JPH01183065A - Metal halogen battery - Google Patents
Metal halogen batteryInfo
- Publication number
- JPH01183065A JPH01183065A JP63002477A JP247788A JPH01183065A JP H01183065 A JPH01183065 A JP H01183065A JP 63002477 A JP63002477 A JP 63002477A JP 247788 A JP247788 A JP 247788A JP H01183065 A JPH01183065 A JP H01183065A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- active layer
- metal halogen
- positive electrode
- absorption
- 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
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 17
- 150000002367 halogens Chemical class 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 17
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 30
- 239000011630 iodine Substances 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 239000004033 plastic Substances 0.000 claims abstract description 17
- 229920003023 plastic Polymers 0.000 claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 claims description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 abstract description 3
- 238000003487 electrochemical reaction Methods 0.000 abstract description 2
- 238000012886 linear function Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 7
- 239000003792 electrolyte Substances 0.000 description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 12
- 229910052794 bromium Inorganic materials 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 description 7
- 239000004744 fabric Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- NIHOUJYFWMURBG-UHFFFAOYSA-N 1-ethyl-1-methylpyrrolidin-1-ium Chemical compound CC[N+]1(C)CCCC1 NIHOUJYFWMURBG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008029 eradication Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Inert Electrodes (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
Ａ、産業上の利用分野
乙の発明は、シー】・状に形成されたカーボンプラスチ
ックの表面に活性層を形成したカーボンプラスチック電
極を使用して成る金属ハロゲン電池、特に電極の活性層
を改良した金属ハロゲン電池に関するものである。[Detailed Description of the Invention] A. Industrial Application Field B's invention relates to a metal halogen battery using a carbon plastic electrode having an active layer formed on the surface of carbon plastic formed in the shape of a sheet. This invention relates to a metal halogen battery with an improved electrode active layer.
Ｂ０発明の概要
この発明は、金属ハロゲン電池を構成するカーボンプラ
スチック電極の活性層として、ヨウ素吸着量の範囲を限
定した活性炭素繊維を用いたことにより、高いクーロン
効率およびエネルギー効率を安定的に維持できる金属ハ
ロゲン電池を提供したものである。B0 Summary of the invention This invention stably maintains high coulombic efficiency and energy efficiency by using activated carbon fiber with a limited range of iodine adsorption as the active layer of the carbon plastic electrode that constitutes a metal halogen battery. The present invention provides a metal halogen battery that can be used.
Ｃ０従来の技術
金属ハロゲン電池、例えば亜鉛臭素電池は電力貯蔵用２
次電池として開発が進んでいる。C0 Conventional technology Metal halogen batteries, such as zinc bromine batteries, are used for power storage2
Development is progressing as a next-generation battery.
第４図は、電解液留環形亜鉛臭素電池の基本構成模式図
である。FIG. 4 is a schematic diagram of the basic configuration of an electrolyte-retained cyclic zinc-bromine battery.
図において、１は電池反応槽、２は正極室、３は負極室
、４は隔膜、５は正極、６は負極、７は正極電解液、８
ば負極電解液、９は正極電解液タンク、１０は、負極電
解液タンク、１１および１２はポンプ、１１ａおよびｌ
ｌｂは充放電切替弁である。In the figure, 1 is a battery reaction tank, 2 is a positive electrode chamber, 3 is a negative electrode chamber, 4 is a diaphragm, 5 is a positive electrode, 6 is a negative electrode, 7 is a positive electrode electrolyte, 8
9 is a negative electrode electrolyte tank, 10 is a negative electrode electrolyte tank, 11 and 12 are pumps, 11a and l
lb is a charge/discharge switching valve.
係る亜鉛臭素電池においては、充放電時には、Ｚ ｎ
Ｂ ｒ ２ Ｆ→Ｚ ｎ 十Ｂ ｒ ２の反応が進行す
る。In such a zinc bromine battery, during charging and discharging, Z n
The reaction B r 2 F → Z n + B r 2 proceeds.
