JPH053111B2 - - Google Patents
Info
- Publication number
- JPH053111B2 JPH053111B2 JP21437283A JP21437283A JPH053111B2 JP H053111 B2 JPH053111 B2 JP H053111B2 JP 21437283 A JP21437283 A JP 21437283A JP 21437283 A JP21437283 A JP 21437283A JP H053111 B2 JPH053111 B2 JP H053111B2
- Authority
- JP
- Japan
- Prior art keywords
- agent
- exothermic
- exothermic agent
- main
- heat generating
- 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
- 239000003795 chemical substances by application Substances 0.000 claims description 64
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011810 insulating material Substances 0.000 claims description 7
- UOYROEWALOHAKD-UHFFFAOYSA-K potassium iron(2+) triperchlorate Chemical group Cl(=O)(=O)(=O)[O-].[K+].[Fe+2].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-] UOYROEWALOHAKD-UHFFFAOYSA-K 0.000 claims description 6
- FUBWVOWJZCHMGC-UHFFFAOYSA-N [Zr+4].[Ba++].[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O Chemical compound [Zr+4].[Ba++].[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O FUBWVOWJZCHMGC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- BCFSVSISUGYRMF-UHFFFAOYSA-N calcium;dioxido(dioxo)chromium;dihydrate Chemical compound O.O.[Ca+2].[O-][Cr]([O-])(=O)=O BCFSVSISUGYRMF-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical group [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 2
- 229920006048 Arlen™ Polymers 0.000 description 1
- 229910020361 KCl—LiCl Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- 229940083898 barium chromate Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003832 thermite Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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】
産業の利用分野
本発明は、熱電池内部で発熱し、熱電池を活性
化させる発熱剤の着火性の改良に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to improving the ignitability of a heat generating agent that generates heat inside a thermal battery and activates the thermal battery.
従来例の構成とその問題点
熱電池は通常350℃以上の融点をもつ溶融塩を
電解質に用いるため、常温では不活性で実用的に
全く電力を供給しないので、長期貯蔵後も新品同
様の電池と変りない特性を示すという長所を活か
して非常用・緊急用電源として主に用いられてい
る電池である。従つてその用途上、使用時には確
実に作動して電力を供給すること、使用が簡便で
あることという要求は満足せねばならない。Structure of conventional examples and their problems Since thermal batteries usually use molten salt with a melting point of 350°C or higher as an electrolyte, they are inactive at room temperature and do not supply any practical power at all, so the batteries remain as good as new even after long-term storage. This battery is mainly used as an emergency power source due to its advantage of exhibiting the same characteristics as other batteries. Therefore, in terms of its intended use, it must satisfy the requirements that it operates reliably and supplies power during use, and that it is easy to use.
そのため、一般形の熱電池には発電部のほかに
溶融塩電解質を加熱溶融させる加熱剤を内蔵さ
せ、その加熱剤に着火させる点火器を組込んでい
る構造としたものが多い。具体的には発電部とし
て、負極にカルシウム、電解質に塩化カリウムと
塩化リチウムとの共融塩（融点352℃）、正極活物
質にクロム酸カルシウム、集電板にニツケルを用
いている。 For this reason, in addition to the power generation section, most general thermal batteries have a built-in heating agent that heats and melts the molten salt electrolyte, and an igniter that ignites the heating agent. Specifically, the power generation section uses calcium for the negative electrode, a eutectic salt of potassium chloride and lithium chloride (melting point: 352°C) for the electrolyte, calcium chromate for the positive electrode active material, and nickel for the current collector plate.
一方、加熱剤は金属粉末と酸化剤との混合物を
用いるテルミツト反応を利用したもので、その組
合せは用途と要求性能によつて種々のものが考え
られているが、近年自ら集電体として働く鉄−過
塩素酸カリウム系の発熱剤がよく用いられてきて
いる。しかし、この系の発熱剤は着火性が悪いた
め、従来の点火方式では着火しない場合があり、
特殊で複雑な方法を用いなければならなかつた。
例えば27回パワーソースシンポジユームでアーレ
ン・バルドウインが報告しているように電池の外
周に着火性の良い発熱剤（例えばZr−BaCrO4混
合物）の細長い着火片を設ける方法がとられてい
る。しかし、このような細長い着火片に強度を持
たせることは難しいために、振動や衝撃によつて
着火片が切断され、発熱剤の一部にしか着火しな
いことがあり、電池の活性化の信頼性を著しく低
下させていた。 On the other hand, heating agents utilize a thermite reaction using a mixture of metal powder and an oxidizing agent, and various combinations have been considered depending on the application and required performance, but in recent years they have been used to act as current collectors. Iron-potassium perchlorate based exothermic agents have been frequently used. However, this type of exothermic agent has poor ignition properties, so it may not ignite using conventional ignition methods.
