JP2015044701A - Method for producing difluorophosphate - Google Patents
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Abstract
Description
本発明は、リチウムイオン二次電池の電解液溶媒及び添加剤や、機能性材料中間体及び医薬品用中間体等に使用が期待されるジフルオロリン酸塩の製造方法に関するものである。 The present invention relates to a method for producing difluorophosphate which is expected to be used for an electrolyte solvent and an additive of a lithium ion secondary battery, a functional material intermediate and a pharmaceutical intermediate.
現在、リチウム二次電池は携帯電話、ビデオカメラやノートパソコン等の電子機器の電源として、広く普及している。また近年、環境保全問題やエネルギー問題から、電気自動車やパワーツール、夜間電力用の安価で安全性の高い大型リチウム二次電池の開発も進められている。これら大型化また高性能化するリチウム二次電池に対する要求として高性能化に向けた出力密度やエネルギー密度の向上、並びに高信頼性に向けた高温時や低温時の容量劣化の抑制、サイクル寿命の向上や安全性の向上が求められている。 Currently, lithium secondary batteries are widely used as power sources for electronic devices such as mobile phones, video cameras, and notebook computers. In recent years, the development of large-sized lithium secondary batteries that are inexpensive and highly safe for electric vehicles, power tools, and nighttime power has been promoted due to environmental conservation problems and energy problems. As demands for these larger and higher performance lithium secondary batteries, improvement of output density and energy density for higher performance, suppression of capacity deterioration at high and low temperatures for high reliability, cycle life Improvements and improvements in safety are required.
これまで上記課題を克服するため様々な改善が提案され、正極材料や負極材料、リチウム二次電池の構成部材の最適化が検討され、電解液についても使用される各種溶媒、例えば環状のエチレンカーボネート、プロピレンカーボネート等や鎖状のジメチルカーボネート、ジエチルカーボネート等や各種電解質としてヘキサフルオロリン酸リチウムや四フッ化ホウ酸リチウム、過塩素酸リチウム等、また、上記特性を改善するための添加剤としてフルオロエチレンカーボネートやｔｒａｎｓ-ジフルオロエチレンカーボネート等の各種添加剤やこれらの組み合わせが提案されてきた。 Various improvements have been proposed to overcome the above-mentioned problems, and optimization of positive electrode materials, negative electrode materials, and components of lithium secondary batteries has been studied, and various solvents used for electrolytes, for example, cyclic ethylene carbonate , Propylene carbonate, etc., chain dimethyl carbonate, diethyl carbonate, etc., lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, etc. as various electrolytes, and fluoro as an additive for improving the above characteristics Various additives such as ethylene carbonate and trans-difluoroethylene carbonate and combinations thereof have been proposed.
このようなリチウム二次電池用電解液は上記電解液や電解質、添加剤の組み合わせや組成により反応性が異なるため、リチウム二次電池の性能や信頼性等の特性は大きく異なるものとなる。 Such lithium secondary battery electrolytes have different reactivities depending on the combination and composition of the above electrolytes, electrolytes, and additives. Therefore, the performance and reliability of lithium secondary batteries vary greatly.
こうした中で特許文献１には添加剤としてモノフルオロリン酸リチウムやジフルオロリン酸リチウムからなる群から選ばれた少なくとも１種を添加した非水系電解液を用いると、この添加剤がリチウムと反応し、良質な被膜が正極及び負極界面に形成されること、及び、この被膜が、充電状態の活物質と有機溶媒との接触を抑制して、活物質と電解液との接触を因とする非水系電解液の分解を抑制し、保存後の保存特性を向上させることが記載されている。 Under these circumstances, in Patent Document 1, when a non-aqueous electrolyte containing at least one selected from the group consisting of lithium monofluorophosphate and lithium difluorophosphate is used as an additive, the additive reacts with lithium. A good quality film is formed at the interface between the positive electrode and the negative electrode, and this film suppresses the contact between the charged active material and the organic solvent, and causes non-contact due to the contact between the active material and the electrolyte. It describes that the decomposition of the aqueous electrolyte is suppressed and the storage characteristics after storage are improved.
フルオロリン酸塩、特にジフルオロリン酸リチウムの製造方法としては様々な手法について検討・開発がなされている。たとえば、ヘキサフルオロリン酸リチウムを原料としてジフルオロリン酸リチウムを製造する方法が特許文献２、３、４および５に記載されている。特許文献２ではヘキサフルオロリン酸リチウムにホウ酸塩を、特許文献３ではヘキサフルオロリン酸リチウムに二酸化ケイ素を、特許文献４ではヘキサフルオロリン酸リチウムと炭酸塩をそれぞれ非水溶媒中で反応させてジフルオロリン酸リチウムを製造する方法が開示されている。しかし、反応時間が４０〜７２時間と長時間を要し生産性の面から有用な方法とは言い難い。また、特許文献５ではヘキサフルオロリン酸リチウムと水にハロゲン化物を添加し、非水溶媒中で反応させてジフルオロリン酸リチウムを製造する方法が開示されている。しかし、この製法では用いる非水溶媒が高価であること、ジフルオロリン酸リチウムは溶媒の種類により溶解度が小さく大量の溶媒を用いるためそれ相応の容積を有する反応器が必要になることやバッチあたりの生産可能な量が少ないことなどから、経済性や生産性の観点から好ましい方法とは言い難い。 Various methods have been studied and developed as methods for producing fluorophosphates, particularly lithium difluorophosphate. For example, Patent Documents 2, 3, 4, and 5 describe methods for producing lithium difluorophosphate using lithium hexafluorophosphate as a raw material. In Patent Document 2, boric acid salt is reacted with lithium hexafluorophosphate, in Patent Document 3, silicon dioxide is reacted with lithium hexafluorophosphate, and in Patent Document 4, lithium hexafluorophosphate and carbonate are reacted in a non-aqueous solvent. A method for producing lithium difluorophosphate is disclosed. However, a reaction time of 40 to 72 hours is required, and it is difficult to say that this is a useful method in terms of productivity. Patent Document 5 discloses a method for producing lithium difluorophosphate by adding a halide to lithium hexafluorophosphate and water and reacting them in a non-aqueous solvent. However, in this production method, the non-aqueous solvent used is expensive, and since lithium difluorophosphate has a low solubility depending on the type of solvent and a large amount of solvent is used, a reactor having a corresponding volume is required, and per batch. Since the amount that can be produced is small, it is difficult to say that the method is preferable from the viewpoints of economy and productivity.
またこれら製法ではヘキサフルオロリン酸リチウムの分解中に生じるフッ化水素、リン酸等の酸が副生し、これら酸の除去が困難であり、さらにジフルオロリン酸リチウムは溶媒中に酸が共存すると分解が加速する。従って、酸が共存する状態で電解液に用いると、分解物による電池サイクル特性の悪化や電解液の着色といった安定性に問題が生じる可能性があり、これら製法は効率良く工業スケールで製造する方法とは言い難い。 In these processes, acids such as hydrogen fluoride and phosphoric acid generated during the decomposition of lithium hexafluorophosphate are by-produced, and it is difficult to remove these acids. Decomposition accelerates. Therefore, when used in an electrolyte solution in the presence of an acid, problems such as deterioration of battery cycle characteristics due to decomposition products and coloration of the electrolyte solution may occur, and these production methods are methods for efficiently producing on an industrial scale. It's hard to say.
また、リチウム塩に加えて、ジフルオロリン酸ナトリウム、ジフルオロリン酸カリウム、ジフルオロリン酸アンモニウムといった他のジフルオロリン酸塩を効率よく工業スケールで製造する方法も同様に求められている。 In addition to lithium salts, a method for efficiently producing other difluorophosphates such as sodium difluorophosphate, potassium difluorophosphate, and ammonium difluorophosphate on an industrial scale is also required.
本発明は、溶媒を用いずに効率的かつ簡便にジフルオロリン酸塩を製造する方法を提供することを目的とする。 An object of this invention is to provide the method of manufacturing a difluorophosphate efficiently and simply, without using a solvent.
