JPH02144855A - Manufacture of positive electrode mix for thermal battery and thermal battery using same - Google Patents
Manufacture of positive electrode mix for thermal battery and thermal battery using sameInfo
- Publication number
- JPH02144855A JPH02144855A JP63299841A JP29984188A JPH02144855A JP H02144855 A JPH02144855 A JP H02144855A JP 63299841 A JP63299841 A JP 63299841A JP 29984188 A JP29984188 A JP 29984188A JP H02144855 A JPH02144855 A JP H02144855A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- electrode mixture
- thermal battery
- powder
- voltage
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 8
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000339 iron disulfide Inorganic materials 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 229910021348 calcium disilicide Inorganic materials 0.000 claims abstract description 5
- 229910052786 argon Inorganic materials 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims 1
- 229910004706 CaSi2 Inorganic materials 0.000 abstract description 11
- 239000011230 binding agent Substances 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 2
- 238000003754 machining Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 23
- 230000000694 effects Effects 0.000 description 15
- 229910052960 marcasite Inorganic materials 0.000 description 15
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 15
- 229910052683 pyrite Inorganic materials 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000007667 floating Methods 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 101000802894 Dendroaspis angusticeps Fasciculin-2 Proteins 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910000358 iron sulfate Inorganic materials 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000002345 surface coating layer Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 101100230509 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) hat-1 gene Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 241000212342 Sium Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- HCQWRNRRURULEY-UHFFFAOYSA-L lithium;potassium;dichloride Chemical compound [Li+].[Cl-].[Cl-].[K+] HCQWRNRRURULEY-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003832 thermite Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
-
- 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
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はリチウム／二硫化鉄系熱電池のスパイク電圧を
抑制し、放電電圧の平坦化に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to suppressing spike voltages and flattening the discharge voltage of lithium/iron disulfide thermal batteries.
従来の技術
熱電池は常温で不活性であるが、高温に加熱すると活性
化して、外部へ電力を供給し得るようになる電池で、貯
蔵型電池の一種である。従って、１０年あるいはそれ以
上の貯蔵後においても製造直後と何ら電池特性が変るこ
となく使用できるため、各種緊急用Ｔ源に利用されてい
る。また、高温で作動させるために電極反応が進み易い
ので犬電流放電性に優れる、使用希望時には簡７１′／
ｌ：操作で起動信号を入れてやると、瞬時に電力を取出
せる等の特徴を有している。一方、使用される機器側の
電圧範囲の制限が厳ｊ〜くなる傾向にあり、出来る限り
作動電圧が平坦であることが望まれている。BACKGROUND TECHNOLOGY A thermal battery is inactive at room temperature, but becomes activated when heated to a high temperature and can supply power to the outside, and is a type of storage battery. Therefore, even after storage for 10 years or more, the battery characteristics can be used without any change from immediately after manufacture, so they are used in various emergency T sources. In addition, because it operates at high temperatures, the electrode reaction progresses easily, so it has excellent dog current discharge properties.
l: It has features such as being able to instantly draw power when a start signal is input by operation. On the other hand, there is a tendency for the voltage range of the equipment used to be more severely restricted, and it is desired that the operating voltage be as flat as possible.
熱電池においてこの具体的現象は、熱電池へ起動信号を
入れ、発熱剤を燃焼し、素電池を加熱した時、電圧が立
上がシ始めた初期状態に現われる、−次的な高電圧であ
シ、これを一般的にスパイク電圧と称している。すなわ
ち起動信号を加えた後０．５〜２秒間位に生じる瞬時的
なピーク電圧を指し、その後直ぐに安定電圧となる電圧
バタ・−ンとなる現象を言っている。この様な電圧特性
を有する電池を使用して機器設計をすると、電気回路上
の安全を考慮し高耐圧部品を用いねばならないので、機
器が大型化１重量化してしまう。In thermal batteries, this specific phenomenon occurs when a start signal is input to the thermal battery, the exothermic agent is burned, and the unit cell is heated.The voltage appears in the initial state when the voltage starts to rise. This is generally called a spike voltage. That is, it refers to an instantaneous peak voltage that occurs for about 0.5 to 2 seconds after a starting signal is applied, and then a voltage fluctuation that becomes stable immediately after that. If a device is designed using a battery having such voltage characteristics, high-voltage components must be used in consideration of the safety of the electric circuit, which results in the device becoming larger and heavier.
スパイク電圧の発生原因は、正極活物質の二硫化鉄（Ｆ
ｅＳ２＞の粉体表面に僅かなから形成されている酸化物
や硫酸塩の被膜によるものと考えられる。これは硫酸鉄
（ＦｅＳ０４）をポリ硫化アルカリと共に封管中で加熱
反応させてＦｅＳ ｚを生成したり、鉄（Ｆ５）粉を亜
硫酸アルカリと共に反応させてＦｅＳ２を製造するとき
に、ＦａＳ２の表面に酸化鉄、硫酸鉄が形成もしくは残
留するからである。The cause of the spike voltage is iron disulfide (F) in the positive electrode active material.
