JPH0334270A - Electrolyte for secondary cell, and secondary cell - Google Patents
Electrolyte for secondary cell, and secondary cellInfo
- Publication number
- JPH0334270A JPH0334270A JP1166599A JP16659989A JPH0334270A JP H0334270 A JPH0334270 A JP H0334270A JP 1166599 A JP1166599 A JP 1166599A JP 16659989 A JP16659989 A JP 16659989A JP H0334270 A JPH0334270 A JP H0334270A
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- negative electrode
- molten salt
- halide
- electrolytic solution
- 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
- 239000003792 electrolyte Substances 0.000 title claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 42
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- -1 (1) Imidazolium halide Chemical class 0.000 claims description 31
- 229910001507 metal halide Inorganic materials 0.000 claims description 28
- 150000005309 metal halides Chemical class 0.000 claims description 28
- 239000008151 electrolyte solution Substances 0.000 claims description 17
- 150000004820 halides Chemical class 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000002635 aromatic organic solvent Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 22
- 238000002844 melting Methods 0.000 abstract description 13
- 230000008018 melting Effects 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 210000004027 cell Anatomy 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 6
- 150000005840 aryl radicals Chemical class 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000036647 reaction Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000011701 zinc Substances 0.000 description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000004070 electrodeposition Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 101100016034 Nicotiana tabacum APIC gene Proteins 0.000 description 4
- 239000002659 electrodeposit Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000005486 organic electrolyte Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 101100514056 Rhodobacter capsulatus modD gene Proteins 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- KVBQNFMTEUEOCD-UHFFFAOYSA-M 1-butylpyridin-1-ium;bromide Chemical compound [Br-].CCCC[N+]1=CC=CC=C1 KVBQNFMTEUEOCD-UHFFFAOYSA-M 0.000 description 1
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910005432 FeSx Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は二次電池用電解液及び二次電池にかか１）、詳
しくはイミダゾリウムハロゲン化物を混合した混合溶融
塩からなる二次電池用電解液と、この電解液を使用した
二次電池に関するものである。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to an electrolytic solution for a secondary battery and a secondary battery. The present invention relates to an electrolytic solution for use in the electrolyte and a secondary battery using this electrolytic solution.
〈従来の技術〉
従来の代表的な二次電池は鉛蓄電池やニッケル／カドニ
ウム電池で、水溶液を特徴とする特許である。また、負
極に亜鉛や鉄を用いた二次電池も知られてお１）、これ
らも電解液は水溶液系である。<Conventional Technology> Typical conventional secondary batteries are lead-acid batteries and nickel/cadmium batteries, which are patented as featuring aqueous solutions. In addition, secondary batteries using zinc or iron for the negative electrode are also known (1), and the electrolyte in these is also an aqueous solution.
〈発明が解決しようとする課題〉
しかし、水ｉ８液系を電解質とする二次電池では、主と
して負極のデンドライト状析出等の電析の問題があ１）
、広く実用化されていない。<Problems to be Solved by the Invention> However, secondary batteries that use aqueous I8 liquid system as an electrolyte mainly suffer from electrodeposition problems such as dendrite precipitation on the negative electrode1)
, has not been widely put into practical use.
また、水？８液系を電解質とする二次電池では、電池電
圧が約２ｖ〜１．２Ｖ程度であることから、近年の高電
圧化の要求に答えることができない。Also, water? A secondary battery using an 8-liquid system as an electrolyte has a battery voltage of about 2V to 1.2V, and therefore cannot meet the recent demand for higher voltage.
この光め、高電圧化を目指して負極にリチウム系を用い
、また有機溶媒に電解質を溶解した有機系電解液を用い
た二次電池の開発が盛んに行われているが、ここでも負
極のデンドライトの問題があ１）、広く実用化されてい
ない。また、有機系電解７＆を用いた二次電池では、電
解液の比抵抗が水溶液系の比抵抗よりも大きいため、高
出力が得られない欠点があった。In light of this, development of secondary batteries using lithium-based negative electrodes and organic electrolyte solutions in which electrolytes are dissolved in organic solvents is being actively conducted with the aim of increasing voltage. Due to the problem of dendrites (1), it has not been widely put into practical use. In addition, the secondary battery using the organic electrolyte 7& has the disadvantage that high output cannot be obtained because the specific resistance of the electrolytic solution is higher than the specific resistance of the aqueous solution.
このような負極のデンドライト等の問題を解決するため
、溶融塩を電解液として使用することが考えられている
。In order to solve the problem of negative electrode dendrites, etc., it has been considered to use a molten salt as an electrolyte.
しかし、負極のデンドライト等の問題を解決出来るもの
の、融点、粘性、導電性等の点で充分ではなかった。However, although it could solve problems such as dendrites in the negative electrode, it was not sufficient in terms of melting point, viscosity, conductivity, etc.
本発明は上記従来技術の課題を解決するためになされた
もので、その目的とするところは、負極のデンドライト
等の問題がなく、また融点、粘性を低下させ、導電性を
向上させ、電池反応で良好な電着物が得られ、を流密度
を上げることが出来る二次電池用電解液を提供すること
であ１）、また負極のデンドライト等の問題がなく、高
電圧、高出力、長寿命の二次電池を提供することである
。The present invention has been made to solve the problems of the prior art described above, and its objectives are to eliminate problems such as dendrites in the negative electrode, lower the melting point and viscosity, improve conductivity, and improve battery reaction. By providing an electrolytic solution for secondary batteries that can obtain good electrodeposit and increase the flow density (1), it also eliminates problems such as negative electrode dendrites, has high voltage, high output, and long life. The aim is to provide rechargeable batteries.
