TW201318972A - Manufacture of mixtures comprising LiPO2F2 and LiPF6 - Google Patents

Abstract

Mixtures comprising LiPO2F2 and LiPF6 both of which are electrolyte salts or additive for, i.a., Li ion batteries, are manufactured by the reaction of POF3 and LiF. The mixtures can be extracted with suitable solvents to provide solutions containing LiPO2F2 and LiPF6 which can be applied for the manufacture of Li ion batteries, Li-air batteries and Li-sulfur batteries. Equimolar mixtures comprising LiPO2F2 and LiPF6 are also described, as well as a method for the manufacture of electrolyte compositions obtained by the extraction of equimolar mixtures comprising LiPO2F2 and LiPF6.

Description

含有LiPO 2 F 2 和LiPF 6 之混合物的製造Manufacture of a mixture containing LiPO 2 F 2 and LiPF 6

本申請要求於2011年8月16日提交的歐洲專利申請號EP 11177718.1的優先權，出於所有的目的將該申請的全部內容藉由引用結合在此。 The present application claims priority to the European Patent Application No. EP 1 117 771 8.1 filed on Aug. 16, 2011, the entire content of which is hereby incorporated by reference.

本發明涉及一種用於製造含LiPO₂F₂與LiPF₆的混合物的方法，包括使磷醯氟(POF₃)與氟化鋰(LiF)反應的一步驟。本發明還針對處於針形式的固體LiPO₂F₂。 The present invention relates to a process for producing a mixture comprising LiPO ₂ F ₂ and LiPF ₆ comprising a step of reacting phosphonium fluoride (POF ₃ ) with lithium fluoride (LiF). The invention is also directed to solid LiPO ₂ F ₂ in the form of a needle.

二氟磷酸鋰，LiPO₂F₂，作為一用於進一步含LiPF₆的電解質組合物的電解質鹽係有用的。因此，EP-A-2 065339揭露了如何用除氟化物之外的一種鹵化物、LiPF₆和水來製造LiPF₆和LiPO₂F₂的混合物。所生成的鹽混合物，溶解在無質子溶劑中，被用作鋰離子電池的電解質溶液。EP-A-2 061 115描述了用P₂O₃F₄和Li的化合物來製造LiPO₂F₂；並且用LiPF₆與具有Si-O-Si鍵的化合物(例如矽氧烷)來製造LiPO₂F₂。US 2008-305402和US 2008/102376揭露了藉由一種碳酸鹽化合物用LiPF₆來製造LiPO₂F₂；根據US 2008/102376，LiPF₆在50℃以及更高溫度分解從而形成PF₅；根據其他公開物，PF₅僅在處於和高於LiPF₆的熔點(約190℃)的溫度下形成。 Lithium difluorophosphate, LiPO ₂ F ₂ , is useful as an electrolyte salt for an electrolyte composition further containing LiPF ₆ . Thus, EP-A-2 065 339 discloses how to make a mixture of LiPF ₆ and LiPO ₂ F ₂ with a halide other than fluoride, LiPF ₆ and water. The resulting salt mixture, dissolved in an aprotic solvent, was used as an electrolyte solution for a lithium ion battery. EP-A-2 061 115 describes the production of LiPO ₂ F ₂ with a compound of P ₂ O ₃ F ₄ and Li; and the manufacture of LiPO with LiPF ₆ and a compound having a Si—O—Si bond, such as a decane. ₂ F ₂ . US 2008-305402 and US 2008/102376 disclose the production of LiPO ₂ F ₂ by LiPF ₆ from a carbonate compound; according to US 2008/102376, LiPF ₆ decomposes at 50 ° C and higher to form PF ₅ ; It is disclosed that PF ₅ is formed only at temperatures at and above the melting point of LiPF ₆ (about 190 ° C).

然而，以上方法在技術上是困難的，並且該起始材料 LiPF₆係昂貴的，並且因此使用它增加了生產成本。由於LiPF₆與LiPO₂F₂一起被用作電解質鹽，因此這對於以LiPF₆的成本來生產LiPO₂F₂係無效的。往往希望的是一用於生產LiPO₂F₂與LiPF₆兩者的方法。因此，對發展能夠避免以上指出的缺點的新方法已經存在著需要。 However, the above method is technically difficult, and the starting material LiPF ₆ is expensive, and thus it is used to increase the production cost. Since LiPF ₆ is used as an electrolyte salt together with LiPO ₂ F ₂ , this is ineffective for producing LiPO ₂ F ₂ system at the cost of LiPF ₆ . What is often desired is a method for producing both LiPO ₂ F ₂ and LiPF ₆ . Therefore, there is a need to develop new methods that avoid the disadvantages noted above.

本發明的目的係以一技術上可行的並且經濟的方式來提供LiPO₂F₂連同LiPF₆。本發明的另一目的係以一更簡單的方式來提供含LiPF₆與LiPO₂F₂兩者的溶液的路徑。該等目的以及其他目的藉由本發明如在專利申請專利範圍概括的來實現。 The object of the present invention is to provide LiPO ₂ F ₂ together with LiPF ₆ in a technically feasible and economical manner. Another object of the invention is to provide a path for a solution containing both LiPF ₆ and LiPO ₂ F ₂ in a simpler manner. These and other objects are achieved by the present invention as outlined in the patent application.

根據本發明的一方面，本發明的用於製造一含近似等莫耳(approximately equimolar)量的LiPO₂F₂與LiPF₆的混合物的方法包括使LiF與POF₃反應的一步驟。 According to an aspect of the invention, a method of the invention for producing a mixture comprising LiPO ₂ F ₂ and LiPF _{6 in} an approximate equimolar amount comprises a step of reacting LiF with POF ₃ .

LiF係一較廉價、易於純化的起始材料，該材料係例如從德國凱密特爾集團(Chemetall GmbH)可商購的。磷醯氟(POF₃)可以在商業上獲得，例如從ABCR GmbH & Co.KG。如果希望的話，POF₃可以用POCl₃與氟化劑，例如HF、ZnF₂或胺-HF來製造。所生產係POF₃可以藉由蒸餾來純化。反應方程係2POF₃+2LiF → LiPO₂F₂+LiPF₆ (I)。 LiF is a relatively inexpensive, easy to purify starting material which is commercially available, for example, from Chemetall GmbH, Germany. Phosphonium fluoride (POF ₃ ) is commercially available, for example, from ABCR GmbH & Co. KG. If desired, POF ₃ can be made with POCl ₃ and a fluorinating agent such as HF, ZnF ₂ or amine-HF. The produced POF ₃ can be purified by distillation. The reaction equation is 2POF ₃ + 2LiF → LiPO ₂ F ₂ + LiPF ₆ (I).

因此，根據方程(I)的反應生產了兩種有價值的產物。一技術優點係，LiF可以很容易進行乾燥，這降低了尤其是LiPF₆的水解的風險。 Therefore, two valuable products are produced according to the reaction of equation (I). A technical advantage is that LiF can be easily dried, which reduces the risk of hydrolysis of LiPF ₆ , especially.

該方法進一步可以包括以下步驟，例如用來提供含LiPO₂F₂與LiPF₆的溶液的一步驟，一或多個如下所述的用來獲得純化的LiPO₂F₂的步驟，以及其他步驟。 The method may further comprise the steps of, for example, a step for providing a solution containing LiPO ₂ F ₂ and LiPF ₆ , one or more steps for obtaining purified LiPO ₂ F ₂ as described below, and other steps.

