JPH07114939A - Manufacture of high purity normal temperature fused salt - Google Patents
Manufacture of high purity normal temperature fused saltInfo
- Publication number
- JPH07114939A JPH07114939A JP5258460A JP25846093A JPH07114939A JP H07114939 A JPH07114939 A JP H07114939A JP 5258460 A JP5258460 A JP 5258460A JP 25846093 A JP25846093 A JP 25846093A JP H07114939 A JPH07114939 A JP H07114939A
- Authority
- JP
- Japan
- Prior art keywords
- room temperature
- molten salt
- halide
- temperature molten
- aluminum
- 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.)
- Withdrawn
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)
Abstract
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からなる高純度常温溶融
塩を製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high-purity room temperature molten salt composed of 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。2. Description of the Related Art Room temperature molten salts composed of aluminum halides and onium halides are liquid at room temperature,
It is known to show good conductivity, especially N, N '
A room-temperature molten salt composed of a dialkyl imidazolium halide and an aluminum halide is highly expected as an electrolytic solution having new characteristics which are significantly different from the organic or inorganic electrolytic solution used conventionally.
【０００３】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ミニウムハロゲン
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６０−１３６１
８０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族金属ハロゲン化物と
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
ている。For example, JP-A-60-133669 and JP-A-133670 each disclose a secondary solution using a room temperature molten salt of a 1,2,3-trialkylimidazolium halide and an aluminum halide as an electrolytic solution. A battery has been proposed, and further, in JP-A-62-165879,
A room temperature molten salt of 1-methyl-3-ethylimidazolium chloride and aluminum trichloride was used as an electrolytic solution.
The next battery is proposed. In addition, JP-A-60-1361
Japanese Patent Laid-Open No. 80 proposes a secondary battery in which an ambient temperature molten salt composed of a 1,3, -dialkylimidazolium halide and a Group IIIa metal halide of the periodic table is used as an electrolytic solution.
【０００４】従来、この溶融塩の製造法には、固体であ
るオニウムハロゲン化物とアルミ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頁参照）。また最近では、低沸点の不活
性溶媒中で、オニウムハロゲン化物とアルミニウムハロ
ゲン化物を反応させる方法が提案されている（特開平３
−２４０８８号公報）。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ができなかっ
た。Conventionally, as a method for producing this molten salt, there is known a solid mixing method in which solid onium halide and aluminum halide are gradually mixed in a nitrogen-substituted glove box (for example, electrochemical, 54 ,
(3) See page 257). Further, recently, a method of reacting an onium halide with an aluminum halide in an inert solvent having a low boiling point has been proposed (Japanese Patent Laid-Open No. Hei 3).
-24088). However, since the chemical substances used in these methods are hygroscopic, it has not been possible to easily produce a high-purity room temperature molten salt on an industrial scale.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記問題点
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 The present invention provides 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. With the goal.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、このため
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、金属塩化物を
添加して処理することによって、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。す
なわち、本発明は、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％とか
らなり、水分由来の含酸素不純物を含有する常温溶融塩
に、金属塩化物処理した後、固形物を除去することを特
徴とする高純度常温溶融塩の製造方法である。The inventors of the present invention have diligently studied for this reason, and as a result, by adding a metal chloride to a room temperature molten salt composed of an aluminum halide and an onium halide and treating it Further, they have found that a high-purity room temperature molten salt can be produced, and completed the present invention. That is, the present invention relates to aluminum halides 20 to 8
A high-purity room temperature characterized by removing a solid after a metal chloride treatment is performed on a room temperature molten salt containing 0 mol% and an onium halide of 80 to 20 mol% and containing oxygen-containing impurities derived from water. It is a method for producing a molten salt.
【０００７】本発明で使用するアルミニウムハロゲン化
物の例としては、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
ハロゲン化物の例としては、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
第四級アンモニウム塩；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 aluminum halides used in the present invention include aluminum trichloride and aluminum tribromide. Examples of onium halides used in the present invention include tetraethylammonium bromide, quaternary ammonium salts such as trimethylethylammonium chloride; pyridinium salts such as butylpyridinium chloride; 1-ethyl-3-methylimidazolium chloride and the like. Imidazolium salts; phosphonium salts such as ethyltributylphosphonium bromide.