＜ｉ１題を解決するための手段〉
上記課題を解決するため、本発明者等は二次電池用電解
液について鋭意研究した結果、イミダゾリウムハロゲン
化物を混合した混合溶融塩を電解液として使用すると、
負極のデンドライトを解決出来る上に、他の溶融塩に比
して融点を下げ、粘性を下げ、導電性を向上し、電池反
応で電着物の光沢、物性の向上を図１）、電流密度を上
げることが出来る等の効果があることを見出して、本発
明をなすに至った。<Means for Solving Problem i1> In order to solve the above problem, the present inventors conducted intensive research on electrolytes for secondary batteries, and found that if a mixed molten salt containing imidazolium halide is used as an electrolyte. ,
In addition to being able to solve dendrites in the negative electrode, it lowers the melting point, lowers viscosity, and improves conductivity compared to other molten salts, improves the gloss and physical properties of electrodeposit in battery reactions (Fig. 1), and lowers current density. The present inventors have discovered that there are effects such as being able to increase
また、この混合溶融塩を使用して二次電池を構成すると
、負極のデンドライトの問題がなく、常温以下から１５
０°Ｃの温度域で負極にＬｉ、Ａｌ、Ｃａ、 Ｍｇ、Ｚ
ｎ、Ｆｅ又はこれらの合金を用いることが可能で、高電
圧、高出力、長寿命の二次電池が得られることを見出し
て、本発明をなすに至った。In addition, if a secondary battery is constructed using this mixed molten salt, there will be no problem with dendrites in the negative electrode, and
Li, Al, Ca, Mg, Z on the negative electrode in the temperature range of 0°C
The present inventors have discovered that it is possible to use n, Fe, or an alloy thereof, and that a secondary battery with high voltage, high output, and long life can be obtained, and the present invention has been completed.
すなわち、本発明の二次電池用電解液は、次式で示され
るイミダゾリウムハロゲン化物（Ｒ１−Ｒ５は水素原子
又は置換されてもよい炭素数Ｃ１〜Ｃ６の範囲のアルキ
ル、アルケニル、アルキニル、シクロアルキル若しくは
アリール基：ＸはＣＩ、 Ｂｒ、Ｉ ） ２０〜８０ｓ
ｏｌＸと、各種金属ハロゲン化物ＭＸｎ （Ｍ：に、Ｃ
ａ、Ｌｉ、Ａｌ、Ｍｇ、Ｚｎ、Ｆｅ ；Ｘ：Ｃ１，Ｂ
ｒＳ ｌ ；ｎ＝１゜２．３）とを混合した混合溶融
塩からなることを特徴としている。That is, the electrolytic solution for secondary batteries of the present invention is an imidazolium halide represented by the following formula (R1-R5 are hydrogen atoms or optionally substituted alkyl, alkenyl, alkynyl, cyclo Alkyl or aryl group: X is CI, Br, I) 20-80s
olX and various metal halides MXn (M: to, C
a, Li, Al, Mg, Zn, Fe; X: C1, B
rS l ; n=1°2.3).
また、前記イミダゾリウムハロゲン化物とアルキルピリ
ジニウムハロゲン化物（アルキル基；Ｃ１−ｃｓ ｉ
ハロゲン：ＣＬ Ｂｒ、 Ｉ ）の混合物２０〜８０
■ｏｌｚと、各種金属ハロゲン化物ＭＸｎ（Ｍ：に、Ｃ
ａ、Ｌｉ、、Ａｔ５Ｍｇ、Ｚｎ、Ｆｅ ；Ｘ：Ｃ１，Ｂ
ｒ、Ｉ Ｂｎ＝１．２．３）とを混合した混合溶融塩か
らなることをｅｌ＆としている。Further, the imidazolium halide and the alkylpyridinium halide (alkyl group; C1-cs i
Halogen: CLBr, I) mixture 20-80
■olz and various metal halides MXn (M: ni, C
a, Li, , At5Mg, Zn, Fe; X: C1, B
el& consists of a mixed molten salt mixed with r, I Bn = 1.2.3).
また、前記混合溶融塩に芳香族系有機溶剤を添加するこ
とを特徴としている。Further, it is characterized in that an aromatic organic solvent is added to the mixed molten salt.
また、本発明の二次電池は、前記イミダゾリウムハロゲ
ン化物２０〜８０ｓｏ）χと各種金属ハロゲン化物ＭＸ
ｎとを混合した混合溶融塩、あるいは前記イミダゾリウ
ムハロゲン化物と前記アルキルピリジニウムハロゲン化
物との混合物２０〜８０■ｏｌｚと各種金属ハロゲン化
物ＭＸｎとを混合した混合溶融塩を電解液に使用し、負
極にＬｉ、Ａｌ、Ｃａ、Ｍｇ５ＺｎＳＦｅ又はこれらの
合金を用いたことを特徴としている。Further, the secondary battery of the present invention includes the imidazolium halide 20-80so)χ and various metal halides MX.
A mixed molten salt mixed with n, or a mixed molten salt mixed with 20 to 80 olz of the imidazolium halide and the alkylpyridinium halide and various metal halides MXn is used as the electrolytic solution, and the negative electrode It is characterized by using Li, Al, Ca, Mg5ZnSFe, or an alloy thereof.
まず、イミダゾリウムハロゲン化物を２０〜８０ａ＋ｏ
ｌＸと、各種金属ハロゲン化物とを混合した混合溶融塩
からなる二次電池用電解液について説明する。First, add 20 to 80 a+o of imidazolium halide.
An electrolytic solution for a secondary battery made of a mixed molten salt of lX and various metal halides will be described.
イミダゾリウムハロゲン化物の化学構造式は、次式によ
り表される。The chemical structural formula of imidazolium halide is represented by the following formula.
ここで、Ｒ１−Ｒ２は水素原子又は置換されてもよい炭
素数Ｃ１〜Ｃ，の範囲のアルキル、アルケニル、アルキ
ニル、シクロアルキル若しくはアリール基であ１）、ま
たＸはＣＩ、 Ｏｒ、 Ｔ等のハロゲンである。Here, R1-R2 is a hydrogen atom or an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, or aryl group having a carbon number ranging from C1 to C1), and X is CI, Or, T, etc. It is halogen.
