JP3374865B2 - Method for producing room temperature molten salt - Google Patents
Method for producing room temperature molten saltInfo
- Publication number
- JP3374865B2 JP3374865B2 JP21060893A JP21060893A JP3374865B2 JP 3374865 B2 JP3374865 B2 JP 3374865B2 JP 21060893 A JP21060893 A JP 21060893A JP 21060893 A JP21060893 A JP 21060893A JP 3374865 B2 JP3374865 B2 JP 3374865B2
- Authority
- JP
- Japan
- Prior art keywords
- room temperature
- molten salt
- temperature molten
- thionyl chloride
- halide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アルミニウムハロゲン
化物とオニウムハロゲン化物とを含有する高純度常温溶
融塩の製造方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing a high-purity room temperature molten salt containing an aluminum halide and an onium halide.
【０００２】[0002]
【従来の技術】アルミニウムハロゲン化物とオニウムハ
ロゲン化物とからなる常温溶融塩は、常温で液状であ
り、良好な導電性を示すことが知られており、特にＮ，
Ｎ´−ジアルキルイミダゾリウムハロゲン化物とアルミ
ニウムハロゲン化物からなる常温溶融塩は、従来使用さ
れている有機系又は無機系電解液と大幅に異なる新しい
特性を有する電解液として大いに期待されている。例え
ば、特開昭６０−１３３６６９号及び同１３３６７０号
各公報には、１，２，３−トリアルキルイミダゾリウム
ハロゲン化物とアルキルハロゲン化物とからなる常温溶
融塩を電解液とした２次電池が提案され、更に、特開昭
６２−１６５８７９号公報には、１−メチル−３−エチ
ルイミダゾリウムクロリドと三塩化アルミニウムとから
なる常温溶融塩を電解液とした２次電池が提案されてい
る。また、特開昭６０−１３６１８０号公報には、１，
３−ジアルキルイミダゾリウムハロゲン化物と周期律表
第III ａ族の金属ハロゲン化物からなる常温溶融塩を電
解液とした２次電離が提案されている。従来、この溶融
塩の製造には、固体であるアルミニウムハロゲン化物と
オニウムハロゲン化物を窒素置換したグローブボックス
内で徐々に混合する固体混合法が知られている（例え
ば、電気化学、５４、（３）、２５７参照）。また、最
近では、低沸点の不活性溶媒中で、アルミニウムハロゲ
ン化物とオニウムハロゲン化物とを反応させる方法が提
案されている（特開平３−２４０８８号公報参照）。し
かしながら、これらの方法で用いられる化学物質は、吸
湿性であるため工業的規模で容易に高純度の常温溶融塩
を製造することはできなかった。2. Description of the Related Art It is known that a room temperature molten salt composed of an aluminum halide and an onium halide is a liquid at room temperature and exhibits good conductivity.
A room temperature molten salt composed of an N'-dialkylimidazolium halide and an aluminum halide is greatly expected as an electrolytic solution having new properties which are significantly different from the organic or inorganic electrolytic solutions used conventionally. For example, JP-A-60-133669 and JP-A-133670 each propose a secondary battery in which a room temperature molten salt composed of a 1,2,3-trialkylimidazolium halide and an alkyl halide is used as an electrolytic solution. In addition, Japanese Patent Laid-Open No. 62-165879 proposes a secondary battery using an ambient temperature molten salt of 1-methyl-3-ethylimidazolium chloride and aluminum trichloride as an electrolytic solution. Moreover, in Japanese Patent Laid-Open No. Sho 60-136180,
Secondary ionization using a room temperature molten salt composed of a 3-dialkylimidazolium halide and a metal halide of Group IIIa of the periodic table as an electrolytic solution has been proposed. Conventionally, for the production of this molten salt, a solid mixing method has been known in which solid aluminum halides and onium halides are gradually mixed in a nitrogen-substituted glove box (for example, electrochemical, 54 , (3. ), 257). Further, recently, a method of reacting an aluminum halide and an onium halide in an inert solvent having a low boiling point has been proposed (see JP-A-3-24088). However, since the chemical substances used in these methods are hygroscopic, it was not possible to easily produce a high-purity room temperature molten salt on an industrial scale.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記問題を
解決し、水分由来の含酸素不純物を除去し、工業的規模
で容易に高純度の常温溶融塩を製造する方法を提供する
ことを目的とする。DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a method for solving the above problems, removing oxygen-containing impurities derived from water, and easily producing a high-purity room temperature molten salt on an industrial scale. To aim.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記目的
を達成すべく鋭意検討した結果、アルミニウムハロゲン
化物とオニウムハロゲン化物とからなる常温溶融塩に、
塩化チオニル処理を行うことによって、容易に高純度の
常温溶融塩が製造できることを見出し本発明を完成し
た。本発明の常温溶融塩の製造方法は、水分由来の含酸
素不純物を含有するアルミニウムハロゲン化物２０〜８
０モル％とオニウムハロゲン化物８０〜２０モル％とか
らなる常温溶融塩に、塩化チオニル処理を施し、その後
含酸素不純物を余剰の塩化チオニルと共に除去するもの
である。Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that an ambient temperature molten salt composed of an aluminum halide and an onium halide is
The present invention has been completed by finding that a high-purity room temperature molten salt can be easily produced by performing a thionyl chloride treatment. The method for producing a room temperature molten salt according to the present invention is applied to aluminum halides 20 to 8 containing oxygen-containing impurities derived from water.