充電時においては、式中上の矢印による反応が進行して
、負極では亜鉛が電極表面に電析し、正極においては、
臭素の発生が起こる。発生した臭素は、正極電解液８中
に溶解している４級アンモニウム塩からなる臭素錯化剤
と結合して、臭素錯化物を形成し、正極電解液と分離さ
れる。そして正極電解液タンク９の底部に貯蔵される。During charging, the reaction shown by the arrow above in the equation progresses, and zinc is deposited on the electrode surface at the negative electrode, and at the positive electrode,
Bromine evolution occurs. The generated bromine combines with a bromine complexing agent made of a quaternary ammonium salt dissolved in the positive electrode electrolyte 8 to form a bromine complex, which is separated from the positive electrode electrolyte. Then, it is stored at the bottom of the positive electrode electrolyte tank 9.
放電時においては、式中下の矢印による反応が進行し、
負極では電極表面上に析出していた亜鉛が溶解する。正
極では、正極電解液タンク９から切換弁１１ａを介して
、供給させる臭素錯化物を溶解し、臭素を還元する。During discharge, the reaction shown by the arrow at the bottom of the equation progresses,
At the negative electrode, zinc deposited on the electrode surface is dissolved. At the positive electrode, the bromine complex supplied from the positive electrode electrolyte tank 9 via the switching valve 11a is dissolved to reduce bromine.
ここで亜鉛−臭素電池は、電池のコストの低下、重量エ
ネルギー密度の増大を図るため、耐臭素性の大きいポリ
オレフィン系の樹脂たとえば、ポリエチレンなどにカー
ボンブラック、グラファイトなどの導電性物を添加し、
加熱状態で、混線形成したカーボンプラスチックより構
成されたカーボンプラスチック電極を用いている。Here, zinc-bromine batteries are made by adding conductive materials such as carbon black and graphite to a polyolefin resin with high bromine resistance, such as polyethylene, in order to reduce the cost of the battery and increase the weight energy density.
A carbon plastic electrode made of carbon plastic that is cross-wired in a heated state is used.
なお、カーボンプラスチック電極をバイポーラ電極とし
て使用する場合は、電解液不浸透性とすることが必要で
ある。In addition, when using a carbon plastic electrode as a bipolar electrode, it is necessary to make it impermeable to electrolyte.
カーボンプラスチック電極は、一般に表面が平滑に形成
されており、正極での臭素との反応が十分でない。Carbon plastic electrodes generally have smooth surfaces and do not react sufficiently with bromine at the positive electrode.
このため、臭素との反応を活性化するとともに、電極の
反応面積の増大を図るためカーボンプラスチック電極は
、カーボンプラスチックの表面に活性層を形成して成る
。Therefore, in order to activate the reaction with bromine and increase the reaction area of the electrode, the carbon plastic electrode is formed by forming an active layer on the surface of the carbon plastic.
従来、乙の活性層材とし′（は、）工、ノール系ノボラ
ック繊維等を出発原料とする活性炭素ｌ！Ｉｉ維を平織
、ニット、フェルト状に形成したシー１−が用いられて
おり、バイポーラ電極の場合はカーボンプラスチックの
片面に押し出し機の冷却３本ロールでラミネートされて
いる。Conventionally, active layer materials such as activated carbon l! Sea 1-, which is made of Ii fibers formed into plain weave, knit, or felt shapes, is used, and in the case of bipolar electrodes, it is laminated on one side of carbon plastic with three cooling rolls of an extruder.
Ｄ０発明が解決しようとする課題
上記のような金属ハロゲン電池の電極において、ラミネ
ートされる活性炭素繊維から成るシートは、１本の繊維
ロールの中でもその特性のバラツキが゛ 大きいという
欠点がある。D0 Problems to be Solved by the Invention In the electrodes of metal halogen batteries as described above, the laminated sheets made of activated carbon fibers have the disadvantage that their properties vary widely even within a single fiber roll.
従って、それらを活性層に用いた従来の金属ハロゲン電
池の電極では、積層電池を構成し、運転を行っても予定
どおりのクーロン効率およびエネルギー効率が得られな
い場合が多々あるという問題点を有していた。Therefore, conventional metal halogen battery electrodes that use them in the active layer have the problem that they often do not provide the expected coulombic efficiency and energy efficiency even when a stacked battery is constructed and operated. Was.