This is thought to be due to a small amount of oxide or sulfate coating formed on the powder surface of eS2>. This is because when iron sulfate (FeS04) is heated and reacted with polyalkali sulfide in a sealed tube to produce FeSz, or when iron (F5) powder is reacted with alkali sulfite to produce FeS2, the surface of FaS2 is This is because iron oxide and iron sulfate are formed or remain.
ＦｅＳ ２に対ｌ−これらの化合物は電位が高く、放電
により表面被膜が破れるとＦａＳ２の安定電圧となる。1 for FeS 2 - These compounds have a high potential, and when the surface film is broken by discharge, it becomes a stable voltage of FaS 2.
表面被膜層のあるＦｅＳ ２と、表面被膜層のない単結
晶Ｆｅｄ２の比較において、前者はスパイク電圧の発生
が見られるが、後者のＦａＳ２は見られない事が証明さ
れている。そこで、従来検討された内容は次の３点であ
った。In a comparison of FeS2 with a surface coating layer and single crystal Fed2 without a surface coating layer, it has been proven that spike voltage is observed in the former, but not in the latter FaS2. Therefore, the following three points have been considered in the past.
（１）未熟ＢｌｆｉＦｅＳ２に硫化水素ガス（Ｈ２Ｓ）
を流しなから３５０℃で加熱反応し、表面不純物をＦｅ
５ｚ化する。(1) Hydrogen sulfide gas (H2S) on immature BlfiFeS2
The surface impurities were removed by heating at 350°C without flowing
5z version.
（２）ＦａＳ（硫化鉄）とＬｊ、２Ｂ（硫化リチウム）
を加熱反応により合成させたＬｉｚＦｅＳ２を用いる。(2) FaS (iron sulfide) and Lj, 2B (lithium sulfide)
LizFeS2 synthesized by heating reaction is used.
（＠ 脱酸化剤として２ケイ化力〜シウム（ＣａＳｉ２
）粉末を添加する。(@ As a deoxidizing agent, 2 silicidation power ~ sium (CaSi2
) Add powder.
発明が解決しようとする課題
上記（１）は、５ＡＮＤ７９−００９０．１９了９に示
す先行技術であり、Ｈ２Ｓガスを流しながら（フローテ
ィング）３５０℃で３０分間電気炉中にて焼成すること
で、ＦｅＳ２表面のＦｅ ２０５やＦｅＳＯ４を純粋な
ＦｅＳ２に変化させ、電圧上昇要因を除去するものであ
るが、放出する有毒性のあるＨ２Ｓガスの後処理装置を
必要とする。（２）は、Ｉｎｔｅｒｎａｔｉｏｎａｌ
Ｐｏｗａｒ ５ｏｕｒｃｅｓ Ｓｙｍｐｏｓｉｕｍ（Ｉ
ＰＳＳ）、Ｐ６７γ、１９８６年に示された方法であり
、Ｌ工２Ｓが湿度に対して非常に敏感な性質を有してい
るため、取扱い作業中にＬｉＯＨとＨ７Ｓに分解しやす
く、悪臭を放ち健康に悪い影響を与える。Problems to be Solved by the Invention The above (1) is the prior art shown in 5AND79-0090.19Ryo9, which involves firing in an electric furnace at 350°C for 30 minutes while flowing H2S gas (floating). This method converts Fe 205 and FeSO4 on the FeS2 surface into pure FeS2 and removes the voltage increase factor, but requires a post-processing device for the toxic H2S gas released. (2) is International
Power 5 sources Symposium (I
PSS), P67γ, is a method shown in 1986, and because L-2S is very sensitive to humidity, it easily decomposes into LiOH and H7S during handling, giving off a bad odor. have a negative impact on health.
（３）は、同ＩＰＳＳ、１９８２に記述されているＣａ
、Ｓｉ ２扮末をＦｅＳ２に対し３〜５重情チ添加した
粉末混合物に、溶融塩電解質粉末、溶融塩−２酸化ケイ
素粉末を加え均一な正極合剤粉末とした後、減圧乾燥を
経て電池に用いられていたが、Ｃａｄｉ ２の添加によ
る容量低下、電圧波形に二段変化が生じるという課ＶＡ
があった。(3) is Ca described in the same IPSS, 1982.
A molten salt electrolyte powder and a molten salt-silicon dioxide powder were added to a powder mixture in which 3 to 5 times of Si2 powder was added to FeS2 to form a uniform positive electrode mixture powder, which was then dried under reduced pressure to form a battery. However, the addition of Cadi 2 causes a decrease in capacity and a two-step change in the voltage waveform.
was there.
本発明は、上記のような従来の課電を解消するため、前
記（３）のＣａ Ｓ １２ の添加方法に着目して正極
容量の低下がなく、かつ電圧波形に優れ、更にスパイク
電圧を極力抑制したリチウム／二硫化鉄系熱電池を実現
させ、合せて正極合剤の容易な処理法を提供することを
目的とする。In order to solve the conventional electrification problem as described above, the present invention focuses on the Ca S 12 addition method described in (3) above to avoid a decrease in positive electrode capacity, provide an excellent voltage waveform, and further minimize spike voltage. The purpose of this invention is to realize a lithium/iron disulfide-based thermal battery with a reduced amount of heat, and also to provide an easy treatment method for the positive electrode mixture.