【０００８】常温溶融塩は所定量のアルミニウムハロゲ
ン化物とオニウムハロゲン化物を混合することにより得
られる。混合方法としては、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方法等によって
行うことができる。このとき、原料、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す
るが、この水は混合操作時にハロゲン化水素及び含酸素
不純物を生成する。金属塩化物による処理は、常温溶融
塩に金属塩化物を添加し、反応させることによって行
う。The room temperature molten salt is obtained by mixing a predetermined amount of aluminum halide and onium halide. As a mixing method, a solid mixing method while cooling the reactor, a mixing method using an inert solvent, or the like can be performed. At this time, since the raw material, especially onium halide, has high hygroscopicity, it contains water as an impurity, but this water produces hydrogen halide and oxygen-containing impurities during the mixing operation. The treatment with the metal chloride is performed by adding the metal chloride to the room temperature molten salt and reacting them.
【０００９】金属塩化物としては、当該処理により酸化
アルミニウムより安定な酸化物を生成する金属の塩化物
が有効である。具体例として、三塩化チタン、四塩化チ
タン、三塩化バナジウム、五塩化ニオブ、五塩化タンタ
ル、六塩化タングステン、三塩化モリブデン、五塩化モ
リブデン、三塩化ランタン等が挙げられる。添加する金
属塩化物の量は、常温溶融塩中の含酸素不純物に対し
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、余剰の金属塩化物を除去するの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、赤外線分光分析により、ＯＨ伸縮振動（波数３
３６０cm-1）の吸収強度を測定することにより、一般に
混入する水分量と等モルの含酸素不純物が生成するとし
て、水分量に換算して定量できる。As the metal chloride, a metal chloride which is more stable than aluminum oxide by the treatment is effective. Specific examples include titanium trichloride, titanium tetrachloride, vanadium trichloride, niobium pentachloride, tantalum pentachloride, tungsten hexachloride, molybdenum trichloride, molybdenum pentachloride, lanthanum trichloride and the like. The amount of the metal 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 amount added is more than twice the molar amount, it takes time and energy to remove the excess metal chloride, which is not preferable. The amount of oxygen-containing impurities in the room temperature molten salt was determined by infrared spectroscopic analysis to be OH stretching vibration (wave number 3
By measuring the absorption intensity at 360 cm −1, it can be quantified in terms of the amount of water, assuming that oxygen-containing impurities that are equimolar to the amount of water generally mixed are produced.
【００１０】反応温度は、室温〜１００℃の範囲が好ま
しい。１００℃を超えると、温度上昇の効果があまり見
られないことと、常温溶融塩の分解等の可能性があるた
め好ましくない。反応は金属塩化物添加後５時間以内に
終了する。反応終了後、常温溶融塩中に含まれる固形物
を除去する。余剰の金属塩化物及び生成した金属酸化物
は、反応終了後にろ過することにより除去される。ろ過
は、直径０．５μm 程度の粒子をろ別できるフィルター
を用いることが好ましい。The reaction temperature is preferably in the range of room temperature to 100 ° C. When the temperature exceeds 100 ° C, the effect of increasing the temperature is not so remarkable and the room temperature molten salt may be decomposed, which is not preferable. The reaction is complete within 5 hours after addition of the metal chloride. After the reaction is completed, the solid matter contained in the room temperature molten salt is removed. Excessive metal chloride and the produced metal oxide are removed by filtration after the reaction is completed. For filtration, it is preferable to use a filter capable of filtering particles having a diameter of about 0.5 μm.
【００１１】[0011]
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２８９ｇ（２モル）
とを、シクロヘキサン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６７モル％の常温溶融塩４３６ｇは、赤外
線分光分析（３３６０cm-1）により１重量％（水換算）
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。このものに五塩化モリブデン８６ｇ（０．３モル）
を添加し、８０℃に加熱し、４時間反応処理を行った
後、０．５μm のフィルターにより、固形物をろ別し
た。上記の常温溶融塩を、赤外線分光分析（３３６０cm
-1）により水分由来の含酸素不純物の定量を行ったとこ
ろ、検出限界以下であった。Example 1 1-Ethyl-3-methylimidazolium chloride 147
g (1 mol) and aluminum trichloride 289 g (2 mol)
And were placed in a glass reactor charged with 120 g of cyclohexane and mixed, and then heated at 60 ° C. under reduced pressure (10 mmHg) to distill off cyclohexane. 436 g of a room temperature molten salt having an aluminum trichloride concentration of 67 mol% was obtained by infrared spectroscopic analysis (3360 cm -1 ) at 1% by weight (water conversion).
It was found that the oxygen-containing impurities derived from the water were mixed. 86g (0.3mol) of molybdenum pentachloride
Was added, the mixture was heated to 80 ° C., reacted for 4 hours, and then filtered through a 0.5 μm filter to filter off solids. Infrared spectroscopic analysis (3360 cm) of the above room temperature molten salt
-1 ) quantified the oxygen-containing impurities derived from water and found that it was below the detection limit.