本發明的反應可以按氣固反應藉由使POF₃穿過一LiF床或藉由使兩種組分在一高壓閥中反應來進行。如果希望的話，該LiF可以懸浮在一無質子的有機溶劑中，和/或該POF₃可以引入、溶解在一無質子有機溶劑中，並且因此在這種情況下，進行一氣-液-固反應或一液-固反應。對於POF₃合適的溶劑係例如醯化合物，例如二***，以及作為鋰離子電池中的溶劑有用的有機溶劑；以下給出了此種溶劑的許多例子，例如尤其是有機碳酸酯，而且還有內酯、甲醯胺、吡咯烷酮、噁唑烷酮、硝基烷、N,N-取代的胺基甲酸酯、環丁碸、二烷基亞碸、二烷基亞硫酸酯、乙酸酯、腈、乙醯胺、二醇醚、二氧戊環、二烷氧基乙烷、三氟乙醯胺。 The reaction of the present invention can be carried out by gas-solid reaction by passing POF ₃ through a LiF bed or by reacting the two components in a high pressure valve. If desired, the LiF may be suspended in an aprotic organic solvent, and/or the POF ₃ may be introduced and dissolved in an aprotic organic solvent, and thus, in this case, a gas-liquid-solid reaction is carried out. Or a liquid-solid reaction. Suitable solvents for POF ₃ are, for example, hydrazine compounds, such as diethyl ether, and organic solvents useful as solvents in lithium ion batteries; many examples of such solvents are given below, such as, in particular, organic carbonates, but also within Esters, formamide, pyrrolidone, oxazolidinone, nitroalkane, N,N-substituted urethane, cyclobutyl hydrazine, dialkyl hydrazine, dialkyl sulfite, acetate, Nitrile, acetamide, glycol ether, dioxolane, dialkoxyethane, trifluoroacetamide.

在其他實施方式中，將POF₃以錯合物的形式、尤其是以一供體-受體錯合物的形式(例如POF₃-胺錯合物)而引入到該反應器中。那些錯合物包括：POF₃-吡啶、POF₃-三乙胺、POF₃-三丁胺、POF₃-DMAP(4-(二甲胺基)吡啶)、POF₃-DBN(1,5-二氮雜二環[4.3.0]壬-5-烯)、POF₃-DBU(1,8-二氮雜二環[5.4.0]十一-7-烯)、以及POF₃-甲基咪唑 。在具體實施方式中，可以使用一單獨的容器以便將POF₃供應到該反應器容器中。較佳的是，將POF₃以氣體形式引入到該反應器中。 In other embodiments, the POF ₃ in the form of complexes, in particular in a donor - acceptor complexes form (e.g. POF ₃ - amine complexes) introduced into the reactor. Those complexes comprising: POF ₃ - pyridine, POF ₃ - triethylamine, POF ₃ - tributylamine, POF ₃ -DMAP (4- (dimethylamino) pyridine), POF ₃ -DBN (1,5- Diazabicyclo[4.3.0]non-5-ene), POF ₃ -DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), and POF ₃ -methyl Imidazole. In a specific embodiment, a separate container can be used to supply POF ₃ to the reactor vessel. Preferably, POF ₃ is introduced into the reactor as a gas.

較佳的是，該反應在沒有水或濕氣的情況下進行。如以上所提及的，LiF可以在引入到該反應之前就進行乾燥。作為替代方案或另外地，該反應可以在一惰性氣體的存在下至少在其持續時間的一部分中進行；乾燥的氮氣係非常合適的，但是其他乾燥的惰性氣體也是可施用的。該反應可以在一高壓釜類型的容器內或在其他反應器中進行。較佳的是，反應在由鋼或其他耐腐蝕的材料製成的設備中進行，例如在由蒙乃爾合金(Monel)金屬製成的或包覆的反應器中。 Preferably, the reaction is carried out in the absence of water or moisture. As mentioned above, LiF can be dried prior to introduction into the reaction. Alternatively or additionally, the reaction can be carried out in the presence of an inert gas for at least a portion of its duration; dry nitrogen is very suitable, but other dry inert gases are also applicable. The reaction can be carried out in an autoclave type vessel or in other reactors. Preferably, the reaction is carried out in an apparatus made of steel or other corrosion resistant material, such as in a reactor made of or coated with Monel metal.

LiF較佳的是以小顆粒的形式、例如以粉末的形式施用。 LiF is preferably applied in the form of small particles, for example in the form of a powder.

較佳的是，反應混合物中不加入HF。較佳的是，反應混合物中不加入二氟磷酸。較佳的是，在所生產的LiPO₂F₂與LiPF₆的混合物中等於或大於80%，更佳的是，等於或大於85%，並且最佳的是100%的P含量係源自POF₃。 Preferably, no HF is added to the reaction mixture. Preferably, no difluorophosphoric acid is added to the reaction mixture. Preferably, it is equal to or greater than 80%, more preferably equal to or greater than 85%, and preferably 100% of the P content is derived from the POF in the mixture of LiPO ₂ F ₂ and LiPF ₆ produced. ₃ .

POF₃與LiF的莫耳比理想地是1：1。POF₃與LiF比例的較佳的最小值係0.9：1。如果更低的話，則產量對應地更低，並且未反應的LiF將會在所形成的反應混合物中存在。POF₃與LiF的莫耳比較佳的是等於或大於1：1。較佳的是，它等於或小於5：1，更佳的是等於或小於2：1。它可以甚至大於5：1，但是大量的POF₃損失掉，亦 或它必須進行再利用，這需要另外的裝置零件並且消耗能量。 The molar ratio of POF ₃ to LiF is ideally 1:1. A preferred minimum ratio of POF ₃ to LiF is 0.9:1. If lower, the yield is correspondingly lower and unreacted LiF will be present in the resulting reaction mixture. Preferably, POF ₃ and LiF are more than or equal to 1:1. Preferably, it is equal to or less than 5:1, more preferably equal to or less than 2:1. It can be even larger than 5:1, but a large amount of POF _{3 is} lost, or it must be reused, which requires additional device parts and consumes energy.

反應時間被選擇為使得實現所希望的轉化程度。經常，1秒鐘至5小時的反應時間給出了良好的反應結果。較佳的反應時間係0.5至2小時、最佳的約1小時的反應時間給出了良好的結果。該反應速度非常快。 The reaction time is chosen such that the desired degree of conversion is achieved. Frequently, a reaction time of 1 second to 5 hours gives a good reaction result. A preferred reaction time of 0.5 to 2 hours, and an optimum reaction time of about 1 hour gives good results. The reaction rate is very fast.

較佳的是，該反應溫度係等於或高於0℃。較佳的是，該反應溫度係等於或低於100℃。 Preferably, the reaction temperature is equal to or higher than 0 °C. Preferably, the reaction temperature is equal to or lower than 100 °C.

該反應溫度較佳的是等於或高於環境溫度(25℃)，更佳的是等於或高於40℃。該反應溫度較佳的是等於或低於90℃，更佳的是等於或低於70℃。對於該反應較佳的溫度範圍係在從25℃至90℃，尤其是從40℃至70℃的溫度下進行。 The reaction temperature is preferably equal to or higher than the ambient temperature (25 ° C), and more preferably equal to or higher than 40 ° C. The reaction temperature is preferably equal to or lower than 90 ° C, more preferably equal to or lower than 70 ° C. The preferred temperature range for the reaction is carried out at a temperature of from 25 ° C to 90 ° C, especially from 40 ° C to 70 ° C.

如果希望的話，一反應器可以被施加以內部加熱或冷卻裝置或者外部加熱或冷卻裝置。它可以具有例如帶有熱傳遞試劑(例如水)的線路或管道。 If desired, a reactor can be applied with an internal heating or cooling device or an external heating or cooling device. It may have, for example, a line or conduit with a heat transfer reagent such as water.

POF₃與LiF之間的反應可以在環境壓力(1巴絕對壓力)下進行。較佳的是，該反應係在高於1巴(絕對值)的壓力下進行，並且更佳的是在高於3巴(絕對值)的壓力下進行。較佳的是，該壓力係等於或小於10巴(絕對值)並且更佳的是它係等於或小於5巴(絕對值)。隨著反應的進行，POF₃被消耗掉，並且壓力因此在例如高壓釜內會降低。如果POF₃被連續地引入到該反應中，則壓力降低指示出該反應仍然在進行。 The reaction between POF ₃ and LiF can be carried out at ambient pressure (1 bar absolute). Preferably, the reaction is carried out at a pressure above 1 bar (absolute) and more preferably at a pressure above 3 bar (absolute). Preferably, the pressure system is equal to or less than 10 bar (absolute value) and more preferably it is equal to or less than 5 bar (absolute value). As the reaction progresses, the POF ₃ is consumed, and the pressure is thus lowered, for example, in the autoclave. If POF ₃ is continuously introduced into the reaction, a decrease in pressure indicates that the reaction is still proceeding.