Special and complicated methods had to be used.
For example, as reported by Arlen Baldowin at the 27th Power Source Symposium, a method has been adopted in which a long and narrow ignition strip of a highly ignitable exothermic agent (for example, a Zr-BaCrO 4 mixture) is provided around the outer periphery of the battery. However, because it is difficult to provide strength to such a long and thin ignition strip, the ignition strip may be cut off by vibration or impact, and only a portion of the exothermic agent may ignite, making the reliability of battery activation unreliable. sex was significantly reduced.
発明の目的
本発明は、発電部をとり囲む断熱材に火導孔を
有する熱電池において、着火性の悪い鉄−過塩素
酸カリウム系発熱剤に確実に着火して、熱電池の
活性化の信頼性を向上することを目的とする。Purpose of the Invention The present invention provides a method for activating the thermal battery by reliably igniting an iron-potassium perchlorate exothermic agent with poor ignitability in a thermal battery having a fire guide hole in the heat insulating material surrounding the power generation part. The purpose is to improve reliability.
発明の構成
本発明は素電池と発熱剤とを交互に積み重ねた
積層体の周囲は断熱材で被われ、断熱材の積層体
と接する一部に火導孔が設けられた熱電池におい
て、鉄−過塩素酸カリウム系発熱剤を主発熱剤と
し、その外周部の火導孔に面する付近にのみ主発
熱剤より着火性の秀れた発熱剤を配したことを特
徴としたものである。Structure of the Invention The present invention provides a thermal battery in which the periphery of a laminate in which unit cells and exothermic agents are stacked alternately is covered with a heat insulating material, and a fire guide hole is provided in a part in contact with the laminate of the heat insulating material. - The main heating agent is a potassium perchlorate-based heating agent, and the heating agent, which has better ignitability than the main heating agent, is placed only in the vicinity of the outer periphery facing the flame guide hole. .
実施例の説明
以下、本発明による発熱剤の実施例を第１図と
第２図に示す。第１図ａは平面図を、ｂはａの平
面図におけるＡ−Ｂ間の断面図を表わしている。
鉄−過塩素酸カリウム系の発熱剤１−１（以後主
発熱剤と呼ぶ）の外周部の一部に凹部を設け、そ
こに主発熱剤より着火性の秀れた発熱剤１−２を
配したものである。この主発熱剤より着火性の秀
れた発熱剤１−２は、主発熱剤１−１の外周部に
露出するように位置し、その露出部分が火導孔の
一部もしくは全部に面するように組み立てられ
る。第２図は別の例であり、第１図と同様にａは
平面図を、ｂはａの平面図におけるＡ−Ｂ間の断
面図を示した。第２図の例は発熱剤１−１の外周
部の一部に蟻溝状の欠損部が設けられ、そこに主
発熱剤より着火性の秀れた発熱剤１−２が配置さ
れたもので、この場合も第１図の場合と同様に露
出部分が火導孔の一部もしくは全部に面するよう
に組み立てられる。DESCRIPTION OF EXAMPLES Examples of exothermic agents according to the present invention are shown in FIGS. 1 and 2 below. FIG. 1a shows a plan view, and FIG. 1b shows a sectional view taken along line A-B in the plan view of a.
A recess is provided in a part of the outer periphery of the iron-potassium perchlorate-based exothermic agent 1-1 (hereinafter referred to as the main exothermic agent), and exothermic agent 1-2, which has better ignitability than the main exothermic agent, is inserted therein. It is arranged. The exothermic agent 1-2, which has better ignitability than the main exothermic agent, is located so as to be exposed on the outer periphery of the main exothermic agent 1-1, and its exposed portion faces part or all of the flame guide hole. It can be assembled like this. FIG. 2 is another example, in which a is a plan view and b is a sectional view taken along line A-B in the plan view of a, similar to FIG. 1. In the example shown in Figure 2, a dovetail-shaped defect is provided in a part of the outer periphery of exothermic agent 1-1, and exothermic agent 1-2, which has better ignitability than the main exothermic agent, is placed there. In this case as well, as in the case of FIG. 1, the exposed part is assembled so as to face part or all of the pilot hole.