本発明者らは鋭意検討した結果、本発明を完成するに至った。すなわち、本発明は以下のものを提供する。
［１］
ヘキサフルオロリン酸塩と水分と塩化物とを溶媒を介在させることなく反応させて、ジフルオロリン酸塩を得る工程を含むジフルオロリン酸塩の製造方法であって、
ヘキサフルオロリン酸塩に、ジフルオロリン酸塩を得るのに必要な反応当量以上の水分と反応当量以上の塩化物とを同時に添加して反応させることを特徴とするジフルオロリン酸塩の製造方法。
［２］
水分が、気体、液体又は固体の形態の水分であることを特徴とする［１］記載のジフルオロリン酸塩の製造方法。
［３］
水分と塩化物とを同時に添加する形態として、塩化物と水分とを、それぞれ別個にジフルオロリン酸塩の入った容器に導入することを特徴とする［１］又は［２］記載のジフルオロリン酸塩の製造方法。
［４］
水分が液体の形態の水分であることを特徴とする［１］〜［３］のいずれかに記載の製造方法。
［５］
ヘキサフルオロリン酸塩と水分のモル比が１：１．０５〜１：４．０４の範囲であり、ヘキサフルオロリン酸塩と塩化物のモル比が１：３．０５〜１：４．４４の範囲であることを特徴とする、［１］〜［４］のいずれかに記載のジフルオロリン酸塩の製造方法。
［６］
ヘキサフルオロリン酸塩がヘキサフルオロリン酸リチウム、ヘキサフルオロリン酸ナトリウム、ヘキサフルオロリン酸カリウム、又はヘキサフルオロリン酸アンモニウムのいずれかであることを特徴とする、［１］〜［５］のいずれかに記載のジフルオロリン酸塩の製造方法。
［７］
塩化物がアルカリ金属の塩化物、アルカリ土類金属の塩化物、及び塩化アルミニウムからなる群から選ばれる少なくとも１種であることを特徴とする、［１］〜［６］のいずれかに記載のジフルオロリン酸塩の製造方法。
［８］
アルカリ金属の塩化物が塩化リチウム、塩化ナトリウム、及び塩化カリウムから選ばれる少なくとも１種であり、アルカリ土類金属の塩化物が塩化マグネシウム、塩化カルシウム、塩化ストロンチウム、及び塩化バリウムから選ばれる少なくとも１種であることを特徴とする［７］に記載のジフルオロリン酸塩の製造方法。
［９］
塩化物が塩化オキサリル、塩化アセチル、塩化チオニル及びジメチルジクロロシランからなる群から選ばれる少なくとも１種であることを特徴とする、［１］〜［６］のいずれかに記載のジフルオロリン酸塩の製造方法。
As a result of intensive studies, the present inventors have completed the present invention. That is, the present invention provides the following.
[1]
A process for producing a difluorophosphate comprising a step of reacting hexafluorophosphate, moisture and chloride without intervening a solvent to obtain a difluorophosphate,
A method for producing a difluorophosphate, characterized by simultaneously adding and reacting hexafluorophosphate with a water equivalent to a reaction equivalent or more necessary for obtaining a difluorophosphate and a chloride with a reaction equivalent or more.
[2]
The method for producing a difluorophosphate according to [1], wherein the moisture is moisture in a gas, liquid or solid form.
[3]
The difluorophosphoric acid according to [1] or [2], wherein chloride and moisture are separately introduced into a container containing difluorophosphate as a form in which moisture and chloride are added simultaneously. Method for producing salt.
[4]
The manufacturing method according to any one of [1] to [3], wherein the water is water in a liquid form.
[5]
The molar ratio of hexafluorophosphate to water is in the range of 1: 1.05 to 1: 4.04, and the molar ratio of hexafluorophosphate to chloride is 1: 3.05 to 1: 4.44. The method for producing a difluorophosphate according to any one of [1] to [4], wherein
[6]
Any of [1] to [5], wherein the hexafluorophosphate is any one of lithium hexafluorophosphate, sodium hexafluorophosphate, potassium hexafluorophosphate, or ammonium hexafluorophosphate. A process for producing the difluorophosphate according to claim 1.
[7]
The chloride according to any one of [1] to [6], wherein the chloride is at least one selected from the group consisting of an alkali metal chloride, an alkaline earth metal chloride, and aluminum chloride. A method for producing difluorophosphate.
[8]
The alkali metal chloride is at least one selected from lithium chloride, sodium chloride, and potassium chloride, and the alkaline earth metal chloride is at least one selected from magnesium chloride, calcium chloride, strontium chloride, and barium chloride. [7] The method for producing a difluorophosphate according to [7].
[9]
The difluorophosphate according to any one of [1] to [6], wherein the chloride is at least one selected from the group consisting of oxalyl chloride, acetyl chloride, thionyl chloride and dimethyldichlorosilane. Production method.
本発明によれば、高価な溶媒を用いずに効率的かつ簡便にジフルオロリン酸塩を製造することができる。また、本発明の方法では、反応中に副生するフッ化水素が塩化物と反応して塩化水素として系外へ蒸発するため、未反応のフッ化水素が系内に残留することがない。そのため、酸によってジフルオロリン酸塩が分解されるおそれがなく、酸が共存する状態で電解液に用いた際の、分解物による電池サイクル特性の悪化や電解液の着色といった安定性に関する問題が生じない。 According to the present invention, a difluorophosphate can be produced efficiently and simply without using an expensive solvent. In the method of the present invention, hydrogen fluoride by-produced during the reaction reacts with chloride and evaporates out of the system as hydrogen chloride, so that unreacted hydrogen fluoride does not remain in the system. Therefore, there is no possibility that the difluorophosphate is decomposed by the acid, and there are problems regarding stability such as deterioration of battery cycle characteristics due to decomposition products and coloring of the electrolytic solution when used in the electrolytic solution in the presence of the acid. Absent.
以下、本発明のジフルオロリン酸塩の製造方法を、その好ましい実施形態に基づいて詳述するが、本発明はこれらの内容に限定されない。
原料となるヘキサフルオロリン酸塩は、市販されているグレードのものであれば、特に制限無く使用することができるが、当然に、高純度の原料を使用すれば、高純度の製品を特別な精製方法を経ることなく得られるため、好ましい。
Hereinafter, although the manufacturing method of the difluorophosphate of this invention is explained in full detail based on the preferable embodiment, this invention is not limited to these content.
The hexafluorophosphate used as a raw material can be used without particular limitation as long as it is a commercially available grade. Naturally, if a high-purity raw material is used, a high-purity product is specially used. Since it is obtained without going through a purification method, it is preferable.
ヘキサフルオロリン酸塩としては、ヘキサフルオロリン酸リチウム、ヘキサフルオロリン酸ナトリウム、ヘキサフルオロリン酸カリウムおよびヘキサフルオロリン酸アンモニウムが挙げられる。ヘキサフルオロリン酸リチウムを原料とし、リチウム二次電池等で使用されるジフルオロリン酸リチウムを製造する方法においては、原料であるヘキサフルオロリン酸リチウムは高純度なリチウムイオン電池向け電解質グレードのものを使用すると好ましい。 Examples of hexafluorophosphate include lithium hexafluorophosphate, sodium hexafluorophosphate, potassium hexafluorophosphate, and ammonium hexafluorophosphate. In the method of producing lithium difluorophosphate used in lithium secondary batteries, etc., using lithium hexafluorophosphate as a raw material, the raw material lithium hexafluorophosphate is an electrolyte grade for high-purity lithium ion batteries. It is preferable to use it.
反応に使用する塩化物は少なくとも１種以上であり、特に限定されるものではないが、塩化物が無機塩化物である場合には、
塩化リチウム、塩化ナトリウム、塩化カリウム、塩化セシウムなどのアルカリ金属塩、
塩化マグネシウム、塩化カルシウム、塩化ストロンチウム、塩化バリウムなどのアルカリ土類金属塩、
塩化アルミニウム、塩化アンモニウム、四塩化ケイ素、
塩化鉄(ＩＩ)、塩化鉄(ＩＩＩ)、塩化ニッケル、四塩化チタン、塩化クロム(ＩＩＩ)、塩化マンガン、塩化銅などの遷移金属塩、等を好ましい塩化物として挙げることができる。
The chloride used in the reaction is at least one kind and is not particularly limited, but when the chloride is an inorganic chloride,
Alkali metal salts such as lithium chloride, sodium chloride, potassium chloride, cesium chloride,
Alkaline earth metal salts such as magnesium chloride, calcium chloride, strontium chloride, barium chloride,
Aluminum chloride, ammonium chloride, silicon tetrachloride,
Examples of preferable chlorides include transition metal salts such as iron (II) chloride, iron (III) chloride, nickel chloride, titanium tetrachloride, chromium (III) chloride, manganese chloride, and copper chloride.