POF₃與LF的反應可以是按批次地，例如在一高壓釜中進行。該反應器可以具有多種內部裝置，例如攪拌器，來提供對LiF固體顆粒表面的機械衝擊以便從表面上除去反應產物並且提供一未反應的新鮮表面。還有可能搖動或轉動反應器本身。 The reaction of POF ₃ with LF can be carried out in batches, for example in an autoclave. The reactor can have a variety of internal devices, such as agitators, to provide mechanical impact on the surface of the LiF solid particles to remove reaction products from the surface and provide an unreacted fresh surface. It is also possible to shake or rotate the reactor itself.

作為替代方案，該反應可以連續地例如在一流動反應器中進行。例如，LiF能夠以一種床的形式提供；POF₃可以穿過這個床直至觀察到POF₃的一“穿透”，這種穿透指示了反應的結束。如果希望的話，可以使乾燥的惰性氣體例如氮氣或稀有氣體穿過該LiF床以在進行該反應之前除去氧氣、濕氣或這兩者。 Alternatively, the reaction can be carried out continuously, for example in a flow reactor. For example, LiF can be provided in the form of a bed; POF ₃ can pass through the bed until a "penetration" of POF ₃ is observed, which indicates the end of the reaction. If desired, a dry inert gas such as nitrogen or a rare gas may be passed through the LiF bed to remove oxygen, moisture or both prior to carrying out the reaction.

如果反應連續地進行，則例如可以在流動反應器中將LiF保持為一種床的形式，例如作為流化床，並且使POF₃連續地穿過該床。POF₃和新鮮的LiF可以被連續地引入到該反應器中，並且反應產物可以被連續地從反應器中抽出。 If the reaction is carried out continuously, for example, LiF can be maintained in the form of a bed in a flow reactor, for example as a fluidized bed, and POF _{3 is} continuously passed through the bed. POF ₃ and fresh LiF can be continuously introduced into the reactor, and the reaction product can be continuously withdrawn from the reactor.

如果希望分離LiPO₂F₂和LiPF₆的話，則該反應可以在一無質子溶劑中進行，因為LiPF₆比LiPO₂F₂在該等溶劑中遠遠更好地可溶；LiPF₆被主要地且連同少量的LiPO₂F₂溶解並且可以在該溶液中除去。這種含溶解的LiPF₆與LiPO₂F₂的溶液係一本身如下所描述的有價值的產物。固體的LiPO₂F₂形成了一固體殘餘物，該殘餘物可以如以下所述地純化。因此，POF₃與LiF之間的反應以及所形成的LiPF₆(處於一含LiPF₆與LiPO₂F₂的有價值溶液的形式)和 一LiPO₂F₂的固體殘餘物(這可以進一步進行純化)的隨後分離可以在同一反應器中以一種“1鍋法”的類型來進行。 If it is desired to separate LiPO ₂ F ₂ and LiPF ₆ , the reaction can be carried out in an aprotic solvent since LiPF ₆ is much better soluble in these solvents than LiPO ₂ F ₂ ; LiPF ₆ is predominantly It is dissolved along with a small amount of LiPO ₂ F ₂ and can be removed in the solution. This solution containing dissolved LiPF ₆ and LiPO ₂ F ₂ is a valuable product as described below per se. The solid LiPO ₂ F ₂ forms a solid residue which can be purified as described below. Thus, the reaction between POF ₃ and LiF and the formation of LiPF ₆ (in the form of a valuable solution containing LiPF ₆ and LiPO ₂ F ₂ ) and a solid residue of LiPO ₂ F ₂ (this can be further purified) Subsequent separation can be carried out in the same reactor in a "one-pot" type.

如果希望的話，反應終止之後，可以施加一真空，或者可以使乾燥的惰性氣體(像氮氣或稀有氣體)穿過所形成的LiPO₂F₂與LiPF₆，以除去HF，濕氣或溶劑(如果它們被使用的話)或殘餘的POF₃。 If desired, a vacuum may be applied after the reaction is terminated, or a dry inert gas such as nitrogen or a rare gas may be passed through the formed LiPO ₂ F ₂ and LiPF ₆ to remove HF, moisture or solvent (if They are used) or residual POF ₃ .

如果不使用溶劑的話，所生成的反應混合物包含近似等莫耳量的LiPO₂F₂和LiPF₆並且以固體的形式存在。如果希望的話，可以將固體粉碎(例如研磨)以提供更大的接觸表面(如果旨在溶解其組分的話)。 If no solvent is used, the resulting reaction mixture contains approximately equal molar amounts of LiPO ₂ F ₂ and LiPF ₆ and is present as a solid. If desired, the solid can be comminuted (e.g., ground) to provide a larger contact surface if it is intended to dissolve its components.

在“近似等莫耳量”的背景下術語“近似地”應表示由40莫耳%至60莫耳%的LiPO₂F₂以及40莫耳%至60莫耳%的LiPF₆組成的LiPO₂F₂與1.2LiPF₆的混合物，較佳的是由45莫耳%至55莫耳%的LiPO₂F₂和45莫耳%至55莫耳%的LiPF₆，更佳的是49莫耳%至51莫耳%LiPO₂F₂以及49莫耳%至51莫耳%LiPF₆組成的LiPO₂F₂與LiPF₆的混合物。 Under "approximately equimolar amount" in the context the term "approximately" is represented by 40 mole% to 60 mole% of LiPO ₂ F _2, and 40 mole% to 60 mole% of LiPF ₆ composed LiPO ₂ A mixture of F ₂ and 1.2 LiPF ₆ , preferably from 45 mol % to 55 mol % of LiPO ₂ F ₂ and 45 mol % to 55 mol % of LiPF ₆ , more preferably 49 mol % A mixture of LiPO ₂ F ₂ and LiPF ₆ consisting of 51 mol% LiPO ₂ F ₂ and 49 mol% to 51 mol% LiPF ₆ .

用於處理(work up)該含LiPO₂F₂與LiPF₆的固體反應混合物的最合理的方式係加入一有機溶劑，尤其是適合作為用於Li離子電池、Li空氣電池以及Li硫電池的電解質溶液的一溶劑(當含溶解的LiPF₆與LiPO₂F₂時)。以下給出了許多此種溶劑。最有效的方式係應用一溶解LiPF₆比LiPO₂F₂遠遠更好的一無質子極性溶劑。 The most reasonable way to work up the solid reaction mixture containing LiPO ₂ F ₂ and LiPF ₆ is to add an organic solvent, especially as an electrolyte for Li ion batteries, Li air batteries, and Li sulfur batteries. A solvent for the solution (when containing dissolved LiPF ₆ and LiPO ₂ F ₂ ). Many such solvents are given below. The most effective way is to apply an aprotic polar solvent that dissolves LiPF ₆ far better than LiPO ₂ F ₂ .

對於可以應用LiPO₂F₂與LiPF₆等莫耳混合物的應用 領域，可以無需進一步處理就施加該反應混合物；作為替代方案，任何濕氣、HF或殘餘POF₃可以藉由施用真空除去，如果希望的話，是在升高的溫度下，例如在高於100℃或甚至高於150℃，但是較佳的是不高於200℃的溫度下。 For applications where a molar mixture of LiPO ₂ F ₂ and LiPF ₆ can be applied, the reaction mixture can be applied without further processing; alternatively, any moisture, HF or residual POF ₃ can be removed by applying a vacuum if desired In the case of elevated temperatures, for example at temperatures above 100 ° C or even above 150 ° C, but preferably not above 200 ° C.

考慮到在Li離子電池、Li空氣電池以及Li硫電池中通常使用LiPF₆作為電解質鹽以及使用LiPO₂F₂作為電解質鹽的添加劑，其中經常溶解LiPF₆來提供1莫耳的溶液，並且將LiPO₂F₂以用於提供按重量計1%至2%濃度的量來溶解，處理該等反應混合物的一較佳的替代方案係使用一用於提及類型電池的溶劑來提取該混合物。該提取液中的LiPF₆濃度通常比LiPO₂F₂的濃度遠遠更高。這在以下情況下是非常有利的，其中所希望的是如以上提及的具有1莫耳量的LiPF₆以及連同小至按重量計1%至2%的LiPO₂F₂，包含比LiPO₂F₂更多的LiPF₆的一電解質溶液。實際濃度可以藉由添加LiPF₆、LiPO₂F₂和/或藉由添加溶劑或去除溶劑(例如藉由施加真空)來改變。 Considering that LiPF ₆ is generally used as an electrolyte salt in Li ion batteries, Li air batteries, and Li sulfur batteries, and LiPO ₂ F _{2 is} used as an additive of an electrolyte salt, in which LiPF ₆ is often dissolved to provide a 1 mol solution, and LiPO is to be ₂ F ₂ is dissolved in an amount to provide a concentration of 1% to 2% by weight. A preferred alternative to treating the reaction mixture is to extract the mixture using a solvent for a battery of the type mentioned. The concentration of LiPF ₆ in the extract is generally much higher than the concentration of LiPO ₂ F ₂ . This is very advantageous in the case where LiPF ₆ having a molar amount of 1 mol as mentioned above and together with 1 to 2% by weight of LiPO ₂ F ₂ , including LiPO ₂ is desired. F ₂ more electrolyte solution of LiPF ₆ . The actual concentration can be varied by adding LiPF ₆ , LiPO ₂ F ₂ and/or by adding a solvent or removing the solvent (for example by applying a vacuum).