次に第１図に示した発熱剤を用いて構成した積
層形熱電池について説明する。第３図がその縦断
面図で、１−１と１−２はそれぞれ前述の鉄−過
塩素酸カリウム系の主発熱剤と主発熱剤より着火
性の秀れた発熱剤である。ここで主発熱剤より着
火性の秀れた発熱剤１−２には、例えばジルコニ
ウム−クロム酸バリウム系発熱剤、またはジルコ
ニウム−クロム酸鉛−過マンガン酸カリウム系発
熱剤が使用できる。本実施例ではジルコニウム−
クロム酸バリウム系発熱剤を用いて構成した。２
は素電池であり、負極活物質には金属カルシウ
ム、正極活物質にはクロム酸カルシウム、そして
電解質にKCl−LiCl溶融塩を用いた。この素電池
２と発熱剤１−１，１−２とを交互に積層して積
層形熱電池を構成した。積層体の周囲は無機材料
により作られた断熱材９で被われており、この断
熱材９の積層体と接する一部に火導孔４が設けら
れている。この火導孔４は、点火器用入力端子６
から電気信号を送ると火炎を発する点火器３の火
炎を通し、発熱剤１−１，１−２に着火させるた
めに設けられた透孔である。先に述べた主発熱剤
より着火性の秀れた発熱剤１−２は積層体がこの
火導孔４に露出する面の一部もしくは全部に露出
するように配置されている。電池の出力は出力端
子５より取り出される。以上の様な積層形熱電池
は外装ケース８の中に挿入され外装蓋７と外装ケ
ース８とをアルゴン溶接して完成される。 Next, a laminated thermal battery constructed using the exothermic agent shown in FIG. 1 will be explained. FIG. 3 is a longitudinal cross-sectional view of the same, and 1-1 and 1-2 are the above-mentioned iron-potassium perchlorate-based main heat-generating agent and a heat-generating agent that has better ignitability than the main heat-generating agent, respectively. As the exothermic agent 1-2 having better ignitability than the main exothermic agent, for example, a zirconium-barium chromate exothermic agent or a zirconium-lead chromate-potassium permanganate exothermic agent can be used. In this example, zirconium
It was constructed using a barium chromate exothermic agent. 2
is a unit cell, and used metallic calcium as the negative electrode active material, calcium chromate as the positive electrode active material, and KCl-LiCl molten salt as the electrolyte. This unit cell 2 and exothermic agents 1-1 and 1-2 were alternately stacked to form a stacked thermal battery. The periphery of the laminate is covered with a heat insulating material 9 made of an inorganic material, and a fire guide hole 4 is provided in a part of the heat insulating material 9 that is in contact with the laminate. This fire guide hole 4 is connected to an input terminal 6 for an igniter.
These holes are provided to allow the flame of the igniter 3, which emits a flame when an electric signal is sent from the igniter 3, to pass through and ignite the exothermic agents 1-1 and 1-2. The exothermic agent 1-2, which has better ignitability than the main exothermic agent mentioned above, is arranged so that it is exposed on a part or all of the surface of the laminate exposed to the flame guide hole 4. The output of the battery is taken out from the output terminal 5. The laminated thermal battery as described above is completed by inserting it into the outer case 8 and welding the outer cover 7 and the outer case 8 with argon.
本発明の効果を見るために、先述した積層形熱
電池と先に述べたアーレン・バルドウインの着火
方法による積層形熱電池とを５個づつ試作し、加
速度250G、印加時間11msの衝撃を加えたのち、
最小合成加速度12Grms、加速度パワースペクト
ラム密度0.10G2／Hzのランダム振動を印加しなが
ら放電を行なつた。その結果、従来法では衝撃や
振動によつて細長い着火片が切断されて未着火の
主発熱剤が発生したり、着火が瞬時に行なわれず
電池が活性化しなかつたり、立ち上りの時間が非
常に長くなつたりした。このような現象の発生率
は従来法においては５個中２個で40％という高い
率であつた。一方、本発明による熱電池では、衝
撃や振動によつても発熱剤の切断や破損が発生す
ることがなく、着火も主発熱剤より着火性の秀れ
た発熱剤がまず点火器の火炎により瞬時に着火
し、その熱によつてほとんど同時に主発熱剤を燃
焼させるので、未着火等による電池の不活性化や
立ち上りの遅れ等の問題は全く発生しなかつた。 In order to see the effects of the present invention, five of the above-mentioned laminated thermal batteries and five laminated thermal batteries using the Arlen-Baldwin ignition method described above were manufactured, and a shock was applied at an acceleration of 250 G and an application time of 11 ms. after,
Discharge was performed while applying random vibrations with a minimum combined acceleration of 12 Grms and an acceleration power spectrum density of 0.10 G 2 /Hz. As a result, in conventional methods, the elongated ignition strips are cut off by shock and vibration, resulting in the generation of unignited main exothermic agent, ignition does not occur instantaneously and the battery is not activated, and the start-up time is extremely long. I felt relaxed. In the conventional method, the incidence of such phenomena was as high as 40% in 2 out of 5 cases. On the other hand, in the thermal battery according to the present invention, the exothermic agent is not cut or damaged even by shock or vibration, and the exothermic agent, which has better ignitability than the main exothermic agent, is first ignited by the flame of the igniter. Since it ignites instantaneously and uses the heat to burn the main exothermic agent almost simultaneously, problems such as inactivation of the battery or delay in start-up caused by non-ignition did not occur at all.