これらの中で特に工業的な観点から塩化リチウム、塩化ナトリウム、塩化カリウム、塩化セシウム、塩化マグネシウム、塩化カルシウム、塩化ストロンチウム、塩化バリウム、塩化アルミニウムが好ましい。更に、本発明の製造方法により得られるジフルオロリン酸リチウムをリチウム二次電池の添加剤として使用する場合には、塩化リチウムが不純物としての陽イオンを含まないため好適である。 Among these, lithium chloride, sodium chloride, potassium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, and aluminum chloride are preferable from an industrial viewpoint. Further, when lithium difluorophosphate obtained by the production method of the present invention is used as an additive for a lithium secondary battery, lithium chloride does not contain a cation as an impurity, which is preferable.
また一方、上記以外の塩化物としては、塩化オキサリル、塩化アセチル、塩化チオニル、プロピオン酸塩化物や、ジメチルジクロロシラン、五塩化リン、または塩化ホスホニルなどを挙げることができる。特に、塩化オキサリル、塩化アセチル、及び塩化チオニルの群から選ばれる少なくとも１種が好ましい。 On the other hand, examples of the chloride other than the above include oxalyl chloride, acetyl chloride, thionyl chloride, propionate chloride, dimethyldichlorosilane, phosphorus pentachloride, or phosphonyl chloride. In particular, at least one selected from the group of oxalyl chloride, acetyl chloride, and thionyl chloride is preferable.
本発明の製造方法では、ヘキサフルオロリン酸塩に、ジフルオロリン酸塩を得るのに必要な反応当量以上の水分を、溶媒を介在させることなく反応させるが、その反応の際に、反応当量以上の塩化物を共に添加して、反応に関与させることが望ましい。 In the production method of the present invention, the hexafluorophosphate is reacted with a water equivalent to or higher than the reaction equivalent necessary for obtaining the difluorophosphate without intervening a solvent. It is desirable to add both of the chlorides together to participate in the reaction.
ヘキサフルオロリン酸塩と、反応させる水分中に含まれる水のモル比は、１：１．０〜１：４．０、より詳細には１：１．０５〜１：４．０４の範囲であることが望ましい。他方、ヘキサフルオロリン酸塩と塩化物のモル比は、１：３．０〜１：４．４の範囲、より詳細にはそのモル比が１：３．０５〜１：４．４４の範囲であることが望ましく、特に好ましくは１：３．６０〜１：４．４０の範囲である。水を溶媒の如く過剰に用いると、加水分解反応が進行しモノフルオロリン酸塩が、さらに加水分解反応が進行しリン酸塩がそれぞれ副生するため好ましくない。 The molar ratio of water contained in the water to be reacted with the hexafluorophosphate is in the range of 1: 1.0 to 1: 4.0, more specifically 1: 1.05 to 1: 4.04. It is desirable to be. On the other hand, the molar ratio of hexafluorophosphate to chloride is in the range of 1: 3.0 to 1: 4.4, more specifically the molar ratio is in the range of 1: 3.05 to 1: 4.44. It is desirable that it is in the range of 1: 3.60 to 1: 4.40. If water is used excessively as a solvent, the hydrolysis reaction proceeds and the monofluorophosphate is further produced, and the hydrolysis reaction further proceeds and the phosphate is formed as a by-product.
また、ヘキサフルオロリン酸塩がヘキサフルオロリン酸リチウムである場合に、ヘキサフルオロリン酸リチウムと水のモル比は１：１．０〜１：４．０の範囲であり、好ましくは１：１．０５〜１：４．０４の範囲であることが望ましい。他方、ヘキサフルオロリン酸リチウムと塩化物のモル比は１：３．０５〜１：４．４４の範囲であることが望ましく、特に好ましくは１：３．６０〜１：４．４０の範囲である。 When the hexafluorophosphate is lithium hexafluorophosphate, the molar ratio of lithium hexafluorophosphate to water is in the range of 1: 1.0 to 1: 4.0, preferably 1: 1. It is desirable to be in the range of 0.05 to 1: 4.04. On the other hand, the molar ratio of lithium hexafluorophosphate to chloride is preferably in the range of 1: 3.05 to 1: 4.44, particularly preferably in the range of 1: 3.60 to 1: 4.40. is there.
水分は、塩化物と同時にジフルオロリン酸塩に添加して反応に関与させても良く、予め塩化物と接触させて塩化物の水和物もしくは塩化物の含水物として反応に関与させても良い。前者の方法を用いる場合には、予めジフルオロリン酸塩を容器に封入し、その容器に、塩化物及び水をそれぞれ別々に一定速度で導入することが好ましい。 Water may be added to the difluorophosphate at the same time as the chloride and may be involved in the reaction, or may be contacted with the chloride in advance to be involved in the reaction as a chloride hydrate or chloride hydrate. . When the former method is used, it is preferable that difluorophosphate is sealed in a container in advance, and chloride and water are separately introduced into the container at a constant rate.
ヘキサフルオロリン酸塩、塩化物もしくはその水和物は、予め粉砕するなどして粒子の形状を細かくすると、反応における接触面積が増加し、反応時間を短縮させることができる。粉砕の手法は特に限定されるものではないが、具体的にハンマーミル、ジェットミル、ピンミル、ボールミル、乳鉢等で粉砕することができる。またスプレードライヤー等で予め微粉化した塩化物等も好適である。 When the shape of the particles of hexafluorophosphate, chloride or hydrate thereof is pulverized in advance, the contact area in the reaction increases, and the reaction time can be shortened. The pulverization method is not particularly limited, and specifically, pulverization can be performed with a hammer mill, a jet mill, a pin mill, a ball mill, a mortar, or the like. Also suitable are chlorides or the like finely divided in advance with a spray dryer or the like.
水分は、気体、液体、または固体のいずれの状態でも使用することができる。気体としては水蒸気であるが、水蒸気を含む気体であってもよい。水蒸気を含む気体は不活性ガスまたは空気を含んでいてもよい。不活性ガスまたは空気を含む場合には、その含有比率は、水蒸気に対して０〜９９vol％であることが好ましい。 Moisture can be used in any state of gas, liquid, or solid. The gas is water vapor, but may be a gas containing water vapor. The gas containing water vapor may contain an inert gas or air. When an inert gas or air is included, the content ratio is preferably 0 to 99 vol% with respect to water vapor.
次に、ヘキサフルオロリン酸塩と水とのその他の好適な反応条件を説明する。
反応温度は特に限定されるものではないが、３０〜８０℃であることが好ましく、特には２０〜７０℃であることが好ましい。この温度が低すぎると反応に極めて長時間を要することになる。また、反応中に副生するフッ化水素と塩化物との反応が遅くなり、塩化水素として系外へ蒸発させることが困難となる他、未反応のフッ化水素が系内に残留することとなり、その後精製するときに使用する溶媒を分解するため好ましくない。また一方、反応温度が高すぎるとヘキサフルオロリン酸塩の熱分解が激しくなり、五フッ化リンとして系外に脱離するため、収率が低下する傾向がある。
Next, other suitable reaction conditions between hexafluorophosphate and water will be described.
Although reaction temperature is not specifically limited, It is preferable that it is 30-80 degreeC, and it is especially preferable that it is 20-70 degreeC. If this temperature is too low, the reaction will take a very long time. In addition, the reaction between hydrogen fluoride and chloride produced as a by-product during the reaction slows down, making it difficult to evaporate out of the system as hydrogen chloride, and unreacted hydrogen fluoride remains in the system. This is not preferable because it decomposes the solvent used for subsequent purification. On the other hand, if the reaction temperature is too high, the thermal decomposition of hexafluorophosphate becomes intense, and it is eliminated from the system as phosphorus pentafluoride, so the yield tends to decrease.