イミダゾリウムハロゲン化物としては、例えばｌ−メチ
ル−３−エチルイミダゾリウムブロマイド（以下ＭＥ
Ｉ Ｂと略記する）、１−メチル−３−ブチルイミダゾ
リウムクロライド（以下ＭＢＩＣと略記する）、ｌ−ア
リル−３−プロピルイミダゾリウムクロライド（以下Ａ
ＰＩＣと略記する）がある。ここで、メチル、エチル、
ブチル、アリル、プロピルの代わりに他のアルキル基、
アルケニル基でもよく、またアルキニル、シクロアルキ
ル若しくはアリール基でもよい。また、臭素（Ｂ ｒ
） 、塩素（ＣＩ）の代わりにヨウ素（１）でもよい。Examples of imidazolium halides include l-methyl-3-ethylimidazolium bromide (hereinafter ME
IB), 1-methyl-3-butylimidazolium chloride (hereinafter referred to as MBIC), l-allyl-3-propylimidazolium chloride (hereinafter referred to as A
(abbreviated as PIC). Here, methyl, ethyl,
Other alkyl groups instead of butyl, allyl, propyl,
It may be an alkenyl group, or an alkynyl, cycloalkyl or aryl group. In addition, bromine (Br
), iodine (1) may be used instead of chlorine (CI).
また、金属ハロゲン化物としては、塩化物、臭化物、ヨ
ウ化物があ１）、例えばＬｉＣ１、ＡｌＣｌ、、ＺｎＣ
Ｉｚ ５ＦｅＣＩ＊ 、ＡｌＢｒ＊ 、ＺｎＢｒｚ、Ｆ
ｅＢｒ５等が使用される。In addition, examples of metal halides include chlorides, bromides, and iodides1), such as LiCl, AlCl, and ZnC.
Iz 5FeCI*, AlBr*, ZnBrz, F
eBr5 etc. are used.
イミダゾリウムハロゲン化物と各種金属ハロゲン化物と
の混合溶融塩としては、例えばＭＥＩＢＡＩＢｒｓ 、
ＭＥＩＢ ＡｌＣｌ３ 、ＭＥＩＢＺｎＣＩｔ 、Ｍ
ＥＩＢ ＦｅＣｌ５ 、ＭＥＩＢＺｎＢｒｚ、ＭＥＩ
Ｂ−ＦｅＢｒｓ、ＭＢＩＣＺｎＣｌｚ 、ＡＰ ＩＣＡ
ｌＣ１１等がある。Examples of the mixed molten salt of imidazolium halide and various metal halides include MEIBAIBrs,
MEIBAlCl3, MEIBZnCIt, M
EIB FeCl5, MEIBZnBrz, MEI
B-FeBrs, MBICZnClz, AP ICA
There are lC11 etc.
これら混合溶融塩は常温〜約６０°Ｃで液体となってい
る。特に、金属ハロゲン化物としてＡ Ｉ Ｂ ｒ 、
ｌ、ＦｅＢｒ、を用いると融点を下げて常温以下の低温
で電池作動が行なえる。These mixed molten salts are liquid at room temperature to about 60°C. In particular, as metal halides A I B r ,
When FeBr is used, the melting point is lowered and the battery can be operated at a low temperature below room temperature.
なお、イミダゾリウムハロゲン化物と各種金属ハロゲン
化物を各々２種以上混合してもよい。Note that two or more of each of the imidazolium halide and various metal halides may be mixed.
溶融塩の金属ハロゲン化？１４度としては、４０〜８Ｏ
＠ｏｌχ程度が望ましい、４Ｏ−ｏＩＸよりも少ないと
、溶融塩中のアンモニウムカチオンの濃度が高くな１）
、その還元反応が優先するため、各種金属の析出が困難
にな１）、負極の充電効率が悪くなる。また、逆に８０
＋ｏｌχよりも多くなると、融点が高くなってしま゛う
。Metal halogenation of molten salt? 14 degrees is 40-8O
@olχ is desirable; if it is less than 4O-oIX, the concentration of ammonium cations in the molten salt will be high 1)
Since the reduction reaction takes precedence, it becomes difficult to deposit various metals (1), and the charging efficiency of the negative electrode deteriorates. Also, conversely, 80
If the amount exceeds +olχ, the melting point will become high.
上記混合溶融塩にベンゼン、トルエン、キシレン等の芳
香族系有機溶剤を添加すると、溶融塩中のイオン形態や
解離平衡を変化させずに粘度を低下させることが出来る
上に、導電率を高めることが出来る。When an aromatic organic solvent such as benzene, toluene, or xylene is added to the above mixed molten salt, the viscosity can be lowered without changing the ionic form or dissociation equilibrium in the molten salt, and the conductivity can be increased. I can do it.
芳香族系有ｍ溶剤の添加量は、１０〜８Ｏνｏ１χ程度
が望ましい、１０＊ｏｌχよりも少ないと、殆ど影響が
なく、また８Ｏ＊ｏｌχよりも多いと、溶融塩中でイオ
ン種の濃度が薄くなり過ぎ、充放電効率が著しく低下す
る。The amount of the aromatic solvent added is preferably about 10 to 8Oνo1χ.If it is less than 10*olχ, it will have almost no effect, and if it is more than 8O*olχ, the concentration of ionic species in the molten salt will be low. If it becomes too much, the charge/discharge efficiency will drop significantly.
次に、前記イミダゾリウムハロゲン化物とアルキルピリ
ジニウムハロゲン化物の混合物２０〜８０５ｏｌＸと、
各種金属ハロゲン化物とを混合した混合溶融塩からなる
二次電池用電解液について説明する。Next, the mixture of the imidazolium halide and the alkylpyridinium halide 20 to 805olX,
An electrolytic solution for secondary batteries consisting of a mixed molten salt mixed with various metal halides will be described.
アルキルピリジニウムハロゲン化物としては、ブチルピ
リジニウムクロリド（以下ＢＰＣと略記する）とブチル
ピリジニウムブロマイド（以下ＢＰＢと略記する）等が
ある。ここで、ブチルの代わりにメチル、エチル、プロ
ピル、アミル等のアルキル基でもよい、また、塩素（Ｃ
Ｉ）、臭素（Ｂ「）の代わりにヨウ素（１）でもよい。Examples of alkylpyridinium halides include butylpyridinium chloride (hereinafter abbreviated as BPC) and butylpyridinium bromide (hereinafter abbreviated as BPB). Here, an alkyl group such as methyl, ethyl, propyl, amyl, etc. may be used instead of butyl, or chlorine (C
I), iodine (1) may be used instead of bromine (B'').