課題を解決するだめの手段
この課題を解決するために本発明は、未熟理工硫化鉄と
溶１ａ塩電解質と２ケイ化カルシウムをそれぞれ粉体で
、必要に応じてこれにさらに電Ｍ質を含有した無機バイ
ンダーを加えて混合撹拌する工程と、この合剤をア／ｌ
／ゴン、窒素またはこれらの混合ガスを流通させた高温
炉で加熱処理する工程と、同炉内で冷却する工程と、乾
燥雰囲気中で処理済み正極合剤を粉砕する工程を経て正
極合剤粉末を得るものである。Means to Solve the Problem In order to solve this problem, the present invention uses powders of immature iron sulfide, molten 1a salt electrolyte, and calcium disilicide, and further contains an electrolyte as needed. The process of adding and stirring the inorganic binder, and adding the mixture to a/l.
The positive electrode mixture powder is produced through a process of heat treatment in a high-temperature furnace in which nitrogen gas, nitrogen, or a mixture thereof is passed through, a cooling process in the same furnace, and a process of pulverizing the treated positive electrode mixture in a dry atmosphere. This is what you get.
なお、電池としては負極にはリチウム又はリチウム合金
を使用し、電解質層に溶融塩電解質を保持させた酸化マ
グネシウム（ＭｇＯ）の粉末成型体を用い、そして正直
層に本発明の正極合剤を粉末成型層とした３層からなる
素電池と、テルミット反応を利用した発熱剤を組合せて
Ｌ ｉ ／ ＦｅＳ２ 系熱電池に構成する。As for the battery, lithium or lithium alloy is used for the negative electrode, a molded magnesium oxide (MgO) powder containing a molten salt electrolyte is used for the electrolyte layer, and the positive electrode mixture of the present invention is used as a powder for the straight layer. A unit cell consisting of three layers as molded layers is combined with a heat generating agent utilizing thermite reaction to construct a Li/FeS2 type thermal battery.
作用
この製造法と前記の熱電池を用いれば、従来のようなス
パイク電圧は小さく抑制され、作動電圧が平坦化される
。すなわち、ＦｅＳ２の表面に形成されていた鉄酸化物
や鉄硫酸塩等の不純物は、熱処理中にＣａＳｉ ２
と反応して被模が除去され、活性なＦｅＳ２表面に変る
ためである。Ｃａｄｉ ２ の添加量は出来る限シ少量
で効果を得られるよう量的に制限してスパイク電圧以外
への悪影響が出ないよう配慮を行なう。添加量がＦｅＳ
２に対し１．６重量％を越え２．０重量％以上になると
、顕著に二段波の放電カーブが発生し、放電寿命の低下
も表われてくるので、０．２〜１．６重量％の範囲がよ
い。Effect: By using this manufacturing method and the above-described thermal battery, the spike voltage that occurs in the prior art can be suppressed to a small level, and the operating voltage can be flattened. In other words, impurities such as iron oxide and iron sulfate that were formed on the surface of FeS2 are removed from CaSi2 during heat treatment.
This is because the pattern is removed by reacting with FeS2 and becomes an active FeS2 surface. The amount of Cadi 2 added is quantitatively limited so that the effect can be obtained with as little amount as possible, and care is taken to avoid any adverse effects other than the spike voltage. Addition amount is FeS
If it exceeds 1.6% by weight and exceeds 2.0% by weight, a two-wave discharge curve will occur and the discharge life will be shortened. A range of % is good.
アルゴンや窒素をフローティングして高温焼成炉中で正
極混合物を熱処理すると、不活性雰囲気下でＦｅＳ ２
表面の不純物は溶融塩の効果を受けてＣａＳｉ２ と
の反応を促進し易くなシ、少ない添加量で処理効果を大
きく出来る。従って、放電寿命への影響も受けることな
く、初期のスパイク電圧のみを取除くことができる。When the cathode mixture is heat-treated in a high-temperature calcining furnace with floating argon or nitrogen, FeS2 is formed under an inert atmosphere.
Impurities on the surface are affected by the molten salt and do not easily promote the reaction with CaSi2, so the treatment effect can be increased with a small addition amount. Therefore, only the initial spike voltage can be removed without affecting the discharge life.
尚、従来のようにＦｅＳ２粉末、電解質粉末。In addition, FeS2 powder and electrolyte powder are used as before.
ＱａＳｉ ２粉末をただ単に機械的に混合しただけの正
極合剤を用いて、素電池の正極層を形成した場合に比べ
、本発明品を正極層とした場合には、成型密度が高まシ
、素電池の薄形化によって電池のする。Compared to the case where the positive electrode layer of a unit cell is formed using a positive electrode mixture that is simply mechanically mixed with QaSi 2 powder, when the product of the present invention is used as a positive electrode layer, the molding density is higher and the system is , batteries will become thinner due to the thinner unit cells.
以上のように、製造が容易で、スパイク電圧が抑制され
た平坦な放電カーブが得られ、放電寿命に影響ない、エ
ネルギー密度の改善された熱電池を構成できることとな
る。As described above, it is possible to construct a thermal battery that is easy to manufacture, has a flat discharge curve with suppressed spike voltage, has no influence on discharge life, and has improved energy density.