反応時間としては、実験室規模では５分間〜４８時間程度であり、反応温度の制御により適宜選択する。また、反応の際、攪拌や振動を与えることが好ましい。例えば、２０Lスケール程度の場合、０．５〜１０時間所定の速さで攪拌したり、所定の強度の振動を与えたりすることで、より反応を進行させることができる。攪拌や振動の操作については、マグネチックスターラー等の攪拌機や、超音波などを用いた振動攪拌機等の当業者に良く知られた技術を使用することができる。 The reaction time is about 5 minutes to 48 hours on a laboratory scale, and is appropriately selected by controlling the reaction temperature. In addition, it is preferable to apply stirring and vibration during the reaction. For example, in the case of about 20 L scale, the reaction can be further advanced by stirring at a predetermined speed for 0.5 to 10 hours or applying a vibration with a predetermined intensity. For operations of stirring and vibration, techniques well known to those skilled in the art such as a stirrer such as a magnetic stirrer and a vibration stirrer using ultrasonic waves can be used.
また更に、以上の製造工程により得られたジフルオロリン酸塩を精製する方法としては以下の通り実施することができる。
精製方法は、特に限定されるものではないが、ジフルオロリン酸塩を溶解し、フッ化リチウムの溶解度の小さい溶媒を用いることができる。例えばメタノール、エタノール、プロパノール等のアルコール類、ホルムアルデヒド、アセトン、メチルエチルケトン、イソブチルメチルケトン等のケトン類、酢酸エチル、酢酸ブチル等のエステル類、ジメチルエーテル、ジメトキシエタン等のエーテル類、ジメチルカーボネート、ジエチルカーボネート、プロピレンカーボネート、エチレンカーボネート、フルオロエチレンカーボネート等のカーボネート類が使用でき、これら一種以上の溶媒に反応物を溶解し、不溶解分を分離し、エバポレーター等で脱溶媒することで高純度なジフルオロリン酸塩を得ることができる。
Furthermore, as a method for purifying the difluorophosphate obtained by the above production steps, it can be carried out as follows.
Although the purification method is not particularly limited, a solvent in which difluorophosphate is dissolved and lithium fluoride has low solubility can be used. For example, alcohols such as methanol, ethanol and propanol, ketones such as formaldehyde, acetone, methyl ethyl ketone and isobutyl methyl ketone, esters such as ethyl acetate and butyl acetate, ethers such as dimethyl ether and dimethoxyethane, dimethyl carbonate, diethyl carbonate, Carbonates such as propylene carbonate, ethylene carbonate, and fluoroethylene carbonate can be used. High purity difluorophosphoric acid is obtained by dissolving the reactants in one or more of these solvents, separating the insolubles, and removing the solvent with an evaporator or the like. A salt can be obtained.
以下の実施例により本発明を更に詳細に説明するが、本発明はかかる実施例に限定されるものではない。
反応生成物の分析はＶａｒｉａｎ社製ＮＭＲ Ｓｙｓｔｅｍ３００型を用いて１９Ｆ-ＮＭＲにて行った。また、生成物の収率は、内部標準物質としてヘキサフルオロベンゼンを用いて、１９Ｆ-ＮＭＲ分析により目的物と内部標準物質（ケミカルシフト値-１６６．８ｐｐｍ）との積分値比により定量した。水分は三菱化学社製 Ｍｏｄｅｌ ＣＡ-０６を用い定量した。遊離酸分（ＨＦ）はＤＩＯＮＥＸ社製ＤＸ-１２０ Ｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙを用い、Ｆ-として定量した。不溶解分は１５０ｇのＤＭＥ（１,２‐ジメトキシエタン）に溶解し、ポリテトラフルオロエチレン（ＰＴＦＥ）製メンブレンフィルターでろ過し、不溶解分量を測定した。
The present invention will be described in more detail by the following examples, but the present invention is not limited to such examples.
The analysis of the reaction product was performed by 19 F-NMR using a Varian NMR System 300 type. Further, the yield of the product was quantified by 19 F-NMR analysis using hexafluorobenzene as an internal standard substance, based on an integrated value ratio between the target product and the internal standard substance (chemical shift value—166.8 ppm). The moisture was quantified using Model CA-06 manufactured by Mitsubishi Chemical Corporation. The free acid content (HF) was quantified as F − using DX-120 Ion Chromatography manufactured by DIONEX. The insoluble matter was dissolved in 150 g of DME (1,2-dimethoxyethane), filtered through a membrane filter made of polytetrafluoroethylene (PTFE), and the insoluble matter was measured.
（水蒸気）
露点−５０℃未満のドライボックス中でヘキサフルオロリン酸リチウム３０．０ｇ（０．１９７５ｍｏｌ）に塩化リチウム３５．４ｇ（０．８３５１ｍｏｌ）を加え、乳鉢で粉砕混合した後、２００ｍＬのパーフルオロアルコキシアルカン（ＰＦＡ）製ボトルに回収し、窒素ガスを通気して置換し、５０℃にて３０分間保持した。次に攪拌しながら、７０℃の温水中に窒素ガスをバブリングしてなる７０℃の蒸気圧分の水１４ｇ（０．７７６９ｍｏｌ）をガスとして導入し、５０℃で９時間反応を行い、粗ジフルオロリン酸リチウムを３１．１ｇ得た。得られた結晶は１９Ｆ-ＮＭＲおよび３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶をジメトキシエタンに溶解し、副生したフッ化リチウムをろ別後、脱溶媒し、ジフルオロリン酸リチウムを得た。
(water vapor)
Add 35.4 g (0.8351 mol) of lithium chloride to 30.0 g (0.1975 mol) of lithium hexafluorophosphate in a dry box with a dew point of less than -50 ° C., pulverize and mix in a mortar, and then 200 mL of perfluoroalkoxyalkane. The product was collected in a (PFA) bottle, purged with nitrogen gas, and kept at 50 ° C. for 30 minutes. Next, while stirring, 14 g (0.7769 mol) of water corresponding to a vapor pressure of 70 ° C. obtained by bubbling nitrogen gas into 70 ° C. warm water was introduced as a gas, and the reaction was carried out at 50 ° C. for 9 hours to obtain crude difluoro 31.1 g of lithium phosphate was obtained. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystal was dissolved in dimethoxyethane, and by-product lithium fluoride was filtered off and then removed to obtain lithium difluorophosphate.
（水蒸気）
露点−５０℃未満のドライボックス中でヘキサフルオロリン酸リチウム２１．１ｇ（０．１３８９ｍｏｌ）に塩化リチウム２４．７ｇ（０．５８２７ｍｏｌ）を加え、乳鉢で粉砕混合した後、２００ｍＬのＰＦＡ製ボトルに回収し、窒素ガスを通気して置換しながら卓上ボールミル回転架台にセットし、回転混合させながら４０℃にて３０分間保持した。次に攪拌しながら、５０℃の温水中に窒素ガスをバブリングしてなる５０℃の蒸気圧分の水７．４ｇ（０．４１０７ｍｏｌ）をガスとして導入し、４０℃で１０時間の反応を行った。得られた結晶を１２０℃の乾燥機中で窒素気流の下で乾燥し、粗ジフルオロリン酸リチウムを２０．５ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶をジメトキシエタンに溶解し、副生したフッ化リチウムをろ別後、脱溶媒し、ジフルオロリン酸リチウムを得た。
(water vapor)
Add 24.7 g (0.5827 mol) of lithium chloride to 21.1 g (0.1389 mol) of lithium hexafluorophosphate in a dry box with a dew point of less than -50 ° C., pulverize and mix in a mortar, and then add it to a 200 mL PFA bottle. The sample was collected and set on a table-top ball mill rotating table while being replaced with nitrogen gas, and kept at 40 ° C. for 30 minutes while being rotated and mixed. Next, while stirring, 7.4 g (0.4107 mol) of water corresponding to a vapor pressure of 50 ° C. obtained by bubbling nitrogen gas into 50 ° C. warm water was introduced as a gas, and the reaction was carried out at 40 ° C. for 10 hours. It was. The obtained crystals were dried in a dryer at 120 ° C. under a nitrogen stream to obtain 20.5 g of crude lithium difluorophosphate. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystal was dissolved in dimethoxyethane, and by-product lithium fluoride was filtered off and then removed to obtain lithium difluorophosphate.