また、アルキルピリジニウムハロゲン化物に混合するイ
ミダゾリウムハロゲン化物としては、例えばＭＥＩＢが
ある。Further, as the imidazolium halide to be mixed with the alkylpyridinium halide, there is MEIB, for example.
また、前記金属ハロゲン化物としては、例えばＡｌＣｌ
３ 、ＺｎＣＩｚ 、ＦｅＣｈ、ＡｌＢｒ５ＺｎＢｒ、
、ＦｅＢｒａ等が使用される。Further, as the metal halide, for example, AlCl
3, ZnCIz, FeCh, AlBr5ZnBr,
, FeBra, etc. are used.
アルキルピリジニウムハロゲン化物とイξダゾリ金属ハ
ロゲン化物と金属ハロゲン化物との混合溶融塩としては
、例えばＢＰＣ−ＭＥＩＢ−ＺｎＣ１，、ＢＰＣ−ＭＥ
ＩＢ−ＦｅＣ１，、ＢＰＢＭＥｒＢ ＡｌＢｒ５ 、
ＢＰＢ ＭＥＩＢ−ＺｎＢｒ、等がある。Examples of the mixed molten salt of an alkylpyridinium halide, an idazoli metal halide, and a metal halide include BPC-MEIB-ZnC1, BPC-ME
IB-FeC1,, BPBMErB AlBr5,
BPB MEIB-ZnBr, etc.
なお、アルキルピリジニウムハロゲン化物とイミダゾリ
ウムハロゲン化物と金属ハロゲン化物を各々２種以上混
合してもよい。Note that two or more of each of the alkylpyridinium halide, imidazolium halide, and metal halide may be mixed.
溶融塩の金属ハロゲン化物濃度の点については、前述し
たイミダゾリウムハロゲン化物と金属ハロゲン化物との
混合溶融塩の場合と同じである。また、混合熔融塩にヘ
ンゼン、トルエン、キシレン等の芳香族系有機溶剤を添
加する点についても同じである。The metal halide concentration of the molten salt is the same as in the case of the mixed molten salt of imidazolium halide and metal halide described above. The same applies to the addition of aromatic organic solvents such as Hensen, toluene, and xylene to the mixed molten salt.
次に、前記電解液を使用した二次電池について説明する
。Next, a secondary battery using the electrolyte will be explained.
電解液としてイミダゾリウムハロゲン化物（ＭＥＩＢ）
を２０〜８０ｍｏｌＸと各種金属ハロゲン化物とを混合
した混合溶融塩や、あるいはアルキルピリジニウムハロ
ゲン化物（ＢＰＣ，ＢＰＢ）とイミダゾリウムハロゲン
化物（ＭＥＩＢ）の混合物２０〜８０ａｉｏｌχと金属
ハロゲン化物とを混合した混合溶融塩を使用する。Imidazolium halide (MEIB) as electrolyte
A mixed molten salt of 20 to 80 molX and various metal halides, or a mixture of 20 to 80 aiolχ of alkylpyridinium halides (BPC, BPB) and imidazolium halides (MEIB) and a metal halide. Use molten salt.
また、負極としてＬｉ５Ａｌ、Ｃａ、Ｍｇ、Ｚｎ、Ｆｅ
又はこれらの合金（Ｌｉ−Ａ！、Ｌｉ−３ｉ、Ｃａ−Ｍ
ｇ）を使用する。In addition, as a negative electrode, Li5Al, Ca, Mg, Zn, Fe
Or these alloys (Li-A!, Li-3i, Ca-M
g).
ここで、金属ハロゲン化物、ＢＰＣ，ＢＰＢ、ＭＥＩＢ
は水分を嫌い、また溶融塩並びに各種負極材料はＯ！を
嫌うため、出来るだけ乾燥無酸素雰囲気とし、完全密封
セルで電池作動させることが望ましい。Here, metal halides, BPC, BPB, MEIB
does not like moisture, and molten salts and various negative electrode materials are O! Therefore, it is desirable to operate the battery in a completely sealed cell in as dry an oxygen-free atmosphere as possible.
く作用〉
イミダゾリウムハロゲン化物（例えばＭＥＩＢ、ＭＢＩ
Ｃ，ＡＰＩＣ）を２０〜８（１ｗｏ１％と各種金属ハロ
ゲン化物とを混合した混合溶融塩からなる電解液では、
充電時に水溶液系の電解液や有機系電解液のようにデン
ドライトの問題がなく、また有機系の電解液よりも導電
率が高い、また、他の溶融塩に比して融点や粘性を下げ
、導電性を高し、電池反応で電着物の光沢、物性の向上
を図１）、電流密度を上げることが出来る。Effect> Imidazolium halides (e.g. MEIB, MBI
C, APIC) from 20 to 8 (1wo1%) and various metal halides in an electrolytic solution consisting of a mixed molten salt,
It does not have the problem of dendrites during charging unlike aqueous electrolytes or organic electrolytes, has higher conductivity than organic electrolytes, and has a lower melting point and viscosity than other molten salts. It increases conductivity, improves the gloss and physical properties of electrodeposit through battery reaction (Fig. 1), and increases current density.
このため、極間距離を短くしてエネルギー変換のロスを
少なくすることが出来、また、極間距離が短く出来るこ
とから、ジュール熱による発熱を可及的に少なくするこ
とが出来る。Therefore, the distance between the poles can be shortened to reduce energy conversion loss, and since the distance between the poles can be shortened, the heat generation due to Joule heat can be reduced as much as possible.
イミダゾリウムハロゲン化物と金属ハロゲン化物とを各
々２７１以上混合した場合には、融点、粘性を更に下げ
ることが可能である。When an imidazolium halide and a metal halide are mixed at 271 or more each, it is possible to further lower the melting point and viscosity.
金属ハロゲン化物を２種以上組み合わせると、融点、粘
性を下げると共に、導電性を向上させることが可能であ
るが、この場合金属の共析を考慮して組み合わせる必要
がある。When two or more metal halides are combined, it is possible to lower the melting point and viscosity and improve the conductivity, but in this case, it is necessary to combine them in consideration of metal eutectoid.