実施例
以下に、本発明の実施例を第１図、第２図および第３図
を用いて説明する。Embodiments Below, embodiments of the present invention will be described with reference to FIGS. 1, 2, and 3.
第１図は正極合剤の製造工程図を示す。図において、Ｆ
ｅＳ ２粉末を６９重量％（以下同じ）、塩化リチウム
−塩化カリウム（ＬｉＣ１−ＫＣｌ 、融点３６２°Ｃ
）溶融塩電解質（Ｘで表示）粉末１０％。FIG. 1 shows a manufacturing process diagram of the positive electrode mixture. In the figure, F
69% by weight of eS2 powder (the same applies hereinafter), lithium chloride-potassium chloride (LiC1-KCl, melting point 362 °C
) Molten salt electrolyte (denoted by X) powder 10%.
ＬｉＣ３−ＫＣ１溶融塩電解質を二酸化ケイ素（ＳｉＯ
２）バインダーに保持させた粉末（ＫＢで表示）２０チ
、ＣａＳｉ２ の１００メツシュパス粉末ｏ、ｓチをそ
れぞれ秤取し総量Ｉ Ｋｆとする。次に、ボールミル容
器に入れ密封し、１時間回転して均一混合粉末を得る。LiC3-KC1 molten salt electrolyte is made of silicon dioxide (SiO
2) Weigh out 20 pieces of powder (expressed in KB) held in the binder and 100 mesh pass powders o and s of CaSi2 to obtain a total amount of IKf. Next, it is placed in a ball mill container, sealed, and rotated for 1 hour to obtain a uniform mixed powder.
これをパイレックスガラス容器に移し、不活性ガスが流
通するフローティング方式の電気炉中に入れ、アルゴン
（ムτ）ガスを前記合剤１Ｋｇ当シロ〜５０１２／ｘｍ
のガス流量で流し続け、電気炉を昇温し電解質の融点以
上の３７０〜５００°Ｃ間で１時間保持する。こののち
、Ａｒガスを流し続けながら冷却し、１０ｏ′Ｃ以下で
容器を引出し、乾燥雰囲気中に移す。この状態では、比
較的くずれ易い塊状となっておシ、乳鉢等で粉砕し５０
〜２５０メツ７ユに整粒して正極合剤とする。尚ここで
、ＥＢを用いたが、Ｅ比率を若干増量して除去してもよ
く、またＡｒガスの替シに窒素ガス（Ｎ２）又はムｒと
Ｎ２との混合ガスを流してもよい。This was transferred to a Pyrex glass container, placed in a floating type electric furnace through which inert gas was circulated, and argon (μτ) gas was added per kg of the mixture to 5012/xm.
Continue to flow the gas at a flow rate of , raise the temperature of the electric furnace, and hold it for 1 hour at 370 to 500°C, which is higher than the melting point of the electrolyte. Thereafter, the container is cooled while continuing to flow Ar gas, and the container is pulled out at 10 o'C or lower and transferred to a dry atmosphere. In this state, it becomes a lump that is relatively easy to break down and is crushed in a mortar or mortar.
The particles are sized to ~250 ml and 7 yu to form a positive electrode mixture. Although EB is used here, it may be removed by increasing the E ratio a little, or nitrogen gas (N2) or a mixed gas of Mr and N2 may be flowed instead of Ar gas.
フローティングガス量は、仕込みｔｌＫｆに対し５１／
ａｍよシ少ない場合は炉内に空気の混入の心配があって
、ＦｅＳ２が鉄酸化物を生成する危険があり、一方５０
１１７ｔｉｎ以上では経済的に不利となる。The amount of floating gas is 51/
If the am is less than
If it is 117 tin or more, it will be economically disadvantageous.
また、高温炉の温度は電解質にＬｉＣ＄−ＫＣ１溶融塩
を用いた場合、３７０℃下限、５００℃上限が特性上好
ましく、３７０°Ｃ以下では温度調整バラツキによって
ＣａＳｉ２ の効果が小さく、６００″Ｃ以上ではＦｅ
Ｓ２が徐々に分解するので放電特性を劣下させる。In addition, when using LiC$-KC1 molten salt as the electrolyte, the temperature of the high-temperature furnace is preferably 370°C lower limit and 500°C upper limit from the viewpoint of characteristics. Below 370°C, the effect of CaSi2 is small due to temperature adjustment variations, and 600"C In the above, Fe
Since S2 gradually decomposes, the discharge characteristics deteriorate.
第２図は、本発明の第１図に示した正極合剤層を用いた
素電池の断面図を示す。FIG. 2 shows a cross-sectional view of a unit cell using the positive electrode mixture layer shown in FIG. 1 of the present invention.