（水蒸気）
露点−５０℃未満のドライボックス中でヘキサフルオロリン酸リチウム３０．０ｇ（０．１９７５ｍｏｌ）に塩化リチウム３５．４ｇ（０．８３５１ｍｏｌ）を加え、乳鉢で粉砕混合した後、縦型の流動相式反応器に投入し、窒素ガスを通気して置換し、粉体を流動混合させながら６０℃にて３０分間保持した。次に攪拌しながら、６０℃の温水中に窒素ガスをバブリングしてなる６０℃の蒸気圧分の水８．４ｇ（０．４６６１ｍｏｌ）をガスとして導入し、６０℃で１０時間の反応を行った。得られた結晶を１２０℃の乾燥機中で窒素気流の下で乾燥し、粗ジフルオロリン酸リチウムを２１．５ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶をメチルエチルケトンに溶解し、副生したフッ化リチウムをろ別後、脱溶媒し、ジフルオロリン酸リチウムを得た。
(water vapor)
35.4 g (0.8351 mol) of lithium chloride is added to 30.0 g (0.1975 mol) of lithium hexafluorophosphate in a dry box having a dew point of less than −50 ° C., and pulverized and mixed in a mortar. The reactor was charged and replaced with nitrogen gas, and kept at 60 ° C. for 30 minutes while fluidly mixing the powder. Next, while stirring, 8.4 g (0.4661 mol) of water corresponding to a vapor pressure of 60 ° C. obtained by bubbling nitrogen gas into 60 ° C. warm water was introduced as a gas, and the reaction was performed at 60 ° C. for 10 hours. It was. The obtained crystal was dried in a dryer at 120 ° C. under a stream of nitrogen to obtain 21.5 g of crude lithium difluorophosphate. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystal was dissolved in methyl ethyl ketone, and lithium fluoride produced as a by-product was filtered off and then removed to obtain lithium difluorophosphate.
（水和物）
露点−５０℃未満のドライボックス中で塩化リチウム１４．１ｇ（０．３３２６ｍｏｌ）に純水３．３ｇ（０．１８３１ｍｏｌ）を加え、乳鉢で粉砕混合し、２００ｍＬのＰＦＡ製ボトルに回収した。その後、ＰＦＡボトル中にヘキサフルオロリン酸リチウム１４．１ｇ（０．０９２８ｍｏｌ）を加え、窒素ガスを通気して置換しながら振とう機にセットし、５０℃にて１２時間反応させ、粗ジフルオロリン酸リチウムを１６．１ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶をアセトンに溶解し、副生したフッ化リチウムをろ別後、脱溶媒し、ジフルオロリン酸リチウムを得た。
(Hydrate)
In a dry box having a dew point of less than −50 ° C., 3.3 g (0.1831 mol) of pure water was added to 14.1 g (0.3326 mol) of lithium chloride, pulverized and mixed in a mortar, and collected in a 200 mL PFA bottle. Thereafter, 14.1 g (0.0928 mol) of lithium hexafluorophosphate was added to the PFA bottle, and the mixture was placed on a shaker while replacing with nitrogen gas, and reacted at 50 ° C. for 12 hours. 16.1 g of lithium acid was obtained. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystal was dissolved in acetone, and lithium fluoride produced as a by-product was filtered off and then desolvated to obtain lithium difluorophosphate.
（水和物）
露点−５０℃未満のドライボックス中で塩化リチウム１５．７ｇ（０．３７０４ｍｏｌ）に純水３．３ｇ（０．１８３１ｍｏｌ）を加え、乳鉢で粉砕混合し、２００ｍＬのＰＦＡ製ボトルに回収した。その後、ＰＦＡボトル中にヘキサフルオロリン酸リチウムを１６．９ｇ（０．１１１３ｍｏｌ）加え、窒素ガスを通気して置換しながら振とう機にセットし、５０℃にて１６時間反応させ、粗ジフルオロリン酸リチウムを１９．３ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶をアセトンに溶解し、副生したフッ化リチウムをろ別後、脱溶媒し、ジフルオロリン酸リチウムを得た。
(Hydrate)
In a dry box having a dew point of less than −50 ° C., 3.3 g (0.1831 mol) of pure water was added to 15.7 g (0.3704 mol) of lithium chloride, pulverized and mixed in a mortar, and collected in a 200 mL PFA bottle. Thereafter, 16.9 g (0.1113 mol) of lithium hexafluorophosphate was added to the PFA bottle, and the mixture was placed on a shaker while replacing with nitrogen gas, and reacted at 50 ° C. for 16 hours. 19.3g of lithium acid was obtained. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystal was dissolved in acetone, and lithium fluoride produced as a by-product was filtered off and then desolvated to obtain lithium difluorophosphate.
（水蒸気 塩化リチウム無添加）
露点−５０℃未満のドライボックス中でヘキサフルオロリン酸リチウム３０．０ｇ（０．１９７５ｍｏｌ）を乳鉢で粉砕混合した後、２００ｍＬのＰＦＡ製ボトルに回収し、窒素ガスを通気して置換し５０℃にて３０分間保持した。次に、攪拌しながら７０℃の温水中に窒素ガスをバブリングしてなる７０℃の蒸気圧分の水１４ｇ（０．７７６９ｍｏｌ）をガスとして導入し、５０℃で９時間反応を行い粗生成物を２１．１ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。得られたＮＭＲの測定結果を表１に示す。反応後の生成物は目的物の他、モノフルオロリン酸リチウムやリン酸塩が多く副生した。
(No water vapor lithium chloride added)
30.0 g (0.1975 mol) of lithium hexafluorophosphate was pulverized and mixed in a mortar in a dry box with a dew point of less than −50 ° C., and then collected in a 200 mL PFA bottle and replaced with aerated nitrogen gas. For 30 minutes. Next, 14 g (0.7769 mol) of water corresponding to a vapor pressure of 70 ° C. obtained by bubbling nitrogen gas into 70 ° C. warm water while stirring is introduced as a gas, and the reaction is carried out at 50 ° C. for 9 hours to obtain a crude product. 21.1 g was obtained. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. The obtained NMR measurement results are shown in Table 1. In addition to the target product, the product after the reaction was a by-product of lithium monofluorophosphate and phosphate.
（塩化リチウム無添加）
露点−５０℃未満のドライボックス中でヘキサフルオロリン酸リチウム３０．０ｇ（０．１９７５ｍｏｌ）を乳鉢で粉砕混合した後、２００ｍＬのＰＦＡ製ボトルに回収し、窒素ガスを通気して置換し、５０℃にて３０分間保持した。次に攪拌しながら、純水３．３ｇ（０．１８３１ｍｏｌ）を加え５０℃で９時間反応を行い、粗生成物を２３．１ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。得られたＮＭＲの測定結果を表１に示す。反応後の生成物は目的物の他、モノフルオロリン酸塩やリン酸塩等が多く副生した。
(No lithium chloride added)
30.0 g (0.1975 mol) of lithium hexafluorophosphate was pulverized and mixed in a mortar in a dry box with a dew point of less than −50 ° C., and then collected in a 200 mL PFA bottle, and replaced by aeration with nitrogen gas. Hold at 30 ° C. for 30 minutes. Next, with stirring, 3.3 g (0.1831 mol) of pure water was added and reacted at 50 ° C. for 9 hours to obtain 23.1 g of a crude product. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. The obtained NMR measurement results are shown in Table 1. In addition to the desired product, the product after the reaction was mostly by-produced monofluorophosphate and phosphate.