Ｅ０課題を解決するための手段
この発明においては、金属ハロゲン電池のカーボンプラ
スチック電極の活性層材としてヨウ素吸着量が１８００
〜３０００ｍｇ ７ｇ、好ましくは２０００〜２５００
ｍｇ７ｇの範囲にある活性炭素繊維を用いたことによっ
て、上記の問題点を解決したものである。Means for Solving the E0 Problem In this invention, as an active layer material of a carbon plastic electrode of a metal halogen battery, an iodine adsorption amount of 1800
~3000mg 7g, preferably 2000-2500
The above-mentioned problems are solved by using activated carbon fiber in the mg/7g range.
Ｆ０作用
金属ハロゲン電池、例えば亜鉛臭素電池においては活性
層の臭素吸着能力が高い程、電池の電気化学反応が促進
されて有利であると考えられる。In F0-acting metal halogen batteries, such as zinc-bromine batteries, it is believed that the higher the bromine adsorption capacity of the active layer, the more advantageous the electrochemical reaction of the battery will be promoted.
ここで、この臭素吸着能力は一般的に固体表面の物理吸
着能力を表す場合に用いられるヨウ素吸着量として考え
ることができ、このヨウ素吸着量と正極の放電過電圧の
関係は１次関数的なリニアな関係ではなく、あるレベル
以下の吸着能力では過電圧が非常に大きいが、一定のレ
ベル以上では飽和状態になり、それ以上吸着能力を上げ
ても過電圧は殆ど変化しないという漸近線をもつ指数関
数的な関係にある。Here, this bromine adsorption capacity can be thought of as the amount of iodine adsorption, which is generally used to express the physical adsorption ability of a solid surface, and the relationship between this amount of iodine adsorption and the discharge overvoltage of the positive electrode is a linear function. It is not an exponential relationship with an asymptote that means that the overvoltage is very large when the adsorption capacity is below a certain level, but it becomes saturated above a certain level, and the overvoltage hardly changes even if the adsorption capacity is increased further. There is a relationship.
このため、上記の一定レベル以上の吸着能力を有する活
性炭素繊維シートを活性層に用いれば、電池のクーロン
効率およびエネルギー効率の安定した特性が得られるも
のである。Therefore, if an activated carbon fiber sheet having an adsorption capacity above a certain level is used in the active layer, stable characteristics of coulombic efficiency and energy efficiency of the battery can be obtained.
Ｇ、実施例
実施例１：
亜鉛臭素電池の正極活性層材として、人ｅｅ５０７−２
０（商品名：日本カイノール■製）を選び、種々のロッ
トの中からシート厚みと目付量がほぼ同じものを多数ピ
ックアップしてヨウ素吸着量の値と正極放電過電圧の相
関関係を調へた。G. Examples Example 1: Human ee507-2 as positive electrode active layer material of zinc bromine battery
0 (trade name: manufactured by Nippon Kynor ■), a large number of sheets with almost the same thickness and basis weight were selected from various lots, and the correlation between the value of the amount of iodine adsorption and the positive electrode discharge overvoltage was investigated.
目付量が約８２ｇ／ｒｎ’、厚みが約０．４２ｍｍで、
ヨウ素吸着量が種々異なる２２種類の平織された活性炭
素繊維シート（以下「クロス」という）をカーボンプラ
スチックの片面にラミネートシてバイポーラ電極を作製
した。The basis weight is approximately 82g/rn', the thickness is approximately 0.42mm,
A bipolar electrode was fabricated by laminating 22 types of plain-woven activated carbon fiber sheets (hereinafter referred to as "cloth") with various iodine adsorption amounts on one side of carbon plastic.
上記ラミネートは、押し出し機（日本製鋼所膜Ｐ９０〜
２８Ａｗ）を使用して、カーボンプラスチックペレツ
ｌ−（＃ｖエチレン／カーボン系充填剤＝ ５０７５０
重量比）をＴダイ （特殊水平ハンガータイプ２リツプ
長６ｏ。The above laminate is made using an extruder (Japan Steel Works Membrane P90~
28Aw) to make carbon plastic pellets.
l-(#v ethylene/carbon filler = 50750
Weight ratio) to T die (special horizontal hanger type 2 lip length 6o).