經常，該無質子有機溶劑係選自下組：酮類；腈類；甲醯胺類；碳酸二烷基酯(直鏈的)以及碳酸伸烴酯(環狀的)，並且其中術語“烷基”較佳的是表示C1至C4的烷基，術語“伸烷基”較佳的是表示C2至C7的伸烷基基團，包括伸乙烯基基團，其中伸烷基較佳的是包括在-O-C(O)-O-基團的氧原子之間的一個2碳原子橋；二甲基甲醯胺，羧酸醯胺，例如N,N-二甲基乙醯胺以及N,N-二乙基乙醯胺 ，丙酮，乙腈，直鏈的碳酸二烷基酯例如碳酸二甲酯、碳酸二乙酯、碳酸甲基乙基酯，環狀的碳酸伸烷酯例如碳酸伸乙酯、碳酸伸丙酯，以及碳酸伸乙烯酯係合適的溶劑。 Frequently, the aprotic organic solvent is selected from the group consisting of ketones; nitriles; formamides; dialkyl carbonates (straight chain) and carbonic acid esters (cyclic), and wherein the term "alkane" Preferred is a C1 to C4 alkyl group, and the term "alkylene group" preferably means a C2 to C7 alkylene group, including a vinyl group, wherein the alkyl group is preferably a bridge of 2 carbon atoms between the oxygen atoms of the -OC(O)-O- group; dimethylformamide, decylamine, such as N,N-dimethylacetamide, and N, N-diethylacetamide , acetone, acetonitrile, linear dialkyl carbonate such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, cyclic alkyl carbonate such as ethyl carbonate, propyl carbonate, and Carbonic acid extending vinyl ester is a suitable solvent.

碳酸二甲酯以及碳酸伸丙酯係處於用於反應混合物的較佳溶劑中，因為LiPO₂F₂在該等非常好地適合用於Li離子電池中使用的溶劑中至少是相當可溶。其他非常適當的溶劑係碳酸伸乙酯(EC)，碳酸乙基甲基酯(EMC)，碳酸伸丙酯，乙酸乙酯，碳酸二乙酯，碳酸二甲酯與碳酸伸丙酯(PC)的一混合物，乙腈，二甲氧基乙烷與丙酮。LiPO₂F₂在該等溶劑中在環境溫度下的溶解度彙編在下表1中。 Dimethyl carbonate and propylene carbonate are preferred solvents for use in the reaction mixture because LiPO ₂ F ₂ is at least quite soluble in such solvents which are very well suited for use in Li ion batteries. Other very suitable solvents are ethyl carbonate (EC), ethyl methyl carbonate (EMC), propyl carbonate, ethyl acetate, diethyl carbonate, dimethyl carbonate and propyl carbonate (PC). A mixture of acetonitrile, dimethoxyethane and acetone. The solubility of LiPO ₂ F ₂ in these solvents at ambient temperature is compiled in Table 1 below.

LiPO₂F₂在乙腈並且尤其是在二甲氧基乙烷和丙酮中的溶解度顯著地更高；在本發明的背景下，該等溶劑對於提供還具有LiPO₂F₂與LiPF₆的溶液(其中高濃度的也是LiPO₂F₂)係有用的。已經指出的是，然而，丙酮並不是非常好地適合作為用於Li離子電池的溶劑。 The solubility of LiPO ₂ F ₂ in acetonitrile and especially in dimethoxyethane and acetone is significantly higher; in the context of the present invention, such solvents provide solutions which also have LiPO ₂ F ₂ and LiPF ₆ ( Among them, a high concentration of LiPO ₂ F ₂ ) is useful. It has been pointed out that, however, acetone is not very well suited as a solvent for Li ion batteries.

LiPO₂F₂在二甲氧基乙烷中的溶解度比在丙酮中甚至更高。二甲氧基乙烷被認為是Li離子電池的溶劑或溶劑的添加劑。因此，二甲氧基乙烷可以用來提供具有高濃度的LiPF₆與LiPO₂F₂兩者的溶液。 The solubility of LiPO ₂ F ₂ in dimethoxyethane is even higher than in acetone. Dimethoxyethane is considered to be a solvent or solvent additive for Li-ion batteries. Therefore, dimethoxyethane can be used to provide a solution having a high concentration of both LiPF ₆ and LiPO ₂ F ₂ .

LiPF₆與LiPO₂F₂在碳酸二甲酯、碳酸伸丙酯以及其混合物中的溶液(它溶解了最多是處於可忽略的量值的LiF)係尤其適合於製造電池的電解質的。 A solution of LiPF ₆ and LiPO ₂ F ₂ in dimethyl carbonate, propylene carbonate and mixtures thereof, which dissolves LiF which is at most negligible in magnitude, is particularly suitable for the manufacture of electrolytes for batteries.

除了以上提及的該等溶劑，可以使用經常被用作Li離子電池的電解質溶劑的其他溶劑，作為一種單一溶劑或作為溶劑混合物的一組分。例如，氟化的溶劑，例如碳酸單、二、三、和/或四氟代伸乙酯係非常合適的。其他適合的溶劑係：內酯、甲醯胺、吡咯烷酮、噁唑烷酮、硝基烷、N,N-取代的胺基甲酸酯、環丁碸、二烷基亞碸、二烷基亞硫酸酯(如在M.Ue等人在J.Electrochem.Soc.[電化學雜誌]Vol.141(1994)的公開物，第2989至2996頁中描述的)、或磷酸三烷基酯或烷氧基酯，如在DE-A 10016816中描述的。 In addition to the above-mentioned solvents, other solvents which are often used as electrolyte solvents for Li ion batteries can be used as a single solvent or as a component of a solvent mixture. For example, fluorinated solvents such as mono-, di-, tri-, and/or tetrafluoro-ethyl esters are very suitable. Other suitable solvent systems are: lactones, formamide, pyrrolidone, oxazolidinone, nitroalkane, N,N-substituted urethane, cyclobutane, dialkylarylene, dialkyl Sulfate (as described in M. Ue et al., J. Electrochem. Soc. [Electrochemicals] Vol. 141 (1994), pages 2989 to 2996), or trialkyl phosphate or alkane Oxy esters as described in DE-A 10016816.

可以使用碳酸伸烴酯作為溶劑或溶劑添加劑。焦性碳酸酯也是有用的，參見US-A 5,427,874。乙酸烷基酯，例如乙酸乙酯、N,N-雙取代的乙醯胺、亞碸、腈、乙二醇醚以及醚也是有用的，參見EP-A-0 662 729。經常應用該等溶劑的混合物。二氧戊環係一有用的溶劑，參見EP-A-0 385 724。對於雙-(三氟甲磺醯)醯亞胺鋰，1,2-雙-(三氟乙醯氧基)乙烷以及N,N-二甲基三氟乙醯胺可以施用作溶 劑，參見ITE Battery Letters[ITE電池快報]Vol.1(1999)，第105至109頁。在以上內容中，術語“烷基”較佳的是表示飽和的直鏈的或支鏈的C1至C4的烷基基團；術語“伸烷基”較佳的是表示C2至C7的伸烷基基團，包括伸乙烯基基團，其中該伸烷基基團較佳的是包括在-O-C(O)-O-基團的該等氧原子之間的一個2碳原子橋，由此形成了一個5員環。 Carbonic acid alkyl esters can be used as a solvent or solvent additive. Pyrocarbonates are also useful, see US-A 5,427,874. Alkyl acetates such as ethyl acetate, N,N-disubstituted acetamide, hydrazine, nitrile, glycol ethers and ethers are also useful, see EP-A-0 662 729. Mixtures of such solvents are often employed. Dioxolane is a useful solvent, see EP-A-0 385 724. For lithium bis-(trifluoromethanesulfonate) oxime, 1,2-bis-(trifluoroacetoxy)ethane and N,N-dimethyltrifluoroacetamide can be applied for dissolution. For the agent, see ITE Battery Letters Vol. 1 (1999), pp. 105-109. In the above, the term "alkyl" preferably denotes a saturated straight or branched C1 to C4 alkyl group; the term "alkylene" preferably denotes a C2 to C7 alkylene. a group comprising a vinyl group, wherein the alkyl group is preferably a bridge of 2 carbon atoms between the oxygen atoms of the -OC(O)-O- group, thereby Formed a 5-member ring.