また、アアルキルピリジニ金属ハロゲン化物（例えばＢ
ＰＣ，、ＢＰＢ）とイミダゾリウムハロゲン化物（例え
ばＭＥ ！ Ｂ） の混合物２０〜８０ｍｏｌＸと、金
属ハロゲン化物とを混合した混合溶融塩からなる電解液
でも、上記電解液の場合と同様であるが、ここではアル
キルピリジニウムハロゲン化物とイミダゾリウムハロゲ
ン化物とを混合しているため、融点および粘性を更に下
げることが可能である。Also, alkylpyridini metal halides (e.g. B
An electrolytic solution consisting of a mixed molten salt of a mixture of 20 to 80 molX of a mixture of PC, BPB) and an imidazolium halide (for example, ME!B) and a metal halide is similar to the above electrolytic solution, but Since the alkylpyridinium halide and imidazolium halide are mixed here, it is possible to further lower the melting point and viscosity.
また、これら混合溶融塩を電解液として二次電池を構成
すると、デンドライトの間湖がなく、常温以下から１５
０°Ｃの温度域でＬｉ、Ａｌ、Ｃａ、Ｍｇ、Ｚｎ、Ｆｅ
又はこれらの合金（Ｌｉ−ＡＩ。In addition, when a secondary battery is constructed using these mixed molten salts as an electrolyte, there is no lake between the dendrites, and the
Li, Al, Ca, Mg, Zn, Fe in the temperature range of 0°C
Or these alloys (Li-AI.
Ｌ ｔ −３ｉ、 Ｃａ−Ｍｇ）等を負極に用いること
が可能とな１）、高電圧、高出力、長寿命の二次電池が
得られる。Lt-3i, Ca-Mg), etc. can be used for the negative electrode 1), and a secondary battery with high voltage, high output, and long life can be obtained.
〈実施例〉 以下、本発明の実施例について説明する。<Example> Examples of the present invention will be described below.
なお、本実施例では、イミダゾリウムハロゲン化物とし
て、ＭＥＩＢ、、ＭＢＩＣ，ＡＰＩＣを使用した場合を
示しているが、これ以外のイミダゾリウムハロゲン化物
、例えばＭＥＩＢのメチル、エチルやＭＢＩＣのブチル
やＡＰＩＣのアリル、プロピルの代わりに他のアルキル
基、アルケニル基が結合したイミダゾリウムハロゲン化
物でもほぼ同じ結果が得られたので、その結果について
は実施例から省略した。また、アルキル基、アルケニル
基の代わりにアルキニル、シクロアルキル若しくはアリ
ール基が結合したイミダゾリウムハロゲン化物について
もほぼ同し結果が得られたので、その結果については同
様に実施例から省略した。In this example, MEIB, MBIC, and APIC are used as imidazolium halides, but other imidazolium halides such as methyl and ethyl of MEIB, butyl of MBIC, and APIC are also used. Almost the same results were obtained with imidazolium halides to which other alkyl groups or alkenyl groups were bonded instead of allyl or propyl, and therefore the results were omitted from the examples. Furthermore, almost the same results were obtained with imidazolium halides in which an alkynyl, cycloalkyl, or aryl group was bonded instead of an alkyl group or an alkenyl group, and thus the results were similarly omitted from the examples.
負極の充放電作動試験は、いずれもＮ、、Ａｒ雰囲気中
において定電流によりｊテった。そして、負極にはＬｉ
、Ａｌ、Ｃａ、Ｍｇ、、Ｚｎ、Ｆｅ又はこれらの合金（
ＬＬ−Ａ１．Ｌｉ−３ｉ、ＣａＭｇ）を用いた。The charging/discharging operation test of the negative electrode was carried out using a constant current in a N, Ar atmosphere. And Li on the negative electrode
, Al, Ca, Mg, , Zn, Fe or alloys thereof (
LL-A1. Li-3i, CaMg) was used.
一方、実際の電池作動試験は、正極にＦｅＳ。On the other hand, in actual battery operation tests, FeS was used for the positive electrode.
を用い、負極に各種金属板またはフェルトを用いて定電
流で行った。The tests were carried out using a constant current using various metal plates or felt as the negative electrode.
〔実施例１〕
５０ｍｏｌχＬ ｉ ＣＩ −５０ｍｏｉＸＭＥ Ｉ
Ｂ系のｌ昆合溶融塩を電解液とし、Ｌｉ−Ａ１合金板を
負極に用いて６０”Ｃ，，１，２Ａｄｍ−”で充放電サ
イクル試験を行った。[Example 1] 50molχL i CI -50moiXME I
A charge/discharge cycle test was carried out at 60"C, 1,2Adm-" using a B-based l-kolite molten salt as an electrolyte and a Li-A1 alloy plate as a negative electrode.
この結果、充電時には、負極上に乳白色の光沢のある緻
密な結晶を有するリチウムの電着が得られ、デンドライ
トは見られなかった。続いてその電極を放電すると、電
着したリチウムは均一に溶解し、電流効率はほぼ１００
％であった。As a result, during charging, lithium was electrodeposited on the negative electrode in the form of dense crystals with a milky white luster, and no dendrites were observed. When the electrode is subsequently discharged, the electrodeposited lithium is uniformly dissolved, and the current efficiency is approximately 100%.
%Met.
〔実施例２〕
上記実施例１と同様の負極および電解液を用い、正極に
ＦｅＳｘを用いて電池を作製し、その電池動作を常温、
０．３Ａｄｍ−”の定電流で行ったところ、放電電圧が
２．６〜２．１ｖの放電曲線が得られ、充放電効率はほ
ぼ！００％であった。[Example 2] A battery was fabricated using the same negative electrode and electrolyte as in Example 1 and FeSx for the positive electrode, and the battery operation was performed at room temperature.
When a constant current of 0.3 Adm-'' was used, a discharge curve with a discharge voltage of 2.6 to 2.1 V was obtained, and the charging/discharging efficiency was approximately !00%.