１は正極合剤層であり放電電気量と利用率の関係に応じ
て適量が決定され、規定量秤取し金型内に入れ、低圧の
予備成型ののち、ＬｉＣ，ｄ−ＫＣ１５０％を含浸処理
したＭｇＯバインダーからなる電解質粉末を定量秤取し
て重ねて入れ、高圧で本成型を行なって電解質層２を形
成すると共に、２層一体ペレットを得る。３は負極カッ
プ、４は負極カップ３の内面に配置した純リチウムと鉄
粉の−体温金層もしくはリチウム・アルミニウム合金と
Ｅからなる負極活物質層でこの２つを合せ負極５と呼び
、前記ペレットと組合せ素電池とする。1 is the positive electrode mixture layer, and the appropriate amount is determined according to the relationship between the amount of discharged electricity and the utilization rate, the specified amount is weighed out, placed in a mold, and after preforming at low pressure, it is impregnated with 150% LiC, d-KC. The electrolyte powder made of the treated MgO binder is quantitatively weighed and stacked, and main molding is performed under high pressure to form the electrolyte layer 2 and obtain a two-layer integral pellet. 3 is a negative electrode cup, 4 is a negative electrode active material layer consisting of a temperature gold layer of pure lithium and iron powder or a lithium-aluminum alloy and E arranged on the inner surface of the negative electrode cup 3; these two together are called the negative electrode 5; Combine with pellets to make a unit cell.
第３図は、第１図の製造法を用いた正極合剤、第２図の
素電池を用いた積層型熱電池の縦断面図である。FIG. 3 is a longitudinal cross-sectional view of a stacked thermal battery using the positive electrode mixture manufactured by the manufacturing method shown in FIG. 1 and the unit cell shown in FIG. 2.
６は第２図の素電池で必要数を直列に積層構成すること
で容易に所望の電圧が得られ、過塩素酸カリウムと鉄粉
との均一混合物からなる発熱剤７と交互に積層する。８
．９は前記積層体の上・下部に配置した蓄熱剤層であり
、例えば硫酸リチウムと塩化ナトリウムの混合塩と５ｉ
０２バインダーからなる層で４９５°Ｃで凝固潜熱を発
生して素電池スタック温度を長時間保持させ、電池の長
寿命化に不可欠の蓄熱材である。１０は点火器でそのリ
ード線は一対の起動用端子１１に接続され、この端子よ
りパルス電流を通電すると火炎を発してヒートハツト１
２を燃焼し、その火炎は導火帯１３に燃焼伝ばさせる。A desired voltage can be easily obtained by stacking the necessary number of unit cells 6 in series in FIG. 2, and the exothermic agent 7 made of a homogeneous mixture of potassium perchlorate and iron powder is alternately stacked. 8
．． Reference numeral 9 denotes a heat storage agent layer disposed above and below the laminate, and includes, for example, a mixed salt of lithium sulfate and sodium chloride and 5i.
The layer made of 02 binder generates latent heat of solidification at 495°C, maintains the cell stack temperature for a long time, and is an essential heat storage material for extending battery life. 10 is an igniter whose lead wires are connected to a pair of starting terminals 11, and when a pulse current is applied from these terminals, a flame is emitted and the heat hat 1
2 is combusted, and the flame is transmitted to the fuse cord 13.
１＋、１ｓｔｆ、正、負極出力端子でスタックの最上部
と最下部から取出した内部リード線１６．１７と接続す
る。１８は断熱層でＭＩＮ−に■と呼ばれる高性能の無
機質断熱材を用いてスタックを包囲した。１９は電池蓋
、２ｏは電池ケースでいずれもステンレス鋼からなり、
それらの嵌合部を溶接密封する。1+, 1stf, positive and negative output terminals are connected to internal lead wires 16 and 17 taken out from the top and bottom of the stack. 18 is a heat insulating layer, and the stack is surrounded by a high performance inorganic heat insulating material called MIN-. 19 is the battery cover, 2o is the battery case, both of which are made of stainless steel.
The fitting parts are welded and sealed.
本発明を用いた積層型電池は、一対の起動用端子１１か
らパルス電流を通電することによシ、点火器１０．ヒー
トパッド１２．導火帯１３９発熱剤７の順に燃焼し、素
電池６を加熱して起動する。The stacked battery using the present invention can be activated by applying a pulse current from a pair of starting terminals 11 to an igniter 10. Heat pad 12. The fuse cord 139 burns in the order of the exothermic agent 7, heating the unit cell 6 and starting it up.
素電池は約５００℃に昇温し、ＬｉＧ／−ＫＣ１電解質
が溶融すると、本発明の正極合剤層は放電開始して、ス
パイク電圧の抑制された平坦な出力電圧を供給する。When the temperature of the unit cell rises to about 500° C. and the LiG/-KC1 electrolyte melts, the positive electrode mixture layer of the present invention starts discharging and supplies a flat output voltage with suppressed spike voltage.
次に本実施例の効果を調べた結果を述べる。第４図は、
素電池直径７６Ｈ１電池外径９５ｆｆ、電池高さ９０ｆ
Ｊｆの電池形状における１００１１ム／ｄ電流密度の放
電試験結果を示す。素電池直列数１５、平均作動電圧２
Ｖ／セルである。Next, the results of investigating the effects of this example will be described. Figure 4 shows
Cell diameter: 76H1 Battery outer diameter: 95ff, battery height: 90f
The results of a discharge test at a current density of 10011 μm/d in a Jf battery configuration are shown. Number of cells connected in series: 15, average operating voltage: 2
V/cell.