（カリウム塩、水蒸気）
露点−５０℃未満のドライボックス中でヘキサフルオロリン酸カリウム１８．４ｇ（０．１０ｍｏｌ）に塩化カリウム２５．８ｇ（０．３４５８ｍｏｌ）を加え、乳鉢で粉砕混合した後、縦型の流動相式反応器に投入し、窒素ガスを通気して置換し、粉体を流動混合させながら６０℃にて３０分間保持した。次に攪拌しながら、６０℃の温水中に窒素ガスをバブリングしてなる６０℃の蒸気圧分の水８．４ｇ（０．４６６１ｍｏｌ）をガスとして導入し、６０℃で１０時間の反応を行った。得られた結晶を１２０℃の乾燥機中で窒素気流下乾燥し、粗ジフルオロリン酸カリウムを１４．４ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶をメチルエチルケトンに溶解し、副生したフッ化カリウムをろ別後、脱溶媒し、ジフルオロリン酸カリウムを得た。
(Potassium salt, water vapor)
After adding 25.8 g (0.3458 mol) of potassium chloride to 18.4 g (0.10 mol) of potassium hexafluorophosphate in a dry box having a dew point of less than −50 ° C., and pulverizing and mixing in a mortar, a vertical fluid phase type The reactor was charged and replaced with nitrogen gas, and kept at 60 ° C. for 30 minutes while fluidly mixing the powder. Next, while stirring, 8.4 g (0.4661 mol) of water corresponding to a vapor pressure of 60 ° C. obtained by bubbling nitrogen gas into 60 ° C. warm water was introduced as a gas, and the reaction was performed at 60 ° C. for 10 hours. It was. The obtained crystals were dried in a 120 ° C. drier under a nitrogen stream to obtain 14.4 g of crude potassium difluorophosphate. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystals were dissolved in methyl ethyl ketone, and the by-produced potassium fluoride was filtered off and then removed to obtain potassium difluorophosphate.
（ナトリウム塩、水蒸気）
露点−５０℃未満のドライボックス中でヘキサフルオロリン酸ナトリウム２０．６ｇ（０．１２２６ｍｏｌ）に塩化ナトリウム１４．３ｇ（０．２４４７ｍｏｌ）を加え、乳鉢で粉砕混合した後、２００ｍＬのＰＦＡ製ボトルに回収し、窒素ガスを通気して置換しながら卓上ボールミル回転架台にセットし、回転混合させながら２５℃にて３０分間保持した。次に攪拌しながら、３０℃の温水中に窒素ガスをバブリングしてなる３０℃の蒸気圧分の水３．７ｇ（０．２０５３ｍｏｌ）をガスとして導入し、２５℃で６時間の反応を行った。得られた結晶を１２０℃の乾燥機中で窒素気流下乾燥し、粗ジフルオロリン酸ナトリウムを１７．１ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶をジメトキシエタンに溶解し、副生したフッ化ナトリウムをろ別後、脱溶媒し、ジフルオロリン酸ナトリウムを得た。
(Sodium salt, water vapor)
Add 14.3 g (0.2447 mol) of sodium chloride to 20.6 g (0.1226 mol) of sodium hexafluorophosphate in a dry box with a dew point of less than -50 ° C., pulverize and mix in a mortar, and then add it to a 200 mL PFA bottle. The sample was collected and set on a table-top ball mill rotating table while being replaced with nitrogen gas and kept at 25 ° C. for 30 minutes while being rotated and mixed. Next, while stirring, 3.7 g (0.2053 mol) of water having a vapor pressure of 30 ° C. obtained by bubbling nitrogen gas into 30 ° C. warm water was introduced as a gas, and the reaction was performed at 25 ° C. for 6 hours. It was. The obtained crystal was dried in a dryer at 120 ° C. under a nitrogen stream to obtain 17.1 g of crude sodium difluorophosphate. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystals were dissolved in dimethoxyethane, and sodium fluoride produced as a by-product was filtered off and then removed to obtain sodium difluorophosphate.
（塩化リチウム）
５００ｍLのＰＦＡ製ボトルに顆粒状のヘキサフルオロリン酸リチウム１００．１ｇ（０．６５８９ｍｏｌ）を入れ、窒素ガスでシールしながら振とう機にセットし、純水４７．５ｇ（２．６３７５ｍｏｌ）と塩化リチウム粉末１２３．０ｇ（２．９０１６モル）をそれぞれ０．２ｇ／ｍｉｎ、２．１ｇ／ｍｉｎの速度で導入し、４０℃で２２時間反応を行った。
得られた結晶を１２０℃の乾燥機中で窒素気流下乾燥し、粗ジフルオロリン酸リチウム５６．８ｇを得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶を酢酸エチルに溶解し、副生したフッ化リチウムをろ別後、脱溶媒し、ジフルオロリン酸リチウムを得た。
(Lithium chloride)
Put 100.1 g (0.6589 mol) of granular lithium hexafluorophosphate into a 500 mL PFA bottle, set it on a shaker while sealing with nitrogen gas, 47.5 g (2.6375 mol) of pure water and chloride Lithium powder 123.0 g (2.9016 mol) was introduced at a rate of 0.2 g / min and 2.1 g / min, respectively, and reacted at 40 ° C. for 22 hours.
The obtained crystals were dried in a 120 ° C. dryer under a nitrogen stream to obtain 56.8 g of crude lithium difluorophosphate. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystals were dissolved in ethyl acetate, and lithium fluoride produced as a by-product was filtered off and then removed to obtain lithium difluorophosphate.
（塩化チオニル）
５００ｍＬのＰＦＡ製ボトルに顆粒状のヘキサフルオロリン酸リチウム１００．３ｇ（０．６６０３ｍｏｌ）を入れたものを、窒素ガスでシールしながら振とう機にセットし、その上で純水２７．９ｇ（１．５４８７ｍｏｌ）と塩化チオニル２６０．５ｇ（２．１８９６ｍｏｌ）をそれぞれ０．２ｇ／ｍｉｎ、１．７ｇ／ｍｉｎの速度で導入し、２５℃で２２時間反応を行った。得られた結晶を１２０℃の乾燥機中で窒素気流下乾燥し、粗ジフルオロリン酸リチウムを６１．４ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶を酢酸エチルに溶解し、副生したフッ化リチウムをろ別後、脱溶媒し、ジフルオロリン酸リチウムを得た。
(Thionyl chloride)
A 500 mL PFA bottle containing granular lithium hexafluorophosphate 100.3 g (0.6603 mol) was placed in a shaker while being sealed with nitrogen gas, and then 27.9 g of pure water ( 1.5487 mol) and 260.5 g (2.1896 mol) of thionyl chloride were introduced at a rate of 0.2 g / min and 1.7 g / min, respectively, and the reaction was carried out at 25 ° C. for 22 hours. The obtained crystals were dried in a dryer at 120 ° C. under a nitrogen stream to obtain 61.4 g of crude lithium difluorophosphate. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystals were dissolved in ethyl acetate, and lithium fluoride produced as a by-product was filtered off and then removed to obtain lithium difluorophosphate.
（ジメチルジクロロシラン）
５００ｍＬのＰＦＡ製ボトルに顆粒状のヘキサフルオロリン酸リチウム１００．１ｇ（０．６５８９ｍｏｌ）を入れたものを、窒素ガスでシールしながら振とう機にセットし、純水２８．６ｇ（１．５８７５ｍｏｌ）とジメチルジクロロシラン２６１．４ｇ（２．０２５４ｍｏｌ）をそれぞれ０．２ｇ／ｍｉｎ、１．９ｇ／ｍｉｎの速度で導入し、２０℃で２０時間反応を行った。得られた結晶を１２０℃の乾燥機中で窒素気流下乾燥し、粗ジフルオロリン酸リチウムを６０．５ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶を酢酸エチルに溶解し、副生したフッ化リチウムをろ別後、脱溶媒し、ジフルオロリン酸リチウムを得た。
(Dimethyldichlorosilane)
A 500 mL PFA bottle containing granular lithium hexafluorophosphate (100.1 g, 0.6589 mol) was placed on a shaker while being sealed with nitrogen gas, and 28.6 g (1.5875 mol) of pure water. ) And 261.4 g (2.0254 mol) of dimethyldichlorosilane were introduced at a rate of 0.2 g / min and 1.9 g / min, respectively, and reacted at 20 ° C. for 20 hours. The obtained crystals were dried in a dryer at 120 ° C. under a nitrogen stream to obtain 60.5 g of crude lithium difluorophosphate. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystals were dissolved in ethyl acetate, and lithium fluoride produced as a by-product was filtered off and then removed to obtain lithium difluorophosphate.