氟取代的化合物也是對應地用於溶解LiPO₂F₂或LiPF₆的合適溶劑，例如氟化的碳酸酯，該等氟化的碳酸酯選自下組：氟取代的碳酸伸乙酯、氟取代的碳酸二甲酯、氟取代的碳酸乙基甲基酯、以及氟取代的碳酸二乙酯。它們可以按與非氟化的溶劑的混合物形式應用。例如以上提及的非氟化的有機碳酸酯係非常合適的。 Fluorine-substituted compounds are also suitable solvents for the dissolution of LiPO ₂ F ₂ or LiPF ₆ , such as fluorinated carbonates, which are selected from the group consisting of fluorine-substituted ethyl carbonates and fluorine substitutions. Dimethyl carbonate, fluorine-substituted ethyl methyl carbonate, and fluorine-substituted diethyl carbonate. They can be applied in the form of a mixture with a non-fluorinated solvent. For example, the non-fluorinated organic carbonates mentioned above are very suitable.

較佳的氟取代的碳酸酯係：單氟代碳酸伸乙酯、4,4-二氟代碳酸伸乙酯、4,5-二氟代碳酸伸乙酯、4-氟-4-甲基碳酸伸乙酯、4,5-二氟-4-甲基碳酸伸乙酯、4-氟-5-甲基碳酸伸乙酯、4,4-二氟-5-甲基碳酸伸乙酯、4-(氟甲基)-碳酸伸乙酯、4-(二氟甲基)-碳酸伸乙酯、4-(三氟甲基)-碳酸伸乙酯、4-(氟甲基)-4-氟代碳酸伸乙酯、4-(氟甲基)-5-氟代碳酸伸乙酯、4-氟-4,5-二甲基碳酸伸乙酯、4,5-二氟-4,5-二甲基碳酸伸乙酯、以及4,4-二氟-5,5-二甲基碳酸伸乙酯；碳酸二甲酯的衍生物，包括碳酸氟甲基甲酯、碳酸二氟甲基甲酯、碳酸三氟甲基甲酯、碳酸雙(氟甲基)酯、碳酸雙(二氟)甲酯、以及碳酸雙(三氟)甲酯；碳酸乙基甲基酯 的衍生物，包括碳酸2-氟乙基甲酯、碳酸乙基氟甲酯、碳酸2,2-二氟乙基甲酯、碳酸2-氟乙基氟甲酯、碳酸乙基二氟甲酯、碳酸2,2,2-三氟乙基甲酯、碳酸2,2-二氟乙基氟甲酯、碳酸2-氟乙基二氟甲酯、以及碳酸乙基三氟甲酯；以及碳酸二乙酯的衍生物，包括碳酸乙基(2-氟乙基)酯、碳酸乙基(2,2-二氟乙基)酯、碳酸雙(2-氟乙基)酯、碳酸乙基(2,2,2-三氟乙基)酯、碳酸2,2-二氟乙基2'-氟乙基酯、碳酸雙(2,2-二氟乙基)酯、碳酸2,2,2-三氟乙基2'-氟乙基酯、碳酸2,2,2-三氟乙基2',2'-二氟乙基酯、以及碳酸雙(2,2,2-三氟乙基)酯。 Preferred fluorine-substituted carbonates are: ethyl monofluorocarbonate, ethyl 4,4-difluorocarbonate, ethyl 4,5-difluorocarbonate, 4-fluoro-4-methyl Ethyl carbonate, 4,5-difluoro-4-methylcarbonate ethyl ester, 4-fluoro-5-methylcarbonate ethyl ester, 4,4-difluoro-5-methylcarbonate ethyl ester, 4-(fluoromethyl)-ethyl carbonate, 4-(difluoromethyl)-carbonic acid ethyl ester, 4-(trifluoromethyl)-carbonic acid ethyl ester, 4-(fluoromethyl)-4 - fluorocarbonic acid ethyl ester, 4-(fluoromethyl)-5-fluorocarbonic acid ethyl ester, 4-fluoro-4,5-dimethyl carbonate ethyl ester, 4,5-difluoro-4, 5-dimethyl carbonate ethyl ester, and 4,4-difluoro-5,5-dimethyl carbonate ethyl ester; dimethyl carbonate derivatives, including fluoromethyl methyl carbonate, difluorocarbonate Methyl ester, trifluoromethyl methyl carbonate, bis(fluoromethyl) carbonate, bis(difluoro)methyl carbonate, and bis(trifluoro)methyl carbonate; ethyl methyl carbonate Derivatives, including 2-fluoroethyl methyl carbonate, ethyl fluorocarbonate, 2,2-difluoroethyl methyl carbonate, 2-fluoroethylfluoromethyl carbonate, ethyl difluorocarbonate , 2,2,2-trifluoroethyl methyl carbonate, 2,2-difluoroethylfluoromethyl carbonate, 2-fluoroethyl difluoromethyl carbonate, and ethyl trifluoromethyl carbonate; and carbonic acid Derivatives of diethyl esters, including ethyl (2-fluoroethyl) carbonate, ethyl (2,2-difluoroethyl) carbonate, bis(2-fluoroethyl) carbonate, ethyl carbonate ( 2,2,2-trifluoroethyl)ester, 2,2-difluoroethyl 2'-fluoroethyl carbonate, bis(2,2-difluoroethyl) carbonate, carbonic acid 2,2,2 -Trifluoroethyl 2'-fluoroethyl ester, 2,2,2-trifluoroethyl 2',2'-difluoroethyl carbonate, and bis(2,2,2-trifluoroethyl carbonate) )ester.

還可以使用具有一不飽和鍵以及一氟原子兩者的碳酸酯(以下簡稱為“氟化的不飽和碳酸酯”)作為溶劑以便溶解大量的LiPF₆與少量的LiPO₂F₂。這種氟化的不飽和的碳酸酯包括任何不會顯著地損害本發明優點的氟化的不飽和的碳酸酯。 It is also possible to use a carbonate having both an unsaturated bond and a fluorine atom (hereinafter abbreviated as "fluorinated unsaturated carbonate") as a solvent to dissolve a large amount of LiPF ₆ and a small amount of LiPO ₂ F ₂ . Such fluorinated unsaturated carbonates include any fluorinated unsaturated carbonate which does not significantly impair the advantages of the present invention.

氟化的不飽和碳酸酯的例子包括氟取代的碳酸伸乙烯基酯的衍生物、被一具有芳香族環或碳碳不飽和鍵的取代基所取代的氟取代的碳酸伸乙酯衍生物，以及氟取代的碳酸烯丙基酯。 Examples of the fluorinated unsaturated carbonate include a derivative of a fluorine-substituted carbonic acid vinyl ester, a fluorine-substituted ethylene carbonate derivative substituted with a substituent having an aromatic ring or a carbon-carbon unsaturated bond, And a fluorine-substituted allyl carbonate.

碳酸伸乙烯基酯的衍生物的例子包括：碳酸氟伸乙烯基酯、4-氟-5-甲基伸乙烯基碳酸酯以及4-氟-5苯基伸乙烯基碳酸酯。 Examples of the derivative of the carbonic acid vinyl ester include: fluorovinyl carbonate, 4-fluoro-5-methylvinyl carbonate, and 4-fluoro-5phenylvinyl carbonate.