発明の効果
以上の様に本発明を用いることによつて、鉄−
過塩素酸カリウム系主発熱剤を主熱源とする熱電
池の電池活性化の信頼性を、衝撃や振動印加時で
も格段に向上することができる。Effects of the invention By using the present invention as described above, iron-
The reliability of battery activation of a thermal battery whose main heat source is a potassium perchlorate-based exothermic agent can be significantly improved even when shock or vibration is applied.
第１図と第２図は本発明の実施例による発熱剤
を示し、ａは平面図、ｂはａの平面図のＡ−Ｂ部
分の断面図であり、第３図は本発明の発熱剤を用
いた積層形熱電池の一実施例における縦断面図で
ある。
１−１……鉄−過塩素酸カリウム系の発熱剤、
１−２……主発熱剤より着火性の秀れた発熱剤、
２……素電池、３……点火器、４……火導孔、９
……断熱材。
1 and 2 show exothermic agents according to embodiments of the present invention, a is a plan view, b is a sectional view taken along line A-B in the plan view of a, and FIG. 3 is a exothermic agent of the present invention. FIG. 2 is a longitudinal cross-sectional view of an example of a stacked thermal battery using a laminate type thermal battery. 1-1... Iron-potassium perchlorate-based exothermic agent,
1-2... exothermic agent with better ignitability than the main exothermic agent,
2...Battery, 3...Igniter, 4...Fire pipe, 9
...Insulation material.
Claims (1)
の周囲は断熱材で被われ、断熱材の積層体と接す
る一部に火導孔が設けられた積層形熱電池であつ
て、発熱剤が２種類より構成され、鉄−過塩素酸
カリウム系発熱剤を主発熱剤とし、発熱剤の火導
孔に面する付近にのみ主発熱剤より着火性の秀れ
た発熱剤を配し、火導孔に接する発熱剤における
露出部の一部又は全部を主発熱剤より着火性の秀
れた発熱剤で構成したことを特徴とする熱電池。 ２ 主発熱剤より着火性の秀れた発熱剤として、
ジルコニウム−クロム酸バリウム系発熱剤または
ジルコニウム−クロム酸鉛−過マンガン酸カリウ
ム系発熱剤を用いた特許請求の範囲第１項記載の
熱電池。[Scope of Claims] 1. A laminated thermal battery in which a laminate in which unit cells and exothermic agents are alternately stacked is covered with a heat insulating material, and a fire guide hole is provided in a portion in contact with the laminate of the heat insulating material. The exothermic agent is composed of two types, the main exothermic agent is an iron-potassium perchlorate exothermic agent, and the exothermic agent has superior ignitability than the main exothermic agent only in the vicinity facing the flame guide hole of the exothermic agent. 1. A thermal battery characterized in that a heat generating agent is arranged, and a part or all of the exposed portion of the heat generating agent in contact with a fire guide hole is made of a heat generating agent that has better ignitability than the main heat generating agent. 2. As a heat generating agent with better ignitability than the main heat generating agent,
The thermal battery according to claim 1, which uses a zirconium-barium chromate heating agent or a zirconium-lead chromate-potassium permanganate heating agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21437283A JPS60107266A (en) | 1983-11-14 | 1983-11-14 | Thermal battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21437283A JPS60107266A (en) | 1983-11-14 | 1983-11-14 | Thermal battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60107266A JPS60107266A (en) | 1985-06-12 |
| JPH053111B2 true JPH053111B2 (en) | 1993-01-14 |
Family
ID=16654694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21437283A Granted JPS60107266A (en) | 1983-11-14 | 1983-11-14 | Thermal battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60107266A (en) |
-
1983
- 1983-11-14 JP JP21437283A patent/JPS60107266A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60107266A (en) | 1985-06-12 |
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