ｍｍ、 リップ厚１．２ｍｎ）より押し出し、３本ロ
ールで冷却し、厚薄調整する際最下段田−ルと中間ロー
ルの間にクロスを挿入して行った。mm, lip thickness 1.2 mm), cooled with three rolls, and when adjusting the thickness, a cloth was inserted between the bottom roll and the middle roll.
以上のようにして作製した２２枚の電極の正極数重過電
圧を測定した結果とヨウ素吸着量の関係を第１図に示す
。図に示されるように、クロスの目付量およびシート厚
みが一定の場合、放電過電圧の値はクロスのヨウ素吸着
量に依存しており、その傾向は放電電流密度が大きい程
顕著である。FIG. 1 shows the relationship between the results of measuring the positive electrode multiple overvoltage of the 22 electrodes prepared as described above and the amount of iodine adsorbed. As shown in the figure, when the basis weight of the cloth and the sheet thickness are constant, the value of the discharge overvoltage depends on the amount of iodine adsorbed by the cloth, and this tendency becomes more pronounced as the discharge current density increases.
また、ヨウ素吸着量が２０００＋ｎｇ ／ ｇ以上では
飽和状態になり、放電過電圧はほとんど変化しないのに
対し、１８００ＩＩＩｇ／ ｇ以下のものは過電圧が急
激に高くなる傾向が明確に認められる。In addition, when the amount of iodine adsorption is 2000+ng/g or more, it becomes saturated and the discharge overvoltage hardly changes, whereas it is clearly recognized that when the amount of iodine adsorption is 1800IIIg/g or less, the overvoltage tends to increase rapidly.
以上の結果から、正極の活性層材として活性炭素繊維シ
ートを用いる場合には、ヨウ素吸着量が１８００ｍｇ
／ ｇ以上のものが適していると言える。From the above results, when using an activated carbon fiber sheet as the active layer material of the positive electrode, the amount of iodine adsorption is 1800 mg.
/ g or more is suitable.
実施例２：
実施例１と同様にしてクロスＡｅｃ５０７−２０ （商
品名二日本カイソール■製）をカーボンプラスチックに
ラミネートシて電極を作成し、ヨウ素吸着量の値が１７
０Ｏｎ１ｇ／ｇ以下をＡ郡、１７００〜１８００１１ｇ
／ｇｌｅＢ郡、１８００〜１９００ｍｇ／ｇヲＣ郡、１
９００〜２００ｏＩＩＩｇ／ｇｒｅＤ郡、および２００
０ｍｇ／ｇ以上をＥ郡として選別した。Example 2: In the same manner as in Example 1, an electrode was created by laminating cloth Aec507-20 (product name: manufactured by Nippon Kaisoru ■) on carbon plastic, and the value of iodine adsorption amount was 17.
0On1g/g or less in A group, 1700-180011g
/gleB county, 1800-1900mg/gwoC county, 1
900-200oIIIg/greD county, and 200
0 mg/g or more was selected as Group E.
これらのＡ−Ｅ郡のそれぞれからサップリングしく８）
た電極を、セパレータとともに積層して５種類の１０セ
ル積層のバイポーラ積層電池ａ −ｅを構成した。The electrodes from each of these groups A to E were laminated together with separators to construct five types of bipolar stacked batteries a to e with 10 cells stacked.
この様にして構成した各電池にそれぞれ電解液として２
．５ｍｏｌ／Ｉ臭化亜鉛水溶液、３ｍｏ ｌ ／ Ｉ塩
化アンモニ ウ ム 、 ０．５ｍｏｌ／ｌメチルーエ
チルーモル本ルニウムプロマイド、０．５１１＋０１７
１メチル−エチル−ピロリじニウム知マイト、 １０
’ｍｏｌ／Ｉ塩化錫および５ｘ１０づｍｏｌ／ｌ臭化
鉛を用いて２０ｍＡ／ｃｎｆで８時間充電し、同電流密
度２０ｍＡ／ｃｎｒで放電し、ＩＯＶでカットオフした
。Each battery constructed in this way has 2 ml of electrolyte.