（塩化オキサリル）
５００ｍＬのＰＦＡ製ボトルに顆粒状のヘキサフルオロリン酸リチウム１００．２ｇ（０．５６６２ｍｏｌ）を入れたものを、窒素ガスでシールしながら振とう機にセットし、純水２４．５ｇ（１．３６００ｍｏｌ）と塩化オキサリル２５９．２ｇ（２．０４２１ｍｏｌ）をそれぞれ０．２ｇ／ｍｉｎ、２．０ｇ／ｍｉｎの速度で導入し、３０℃で２１時間反応を行った。得られた結晶を１２０℃の乾燥機中で窒素気流下乾燥し、粗ジフルオロリン酸リチウムを５４．９ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶を酢酸エチルに溶解し、副生したフッ化リチウムをろ別後、脱溶媒し、ジフルオロリン酸リチウムを得た。
(Oxalyl chloride)
A 500 mL PFA bottle containing 100.2 g (0.5662 mol) of granular lithium hexafluorophosphate is placed in a shaker while being sealed with nitrogen gas, and 24.5 g (1.3600 mol) of pure water. ) And 259.2 g (2.0421 mol) of oxalyl chloride were introduced at a rate of 0.2 g / min and 2.0 g / min, respectively, and reacted at 30 ° C. for 21 hours. The obtained crystal was dried in a dryer at 120 ° C. under a nitrogen stream to obtain 54.9 g of crude lithium difluorophosphate. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystals were dissolved in ethyl acetate, and lithium fluoride produced as a by-product was filtered off and then removed to obtain lithium difluorophosphate.
（塩化アセチル）
５００ｍＬのＰＦＡ製ボトルに顆粒状のヘキサフルオロリン酸リチウム１００．３ｇ（０．６６０３ｍｏｌ）を入れ、窒素ガスでシールしながら振とう機にセットし、純水２８．５ｇ（１．５８２０ｍｏｌ）と塩化アセチル１７６．３ｇ（２．２４５９ｍｏｌ）をそれぞれ０．２ｇ／ｍｉｎ、１．２ｇ／ｍｉｎの速度で導入し、３０℃で２２時間反応を行った。得られた結晶を１２０℃の乾燥機中で窒素気流下乾燥し、粗ジフルオロリン酸リチウムを５８．４ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶を酢酸エチルに溶解し、副生したフッ化リチウムをろ別後、脱溶媒し、ジフルオロリン酸リチウムを得た。
(Acetyl chloride)
Put a granular lithium hexafluorophosphate 100.3g (0.6603mol) into a 500mL PFA bottle, set it on a shaker while sealing with nitrogen gas, 28.5g (1.5820mol) pure water and chloride 176.3 g (2.2459 mol) of acetyl was introduced at a rate of 0.2 g / min and 1.2 g / min, respectively, and reacted at 30 ° C. for 22 hours. The obtained crystals were dried in a dryer at 120 ° C. under a nitrogen stream to obtain 58.4 g of crude lithium difluorophosphate. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystals were dissolved in ethyl acetate, and lithium fluoride produced as a by-product was filtered off and then removed to obtain lithium difluorophosphate.
（プロピオン酸塩化物）
５００ｍＬのＰＦＡ製ボトルに顆粒状のヘキサフルオロリン酸リチウム１００．３ｇ（０．６６０３ｍｏｌ）を入れ、窒素ガスでシールしながら振とう機にセットし、純水２８．６ｇ（１．５８８０ｍｏｌ）とプロピオン酸塩化物２０３．５ｇ（２．１９９５ｍｏｌ）をそれぞれ０．２ｇ／ｍｉｎ、１．４ｇ／ｍｉｎの速度で導入し、４５℃で２４時間反応を行った。得られた結晶を１２０℃の乾燥機中で窒素気流下乾燥し、粗ジフルオロリン酸リチウムを５０．７ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶を酢酸エチルに溶解し、副生したフッ化リチウムをろ別後、脱溶媒し、ジフルオロリン酸リチウムを得た。
(Propionate chloride)
Put 100.3 g (0.6603 mol) of granular lithium hexafluorophosphate into a 500 mL PFA bottle, and set it on a shaker while sealing with nitrogen gas. 28.6 g (1.5880 mol) of pure water and propion 203.5 g (2.9995 mol) of acid chloride was introduced at a rate of 0.2 g / min and 1.4 g / min, respectively, and reacted at 45 ° C. for 24 hours. The obtained crystals were dried in a 120 ° C. dryer under a nitrogen stream to obtain 50.7 g of crude lithium difluorophosphate. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystals were dissolved in ethyl acetate, and lithium fluoride produced as a by-product was filtered off and then removed to obtain lithium difluorophosphate.
（五塩化リン）
５００ｍＬのＰＦＡ製ボトルに顆粒状のヘキサフルオロリン酸リチウム１００．１ｇ（０．６５８９ｍｏｌ）を入れ、窒素ガスでシールしながら振とう機にセットし、純水２５．５ｇ（１．４１５９ｍｏｌ）と五塩化リン粉末４５６．５ｇ（２．１９２２ｍｏｌ）をそれぞれ０．２ｇ／ｍｉｎ、３．５ｇ／ｍｉｎの速度で導入し、３０℃で２０時間反応を行った。得られた結晶を１２０℃の乾燥機中で窒素気流下乾燥し、粗ジフルオロリン酸リチウムを５５．８ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶を酢酸エチルに溶解し、副生したフッ化リチウムをろ別後、脱溶媒し、ジフルオロリン酸リチウムを得た。
(Phosphorus pentachloride)
Put 100.1 g (0.6589 mol) of granular lithium hexafluorophosphate into a 500 mL PFA bottle, set it on a shaker while sealing with nitrogen gas, and add 25.5 g (1.4159 mol) of pure water and 5 456.5 g (2.1922 mol) of phosphorus chloride powder was introduced at a rate of 0.2 g / min and 3.5 g / min, respectively, and reacted at 30 ° C. for 20 hours. The obtained crystals were dried in a dryer at 120 ° C. under a nitrogen stream to obtain 55.8 g of crude lithium difluorophosphate. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystals were dissolved in ethyl acetate, and lithium fluoride produced as a by-product was filtered off and then removed to obtain lithium difluorophosphate.
（三塩化リン）
５００ｍＬのＰＦＡ製ボトルに顆粒状のヘキサフルオロリン酸リチウム１００．３ｇ（０．６６０３ｍｏｌ）を入れ、窒素ガスでシールしながら振とう機にセットし、純水２６．１ｇ（１．４４９２ｍｏｌ）と三塩化リン３００．２ｇ（２．１８６０ｍｏｌ）をそれぞれ０．２ｇ／ｍｉｎ、２．２ｇ／ｍｉｎの速度で導入し、３０℃で２０時間反応を行った。得られた結晶を１２０℃の乾燥機中で窒素気流下乾燥し、粗ジフルオロリン酸リチウムを５６．６ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶を酢酸エチルに溶解し、副生したフッ化リチウムをろ別後、脱溶媒し、ジフルオロリン酸リチウムを得た。
(Phosphorus trichloride)
Put 100.3 g (0.6603 mol) of granular lithium hexafluorophosphate into a 500 mL PFA bottle, set it on a shaker while sealing with nitrogen gas, and add 26.1 g (1.4492 mol) of pure water and three 300.2 g (2.1860 mol) of phosphorus chloride was introduced at a rate of 0.2 g / min and 2.2 g / min, respectively, and reacted at 30 ° C. for 20 hours. The obtained crystals were dried in a dryer at 120 ° C. under a nitrogen stream to obtain 56.6 g of crude lithium difluorophosphate. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystals were dissolved in ethyl acetate, and lithium fluoride produced as a by-product was filtered off and then removed to obtain lithium difluorophosphate.