A room temperature molten salt consisting of 0 mol% and an onium halide of 80 to 20 mol% is subjected to a thionyl chloride treatment, and then oxygen-containing impurities are removed together with an excess of thionyl chloride.
【０００５】本発明で使用するアルミニウムハロゲン化
物としては、三塩化アルミニウム、三臭化アルミニウム
などが挙げられる。また、本発明で使用するオニウムハ
ロゲン化物としては、テトラエチルアンモニウムブロミ
ド、トリメチルエチルアンモニウムクロリド等の第４級
アンモニウム塩；ブチルピリジニウムクロリド等のピリ
ジニウム塩；１−エチル−３−メチルイミダゾリウムク
ロリド等のイミダゾリウム塩；エチルトリブチルホスホ
ニウムブロミド等のホスホニウム塩などが挙げられる。Examples of the aluminum halide used in the present invention include aluminum trichloride and aluminum tribromide. The onium halides used in the present invention include quaternary ammonium salts such as tetraethylammonium bromide and trimethylethylammonium chloride; pyridinium salts such as butylpyridinium chloride; and imidazo compounds such as 1-ethyl-3-methylimidazolium chloride. Lithium salt; phosphonium salts such as ethyltributylphosphonium bromide and the like can be mentioned.
【０００６】アルミニウムハロゲン化物とオニウムハロ
ゲン化物の混合は、反応器を冷却しながらの固体混合方
法又は不活性溶媒を用いる混合法等によって行うことが
できる。このとき、特にオニウムハロゲン化物は、吸湿
性が高いため水を不純物として含有していることがあ
る。この水は、混合操作時にハロゲン化水素及び含酸素
不純物に分解することが知られている。本発明で対象と
なる常温溶融塩は、アルミニウムハロゲン化物２０〜８
０モル％とオニウムハロゲン化物８０〜２０モル％とを
混合したものを用いることができるが、特にアルミニウ
ムハロゲン化物３０〜５０モル％とオニウムハロゲン化
物７０〜５０モル％の組成の溶融塩に塩化チオニル処理
を行うことが好ましい。アルミニウムハロゲン化物の濃
度が３０モル％未満の場合には、常温溶融塩の粘度が高
く、オニウムハロゲン化物の種類によっては固化するこ
とがあるため好ましくない。またアルミニウムハロゲン
化物の濃度が５０モル％を超える場合には、後述する塩
化チオニル処理が進行し難くいことがあるため好ましく
ない。The aluminum halide and the onium halide can be mixed by a solid mixing method while cooling the reactor or a mixing method using an inert solvent. At this time, in particular, the onium halide has a high hygroscopic property, and thus may contain water as an impurity. It is known that this water decomposes into hydrogen halide and oxygen-containing impurities during the mixing operation. The room temperature molten salt that is the object of the present invention is an aluminum halide 20-8.
A mixture of 0 mol% and 80 to 20 mol% of onium halide can be used, and particularly thionyl chloride is added to a molten salt having a composition of 30 to 50 mol% of aluminum halide and 70 to 50 mol% of onium halide. Treatment is preferred. When the concentration of the aluminum halide is less than 30 mol%, the viscosity of the room temperature molten salt is high and it may be solidified depending on the type of the onium halide, which is not preferable. Further, when the concentration of the aluminum halide exceeds 50 mol%, it may be difficult to proceed with the thionyl chloride treatment described below, which is not preferable.