．． 5 mol/I zinc bromide aqueous solution, 3 mol/I ammonium chloride, 0.5 mol/l methyl-ethyl mol Honolium bromide, 0.511+017
1 Methyl-ethyl-pyrrolidinium chiromite, 10
The battery was charged with 'mol/I tin chloride and 5x10mol/l lead bromide at 20 mA/cnf for 8 hours, discharged at the same current density of 20 mA/cnr, and cut off at IOV.
この時の電圧効率、クーロン効率、エネルギー効率を表
１に示した。表から明らがなようにヨウ素吸着量が大き
くなる程、即ち電池ａ ＜ ｂ ＜ ｃ ＜ｄ ＜ ｅ
の順に効率が向上している。Table 1 shows the voltage efficiency, coulomb efficiency, and energy efficiency at this time. As is clear from the table, the larger the amount of iodine adsorption, that is, the battery a < b < c < d < e.
Efficiency improves in this order.
特にクロスのヨウ素吸着量が１８００ｍｇ／ｇ以上の電
池Ｃｙ ｄｙ ｅはクーロン効率９２％以上、エネルギ
ー効率８２％以上でともに優れている。In particular, the battery Cy dy e, in which the amount of iodine adsorbed by the cloth is 1800 mg/g or more, is excellent with both a Coulombic efficiency of 92% or more and an energy efficiency of 82% or more.
第１表 単位（Ｘ）
実施例３：
実施例２で用いた電池ａ〜ｅについて、２０ｍＡ／ｃｄ
で８時間充電後、同電流密度で放電し、放電末期５ｖに
なった時点で電池電極の正負を逆にして、逆充電を２時
間、次に逆放電（臭素消し）を３時間行うことを１サイ
クルとするサイクルテストをそれぞれ２００回行い、エ
ネルギー効率の再現性を確認した。Table 1 Unit (X) Example 3: For batteries a to e used in Example 2, 20 mA/cd
After charging for 8 hours, discharge at the same current density, and at the end of discharge to 5V, reverse the positive and negative polarities of the battery electrodes, reverse charge for 2 hours, and then reverse discharge (bromine eradication) for 3 hours. Each cycle test was performed 200 times to confirm the reproducibility of energy efficiency.
第２図および第３図は上記のサイクルテストの結果を示
すものである。なお、図においてエネルギー効率は１０
サイクル毎に平均値を算出して表している。FIGS. 2 and 3 show the results of the above cycle test. In addition, in the figure, the energy efficiency is 10
The average value is calculated and expressed for each cycle.
その結果、電池ａおよびｂは各サイクルでの効率にバラ
ツキがあり、また第３図に見られるように１５０サイク
ルを過ぎると徐々に効率が低下して、２００サイクルで
はエネルギー効率が８０ｚ以下となっている。As a result, the efficiency of batteries a and b varies with each cycle, and as shown in Figure 3, the efficiency gradually decreases after 150 cycles, and at 200 cycles, the energy efficiency drops to 80z or less. ing.
これに対して、ヨウ素吸着量が１８００■／ｇ以上の活
性炭素繊維を活性層に用いた電池ｃ、ｄ、およびｅは、
第２図に示されるように初めの１０サイクルは効率が若
干低いが、エージングがよく行われて作動状態が安定す
ると各電池とも安定した効率でサイクルが進み、１５０
サイクルを過ぎても電池ａおよびｂのような効率の低下
はみられない。On the other hand, batteries c, d, and e, which use activated carbon fibers with an iodine adsorption amount of 1800 μg or more in the active layer,
As shown in Figure 2, the efficiency is slightly low for the first 10 cycles, but once the battery is well aged and the operating condition stabilizes, each battery continues to cycle at a stable efficiency, reaching 150 cycles.
Even after the cycle, there is no decrease in efficiency like in batteries a and b.
しかも、２００サイクルまで常に８２％以上のエネルギ
ー効率を維持しているので、ボンブロス、インバーター
及び冷却装置等の補機損失分を考慮しても電池システム
全体のエネルギー効率は７０〜８０に以上を常時維持で
きるものである。Moreover, the energy efficiency of the entire battery system is always maintained at 82% or higher up to 200 cycles, so even considering the loss of auxiliary equipment such as the bomb broth, inverter, and cooling device, the energy efficiency of the entire battery system is always 70-80% or higher. It is something that can be maintained.