〔実施例３〕
上記実施例１と同様の電解液に芳香族系有８！溶剤とし
てベンゼンを５０ｖｏｌＸ添加し、実施例１と同様の負
極を用いて、４０°Ｃ，０，７Ａｄｒ＋ｒ”で充放電サ
イクル試験を行った。[Example 3] The same electrolyte as in Example 1 above contains an aromatic system! 50 volX of benzene was added as a solvent, and using the same negative electrode as in Example 1, a charge/discharge cycle test was conducted at 40°C and 0.7 Adr+r''.
この結果、充電時には、負極上に乳白色の光沢のある緻
密な結晶を有するリチウムの電着が得られ、デンドライ
トは見られなかった。続いてその電極を放電すると、電
着したリチウムは均一に溶解し、電流効率はほぼ１００
％であった。As a result, during charging, lithium was electrodeposited on the negative electrode in the form of dense crystals with a milky white luster, and no dendrites were observed. When the electrode is subsequently discharged, the electrodeposited lithium is uniformly dissolved, and the current efficiency is approximately 100%.
%Met.
〔実施例４〕
７０ｍｏｌＸＺｎＣＩｚ ２０ｗｏｌＸＢＰｃ
−１０ａ＋ｏＨＭＥＩＢ系の混合溶融塩を電解液とし、
９９゜９％亜鉛（Ｚｎ）板を負極に用いて６０ ’Ｃ１
０，７Ａ ｄ ｍ−”で充放電サイクル試験を行った。[Example 4] 70molXZnCIz 20wolXBPc
-10a+oHMEIB system mixed molten salt as electrolyte,
60'C1 using 99°9% zinc (Zn) plate as the negative electrode
A charge/discharge cycle test was conducted at 0.7 A d m-''.
この結果、充電時には、負極上に緻密な灰白色の光沢の
ある亜鉛の電着が得られ、デンドライトは見られなかっ
た。続いてその電極を放電すると、電着した亜鉛は均一
に溶解し、電流効率はほぼ１００％であった。As a result, during charging, dense gray-white, shiny zinc electrodeposition was obtained on the negative electrode, and no dendrites were observed. When the electrode was subsequently discharged, the electrodeposited zinc was uniformly dissolved and the current efficiency was approximately 100%.
〔実施例５］
７０ｍｏｌＸＦｅＣＩ＊ ２０＋＋ｏｌＺＢＰ
Ｃ−１０ｍｏｌχＭＥＩＢ系の混合溶融塩を電解液とし
、９９゜９％鉄（Ｆｅ）板を負極に用いて６０゛Ｃ１０
，７Ａｄ ｍ−”で充放電サイクル試験を行った。[Example 5] 70molXFeCI* 20++olZBP
Using C-10molχMEIB-based mixed molten salt as the electrolyte and using a 99°9% iron (Fe) plate as the negative electrode, 60°C10
, 7Ad m-'' was subjected to a charge/discharge cycle test.
この結果、充電時には、負極上に緻密な灰白色の光沢の
ある鉄の電着が得られ、デンドライトは見られなかった
。続いてその電極を放電すると、電着した鉄は均一に溶
解し、電流効率はほぼ１００％であった。As a result, during charging, dense grayish-white, shiny iron electrodeposition was obtained on the negative electrode, and no dendrites were observed. When the electrode was subsequently discharged, the electrodeposited iron was uniformly dissolved and the current efficiency was approximately 100%.
〔実施例６〕
６７ｍｏｌ＄ＡｌＢｒ５ ２３ｍｏｌＸＢＰＢ−
１０ｓｏｌｘＭＥＩＢ系の混合溶融塩を電解液とし、９
９゜９％アルミニウム（ＡＩ）板を負極に用いて２７℃
、２．０Ａｄｍ−”で充放電サイクル試験を行った。[Example 6] 67mol$AlBr5 23molXBPB-
10solxMEIB-based mixed molten salt as electrolyte, 9
9.9% aluminum (AI) plate was used as the negative electrode at 27°C.
, 2.0 Adm-'', a charge/discharge cycle test was conducted.
この結果、充電時には、負極上に緻密な乳白色の光沢の
あるアルミニウムの電着が得られ、デンドライトは見ら
れなかった。続いてその電極を放電すると、電着したア
ルミニウムは均一に溶解し、電流効率はほぼ１００％で
あった。As a result, during charging, dense, milky, shiny aluminum electrodeposition was obtained on the negative electrode, and no dendrites were observed. When the electrode was subsequently discharged, the electrodeposited aluminum was uniformly dissolved and the current efficiency was approximately 100%.
〔実施例７〕
７０＠ｏｌχＺｎＢｒｚ ２０ｓｏｌ′１８ＰＢ−１
０ｓｏｌｚＭＥＩＢ系の混合溶融塩を電解液とし、９９
゜９％亜鉛（Ｚｎ）板を負極に用いて６０゛Ｃ１０，７
Ａ ｄ ｍ−’で充放電サイクル試験を行った。[Example 7] 70@olχZnBrz 20sol'18PB-1
Using 0solzMEIB-based mixed molten salt as the electrolyte, 99
60゛C10,7 using ゜9% zinc (Zn) plate as the negative electrode
A charge/discharge cycle test was conducted with A d m-'.
この結果、充電時には、負極上に緻密な乳白色の光沢の
ある亜鉛の電着が得られ、デンドライトは見られなかっ
た。続いてその電極を放電すると、電着した亜鉛は均一
に溶解し、電流効率はほぼ１００％であった。As a result, during charging, dense, milky, glossy zinc electrodeposition was obtained on the negative electrode, and no dendrites were observed. When the electrode was subsequently discharged, the electrodeposited zinc was uniformly dissolved and the current efficiency was approximately 100%.
７０ｍｏｌＸＺ ｎ Ｃ１！ −３０ｍｏｌＸＭＢ Ｉ
Ｃ系の混合溶融塩を電解液とし、９９．９％亜鉛（Ｚ
ｎ）板を負極に用いて８０°Ｃ，，０，５Ａｄｍ−”で
充放電サイクル試験を行った。70molXZnC1! -30molXMB I
C-based mixed molten salt is used as the electrolyte, and 99.9% zinc (Z
n) A charge/discharge cycle test was conducted at 80°C and 0.5Adm-'' using the plate as a negative electrode.