【０００７】塩化チオニル処理は、含酸素不純物を含有
する溶融塩に塩化チオニルを添加し、反応させることに
よって行う。添加する塩化チオニルの量は、常温溶融塩
中の含酸素不純物の量に対して０．１〜２倍モルが好ま
しい。添加量が０．１倍モル未満の場合には、含酸素不
純物の除去が十分でないため好ましくない。また添加量
が２倍モルを超える場合には、余剰の塩化チオニルの留
去に時間とエネルギーを要し好ましくない。なお、常温
溶融塩中の含酸素不純物量は、赤外分光分析により、Ｏ
Ｈ伸縮振動（波数３３６０ｃｍ-1）の吸収強度を測定す
ることにより定量できる。反応温度は、室温〜８０℃の
範囲が好ましい。反応温度が８０℃を超える場合には、
反応途中で塩化チオニルが留出するので好ましくない。
反応は、塩化チオニルの添加とともに進行し、添加後５
時間以内に終了する。The thionyl chloride treatment is carried out by adding thionyl chloride to a molten salt containing oxygen-containing impurities and reacting them. The amount of thionyl chloride added is preferably 0.1 to 2 times the mol of the oxygen-containing impurities in the room temperature molten salt. If the amount added is less than 0.1 times the molar amount, the oxygen-containing impurities are not sufficiently removed, which is not preferable. On the other hand, if the addition amount exceeds 2 times the molar amount, it takes time and energy to distill off the excess thionyl chloride, which is not preferable. The amount of oxygen-containing impurities in the room temperature molten salt was determined by infrared spectroscopy to
It can be quantified by measuring the absorption intensity of H stretching vibration (wave number 3360 cm −1 ). The reaction temperature is preferably in the range of room temperature to 80 ° C. If the reaction temperature exceeds 80 ° C,
Thionyl chloride is distilled off during the reaction, which is not preferable.
The reaction proceeds with the addition of thionyl chloride and after addition 5
Finish in time.
【０００８】含酸素不純物は、反応終了後、余剰の塩化
チオニルと共に留去する。また常温溶融塩の組成を調製
する必要がある場合には、組成調製後に留去を行っても
よい。塩化チオニルの留去は、減圧下、８０℃以下の加
熱によって容易に行える。このとき塩化チオニル残量
は、５重量％以下が好ましい。５重量％を超える場合に
は、常温溶融塩特性、例えばアルミニウム電析特性が低
下するので好ましくない。After completion of the reaction, oxygen-containing impurities are distilled off together with excess thionyl chloride. When it is necessary to prepare the composition of the room temperature molten salt, the composition may be distilled off. The thionyl chloride can be easily distilled off by heating at 80 ° C. or lower under reduced pressure. At this time, the remaining amount of thionyl chloride is preferably 5% by weight or less. If it exceeds 5% by weight, room temperature molten salt characteristics, for example, aluminum electrodeposition characteristics deteriorate, which is not preferable.
【０００９】[0009]
実施例１
１−エチル−３−メチルイミダゾリウムクロリド１４７
ｇ（１モル）と三塩化アルミニウム１２０ｇ（０．９モ
ル）とを、シクロへキサノン１２０ｇを投入したガラス
製反応器に入れ混合した後、減圧下（１０ｍｍＨｇ）、
６０℃に加熱してシクロヘキサンを留去した。得られた
三塩化アルミニウム濃度４７重量％の常温溶融塩２６７
ｇは、赤外分光分析法により、２重量％（３３６０ｃｍ
-1）の水分由来の含酸素不純物が混入していることがわ
かった。上記常温溶融塩に、塩化チオニル５３ｇ（０．
４５モル）を徐々に滴下したところ、激しい発泡が見ら
れた。反応器を７０℃に加熱し、４時間反応させた後、
減圧下（１０ｍｍＨｇ）、９０℃で２時間加熱して余剰
の塩化チオニルを留去した。この時、常温溶融塩中に残
留している塩化チオニル濃度は、赤外分光分析により、
０．３％（１２３０ｃｍ-1）であった。塩化チオニル処
理した常温溶融塩に、三塩化アルミニウム１４７ｇ
（１．１モル）を投入し、三塩化アルミニウム濃度６７
モル％、１−エチル−３−メチルイミダゾリウムクロリ
ド３３モル％のめっき浴に調製し直した。赤外分光分析
により、水分由来の含酸素不純物は検出限界以下（３３
６０ｃｍ-1）であった。Example 1 1-Ethyl-3-methylimidazolium chloride 147
g (1 mol) and 120 g (0.9 mol) of aluminum trichloride were put into a glass reactor charged with 120 g of cyclohexanone and mixed, and then under reduced pressure (10 mmHg),
Cyclohexane was distilled off by heating to 60 ° C. The obtained room temperature molten salt 267 having an aluminum trichloride concentration of 47% by weight.
g is 2% by weight (3360 cm) by infrared spectroscopy.
It was found that the oxygen-containing impurities derived from the water of ( -1 ) are mixed. 53 g of thionyl chloride (0.
(45 mol) was gradually added dropwise, and vigorous foaming was observed. After heating the reactor to 70 ° C. and reacting for 4 hours,
The mixture was heated at 90 ° C. for 2 hours under reduced pressure (10 mmHg) to distill off excess thionyl chloride. At this time, the concentration of thionyl chloride remaining in the room temperature molten salt was determined by infrared spectroscopic analysis.
