JPH06279010A - Stabilized lithium hexafluorophosphate - Google Patents
Stabilized lithium hexafluorophosphateInfo
- Publication number
- JPH06279010A JPH06279010A JP6530693A JP6530693A JPH06279010A JP H06279010 A JPH06279010 A JP H06279010A JP 6530693 A JP6530693 A JP 6530693A JP 6530693 A JP6530693 A JP 6530693A JP H06279010 A JPH06279010 A JP H06279010A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- lithium hexafluorophosphate
- lithium fluoride
- hexafluorophosphate
- stabilized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y02E60/12—
Landscapes
- Primary Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、リチウム２次電池用電
解質や、有機合成反応用触媒として有用な安定化された
六フッ化リン酸リチウムに関する。TECHNICAL FIELD The present invention relates to a stabilized lithium hexafluorophosphate useful as an electrolyte for a lithium secondary battery and a catalyst for an organic synthesis reaction.
【０００２】[0002]
【従来技術】六フッ化リン酸リチウムは、非常に不安定
な化合物である。そのために製造工程上からあるいは保
管取り扱い上から、不純物として系内に混入してくる水
分等による加水分解のためにその品質が低下する。Lithium hexafluorophosphate is a very unstable compound. Therefore, from the viewpoint of manufacturing process or storage and handling, the quality is deteriorated due to hydrolysis due to water mixed in the system as impurities.
【０００３】このような分解により発生した不純物を除
去するための精製方法は種々提案されているが、この分
解を根本的に抑える方法はまだ見いだされていなかっ
た。Although various purification methods for removing impurities generated by such decomposition have been proposed, a method for fundamentally suppressing this decomposition has not been found yet.
【０００４】[0004]
【問題点を解決するための具体的手段】本発明者らは、
かかる従来技術の問題点に鑑み鋭意検討の結果、本発明
に到達したものである。[Means for Solving the Problems] The present inventors
As a result of intensive studies in view of the problems of the conventional art, the present invention has been achieved.
【０００５】すなわち本発明は、フッ化リチウム層表面
を有することを特徴とする安定化された六フッ化リン酸
リチウムを提供するものである。本発明において用いる
六フッ化リン酸リチウムは、非常に不安定な化合物であ
り、製造工程上からあるいは保管取り扱い上から、不純
物として系内に混入してくる水分により次のような加水
分解反応を起こし、品質を低下させる。 ＬｉＰＦ6 ＋ xＨ2 Ｏ → ＬｉＰＯX Ｆ(6-2X)＋ 2xＨＦ （１） この分解反応により発生するＬｉＰＯX Ｆ(6-2X)、ＨＦ
等の不純物は六フッ化リン酸リチウムの用途であるリチ
ウム電池用電解質として使用されたとき、その電池性能
に大きく影響を及ぼすことが知られている。That is, the present invention provides a stabilized lithium hexafluorophosphate characterized by having a lithium fluoride layer surface. Lithium hexafluorophosphate used in the present invention is a very unstable compound and undergoes the following hydrolysis reaction due to water mixed into the system as an impurity from the manufacturing process or storage and handling. Wake up and reduce the quality. LiPF 6 + xH 2 O → LiPO X F (6-2X) + 2xHF (1) LiPO X F (6-2X) , HF generated by this decomposition reaction
It is known that impurities such as the following significantly affect the battery performance when used as an electrolyte for a lithium battery, which is an application of lithium hexafluorophosphate.
【０００６】本発明者らは、種々検討した結果、六フッ
化リン酸リチウムの表面を製造段階で故意にフッ化リチ
ウム層とした組成物を作ることにより、従来の純粋な六
フッ化リン酸リチウムよりも耐加水分解性、耐自己分解
性の優れたものにできることを見いだした。As a result of various studies, the inventors of the present invention have prepared a composition in which the surface of lithium hexafluorophosphate was intentionally formed into a lithium fluoride layer at the production stage, whereby conventional pure hexafluorophosphate was prepared. It was found that it can be made more resistant to hydrolysis and self-decomposition than lithium.