この結果、充電時には、負極上に灰白色の光沢のある亜
鉛の電着が得られ、デンドライトは見られなかった。続
いてその電極を放電すると、電着した亜鉛は均一に溶解
し、電流効率はほぼ１００％であった。As a result, during charging, a grayish white, shiny zinc electrodeposition was obtained on the negative electrode, and no dendrites were observed. When the electrode was subsequently discharged, the electrodeposited zinc was uniformly dissolved and the current efficiency was approximately 100%.
〔実施例９〕
６７ｍｏｌＸＡＩＣＩｚ ３３ｍｏｌ！ＡＰＩＣ系
の混合溶融塩を電解液とし、９９．９％アルミニウム（
ＡＩ）板を負極に用いて２７°Ｃ，］、７Ａｄｍ−”で
充放電サイクル試験を行った。[Example 9] 67molXAICIz 33mol! APIC-based mixed molten salt is used as the electrolyte, and 99.9% aluminum (
A charge/discharge cycle test was conducted at 27°C, ], 7Adm-'' using the AI) plate as a negative electrode.
この結果、充電時には、負極上に灰白色のなめらかなア
ルごニウムの電着が得られ、デンドライトは見られなか
った。続いてその電極を放電すると、電着したアルミニ
ウムは均一に溶解し、電流効率はほぼ１００％であった
。As a result, smooth gray-white argonium electrodeposition was obtained on the negative electrode during charging, and no dendrites were observed. When the electrode was subsequently discharged, the electrodeposited aluminum was uniformly dissolved and the current efficiency was approximately 100%.
〈発明の効果〉
以上説明したように本発明の二次電池用電解液によれば
、イ柔ダゾリウムハロゲン化物２０〜８０階ｏＩＸと、
各種金属ハロゲン化物とを混合した混合溶融塩から構成
したので、負極のデンドライト等の問題がなく、また融
点、粘性を低下させ、導電性を向上させ、電池反応で良
好な電着物が得られ、電流密度を上げることが出来る。<Effects of the Invention> As explained above, according to the electrolytic solution for a secondary battery of the present invention, infudazolium halide 20 to 80 oIX,
Since it is composed of a mixed molten salt mixed with various metal halides, there are no problems such as dendrites in the negative electrode, and it also lowers the melting point and viscosity, improves conductivity, and provides good electrodeposit in battery reactions. Current density can be increased.
また、イミダゾリウムハロゲン化物とアルキルピリジニ
ウムハロゲン化物の混合物２０〜８０醜Ｏ１χと、各種
金属ハロゲン化物とを混合した混合溶融塩から構成する
と、上記電解液の場合と同様の効果が得られる他に、融
点、粘性を更に下げることが出来る。In addition, when it is composed of a mixed molten salt obtained by mixing a mixture of imidazolium halide and alkylpyridinium halide 20 to 80 O1χ with various metal halides, in addition to obtaining the same effects as the above electrolytic solution, Melting point and viscosity can be further lowered.
また、前記溶融塩に芳香族系有機溶剤を添加すると、粘
度を低下させることが出来る上に、導電率を高めること
が出来る。Further, when an aromatic organic solvent is added to the molten salt, the viscosity can be lowered and the electrical conductivity can be increased.
また、本発明の二次電池によれば、負極にＬｉ、Ａｌ、
Ｃａ、Ｍｇ、Ｚｎ、Ｆｅ又はこれらの合金を用い、かつ
電解液として上記電解液を使用したので、負極のデンド
ライト等の問題がなく、高電圧、高出力、長寿命の二次
電池が得られる。Further, according to the secondary battery of the present invention, the negative electrode includes Li, Al,
Since Ca, Mg, Zn, Fe, or an alloy thereof is used, and the above electrolyte is used as the electrolyte, there are no problems such as negative electrode dendrites, and a secondary battery with high voltage, high output, and long life can be obtained. .
Claims (4)
式、化学式、表等があります▼ （Ｒ＿１〜Ｒ＿５は水素原子又は置換されてもよい炭素
数Ｃ＿１〜Ｃ＿６の範囲のアルキル、アルケニル、アル
キニル、シクロアルキル若しくはアリール基：ＸはＣｌ
、Ｂｒ、Ｉ）２０〜８０ｍｏｌ％と、各種金属ハロゲン
化物ＭＸｎ（Ｍ：Ｋ、Ｃａ、Ｌｉ、Ａｌ、Ｍｇ、Ｚｎ、
Ｆｅ；Ｘ：Ｃｌ、Ｂｒ、Ｉ：ｎ＝１、２、３）とを混合
した混合溶融塩からなることを特徴とする二次電池用電
解液。(1) Imidazolium halide represented by the following formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (R_1 to R_5 are hydrogen atoms or optionally substituted alkyl, alkenyl, alkynyl, cyclo Alkyl or aryl group: X is Cl
, Br, I) 20 to 80 mol% and various metal halides MXn (M: K, Ca, Li, Al, Mg, Zn,
An electrolytic solution for a secondary battery characterized by comprising a mixed molten salt containing Fe; X: Cl, Br, I: n=1, 2, 3).
ジニウムハロゲン化物（アルキル基：Ｃ＿１〜Ｃ＿５：
ハロゲン：Ｃｌ、Ｂｒ、Ｉ）の混合物２０〜８０ｍｏｌ
％と、各種金属ハロゲン化物ＭＸｎ（Ｍ：Ｋ、Ｃａ、Ｌ
ｉ、Ａｌ、Ｍｇ、Ｚｎ、Ｆｅ；Ｘ：Ｃｌ、Ｂｒ、Ｉ；ｎ
＝１、２、３）とを混合した混合溶融塩からなることを
特徴とする二次電池用電解液。(2) The imidazolium halide and the alkylpyridinium halide (alkyl group: C_1 to C_5:
Halogen: Cl, Br, I) mixture 20-80 mol
% and various metal halides MXn (M: K, Ca, L
i, Al, Mg, Zn, Fe; X: Cl, Br, I; n
= 1, 2, 3).