図中ムは、本発明実施例の放電カーブを示し、Ｃａｄｉ
２ の添加比は０．５％である。Ｂは従来例１を示し
、ＣａＳｉ２ 無添加、熱処理工程のない粉末混合の
みで作られた正極合剤を用いた電池である。In the figure, the symbol indicates the discharge curve of the embodiment of the present invention, and Cadi
The addition ratio of 2 is 0.5%. B shows Conventional Example 1, which is a battery using a positive electrode mixture made only by powder mixing without adding CaSi2 and without a heat treatment process.
Ｃは従来例２を示し、Ｇａｓ工２５チ添加、熱処理工程
のない粉末混合のみで作られた正極合剤を用いた電池で
ある。電池Ｂは作動直後に生じるスパイク電圧が３５Ｖ
を示した後急落して約３０Ｖで安定的な電圧を維持、２
５Ｖ以上の持続時間は１６分以上である。電池Ｃはスパ
イク電圧が抑制されて３２Ｖとなるが、電圧２段波、電
圧傾斜の増大、持続時間の短縮が生じるという結果であ
った。本発明例人は、スパイク電圧は完壁に取除かれて
いないものの３１，５Ｖと実用的に問題のない値まで改
善され、電圧２段波および持続時間への影響もなく、電
圧の平坦性が改良されるという効果を示した。C shows Conventional Example 2, which is a battery using a positive electrode mixture made only by powder mixing without addition of 25% gas and no heat treatment process. Battery B has a spike voltage of 35V immediately after activation.
After showing , it suddenly dropped and maintained a stable voltage of about 30V, 2
The duration of 5V or more is 16 minutes or more. In battery C, the spike voltage was suppressed to 32V, but the results were that a two-step voltage wave, an increase in the voltage slope, and a shortening of the duration occurred. Although the spike voltage has not been completely removed, it has been improved to 31.5V, which is a value that does not cause any practical problems, and there is no effect on the voltage two-step wave or duration, and the voltage is flat. It was shown that the effect was improved.
第６図は、本発明の方法を用いて、ＦｅＳ２ 。FIG. 6 shows FeS2 obtained using the method of the present invention.
ＣａＳｉ２ 、Ｅ 、 ＫＢの組成を変化し、Ｃａｄｉ
２の添加比率がスパイク電圧とスタック高さに与える
影響を調べる目的で実施した。従来例１では正極合剤の
充填密度がやや低く層厚みが厚くなるため、１６枚の素
電池と１６枚の発熱剤からなるスタック高さは４７ｆｆ
であった。試料風１〜７は熱処理によって正極合剤９粒
子間が固くしまるようになシ充填密度が高まる効果が得
られ、正極合剤層が従来例１よりも薄く成型できるので
、スタック高さは約１．７ｆｆ低くなった。また、スパ
イク電圧は従来例１と同組成で熱処理を施した試料風１
は逆に上昇したが、０．１〜６％の範囲で添加した試料
隘２〜１２はいずれも低下傾向を示し、特に０．３〜１
．５％の範囲の試料風３〜７はスパイク電圧、スタック
高さの両方の効果も得られ実用的であった。試料隘８〜
１２は放電度応に直接関与しないＣａＳｉ２ が電池抵
抗として悪効果となり、添加効果よりも作動電圧の低下
、素電池厚みの増加によるスタック高さの増加となって
実用的な範囲でなかった。By changing the composition of CaSi2, E, KB,
The purpose of this experiment was to investigate the effect of the addition ratio of 2 on spike voltage and stack height. In Conventional Example 1, the packing density of the positive electrode mixture is somewhat low and the layer thickness is thick, so the stack height consisting of 16 unit cells and 16 heat generating materials is 47ff.
Met. For sample winds 1 to 7, the heat treatment made the spaces between the 9 positive electrode mixture particles harden, which had the effect of increasing the packing density, and the positive electrode mixture layer could be formed thinner than in conventional example 1, so the stack height could be reduced. Approximately 1.7ff lower. In addition, the spike voltage was measured using sample wind 1, which had the same composition as conventional example 1 and underwent heat treatment.
On the contrary, sample numbers 2 to 12, in which the concentration was added in the range of 0.1 to 6%, showed a decreasing tendency, especially in the range of 0.3 to 1%.
．． Sample winds 3 to 7 in the range of 5% were practical as they provided both spike voltage and stack height effects. Sample depth 8~
In No. 12, CaSi2, which does not directly affect the degree of discharge, had a negative effect as a battery resistance, and the effect of addition was more than a decrease in operating voltage and an increase in stack height due to an increase in the thickness of the unit cell, which was out of a practical range.
本実施例ではＦｅＳ２ 、 ＣａＳｉ２ 、 Ｅ 、
ＫＢを同時に混合する例について記述したが、次のよう
な工程を経た場合も同様の効果が得られる。In this example, FeS2, CaSi2, E,
Although the example in which KB is mixed at the same time has been described, the same effect can be obtained by going through the following steps.