これらの結果は、ヨウ素吸着量が１８００呵／ｇ以上、
好ましくは２０００ｍｇ／ｇ以上の活性炭素繊維を正極
活性層に用いれば安定的に高いエネルギー効率で電池を
運転できることを示している。These results indicate that the iodine adsorption amount is 1800 tsu/g or more,
It is shown that if activated carbon fiber of preferably 2000 mg/g or more is used in the positive electrode active layer, the battery can be stably operated with high energy efficiency.
Ｈ０発明の効果
この発明は、金属ハロゲン電池の正極活性層のヨウ素吸
着量と正極放電過電圧が漸近線をもつ指数関数的な関係
にあり、一定レベル以上のヨウ素吸着量においては放電
過電圧を安定的に小さくできることを見出し、ヨウ素吸
着量が１８００ｍｇ／ｇ以上、好ましくは２０００ｎ１
ｇ／ｇ以上の活性炭素繊維を活性層材に用いたことによ
り、充放電サイクルを連続して行う場合にも安定して電
池の高いエネルギー効率を維持できるという極めて優れ
た効果を有するものである。H0 Effects of the Invention This invention shows that the amount of iodine adsorbed in the positive electrode active layer of a metal halogen battery and the positive electrode discharge overvoltage have an exponential relationship with an asymptote, and that the amount of iodine adsorbed in the positive electrode active layer of a metal halogen battery is in an exponential relationship with an asymptote. We found that the amount of iodine adsorption can be reduced to 1800 mg/g or more, preferably 2000 n1
By using activated carbon fiber of g/g or more in the active layer material, it has an extremely excellent effect of stably maintaining high energy efficiency of the battery even when performing charge/discharge cycles continuously. .
第１図は活性炭素繊維シートのヨウ素吸着量と正極放電
過電圧の関係を示すグラフ、第２図はヨウ素吸着量１８
００ＩＩＩｇ／ｇ以上の活性炭素繊維シートを用いた電
池の充放電サイクル数とエネルギー効率の関係を示すグ
ラフ、第３図はヨウ素吸着量１８００ＩＩｇ／ｇ未満の
活性炭素繊維シートを用いた電池の充放電サイクル数と
エネルギー効率の関係を示すグラフ、第４図は亜鉛臭素
電池の基本構成模式図である。
１：電池反応層、２：正極室、３：負極室、４：隔膜、
５：正極、６：負極、７：正極電解液、８：負極電解液
、９，１０：電解液タンク、１１，１２：ポンプ、ｌｌ
ａ、ｌｌｂ：切換弁。
代理人 弁理士 佐藤正年
１：電池反応槽
２：正極室
３：負極室
４：隔膜
５：正極
６：負極
７：正極電解液
８：負極電解液
９．１０：電解液タンク
１１．１２：ボノブ
１１ａ 、 ｌｌｂ ：切換弁Figure 1 is a graph showing the relationship between the amount of iodine adsorbed by the activated carbon fiber sheet and the positive electrode discharge overvoltage, and Figure 2 is a graph showing the relationship between the amount of iodine adsorbed on the activated carbon fiber sheet and the amount of iodine adsorbed at 18
A graph showing the relationship between the number of charging/discharging cycles and energy efficiency of a battery using an activated carbon fiber sheet with an iodine adsorption amount of 0.00IIIg/g or more, and Figure 3 shows the charging/discharging of a battery using an activated carbon fiber sheet with an iodine adsorption amount of less than 1800IIg/g. FIG. 4 is a graph showing the relationship between the number of cycles and energy efficiency, and is a schematic diagram of the basic configuration of a zinc bromine battery. 1: battery reaction layer, 2: positive electrode chamber, 3: negative electrode chamber, 4: diaphragm,
5: positive electrode, 6: negative electrode, 7: positive electrode electrolyte, 8: negative electrode electrolyte, 9, 10: electrolyte tank, 11, 12: pump, ll
a, llb: switching valve. Agent Patent Attorney Masatoshi Sato 1: Battery reaction tank 2: Positive electrode chamber 3: Negative electrode chamber 4: Diaphragm 5: Positive electrode 6: Negative electrode 7: Positive electrode electrolyte 8: Negative electrode electrolyte 9.10: Electrolyte tank 11.12: Bonob 11a, llb: switching valve
Claims (3)
面に活性層を形成したカーボンプラスチック電極を使用
して成る金属ハロゲン電池において、前記カーボンプラ
スチック電極の活性層として、ヨウ素吸着量が１８００
〜３０００ｍｇ／ｇの範囲にある活性炭素繊維を用いた
ことを特徴とする金属ハロゲン電池。(1) In a metal halogen battery using a carbon plastic electrode in which an active layer is formed on the surface of carbon plastic formed in the form of a sheet, the active layer of the carbon plastic electrode has an iodine adsorption amount of 1800
A metal halogen battery characterized by using activated carbon fiber in the range of ~3000 mg/g.