【００１２】実施例２ 三塩化アルミニウム１２０ｇ（０．９モル）を使用した
以外は、実施例１と同様に実施して三塩化アルミニウム
濃度４７モル％の常温溶融塩２６７ｇを得た。このもの
は赤外線分光分析（３３６０cm-1）により２重量％（水
換算）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。このものに五塩化ニオブ１６９ｇ（０．６モ
ル）を添加し、実施例１と同様に処理し固形物をろ過し
た。得られた常温溶融塩を、赤外線分光分析（３３６０
cm-1）により水分由来の含酸素不純物の定量を行ったと
ころ、検出限界以下であった。Example 2 The same procedure as in Example 1 was carried out except that 120 g (0.9 mol) of aluminum trichloride was used to obtain 267 g of a room temperature molten salt having an aluminum trichloride concentration of 47 mol%. Infrared spectroscopic analysis (3360 cm −1 ) of this product revealed that 2% by weight (water equivalent) of oxygen-containing impurities derived from water were mixed. To this, 169 g (0.6 mol) of niobium pentachloride was added, treated in the same manner as in Example 1, and the solid substance was filtered. The obtained room temperature molten salt was analyzed by infrared spectroscopy (3360
The oxygen-containing impurities derived from water were quantified by cm -1 ) and found to be below the detection limit.
【００１３】[0013]
【発明の効果】以上のように、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高純度常温溶
融塩を工業的規模で容易に製造することができる。INDUSTRIAL APPLICABILITY As described above, according to the present invention, a high-purity room temperature molten salt composed of a high-purity aluminum halide and an onium halide containing less oxygen-containing impurities derived from water can be easily produced on an industrial scale. can do.
Claims (3)
ル％とオニウムハロゲン化物８０〜２０モル％とからな
り、水分由来の含酸素不純物を含有する常温溶融塩に、
金属塩化物処理した後、固形物を除去することを特徴と
する高純度常温溶融塩の製造方法。1. A room temperature molten salt containing 20 to 80 mol% of an aluminum halide and 80 to 20 mol% of an onium halide, containing an oxygen-containing impurity derived from water.
A method for producing a high-purity room temperature molten salt, which comprises removing a solid matter after treating with a metal chloride.
ルミニウムより安定な酸化物を生成する金属の塩化物で
ある請求項１の常温溶融塩の製造方法。2. The method for producing an ambient temperature molten salt according to claim 1, wherein the metal chloride is a chloride of a metal that forms a more stable oxide than aluminum oxide as a treatment product.
素不純物に対し０．１〜２倍モルの金属塩化物を加え、
室温〜１００℃で反応させるものである請求項１の常温
溶融塩の製造方法。3. The metal chloride treatment comprises adding a metal chloride in an amount of 0.1 to 2 times the molar amount of oxygen-containing impurities in the room temperature molten salt,
The method for producing a room temperature molten salt according to claim 1, wherein the reaction is carried out at room temperature to 100 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5258460A JPH07114939A (en) | 1993-10-15 | 1993-10-15 | Manufacture of high purity normal temperature fused salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5258460A JPH07114939A (en) | 1993-10-15 | 1993-10-15 | Manufacture of high purity normal temperature fused salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07114939A true JPH07114939A (en) | 1995-05-02 |
Family
ID=17320537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5258460A Withdrawn JPH07114939A (en) | 1993-10-15 | 1993-10-15 | Manufacture of high purity normal temperature fused salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07114939A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002246661A (en) * | 2001-02-20 | 2002-08-30 | Toshiba Corp | Processing system of thermoelectric element |
| JP2014062278A (en) * | 2012-09-20 | 2014-04-10 | Sumitomo Electric Ind Ltd | Method for quantitatively determining aluminum oxide ion, method for quantitatively determining water content in molten salt, and method for producing aluminum structure |
| 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 |
-
1993
- 1993-10-15 JP JP5258460A patent/JPH07114939A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002246661A (en) * | 2001-02-20 | 2002-08-30 | Toshiba Corp | Processing system of thermoelectric element |
| JP2014062278A (en) * | 2012-09-20 | 2014-04-10 | Sumitomo Electric Ind Ltd | Method for quantitatively determining aluminum oxide ion, method for quantitatively determining water content in molten salt, and method for producing aluminum structure |
| 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 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20001226 |