被一具有芳香族環或碳碳不飽和鍵的取代基所取代的碳酸伸乙酯的衍生物的例子包括：4-氟-4-乙烯基碳酸伸乙 酯、4-氟-5-乙烯基碳酸伸乙酯、4,4-二氟-4-乙烯基碳酸伸乙酯、4,5-二氟-4-乙烯基碳酸伸乙酯、4-氟-4,5-二乙烯基碳酸伸乙酯、4,5-二氟-4,5-二乙烯基碳酸伸乙酯、4-氟-4-苯基碳酸伸乙酯、4-氟-5-苯基碳酸伸乙酯、4,4-二氟-5-苯基碳酸伸乙酯、4,5-二氟-4-苯基碳酸伸乙酯以及4,5-二氟-4,5-二苯基碳酸伸乙酯。 Examples of derivatives of ethyl carbonate which are substituted by a substituent having an aromatic ring or a carbon-carbon unsaturated bond include 4-fluoro-4-vinyl carbonate Ester, 4-fluoro-5-vinyl carbonate ethyl ester, 4,4-difluoro-4-vinyl carbonate ethyl ester, 4,5-difluoro-4-vinyl carbonate ethyl ester, 4-fluoro -4,5-divinylcarbonate ethyl ester, 4,5-difluoro-4,5-divinylcarbonate ethyl ester, 4-fluoro-4-phenylcarbonic acid ethyl ester, 4-fluoro-5 -phenylphenyl carbonate, 4,4-difluoro-5-phenylethyl carbonate, 4,5-difluoro-4-phenylcarbonate ethyl ester and 4,5-difluoro-4,5 - Diphenyl carbonate extended ethyl ester.

氟取代的碳酸苯基酯的例子包括碳酸氟甲基苯基酯、碳酸2-氟乙基苯基酯、碳酸2,2-二氟乙基苯基酯以及碳酸2,2,2-三氟乙基苯基酯。 Examples of the fluorine-substituted phenyl carbonate include fluoromethylphenyl carbonate, 2-fluoroethylphenyl carbonate, 2,2-difluoroethylphenyl carbonate, and 2,2,2-trifluorocarbonate. Ethyl phenyl ester.

氟取代的碳酸乙烯酯的例子包括：碳酸氟甲基乙烯酯、碳酸2-氟乙基乙烯酯、碳酸2,2-二氟乙基乙烯酯以及碳酸2,2,2-三氟乙基乙烯酯。 Examples of the fluorine-substituted ethylene carbonate include: fluoromethyl vinyl carbonate, 2-fluoroethyl vinyl carbonate, 2,2-difluoroethyl vinyl carbonate, and 2,2,2-trifluoroethyl ethylene carbonate. ester.

氟取代的碳酸烯丙酯的例子包括：碳酸氟甲基烯丙酯、碳酸2-氟乙基烯丙酯、碳酸2,2-二氟乙基烯丙酯以及碳酸2,2,2-三氟乙基烯丙酯。 Examples of the fluorine-substituted allyl carbonate include fluoromethylallyl carbonate, 2-fluoroethylallyl carbonate, 2,2-difluoroethylallyl carbonate, and 2,2,2-three carbonate. Fluoroethyl allyl ester.

從用來提供具有大量LiPF₆以及少量LiPO₂F₂的溶液的反應混合物中提取LiPF₆與LiPO₂F₂可以按一種已知的方式進行，例如藉由直接在反應器中將該反應混合物與該溶劑(萃取劑)一起攪拌、或者在從反應器中移除反應混合物之後並且可隨意地在一適當的容器(例如Soxhlet容器)中進行粉碎或研磨。萃取液包括該等Li鹽並且可以被進一步加工。 The extraction of LiPF ₆ from LiPO ₂ F ₂ from a reaction mixture for providing a solution having a large amount of LiPF ₆ and a small amount of LiPO ₂ F ₂ can be carried out in a known manner, for example by directly reacting the reaction mixture in a reactor. The solvent (extractant) is stirred together or after being removed from the reactor and optionally comminuted or ground in a suitable container, such as a Soxhlet container. The extract includes the Li salts and can be further processed.

包含溶解在該溶劑中的大量的LiPF₆與少量的LiPO₂F₂的液相可以按一種已知的方式從非溶解的固體 LiPO₂F₂中分離出。例如，該溶液可以穿過一過濾器，或者它可以被傾析，或者這種分離可以藉由離心作用而完成。 A liquid phase comprising a large amount of LiPF ₆ dissolved in the solvent and a small amount of LiPO ₂ F ₂ can be separated from the undissolved solid LiPO ₂ F ₂ in a known manner. For example, the solution can pass through a filter, or it can be decanted, or this separation can be accomplished by centrifugation.

如果希望的話，可以回收高純度的固體LiPO₂F₂。例如，將含LiPO₂F₂固體的殘餘物溶解，並且可以將對應的溶液冷卻使得固體LiPO₂F₂沉澱，或可以加入一非極性的或有機液體來引起結晶。例如，可以將LiPO₂F₂溶解在二甲氧基乙烷中，並且可以加入一種烴，例如己烷。LiPO₂F₂以一凝膠狀固體的形式沉澱。如果使用丙酮作為溶劑，則有可能獲得20%濃度的LiPO₂F₂。當冷卻到0℃時，沉澱出固體，針狀LiPO₂F₂。 If desired, high purity solid LiPO ₂ F ₂ can be recovered. For example, the residue containing the LiPO ₂ F ₂ solid is dissolved, and the corresponding solution may be cooled to precipitate the solid LiPO ₂ F ₂ , or a non-polar or organic liquid may be added to cause crystallization. For example, LiPO ₂ F ₂ can be dissolved in dimethoxyethane, and a hydrocarbon such as hexane can be added. LiPO ₂ F ₂ precipitates as a gelatinous solid. If acetone is used as the solvent, it is possible to obtain a 20% concentration of LiPO ₂ F ₂ . When cooled to 0 ° C, a solid, needle-like LiPO ₂ F ₂ precipitated.

因此，本發明提供了一用於獲得純化的LiPO₂F₂的方法，其中在第一步驟中，LiPF₆主要藉由用主要溶解的LiPF₆的溶劑提取該混合物而從該含LiPO₂F₂與LiPF₆的混合物中分離，並且a)將剩餘的未溶解的LiPO₂F₂溶解在極性無質子溶劑中，直至達到至少90%的飽和濃度，將該溶劑冷卻以沉澱出LiPO₂F₂，將該沉澱的LiPO₂F₂從溶劑中分離出並且進行處理以除去任何溶劑，或b)將剩餘的未溶解的LiPO₂F₂溶解在極性無質子溶劑中，加入非極性的有機溶劑以沉澱溶解的LiPO₂F₂，將該沉澱的LiPO₂F₂從溶劑中分離出並且進行處理(例如加熱和/或施加真空)以除去任何溶劑。 Accordingly, the present invention provides a process for obtaining purified LiPO ₂ F ₂ wherein, in the first step, LiPF _{6 is} mainly extracted from the LiPO ₂ F ₂ -containing solution by using a solvent of mainly dissolved LiPF ₆ . Separating from the mixture with LiPF ₆ and a) dissolving the remaining undissolved LiPO ₂ F ₂ in a polar aprotic solvent until a saturation concentration of at least 90% is reached, cooling the solvent to precipitate LiPO ₂ F ₂ , The precipitated LiPO ₂ F ₂ is separated from the solvent and treated to remove any solvent, or b) the remaining undissolved LiPO ₂ F _{2 is} dissolved in a polar aprotic solvent, and a non-polar organic solvent is added to precipitate Dissolved LiPO ₂ F ₂ , the precipitated LiPO ₂ F ₂ is separated from the solvent and treated (eg, heated and/or vacuum applied) to remove any solvent.

較佳的是步驟a)中的溶劑係丙酮。 Preferably, the solvent in step a) is acetone.

較佳的是，其中在步驟b)中，該無質子溶劑係二甲氧 基乙烷，並且該非極性的溶劑係烴，較佳的是己烷。 Preferably, wherein in step b), the aprotic solvent is dimethoxy The ethyl ethane, and the non-polar solvent is a hydrocarbon, preferably hexane.