【０００７】従来は単純に（１）式のような機構で加水
分解反応が進行すると考えられていたが、検討した結
果、次のような２段反応機構で加水分解が進行するもの
と推定される。 ＬｉＰＦ6 → ＬｉＦ ＋ ＰＦ5 （２） ＰＦ5 ＋ xＨ2 Ｏ → ＰＯX Ｆ(5-2X) ＋ 2xＨＦ （３） フッ化リチウム層による安定化の理由としては、単純に
物理的な表面保護だけではなく、表面のフッ化リチウム
濃度が異常に高いために、（２）式の解離平衡がくず
れ、逆反応が進行して、加水分解しやすいＰＦ5 の発生
が抑えられるということがあると推測される。Conventionally, it was thought that the hydrolysis reaction proceeded simply by the mechanism of the formula (1), but as a result of investigation, it is presumed that the hydrolysis proceeds by the following two-step reaction mechanism. It LiPF 6 → LiF + PF 5 (2) PF 5 + xH 2 O → PO X F (5-2X) + 2xHF (3) The reason for stabilization by the lithium fluoride layer is simply physical surface protection. Instead, it is assumed that the concentration of lithium fluoride on the surface is abnormally high, and the dissociation equilibrium of equation (2) is disrupted, which promotes the reverse reaction and suppresses the generation of PF 5 , which is susceptible to hydrolysis. To be done.
【０００８】この安定化させるためのフッ化リチウム
は、ＰＦ5 ガスが進入可能な表層に六フッ化リン酸リチ
ウムに対して０．０１〜０．５ｗｔ％好ましくは、０．
０２〜０．１ｗｔ％存在することが必要である。Lithium fluoride for stabilizing is 0.01 to 0.5 wt% with respect to lithium hexafluorophosphate in the surface layer into which PF 5 gas can enter, and preferably 0.
It is necessary to exist in an amount of 02 to 0.1 wt%.
【０００９】０．０１ｗｔ％以下では安定化の効果がな
く、０．５ｗｔ％以上では効果があるものの六フッ化リ
ン酸リチウムを溶媒に溶かしたときに大量のＬｉＦが未
溶解分として残り濾過等の操作が必要となり煩雑であ
る。If it is 0.01 wt% or less, there is no stabilizing effect, and if it is 0.5 wt% or more, it is effective, but when lithium hexafluorophosphate is dissolved in a solvent, a large amount of LiF remains as an undissolved component and is filtered. The operation is required, which is complicated.
【００１０】このような方法で安定化した六フッ化リン
酸リチウムは−２０℃の露点を持つ空気中での取り扱い
を行っても、ほとんど分解は起こらなかったが、フッ化
リチウム層のない六フッ化リン酸リチウムは分解により
発生する不純物の一つであるＨＦの濃度が４００ｐｐｍ
ほど増加した。Lithium hexafluorophosphate stabilized by such a method hardly decomposed even when it was handled in air having a dew point of -20 ° C. Lithium fluorophosphate has an HF concentration of 400 ppm, which is one of the impurities generated by decomposition.
Increased.
【００１１】六フッ化リン酸リチウムの結晶表面をフッ
化リチウム層とするための具体的な手段としては、結晶
を加熱処理して、表面のみを分解し、フッ化リチウムに
変換する方法などがあるが、方法については特に限定す
るものではない。As a specific means for forming a lithium fluoride layer on the surface of a crystal of lithium hexafluorophosphate, there is a method of heating the crystal to decompose only the surface and convert it into lithium fluoride. However, the method is not particularly limited.
【００１２】[0012]
【実施例】以下実施例により本発明を具体的に説明する
が、本発明はかかる実施例により限定されるものではな
い。EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples.
【００１３】実施例１ フッ化リチウム３２ｇを無水フッ酸５００ｇに溶解させ
る。この溶液に五フッ化リンガス１５５ｇを吹き込み、
フッ化リチウムと反応させた。得られた反応溶液を一晩
かけてゆっくりと−２０℃まで冷却することにより、六
フッ化リン酸リチウムの結晶を析出させた。これを濾別
し、減圧下で付着フッ酸を除いた。これにより、１ｍｍ
程度の粒径の揃った六フッ化リン酸リチウム結晶６５ｇ
が得られた。このものの純度は９９．９％以上であり、
不純物としてのフッ酸は５０ｐｐｍ、フッ化リチウムは
５０ｐｐｍ以下であった。Example 1 32 g of lithium fluoride is dissolved in 500 g of anhydrous hydrofluoric acid. Blowing 155 g of phosphorus pentafluoride gas into this solution,
Reacted with lithium fluoride. The obtained reaction solution was slowly cooled to −20 ° C. overnight to deposit lithium hexafluorophosphate crystals. This was filtered off and the attached hydrofluoric acid was removed under reduced pressure. With this, 1 mm
65g of lithium hexafluorophosphate crystals with uniform particle size
was gotten. The purity of this product is over 99.9%,
Hydrofluoric acid as impurities was 50 ppm, and lithium fluoride was 50 ppm or less.