It was 0.3% (1230 cm -1 ). To room temperature molten salt treated with thionyl chloride, aluminum trichloride 147g
(1.1 mol) was added and the aluminum trichloride concentration was 67.
A plating bath containing mol% and 33 mol% of 1-ethyl-3-methylimidazolium chloride was prepared again. Infrared spectroscopic analysis showed that oxygen-containing impurities derived from water were below the detection limit (33
It was 60 cm -1 ).
【００１０】比較例１
実施例１において、塩化チオニル５３ｇを滴下しなかっ
たこと以外は、実施例１と同様に行った。得られた常温
溶融塩は、赤外分光分析により、１％（３３６０ｃ
ｍ-1）の水分由来の含酸素不純物が混入していることが
わかった。Comparative Example 1 Example 1 was repeated except that 53 g of thionyl chloride was not added dropwise. The obtained room temperature molten salt was 1% (3360c
It was found that oxygen-containing impurities derived from water of m −1 ) were mixed.
【００１１】[0011]
【発明の効果】本発明によれば、水分由来の含酸素不純
物の少ない高純度なアルミニウムハロゲン化物とオニウ
ムハロゲン化物とからなる常温溶融塩を製造することが
できる。EFFECTS OF THE INVENTION According to the present invention, it is possible to produce a room temperature molten salt composed of a high-purity aluminum halide and onium halide containing few oxygen-containing impurities derived from water.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小湊 あさを 茨城県稲敷郡阿見町中央８丁目３番１号 三菱油化株式会社 筑波総合研究所内 (56)参考文献 特開 昭63−264878（ＪＰ，Ａ) 特開 平１−264182（ＪＰ，Ａ) 特開 平３−238769（ＪＰ，Ａ) 特開 平３−24088（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 10/36 - 10/40 C07F 5/06 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Asahi Kominato, 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Mitsubishi Petrochemical Co., Ltd., Tsukuba Research Institute (56) Reference JP-A-63-264878 (JP , A) JP-A-1-264182 (JP, A) JP-A-3-238769 (JP, A) JP-A-3-24088 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB) Name) H01M 10/36-10/40 C07F 5/06
Claims (2)
ミニウムハロゲン化物２０〜８０モル％とオニウムハロ
ゲン化物８０〜２０モル％とからなる常温溶融塩に、塩
化チオニル処理を施し、その後含酸素不純物を余剰の塩
化チオニルと共に除去することを特徴とする常温溶融塩
の製造方法。1. A room temperature molten salt consisting of 20 to 80 mol% of an aluminum halide and 80 to 20 mol% of an onium halide containing oxygen-containing impurities derived from water is subjected to a thionyl chloride treatment, and then oxygen-containing impurities are added. A method for producing a room temperature molten salt, which comprises removing with excess thionyl chloride.
酸素不純物に対し、０．１〜２倍モルの塩化チオニルを
添加し、室温〜８０℃で反応させる請求項１に記載の常
温溶融塩の製造方法。2. The room temperature melting according to claim 1, wherein in the thionyl chloride treatment, 0.1 to 2 moles of thionyl chloride is added to the oxygen-containing impurities in the room temperature molten salt and the mixture is reacted at room temperature to 80 ° C. Method for producing salt.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21060893A JP3374865B2 (en) | 1993-08-25 | 1993-08-25 | Method for producing room temperature molten salt |
| US08/295,422 US5543522A (en) | 1993-08-25 | 1994-08-25 | Process for preparing an ambient temperature molten salt using thionyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21060893A JP3374865B2 (en) | 1993-08-25 | 1993-08-25 | Method for producing room temperature molten salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0765858A JPH0765858A (en) | 1995-03-10 |
| JP3374865B2 true JP3374865B2 (en) | 2003-02-10 |
Family
ID=16592147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21060893A Expired - Fee Related JP3374865B2 (en) | 1993-08-25 | 1993-08-25 | Method for producing room temperature molten salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3374865B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014237606A (en) * | 2013-06-07 | 2014-12-18 | 住友電気工業株式会社 | Method for producing molten salt, molten salt, and method for producing aluminum |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63264878A (en) * | 1986-12-25 | 1988-11-01 | Tosoh Corp | Aluminum-conductive polymer secondary battery using cold molten salt electrolyte |
| JPH01264182A (en) * | 1988-04-15 | 1989-10-20 | Tosoh Corp | Battery |
| JP2771607B2 (en) * | 1989-06-22 | 1998-07-02 | 三菱化学株式会社 | Method for producing room temperature molten salt |
| JPH03238769A (en) * | 1990-02-16 | 1991-10-24 | Nisshin Steel Co Ltd | Aluminum secondary battery |
-
1993
- 1993-08-25 JP JP21060893A patent/JP3374865B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0765858A (en) | 1995-03-10 |
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