如果希望的話，可以對在該反應混合物中仍然未溶解的LiPO₂F₂進行儲存或者使其經受進一步的純化處理以獲得純的固體LiPO₂F₂，例如在以上所描述的藉由溶解在二甲氧基乙烷、丙酮或溶劑中。粘著溶劑可以藉由蒸發除去，這種蒸發可以較佳的是在取決於這種或該等粘著溶劑的沸點的一真空中進行。 If desired, LiPO ₂ F ₂ which is still undissolved in the reaction mixture may be stored or subjected to further purification treatment to obtain pure solid LiPO ₂ F ₂ , for example by dissolving in two as described above. In methoxyethane, acetone or solvent. The adhesion solvent can be removed by evaporation, and the evaporation can preferably be carried out in a vacuum depending on the boiling point of the or the binder solvent.

溶解的LiPO₂F₂可以藉由蒸發溶劑而從溶液中回收，以獲得純的固體LiPO₂F₂。這能夠以一種已知的方式進行。例如，粘著溶劑可以藉由蒸發除去，這種蒸發可以較佳的是在取決於這種或該等粘著溶劑的沸點的一真空中進行。 The dissolved LiPO ₂ F ₂ can be recovered from the solution by evaporating the solvent to obtain a pure solid LiPO ₂ F ₂ . This can be done in a known manner. For example, the adhesion solvent can be removed by evaporation, and such evaporation can preferably be carried out in a vacuum depending on the boiling point of the or the binder solvent.

分離出的固體LiPO₂F₂可以在任何適當的溶劑或溶劑混合物中再溶解。以上提及的溶劑、包括丙酮以及二甲氧基乙烷係非常合適的。由於其主要用途係作為鋰離子電池領域中的電解質鹽或鹽的添加劑，它可以較佳的是溶解在用於製造鋰離子電池的電解質溶液的無水溶劑中。在以上揭露了此種溶劑。 The isolated solid LiPO ₂ F ₂ can be redissolved in any suitable solvent or solvent mixture. The solvents mentioned above, including acetone and dimethoxyethane, are very suitable. Since its main use is an additive for an electrolyte salt or a salt in the field of lithium ion batteries, it may preferably be dissolved in an anhydrous solvent for producing an electrolyte solution of a lithium ion battery. Such a solvent is disclosed above.

藉由本發明的方法可以從廉價的起始材料中分離之後而單獨地獲得LiPF₆與LiPO₂F₂的等莫耳混合物，兩者均是有價值的化合物並且作為混合物係有用的(如以上描述的)。純的針狀LiPO₂F₂可以從LiPO₂F₂在丙酮的濃縮溶液中獲得，並且隨後冷卻。 An equimolar mixture of LiPF ₆ and LiPO ₂ F ₂ can be obtained separately by separation from an inexpensive starting material by the process of the invention, both of which are valuable compounds and useful as a mixture (as described above) of). Pure needle-like LiPO ₂ F ₂ can be obtained from a concentrated solution of LiPO ₂ F ₂ in acetone and then cooled.

使用POF₃的一優點係它可以甚至在氯-氟交換反應中 基本上無HCl地進行製備。由於POF₃的沸點(b.p.)，-40℃係比HCl的(HCl的沸點係-85.1℃)更高，可以將在壓力下的簡單蒸餾或冷凝技術用於POF₃中間產物的純化，這使得本方法更經濟。 An advantage of using POF ₃ is that it can be prepared substantially without HCl in the chloro-fluorine exchange reaction. Due to the boiling point (bp) of POF ₃ , which is higher than HCl (the boiling point of HCl is -85.1 ° C), a simple distillation or condensation technique under pressure can be used for the purification of POF ₃ intermediates, which makes This method is more economical.

本發明的另一方面涉及LiPO₂F₂與LiPF₆的等莫耳混合物。如上所示的，該等混合物係用於電池的電解質組合物的電解質溶液以及製造針狀LiPO₂F₂的有價值的來源。 Another aspect of the invention relates to an equimolar mixture of LiPO ₂ F ₂ and LiPF ₆ . As indicated above, these mixtures are electrolyte solutions for electrolyte compositions of batteries and a valuable source for the manufacture of acicular LiPO ₂ F ₂ .

本發明的還另一方面涉及針狀的固體LiPO₂F₂。該等針具有等於或大於3的長度與直徑比例。LiPO₂F₂同樣是一有價值的產物，因為它可以用作如以上提及的電池電解質組合物的添加劑，並且是處於晶體的形式，容易加工。 Still another aspect of the invention relates to needle-like solid LiPO ₂ F ₂ . The needles have a length to diameter ratio equal to or greater than three. LiPO ₂ F _{2 is} also a valuable product because it can be used as an additive for the battery electrolyte composition as mentioned above, and is in the form of a crystal which is easy to process.

若任何藉由引用結合在此的專利案、專利申請案以及公開物中的揭露內容與本說明相衝突，而這種衝突的程度使得一術語變得不清楚，則應該優先採取本說明。 In the event that any disclosure of patents, patent applications, and publications incorporated by reference is inconsistent with the present disclosure, and the extent of such conflicts renders the term unclear, the present description should be preferred.

以下該等實例將更詳細地描述本發明而無意限制本發明。 The following examples are intended to describe the invention in more detail and are not intended to limit the invention.

實例1：製造LiPO₂F₂和LiPF₆的等莫耳混合物 Example 1: Making a molar mixture of LiPO ₂ F ₂ and LiPF ₆

將225 g的LiF(供應商：阿爾德林(Aldrich))引入到一可動的高壓釜反應器中並且在真空下乾燥(從外部施加熱)。 225 g of LiF (supplier: Aldrich) was introduced into a mobile autoclave reactor and dried under vacuum (heat applied from the outside).

將該封閉的反應器啟動並且進行移動以機械的方式來影響該固體起始材料並且改進該反應，並且使氣態的POF₃ 經由一PTFE管道從一氣體瓶穿過該反應器，該瓶配備有一壓力調節閥。添加速度藉由保持總反應溫度(在反應器內測量的)低於32℃而進行限制。壓力不升高直至反應結束，由於LiF與POF₃之間的快速反應。POF₃的74 g/h平均加料速度係有可能的同時保持反應器內的溫度低於32℃。 The closed reactor is activated and moved to mechanically affect the solid starting material and to improve the reaction, and the gaseous POF _{3 is} passed through a PTFE pipe from a gas bottle through the reactor. A pressure regulating valve. The rate of addition was limited by keeping the total reaction temperature (measured in the reactor) below 32 °C. The pressure does not rise until the end of the reaction due to the rapid reaction between LiF and POF ₃ . The average feed rate of 74 g/h of POF ₃ is possible while keeping the temperature inside the reactor below 32 °C.

9小時之後，壓力升高到約4個大氣壓並且將該系統保持在該等條件下持續另外的兩個小時。這個時間之後，將該反應器排空並且從外部加熱直至內部溫度達到70℃；將該溫度在該水平下保持2.5小時。 After 9 hours, the pressure was raised to about 4 atmospheres and the system was maintained under these conditions for an additional two hours. After this time, the reactor was evacuated and heated from the outside until the internal temperature reached 70 ° C; the temperature was maintained at this level for 2.5 hours.

將產物從該反應器中以白色粉末的形式移出，從而產出730 g的總質量(質量增益：730 g-225 g=505 g：等於4.9 mol POF₃)。 The product was removed from the reactor as a white powder to yield a total mass of 730 g (mass gain: 730 g - 225 g = 505 g: equal to 4.9 mol POF ₃ ).

對於225 g LiF(8.7 mol)理論量POF₃(根據化學計算法)：8.7 mol POF₃=905 g For 225 g LiF (8.7 mol) theoretical amount POF ₃ (according to stoichiometry): 8.7 mol POF ₃ =905 g

反應後產物的XRD在表1中給出。 The XRD of the product after the reaction is given in Table 1.

表示為a的峰指示LiPF₆；表示為b的峰指示LiPO₂F₂；表示為c的峰指示LiF。 The peak indicated as a indicates LiPF ₆ ; the peak indicated as b indicates LiPO ₂ F ₂ ; the peak indicated as c indicates LiF.

LiPF₆示出了處於以下位置的2-θ值：17；19(強)；26(強)；29；30；40；43；45和54。 LiPF ₆ shows 2-theta values at the following positions: 17; 19 (strong); 26 (strong); 29; 30; 40; 43; 45 and 54.