【００１４】この六フッ化リン酸リチウムをＳＵＳ３０
４製の処理装置に入れて、１６０℃に加熱した後に、１
ｔｏｒｒの減圧下で１時間加熱処理を行った。得られた
六フッ化リン酸リチウム中のフッ酸濃度は５０ｐｐｍ、
フッ化リチウムは９００ｐｐｍ（０．０９ｗｔ％）であ
った。なお、この処理後の結晶の表面にＰＦ5 ガスを導
入したところ、フッ化リチウムが５０ｐｐｍ以下に減少
したという事実から、このフッ化リチウムがＰＦ5 ガス
が進入可能な表層に存在することが確認できた。This lithium hexafluorophosphate was added to SUS30
Put it in the processing equipment made of 4 and heat it to 160 ° C, then
Heat treatment was performed for 1 hour under reduced pressure of torr. The concentration of hydrofluoric acid in the obtained lithium hexafluorophosphate was 50 ppm,
The lithium fluoride content was 900 ppm (0.09 wt%). When PF 5 gas was introduced to the surface of the crystal after this treatment, the fact that lithium fluoride was reduced to 50 ppm or less confirmed that this lithium fluoride exists in the surface layer into which PF 5 gas can enter. did it.
【００１５】処理後の六フッ化リン酸リチウムを−２０
℃の露点を持つ空気中に５時間放置したところ、フッ酸
の増加が認められなかった。 実施例２ 実施例１と同様の方法により、合成した六フッ化リン酸
リチウムをＳＵＳ３０４製の処理装置に入れて、４０℃
で２４時間、５Ｌ／ｍｉｎ．の流速で窒素ガスを装置内
に流通させた。その結果、不純物のフッ酸濃度が５０ｐ
ｐｍ、表面のフッ化リチウム濃度が４００ｐｐｍ（０．
０４ｗｔ％）の六フッ化リン酸リチウムが得られた。The treated lithium hexafluorophosphate is -20
When left in air having a dew point of ° C for 5 hours, no increase in hydrofluoric acid was observed. Example 2 By the same method as in Example 1, the synthesized lithium hexafluorophosphate was placed in a processing device made of SUS304, and the temperature was 40 ° C.
24 hours at 5 L / min. Nitrogen gas was passed through the apparatus at a flow rate of. As a result, the concentration of impurities hydrofluoric acid was 50p.
pm, the concentration of lithium fluoride on the surface is 400 ppm (0.
(04 wt%) lithium hexafluorophosphate was obtained.
【００１６】処理後の六フッ化リン酸リチウムを−２０
℃の露点を持つ空気中に５時間放置したところ、フッ酸
濃度が１００ｐｐｍになった。 実施例３ 実施例１と同様の方法により、合成した六フッ化リン酸
リチウムをＳＵＳ３０４製の処理装置に入れて、４０℃
で１２時間、５Ｌ／ｍｉｎ．の流速で窒素ガスを装置内
に流通させた。その結果、不純物のフッ酸濃度が５０ｐ
ｐｍ、表面のフッ化リチウム濃度が２００ｐｐｍ（０．
０２ｗｔ％）の六フッ化リン酸リチウムが得られた。The treated lithium hexafluorophosphate is -20
When left in air having a dew point of ° C for 5 hours, the concentration of hydrofluoric acid became 100 ppm. Example 3 By the same method as in Example 1, the synthesized lithium hexafluorophosphate was placed in a processing apparatus made of SUS304, and the temperature was 40 ° C.
12 hours at 5 L / min. Nitrogen gas was passed through the apparatus at a flow rate of. As a result, the concentration of impurities hydrofluoric acid was 50p.
pm, the concentration of lithium fluoride on the surface is 200 ppm (0.
(02 wt%) lithium hexafluorophosphate was obtained.