とを特徴とする請求項（１）又は（２）記載の二次電池
用電解液。(3) The electrolytic solution for a secondary battery according to claim (1) or (2), wherein an aromatic organic solvent is added to the mixed molten salt.
これらの合金を用い、かつ電解液として請求項（１）、
（２）又は（３）記載の二次電池用電解液を使用したこ
とを特徴とする二次電池。(4) Li, Al, Ca, Mg, Zn, Fe or an alloy thereof is used for the negative electrode, and claim (1) is used as the electrolyte,
A secondary battery characterized by using the electrolytic solution for secondary batteries described in (2) or (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1166599A JPH0334270A (en) | 1989-06-30 | 1989-06-30 | Electrolyte for secondary cell, and secondary cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1166599A JPH0334270A (en) | 1989-06-30 | 1989-06-30 | Electrolyte for secondary cell, and secondary cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0334270A true JPH0334270A (en) | 1991-02-14 |
Family
ID=15834281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1166599A Pending JPH0334270A (en) | 1989-06-30 | 1989-06-30 | Electrolyte for secondary cell, and secondary cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0334270A (en) |
Cited By (11)
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|---|---|---|---|---|
| JP2001526450A (en) * | 1997-12-10 | 2001-12-18 | イギリス国 | Electrochemical cell containing liquid organic electrolyte with conductive additives |
| US6413486B2 (en) | 1998-06-05 | 2002-07-02 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous secondary battery, constituent elements of battery, and materials thereof |
| JP2002313414A (en) * | 2001-04-06 | 2002-10-25 | Tokuyama Corp | Electrolyte for non-aqueous electrolyte |
| KR100478554B1 (en) * | 2001-10-17 | 2005-03-23 | 엔이씨 도낀 가부시끼가이샤 | Electrolytic Solution and Electrochemical Cell Using the Same |
| WO2005080347A1 (en) * | 2004-02-24 | 2005-09-01 | Kanto Kagaku Kabushiki Kaisha | Novel imidazolium compound |
| JP2010235526A (en) * | 2009-03-31 | 2010-10-21 | Otsuka Chem Co Ltd | Imidazolium salt, electrolyte, and electrochemical device |
| CN102195091A (en) * | 2010-03-10 | 2011-09-21 | 中国科学院过程工程研究所 | Ionic liquid electrolyte for lithium secondary battery |
| JP2012048874A (en) * | 2010-08-25 | 2012-03-08 | Yamaguchi Univ | Electrolyte for magnesium secondary battery, and magnesium secondary battery using the same |
| JP2012182124A (en) * | 2011-02-28 | 2012-09-20 | Toyota Motor Corp | Magnesium secondary battery, method for using electrolyte in magnesium secondary battery, and electrolyte for magnesium secondary battery |
| WO2014030761A1 (en) * | 2012-08-21 | 2014-02-27 | 本田技研工業株式会社 | Device provided with positive electrode and salt, and secondary battery |
| WO2014030500A1 (en) * | 2012-08-21 | 2014-02-27 | トヨタ自動車株式会社 | Electrode body and cell provided with same |
-
1989
- 1989-06-30 JP JP1166599A patent/JPH0334270A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6596441B1 (en) * | 1997-12-10 | 2003-07-22 | Qinetiq Limited | Electrochemical cell comprising a liquid organic electrolyte with a conductive additive |
| JP2001526450A (en) * | 1997-12-10 | 2001-12-18 | イギリス国 | Electrochemical cell containing liquid organic electrolyte with conductive additives |
| US6413486B2 (en) | 1998-06-05 | 2002-07-02 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous secondary battery, constituent elements of battery, and materials thereof |
| JP2002313414A (en) * | 2001-04-06 | 2002-10-25 | Tokuyama Corp | Electrolyte for non-aqueous electrolyte |
| JP4641646B2 (en) * | 2001-04-06 | 2011-03-02 | 株式会社トクヤマ | Electrolyte for non-aqueous electrolyte |
| KR100478554B1 (en) * | 2001-10-17 | 2005-03-23 | 엔이씨 도낀 가부시끼가이샤 | Electrolytic Solution and Electrochemical Cell Using the Same |
| TWI392668B (en) * | 2004-02-24 | 2013-04-11 | Hiroyuki Ohno | A new imidazolium compound |
| WO2005080347A1 (en) * | 2004-02-24 | 2005-09-01 | Kanto Kagaku Kabushiki Kaisha | Novel imidazolium compound |
| JP2005239580A (en) * | 2004-02-24 | 2005-09-08 | Hiroyuki Ono | New imidazolium compound |
| US7517999B2 (en) * | 2004-02-24 | 2009-04-14 | Kanto Kagaku Kabushiki Kaisha | Imidazolium compound |
| JP2010235526A (en) * | 2009-03-31 | 2010-10-21 | Otsuka Chem Co Ltd | Imidazolium salt, electrolyte, and electrochemical device |
| CN102195091A (en) * | 2010-03-10 | 2011-09-21 | 中国科学院过程工程研究所 | Ionic liquid electrolyte for lithium secondary battery |
| JP2012048874A (en) * | 2010-08-25 | 2012-03-08 | Yamaguchi Univ | Electrolyte for magnesium secondary battery, and magnesium secondary battery using the same |
| JP2012182124A (en) * | 2011-02-28 | 2012-09-20 | Toyota Motor Corp | Magnesium secondary battery, method for using electrolyte in magnesium secondary battery, and electrolyte for magnesium secondary battery |
| WO2014030761A1 (en) * | 2012-08-21 | 2014-02-27 | 本田技研工業株式会社 | Device provided with positive electrode and salt, and secondary battery |
| WO2014030500A1 (en) * | 2012-08-21 | 2014-02-27 | トヨタ自動車株式会社 | Electrode body and cell provided with same |
| JP2014041709A (en) * | 2012-08-21 | 2014-03-06 | Honda Motor Co Ltd | Device including positive electrode and salt, and secondary battery |
| JP2014041722A (en) * | 2012-08-21 | 2014-03-06 | Toyota Motor Corp | Electrode body, and battery including the electrode body |
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