LiPO₂F₂示出了處於以下位置的2-θ值：21.5(強)；22.0；23.5；27.0(強)；34.2；43.2。 LiPO ₂ F ₂ shows the 2-theta value at the following position: 21.5 (strong); 22.0; 23.5; 27.0 (strong); 34.2; 43.2.

LiF示出了處於以下位置的2-θ值：39和44(弱)。 LiF shows 2-theta values at the following positions: 39 and 44 (weak).

實例2：製造針狀LiPO₂F₂ Example 2: Production of acicular LiPO ₂ F ₂

將在實例1中獲得的LiPO₂F₂粉末溶解在丙酮中以獲得一飽和溶液。然後將該溶液冷卻至0℃。LiPO₂F₂以針的形式沉澱。 The LiPO ₂ F ₂ powder obtained in Example 1 was dissolved in acetone to obtain a saturated solution. The solution was then cooled to 0 °C. LiPO ₂ F ₂ precipitates in the form of a needle.

實例3：用於鋰離子電池、鋰-硫電池以及鋰-氧電池的電解質溶液 Example 3: Electrolyte solution for lithium ion batteries, lithium-sulfur batteries, and lithium-oxygen batteries

實例1的固體使用等莫耳體積的碳酸伸乙酯(“EC”)以及碳酸伸丙酯(“PP”)的一混合物進行提取，該碳酸伸乙酯以及碳酸伸丙酯進行混合的量值係為使得獲得1升的總體積。所生成的溶液包含LiPF₆以及另外按重量計約0.5%的LiPO₂F₂。 The solid of Example 1 was extracted using a mixture of an equimolar volume of ethyl acetate ("EC") and propyl carbonate ("PP"), and the amount of the ethyl carbonate and propyl carbonate was mixed. This is such that a total volume of 1 liter is obtained. The resulting solution contained LiPF ₆ and additionally about 0.5% by weight of LiPO ₂ F ₂ .

實例4：用於鋰離子電池、鋰-硫電池以及鋰-氧電池的電解質溶液 Example 4: Electrolyte solution for lithium ion batteries, lithium-sulfur batteries, and lithium-oxygen batteries

實例2的針狀體溶解在等莫耳體積的碳酸伸乙酯(“EC”)以及碳酸伸丙酯(“PP”)的混合物中，混合量值為使得獲得了1升的總體積。所生成的溶液包含按重量計約0.5%的LiPO₂F₂。 The needles of Example 2 were dissolved in a mixture of equimolar volume of ethyl carbonate ("EC") and propylene carbonate ("PP") in a mixture such that a total volume of 1 liter was obtained. The resulting solution contained about 0.5% by weight of LiPO ₂ F ₂ .

圖1示出了從LiF與POF₃反應獲得的產物的XRD的光譜，具有指示LiPF₆的峰“a”，指示LiPO₂F₂的峰“b”以及指示LiF的峰“c”。 1 shows a spectrum of XRD of a product obtained by reacting LiF with POF ₃ , having a peak "a" indicating LiPF _{6 ,} a peak "b" indicating LiPO ₂ F ₂ , and a peak "c" indicating LiF.

Claims (15)

一種用於製造含有LiPO₂F₂與LiPF₆的混合物之方法，包括使LiF與POF₃反應的一步驟。 A method for producing a mixture comprising LiPO ₂ F ₂ and LiPF ₆ comprising a step of reacting LiF with POF ₃ . 如申請專利範圍第1項之方法，其中，使POF₃與LiF以0.9：1至2：1的莫耳比進行反應。 The method of claim 1, wherein POF ₃ and LiF are reacted at a molar ratio of from 0.9:1 to 2:1. 如申請專利範圍第1項之方法，其中，該反應時間係從0.5至2小時。 The method of claim 1, wherein the reaction time is from 0.5 to 2 hours. 如申請專利範圍第1項之方法，其中，該反應係在從25℃至90℃的溫度下進行的。 The method of claim 1, wherein the reaction is carried out at a temperature of from 25 ° C to 90 ° C. 如申請專利範圍第1項之方法，其中，該反應係在等於或低於5巴(絕對值)的壓力下進行的。 The method of claim 1, wherein the reaction is carried out at a pressure equal to or lower than 5 bar (absolute value). 如申請專利範圍第1項之方法，其中，將該含LiPO₂F₂與LiPF₆的混合物使用一溶劑進行提取，該溶劑適合作為用於Li離子電池、Li空氣電池以及Li硫電池的電解質溶劑。 The method of claim 1, wherein the mixture containing LiPO ₂ F ₂ and LiPF ₆ is extracted using a solvent suitable as an electrolyte solvent for Li ion batteries, Li air batteries, and Li sulfur batteries. . 如申請專利範圍第6項之方法，其中，該溶劑係選自由有機碳酸酯組成的組。 The method of claim 6, wherein the solvent is selected from the group consisting of organic carbonates. 如申請專利範圍第1項之方法，其中，在第一步驟中，從該含LiPO₂F₂與LiPF₆的混合物中將LiPF₆主要藉由用主要溶解LiPF₆的溶劑來提取該混合物而進行分離，並且a)將該剩餘的未溶解的LiPO₂F₂溶解在極性無質子溶劑中，直至達到至少90%的飽和濃度，將該溶劑冷卻以沉澱出LiPO₂F₂，將該沉澱的LiPO₂F₂從該溶劑中分離出並 且進行處理以除去任何溶劑，或b)將該剩餘的未溶解LiPO₂F₂溶解在一極性無質子溶劑中，加入非極性的有機溶劑以沉澱出溶解的LiPO₂F₂，將該沉澱的LiPO₂F₂從該溶劑中分離出並且進行處理以除去剩餘溶劑。 The method of claim 1, wherein in the first step, LiPF _{6 is} mainly extracted from the mixture containing LiPO ₂ F ₂ and LiPF ₆ by extracting the mixture mainly with a solvent mainly dissolving LiPF ₆ . Separating, and a) dissolving the remaining undissolved LiPO ₂ F ₂ in a polar aprotic solvent until a saturation concentration of at least 90% is reached, cooling the solvent to precipitate LiPO ₂ F ₂ , the precipitated LiPO ₂ F ₂ is separated from the solvent and treated to remove any solvent, or b) the remaining undissolved LiPO ₂ F _{2 is} dissolved in a polar aprotic solvent, and a non-polar organic solvent is added to precipitate the dissolved LiPO ₂ F ₂ , the precipitated LiPO ₂ F ₂ was separated from the solvent and treated to remove residual solvent. 如申請專利範圍第8項之方法，其中，該步驟a)中的溶劑係丙酮。 The method of claim 8, wherein the solvent in the step a) is acetone. 如申請專利範圍第8項之方法，其中，在步驟b)中，該無質子溶劑係二甲氧基乙烷，並且該非極性溶劑係烴。 The method of claim 8, wherein in the step b), the aprotic solvent is dimethoxyethane, and the non-polar solvent is a hydrocarbon. 一種由LiPO₂F₂和LiPF₆組成的近似等莫耳混合物。 An approximate isomer mixture consisting of LiPO ₂ F ₂ and LiPF ₆ . 如申請專利範圍第11項之混合物，其係由40莫耳%至60莫耳%的LiPO₂F₂以及40莫耳%至60莫耳%的LiPF₆組成。 The patentable scope of the application mixture of 11 items, which by a line 40 mole% to 60 mole% of LiPO ₂ F _2, and 40 mole% to 60 mole% of the composition of LiPF _6. 一種固體針狀的LiPO₂F₂。 A solid needle-like LiPO ₂ F ₂ . 一種製備含有LiPO₂F₂與LiPF₆的溶液之方法，其中，將如申請專利範圍第11項之由LiPO₂F₂和LiPF₆組成的該近似等莫耳混合物與至少一種用於Li離子電池、Li空氣電池以及Li硫電池的溶劑相接觸。 A method of preparing a solution containing LiPO ₂ F ₂ and LiPF ₆ , wherein the approximate equimolar mixture consisting of LiPO ₂ F ₂ and LiPF ₆ as in claim 11 and at least one for Li ion battery The Li air battery and the solvent of the Li sulfur battery are in contact with each other. 一種含有如申請專利範圍第11項之近似等莫耳混合物的Li離子電池、Li空氣電池、或Li硫電池。 A Li ion battery, a Li air battery, or a Li sulfur battery containing an approximate molar mixture as in claim 11 of the patent application.