を出発原料としたものである特許請求の範囲第１項記載
の金属ハロゲン電池。(2) The metal halogen battery according to claim 1, wherein the activated carbon fiber is made from phenolic novolac fiber as a starting material.
２５００ｍｇ／ｇの範囲にある特許請求の範囲第１項記
載の金属ハロゲン電池。(3) The amount of iodine adsorbed by the activated carbon fiber is 2000~
The metal halogen battery according to claim 1, in the range of 2500 mg/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63002477A JPH01183065A (en) | 1988-01-11 | 1988-01-11 | Metal halogen battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63002477A JPH01183065A (en) | 1988-01-11 | 1988-01-11 | Metal halogen battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01183065A true JPH01183065A (en) | 1989-07-20 |
Family
ID=11530420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63002477A Pending JPH01183065A (en) | 1988-01-11 | 1988-01-11 | Metal halogen battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01183065A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2022118733A (en) * | 2013-03-15 | 2022-08-15 | ２４エム・テクノロジーズ・インコーポレイテッド | Asymmetric battery having semi-solid cathode and high energy density anode |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5996662A (en) * | 1982-11-24 | 1984-06-04 | Meidensha Electric Mfg Co Ltd | Plastic electrode for zinc bromine battery |
| JPS59215667A (en) * | 1983-05-24 | 1984-12-05 | Meidensha Electric Mfg Co Ltd | Electrode of zinc-bromine cell |
| JPS6025152A (en) * | 1983-07-20 | 1985-02-07 | Matsushita Electric Ind Co Ltd | Rechargeable battery |
| JPS61158673A (en) * | 1984-08-16 | 1986-07-18 | Meidensha Electric Mfg Co Ltd | Zinc-halogen battery with porous electrode |
| JPS61277156A (en) * | 1985-06-03 | 1986-12-08 | Mitsui Toatsu Chem Inc | Zinc iodine secondary cell |
| JPH01169876A (en) * | 1987-12-25 | 1989-07-05 | Meidensha Corp | Metallic halogen cell |
-
1988
- 1988-01-11 JP JP63002477A patent/JPH01183065A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5996662A (en) * | 1982-11-24 | 1984-06-04 | Meidensha Electric Mfg Co Ltd | Plastic electrode for zinc bromine battery |
| JPS59215667A (en) * | 1983-05-24 | 1984-12-05 | Meidensha Electric Mfg Co Ltd | Electrode of zinc-bromine cell |
| JPS6025152A (en) * | 1983-07-20 | 1985-02-07 | Matsushita Electric Ind Co Ltd | Rechargeable battery |
| JPS61158673A (en) * | 1984-08-16 | 1986-07-18 | Meidensha Electric Mfg Co Ltd | Zinc-halogen battery with porous electrode |
| JPS61277156A (en) * | 1985-06-03 | 1986-12-08 | Mitsui Toatsu Chem Inc | Zinc iodine secondary cell |
| JPH01169876A (en) * | 1987-12-25 | 1989-07-05 | Meidensha Corp | Metallic halogen cell |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2022118733A (en) * | 2013-03-15 | 2022-08-15 | ２４エム・テクノロジーズ・インコーポレイテッド | Asymmetric battery having semi-solid cathode and high energy density anode |
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