（塩化ホスホニル）
５００ｍＬのＰＦＡ製ボトルに顆粒状のヘキサフルオロリン酸リチウム１００．２ｇ（０．６５９６ｍｏｌ）を入れ、窒素ガスでシールしながら振とう機にセットし、純水２７．２ｇ（１．５１０３ｍｏｌ）と塩化ホスホニル３３５．２ｇ（２．１８６１ｍｏｌ）をそれぞれ０．２ｇ／ｍｉｎ、２．５ｇ／ｍｉｎの速度で導入し、３０℃で２０時間反応を行った。得られた結晶を１２０℃の乾燥機中で窒素気流下乾燥し、粗ジフルオロリン酸リチウムを５７．１ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶を酢酸エチルに溶解し、副生したフッ化リチウムをろ別後、脱溶媒し、ジフルオロリン酸リチウムを得た。
(Phosphonyl chloride)
Put 100.2 g (0.6596 mol) of granular lithium hexafluorophosphate into a 500 mL PFA bottle, set it on a shaker while sealing with nitrogen gas, and add 27.2 g (1.5103 mol) of pure water and chloride. Phosphonyl 335.2 g (2.1861 mol) was introduced at a rate of 0.2 g / min and 2.5 g / min, respectively, and reacted at 30 ° C. for 20 hours. The obtained crystals were dried in a dryer at 120 ° C. under a nitrogen stream to obtain 57.1 g of crude lithium difluorophosphate. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystals were dissolved in ethyl acetate, and lithium fluoride produced as a by-product was filtered off and then removed to obtain lithium difluorophosphate.
（塩化チオニル）
２０Ｌのテフロン（登録商標）製反応器にヘキサフルオロリン酸リチウム１５００．０ｇ（９．８７４３ｍｏｌ）の顆粒を導入した。次いで純水４００．０ｇ（２２．２０３７ｍｏｌ）と塩化チオニル３９２５．０ｇ（３２．９９１３ｍｏｌ）をそれぞれ２．９ｇ／ｍｉｎ、２９．４ｇ／ｍｉｎの速度で導入し、窒素ガスでシールし、攪拌しながら３０℃で２０時間反応を行った。得られた結晶を１２０℃で窒素気流下乾燥し、粗ジフルオロリン酸リチウムを８２２．２ｇ得た。得られた結晶を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。結果、ほぼ定量的に反応が進行していることを確認した。得られたＮＭＲの測定結果を表１に示す。次に、得られた結晶を酢酸エチルに溶解し、副生したフッ化リチウムをろ別後、脱溶媒し、ジフルオロリン酸リチウムを得た。
(Thionyl chloride)
Into a 20 L Teflon (registered trademark) reactor, 1500.0 g (9.8743 mol) of granules of lithium hexafluorophosphate were introduced. Next, 400.0 g (22.2037 mol) of pure water and 3925.0 g (32.9913 mol) of thionyl chloride were introduced at a rate of 2.9 g / min and 29.4 g / min, respectively, sealed with nitrogen gas, and stirred. The reaction was performed at 30 ° C. for 20 hours. The obtained crystals were dried at 120 ° C. under a nitrogen stream to obtain 822.2 g of crude lithium difluorophosphate. The production ratio of the obtained crystals was calculated by 19 F-NMR and 31 P-NMR. As a result, it was confirmed that the reaction proceeded almost quantitatively. The obtained NMR measurement results are shown in Table 1. Next, the obtained crystals were dissolved in ethyl acetate, and lithium fluoride produced as a by-product was filtered off and then removed to obtain lithium difluorophosphate.
（塩化チオニル ＤＭＥ溶媒）
２５０ｍＬのＰＦＡ製ボトルに顆粒状のヘキサフルオロリン酸リチウム７．１ｇ（０．０４６７ｍｏｌ）と塩化チオニル１１．０ｇ（０．０９２５ｍｏｌ）を入れ、そこにジメトキシエタン３４ｇを加えてヘキサフルオロリン酸リチウムを溶解させた。その後、純水１．７ｇ（０．０９４４ｍｏｌ）を滴下し、７０℃で３０分間反応を行った。得られた反応液を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。得られたＮＭＲの測定結果を表１に示す。結果、ヘキサフルオロリン酸リチウムの加水分解反応が十分に進行していないことが確認できた。
(Thionyl chloride DME solvent)
In a 250 mL PFA bottle, put granular lithium hexafluorophosphate (7.1 g, 0.0467 mol) and thionyl chloride (11.0 g, 0.0925 mol), add dimethoxyethane (34 g), and add lithium hexafluorophosphate. Dissolved. Thereafter, 1.7 g (0.0944 mol) of pure water was added dropwise and reacted at 70 ° C. for 30 minutes. The production ratio of the obtained reaction solution was calculated by 19 F-NMR and 31 P-NMR. The obtained NMR measurement results are shown in Table 1. As a result, it was confirmed that the hydrolysis reaction of lithium hexafluorophosphate did not proceed sufficiently.
（塩化リチウム 酢酸エチル溶媒）
露点−５０℃未満のドライボックス中でヘキサフルオロリン酸リチウム１０．０ｇ（０．０６５８ｍｏｌ）に塩化リチウム１１．２ｇ（０．２６４２ｍｏｌ）を加え、乳鉢で粉砕混合した後、２００ｍＬのＰＦＡ製ボトルに回収し、そこに酢酸エチル４９ｇを加えてヘキサフルオロリン酸リチウムを溶解させた。次に、窒素ガスを通気して置換し、５０℃にて３０分間保持した後、７０℃で攪拌しながら純水２．４ｇ（０．１３３３ｍｏｌ）を滴下し、７０℃で６０分間反応を行った。得られた反応液を１９Ｆ-ＮＭＲ、３１Ｐ-ＮＭＲにて生成比を算出した。得られたＮＭＲの測定結果を表１に示す。ジフルオロリン酸リチウムが９９．４％の選択性で得られたが、反応液に黄色い着色が見られたことから、電池特性への悪影響が考えられる。
(Lithium chloride ethyl acetate solvent)
Add 11.2 g (0.2642 mol) of lithium chloride to 10.0 g (0.0658 mol) of lithium hexafluorophosphate in a dry box with a dew point of less than −50 ° C., pulverize and mix in a mortar, and then add it to a 200 mL PFA bottle. Then, 49 g of ethyl acetate was added to dissolve lithium hexafluorophosphate. Next, the gas was replaced with nitrogen gas, held at 50 ° C. for 30 minutes, 2.4 g (0.1333 mol) of pure water was added dropwise with stirring at 70 ° C., and the reaction was performed at 70 ° C. for 60 minutes. It was. The production ratio of the obtained reaction solution was calculated by 19 F-NMR and 31 P-NMR. The obtained NMR measurement results are shown in Table 1. Although lithium difluorophosphate was obtained with a selectivity of 99.4%, yellow coloration was seen in the reaction solution, which may have an adverse effect on battery characteristics.
Claims (9)
ヘキサフルオロリン酸塩に、ジフルオロリン酸塩を得るのに必要な反応当量以上の水分と反応当量以上の塩化物とを同時に添加して反応させることを特徴とするジフルオロリン酸塩の製造方法。 A process for producing a difluorophosphate comprising a step of reacting hexafluorophosphate, moisture and chloride without intervening a solvent to obtain a difluorophosphate,
A method for producing a difluorophosphate, characterized by simultaneously adding and reacting hexafluorophosphate with a water equivalent to a reaction equivalent or more necessary for obtaining a difluorophosphate and a chloride with a reaction equivalent or more.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016175186A1 (en) * | 2015-04-27 | 2016-11-03 | 関東電化工業株式会社 | Method for purifying difluorophosphate |
| CN108147385A (en) * | 2016-12-02 | 2018-06-12 | 中央硝子株式会社 | The manufacturing method of difluorophosphate |
| JP2019172475A (en) * | 2018-03-26 | 2019-10-10 | 三井化学株式会社 | Method for producing lithium difluorophosphate |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008111367A1 (en) * | 2007-03-12 | 2008-09-18 | Central Glass Company, Limited | Method for producing lithium difluorophosphate and nonaqueous electrolyte battery using the same |
| JP2010155773A (en) * | 2008-12-02 | 2010-07-15 | Stella Chemifa Corp | Method for producing difluorophosphate |
-
2013
- 2013-08-27 JP JP2013175924A patent/JP6199117B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008111367A1 (en) * | 2007-03-12 | 2008-09-18 | Central Glass Company, Limited | Method for producing lithium difluorophosphate and nonaqueous electrolyte battery using the same |
| JP2010155773A (en) * | 2008-12-02 | 2010-07-15 | Stella Chemifa Corp | Method for producing difluorophosphate |
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