【００１７】処理後の六フッ化リン酸リチウムを−２０
℃の露点を持つ空気中に５時間放置したところ、フッ酸
濃度が２００ｐｐｍになった。 比較例１ 実施例１と同様の方法により、六フッ化リン酸リチウム
を合成した。そのものの純度は９９．９％以上で、不純
物のフッ酸濃度は５０ｐｐｍ、フッ化リチウム濃度は５
０ｐｐｍ以下であった。The treated lithium hexafluorophosphate is -20
When left in air having a dew point of ° C for 5 hours, the concentration of hydrofluoric acid became 200 ppm. Comparative Example 1 Lithium hexafluorophosphate was synthesized by the same method as in Example 1. Its purity is 99.9% or more, the concentration of impurities hydrofluoric acid is 50 ppm, and the concentration of lithium fluoride is 5
It was 0 ppm or less.
【００１８】この安定化させていない六フッ化リン酸リ
チウムを−２０℃の露点を持つ空気中に５時間放置した
ところ、フッ酸濃度は７００ｐｐｍまで増加した。When this unstabilized lithium hexafluorophosphate was allowed to stand in air having a dew point of -20 ° C. for 5 hours, the hydrofluoric acid concentration increased to 700 ppm.
【００１９】[0019]
【発明の効果】本発明の安定化した六フッ化リン酸リチ
ウムは、従来のものよりも取り扱いが容易であり、リチ
ウム２次電池用等に用いる場合に有害とされているフッ
酸等の分解生成物の発生がきわめて少ないものである。INDUSTRIAL APPLICABILITY The stabilized lithium hexafluorophosphate of the present invention is easier to handle than conventional ones, and decomposes hydrofluoric acid, which is harmful when used for a lithium secondary battery or the like. Very little product is generated.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 伊東 久和 山口県宇部市大字沖宇部5253番地 セント ラル硝子株式会社宇部研究所内 (72)発明者 宗野 靖 山口県宇部市大字沖宇部5253番地 セント ラル硝子株式会社宇部研究所内 (72)発明者 阿瀬川 誠 山口県宇部市大字沖宇部5253番地 セント ラル硝子株式会社宇部研究所内 (72)発明者 兼重 和美 山口県宇部市大字沖宇部5253番地 セント ラル硝子株式会社宇部研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hisawa Ito 5253 Oki Obe, Ube City, Yamaguchi Prefecture Ube Laboratory, Central Rural Glass Co., Ltd. (72) Inventor Yasushi Sono 5253 Oki Ube, Ube City, Yamaguchi Prefecture Central Glass Co., Ltd., Ube Laboratory (72) Inventor, Makoto Asagawa, 5253 Oki, Ube, Yamaguchi Prefecture Ube Research Center, Central Glass Co., Ltd., Ube Laboratory (72) Inventor, Kazumi, Kazumi, Uguchi City, Yamaguchi Prefecture 5253, Ube City, Central Glass Ube Institute Co., Ltd.
Claims (1)
徴とする安定化された六フッ化リン酸リチウム。1. Stabilized lithium hexafluorophosphate, having a lithium fluoride layer surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6530693A JP2898163B2 (en) | 1993-03-24 | 1993-03-24 | Stabilized lithium hexafluorophosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6530693A JP2898163B2 (en) | 1993-03-24 | 1993-03-24 | Stabilized lithium hexafluorophosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06279010A true JPH06279010A (en) | 1994-10-04 |
| JP2898163B2 JP2898163B2 (en) | 1999-05-31 |
Family
ID=13283097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6530693A Expired - Lifetime JP2898163B2 (en) | 1993-03-24 | 1993-03-24 | Stabilized lithium hexafluorophosphate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2898163B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998023536A1 (en) * | 1996-11-26 | 1998-06-04 | Fmc Corporation | Process for removing acids from lithium salt solutions |
| CN105098189A (en) * | 2014-05-21 | 2015-11-25 | 微宏动力系统（湖州）有限公司 | Anode material additive and preparation method thereof |
-
1993
- 1993-03-24 JP JP6530693A patent/JP2898163B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998023536A1 (en) * | 1996-11-26 | 1998-06-04 | Fmc Corporation | Process for removing acids from lithium salt solutions |
| US6001325A (en) * | 1996-11-26 | 1999-12-14 | Fmc Corporation | Process for removing acids from lithium salt solutions |
| CN105098189A (en) * | 2014-05-21 | 2015-11-25 | 微宏动力系统（湖州）有限公司 | Anode material additive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2898163B2 (en) | 1999-05-31 |
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