the mixed composition ratio of Fe and KClO 4 is made larger than 90%,
Burning time becomes longer and exceeds the target of 1 second. Conversely, 7
If it is less than 5%, the amount of KClO 4 increases, and there is a risk of explosion such as explosion at the time of pressure molding of the mixture, which is a problem in the process, and also in terms of conductivity, it deteriorates as the amount of iron powder decreases. There is a problem, the preferred composition ratio is 90% to 75%
Was in the range.
第１表は、FeO(OH)にかえて種々の原材料を同意し、第
１図と同じ工程によって鉄粉を得、それらを用いた加熱
剤の特性を調べたものである。Table 1 is a table in which various raw materials were used instead of FeO (OH), iron powder was obtained by the same process as in FIG. 1, and the properties of the heating agent using them were examined.
表中、見掛密度（ｇ／cm3）とは一定高さより一定容器
中に落下して一定量入れ、１cm3当りの重量を求めたも
ので、数値の小さい程「粗」，大きい程「密」であり、
「粗」であれば粒子は凹凸が大きく表面積も大きいと推
定できる。本発明に用いたFeO(OH)を原材料としたもの
は、他に比べて非常に「粗」であって活性な鉄粉である
といえる。従って、燃焼時間は最も短かい。 In the table, the apparent density (g / cm 3 ) means the weight per 1 cm 3 after dropping into a certain container from a certain height and putting it in a certain amount. "Dense",
If “coarse”, it can be estimated that the particles have large irregularities and a large surface area. It can be said that the raw material made of FeO (OH) used in the present invention is an iron powder which is very “coarse” and active as compared with the others. Therefore, the burning time is the shortest.
前記の性質をもつ、FeO(OH)を水素ガス雰囲気中で加熱
還元して得た鉄粉と、過塩素酸カリウム粉末をその組成
比８５：１５で混合したものを成形して作った本発明の
加熱剤を用い、熱電池に組込んで−５０℃〜＋７０℃で
電池電圧の立上がり時間を求めたところ、第２表のよう
に全環境温度において、１秒以内で最大電圧の７０％以
上の電圧を発生した。なお電池は負極にCa，正極にCaCr
O4，電解質にLiCl−KCl共融塩を用いた電池系を、１０
セル直列構成したものである。The present invention formed by molding a mixture of iron powder obtained by heating and reducing FeO (OH) in a hydrogen gas atmosphere and potassium perchlorate powder having a composition ratio of 85:15 having the above-mentioned properties. When the rise time of the battery voltage was determined at -50 ° C to + 70 ° C by incorporating the above heating agent into a thermal battery, 70% or more of the maximum voltage was obtained within 1 second at all environmental temperatures as shown in Table 2. Generated voltage. The battery uses Ca for the negative electrode and CaCr for the positive electrode.
O 4 and battery system using LiCl-KCl eutectic salt as electrolyte
The cells are configured in series.
発明の効果 以上のように、本発明によれば電池電圧の立上がり時間
を早めることができ、熱電池の特性を向上させることが
可能となった。 Effects of the Invention As described above, according to the present invention, the rise time of the battery voltage can be shortened and the characteristics of the thermal battery can be improved.
第１図は本発明の鉄粉とそれを用いた加熱剤の製造工程
を示すフローチャート、第２図は本発明の加熱剤と従来
の加熱剤の組成比と燃焼時間との関係を示す図である。FIG. 1 is a flow chart showing the manufacturing process of the iron powder of the present invention and a heating agent using the same, and FIG. 2 is a diagram showing the relationship between the composition ratio of the heating agent of the present invention and the conventional heating agent and the burning time. is there.
フロントページの続き (72)発明者 原口 和典 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (56)参考文献 特開 昭57−116713（ＪＰ，Ａ) 特開 昭50−61632（ＪＰ，Ａ) 実開 昭59−62675（ＪＰ，Ｕ)Front page continued (72) Inventor Kazunori Haraguchi 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) References JP 57-116713 (JP, A) JP 50-61632 (JP, JP, A) Actual development Sho 59-62675 (JP, U)
Claims (1)
還元して得た鉄粉に、過塩素酸カリウム粉末を加え、そ
の組成比を９０：１０から７５：２５の範囲に規制した
混合物を加圧成型した熱電池用加熱剤。1. A mixture in which potassium perchlorate powder is added to iron powder obtained by heating and reducing iron oxyhydroxide in a hydrogen gas atmosphere and the composition ratio thereof is regulated in the range of 90:10 to 75:25. A heating agent for thermal batteries that is pressure-molded.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59223407A JPH0666143B2 (en) | 1984-10-23 | 1984-10-23 | Heating agent for thermal batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59223407A JPH0666143B2 (en) | 1984-10-23 | 1984-10-23 | Heating agent for thermal batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61101962A JPS61101962A (en) | 1986-05-20 |
| JPH0666143B2 true JPH0666143B2 (en) | 1994-08-24 |
Family
ID=16797655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59223407A Expired - Lifetime JPH0666143B2 (en) | 1984-10-23 | 1984-10-23 | Heating agent for thermal batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0666143B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115458704B (en) * | 2022-10-19 | 2025-08-26 | 贵州梅岭电源有限公司 | A single cell battery and composite sheet used therein, and a method for preparing the composite sheet |
| CN116162008B (en) * | 2023-01-18 | 2024-04-09 | 贵州梅岭电源有限公司 | A heating material for a miniaturized fast-activated thermal battery and a preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57116713A (en) * | 1981-01-10 | 1982-07-20 | Hitachi Maxell Ltd | Manufacture of metallic magnetic powder |
-
1984
- 1984-10-23 JP JP59223407A patent/JPH0666143B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61101962A (en) | 1986-05-20 |
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