ａ）ＦｅＳ２とＣａＳｉ２を所望組成で混合し、これを
ムｒガスフローティング電気炉で焼成し、冷却後取出し
て、Ｋ 、ＥＢを加え再混合したものを、再び人ｒガス
フローティング電気炉中で焼成。a) Mix FeS2 and CaSi2 with a desired composition, fire this in a gas floating electric furnace, take it out after cooling, add K and EB, mix it again, and fire it again in a human gas floating electric furnace. .
冷却、粉砕を行なう方法。Method of cooling and crushing.
ｂ） ＦｅＳ２とＣａｄｉ２とＸの３種類とし、混合、
焼成、冷却、粉砕を行なう方法で、ＫＢを削除した一部
の電解質をＥに増量させる。b) Three types, FeS2, Cadi2 and X, mixed,
A portion of the electrolyte from which KB has been removed is increased to E by firing, cooling, and pulverizing.
発明の効果
以上の説明から明らかなように、２ケイ化カルンウムを
ただ単に正極合剤に粉末状で混ぜ込むだけではなく、粉
末で混合した後、ムｒガス、窒素ガス又はこれらの混合
ガスを流通させた高温炉中で加熱処理後、同炉内で冷却
、のち乾燥雰囲気で粉砕した各工程を経た正極合剤粉末
を素電池の正極合剤層に成型して使用し、そして発熱剤
と組合せた本発明の積層型電池は、起動初期に生じる一
次的なスパイク状高電圧が抑制され、作動電圧の平坦化
が得られる。更にＣａｄｉ ｚ量が０．３−１．５重量
％の範囲の同処理工程を経た正極合剤層、放電持続時間
が同等であり、成型密度が大きくなるのでスタック高さ
が低くなって電池の小型化が図れる。Effects of the Invention As is clear from the above explanation, carunium disilicide is not simply mixed into the positive electrode mixture in powder form, but after being mixed in powder form, carbon dioxide gas, nitrogen gas, or a mixture thereof is mixed. After being heated in a high-temperature furnace, the positive electrode mixture powder is cooled in the same furnace, and then pulverized in a dry atmosphere.The positive electrode mixture powder is molded into the positive electrode mixture layer of a unit cell and used as a heat generating agent. In the combined stacked battery of the present invention, the temporary spike-like high voltage that occurs at the initial stage of startup is suppressed, and the operating voltage can be flattened. Furthermore, the positive electrode mixture layer that underwent the same treatment process with a Cadiz content in the range of 0.3-1.5% by weight had the same discharge duration and increased molding density, resulting in a lower stack height and improved battery performance. Can be made smaller.
かつ、製造工程も簡単で量産時の不都合も生じないとい
う効果が得られる。Moreover, the manufacturing process is simple and there are no inconveniences during mass production.
第１図は本発明の実施例を示す正極合剤の製造工桿図、
第２図は同合剤を成型し正極合剤層として構成した素電
池の断面図、第３図は第２図の素電池を直列構成した本
発明の積層型熱電池の断面図、第４図は本発明の実施例
および従来例の放電カーブの比較図、第５図は合剤７組
成とスパイク電圧、スタック萬さの特性１頃向図である
。
１・・・・・・正極合剤層、２・・・・・・電解質層、
５・・・・・・負極、８・・・・・・素電池、７・・・
・・・発熱剤。
代理人の氏名 弁理士 粟 野 重 孝 ほか１名第１
図
Ｋｏ、ｐ （”）Ｊ９１ｉ ？ノ ε
５・−１糧
−與 ΣFIG. 1 is a manufacturing process diagram of a positive electrode mixture showing an example of the present invention;
FIG. 2 is a cross-sectional view of a unit cell formed by molding the same material as a positive electrode mixture layer, FIG. 3 is a cross-sectional view of a laminated thermal battery of the present invention in which the unit cells of FIG. 2 are configured in series, and FIG. The figure is a comparison diagram of the discharge curves of the embodiment of the present invention and the conventional example, and FIG. 5 is a diagram showing the characteristics of mixture 7 composition, spike voltage, and stack strength. 1... Positive electrode mixture layer, 2... Electrolyte layer,
5...Negative electrode, 8...Battery, 7...
...Exothermic agent. Name of agent: Patent attorney Shigetaka Awano and 1 other person 1st
Figure Ko, p ('') J91i?ノ ε 5・-1 與 Σ
Claims (5)
を用いた電解質層、二硫化鉄を用いた正極を有する熱電
池において、少なくとも二硫化鉄と溶融塩と２ケイ化カ
ルシウムを含む正極合剤を均質に混合撹拌する工程と、
アルゴン、窒素またはそれらの混合ガスを流通させた高
温炉中で加熱処理する工程と、同炉内で冷却する工程と
を経た後、乾燥雰囲気中で粉砕する工程とからなる熱電
池用正極合剤の製造法。(1) In a thermal battery having a negative electrode using lithium or a lithium alloy, an electrolyte layer using a molten salt, and a positive electrode using iron disulfide, a positive electrode mixture containing at least iron disulfide, a molten salt, and calcium disilicide. a step of homogeneously mixing and stirring the
A positive electrode mixture for thermal batteries that consists of a process of heat treatment in a high-temperature furnace through which argon, nitrogen, or a mixture thereof is passed through, a process of cooling in the same furnace, and a process of pulverizing in a dry atmosphere. manufacturing method.
て０．３０重量％以上、１．５０重量％以下の範囲であ
る特許請求の範囲第１項記載の熱電池用正極合剤の製造
法。(2) The positive electrode mixture for thermal batteries according to claim 1, wherein the amount of calcium disilicide added is in the range of 0.30% by weight or more and 1.50% by weight or less based on iron disulfide. manufacturing method.
て、５〜５０ｌ／ｍｉｎの流量である特許請求の範囲第
１項記載の熱電池用正極合剤の製造法。(3) The method for producing a positive electrode mixture for a thermal battery according to claim 1, wherein the flow rate of gas is 5 to 50 l/min per 1 kg of charged positive electrode mixture.
請求の範囲第１項記載の熱電池用正極合剤の製造法。(4) The method for producing a positive electrode mixture for a thermal battery according to claim 1, wherein the heat treatment temperature is in the range of 370 to 500°C.
末を一定量秤取し、金型内で加圧成型した正極合剤層を
正極に用いた熱電池。(5) A thermal battery using a positive electrode mixture layer obtained by weighing out a certain amount of the positive electrode mixture powder for a thermal battery according to claim 1 and molding the mixture under pressure in a mold as a positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63299841A JPH0740488B2 (en) | 1988-11-28 | 1988-11-28 | Method for producing positive electrode mixture for thermal battery and thermal battery using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63299841A JPH0740488B2 (en) | 1988-11-28 | 1988-11-28 | Method for producing positive electrode mixture for thermal battery and thermal battery using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02144855A true JPH02144855A (en) | 1990-06-04 |
| JPH0740488B2 JPH0740488B2 (en) | 1995-05-01 |
Family
ID=17877574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63299841A Expired - Lifetime JPH0740488B2 (en) | 1988-11-28 | 1988-11-28 | Method for producing positive electrode mixture for thermal battery and thermal battery using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0740488B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8124274B2 (en) | 2003-11-21 | 2012-02-28 | Eveready Battery Company, Inc. | High discharge capacity lithium battery |
| CN108349740A (en) * | 2015-10-29 | 2018-07-31 | 株式会社丰田自动织机 | The manufacturing method of silicon materials |
-
1988
- 1988-11-28 JP JP63299841A patent/JPH0740488B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8124274B2 (en) | 2003-11-21 | 2012-02-28 | Eveready Battery Company, Inc. | High discharge capacity lithium battery |
| CN108349740A (en) * | 2015-10-29 | 2018-07-31 | 株式会社丰田自动织机 | The manufacturing method of silicon materials |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0740488B2 (en) | 1995-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3453099B2 (en) | Method for producing lithium secondary battery | |
| JP2006066173A (en) | Current collector for lead-acid storage battery and lead-acid storage battery | |
| JP2004265685A (en) | Manufacturing method of lithium ion conductive sulfide glass and glass ceramic and all solid type battery using the glass ceramic | |
| KR101043309B1 (en) | Cathodal pellet for thermal battery, method for fablicatign the same, and thermal battery having the same | |
| JP5006548B2 (en) | Thermal battery | |
| JPH02144855A (en) | Manufacture of positive electrode mix for thermal battery and thermal battery using same | |
| JP2751390B2 (en) | Method for producing positive electrode mixture for thermal battery and thermal battery using the same | |
| JP2751389B2 (en) | Method for producing positive electrode mixture for thermal battery and thermal battery using the same | |
| JP2006236990A (en) | Thermal cell | |
| JP2847983B2 (en) | Method for producing positive electrode active material for thermal battery and thermal battery using the same | |
| JP2808627B2 (en) | Thermal battery | |
| JP2010061941A (en) | Coin type lithium secondary battery | |
| JP2563386B2 (en) | Method for manufacturing negative electrode for thermal battery | |
| JPH04155768A (en) | Manufacture of thermobattery electrolyte and thermobattery using same | |
| JPH02295066A (en) | Manufacture of positive active material for thermal battery and thermal battery using this material | |
| JPH05179372A (en) | Production of hydrogen occluding alloy powder | |
| JPH05242896A (en) | Positive electrode active material for thermal cell, manufacture thereof and thermal cell using it | |
| JPH04280070A (en) | Manufacture of positive electrode active material for thermal battery, and thermal battery using same | |
| JPH0461756A (en) | Manufacture of ni-h storage battery | |
| JPH04280072A (en) | Manufacture of positive electrode active material for thermal battery, and thermal battery using same | |
| JPH02299160A (en) | Thermal battery | |
| JPH02284360A (en) | Manufacture of thermo-battery and positive-electrode active material for thermo-battery | |
| JPH04282569A (en) | Manufacture for metal hydride storage battery | |
| JPH02284359A (en) | Manufacture of thermo-battery and positive-electrode active material for thermo-battery | |
| JPS60117566A (en) | Molten carbonate fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090501 Year of fee payment: 14 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090501 Year of fee payment: 14 |