TWI598292B - Method of producing phosphorus pentafluoride, method of producing lithium hexafluorophosphate, lithium hexafluorophosphate, non-aqueous electrolyte solution for battery, and lithium secondary battery - Google Patents

Method of producing phosphorus pentafluoride, method of producing lithium hexafluorophosphate, lithium hexafluorophosphate, non-aqueous electrolyte solution for battery, and lithium secondary battery Download PDF

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TWI598292B
TWI598292B TW103110863A TW103110863A TWI598292B TW I598292 B TWI598292 B TW I598292B TW 103110863 A TW103110863 A TW 103110863A TW 103110863 A TW103110863 A TW 103110863A TW I598292 B TWI598292 B TW I598292B
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phosphorus
producing
carbonate
phosphorus pentafluoride
acid
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TW201444764A (en
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下川床祥城
渡部英司
原田功
吉川明男
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三井化學股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/10—Halides or oxyhalides of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/005—Lithium hexafluorophosphate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Description

五氟化磷之製造方法、六氟化磷酸鋰之製造方法、六氟化磷酸鋰、電池用非水電解液及鋰二次電池 Method for producing phosphorus pentafluoride, method for producing lithium hexafluorophosphate, lithium hexafluorophosphate, nonaqueous electrolyte for battery and lithium secondary battery

本發明係關於一種五氟化磷之製造方法、六氟化磷酸鋰之製造方法、六氟化磷酸鋰、電池用非水電解液、及鋰二次電池。 The present invention relates to a method for producing phosphorus pentafluoride, a method for producing lithium hexafluorophosphate, a lithium hexafluorophosphate, a nonaqueous electrolyte for a battery, and a lithium secondary battery.

五氟化磷(PF5)係用作各種六氟磷酸鹽之原料之化合物，例如可舉出：作為鋰電池及鋰離子電池用之電解質較為有用之六氟磷酸鋰之原料。又，作為聚合物之聚合觸媒或半導體用摻雜劑，為較為有用之化合物。 Phosphorus pentafluoride (PF 5 ) is a compound which is used as a raw material of various hexafluorophosphates, and examples thereof include raw materials of lithium hexafluorophosphate which are useful as electrolytes for lithium batteries and lithium ion batteries. Further, as a polymerization catalyst for a polymer or a dopant for a semiconductor, it is a compound which is useful.

作為五氟化磷之公知之製造方法，例如可舉出以下之方法。 As a known production method of phosphorus pentafluoride, the following methods are mentioned, for example.

1.藉由三氟化砷之五氯化磷之鹵素交換反應(參照美國專利第3584999號說明書) 1. A halogen exchange reaction by phosphorus pentachloride of arsenic trifluoride (refer to the specification of U.S. Patent No. 3,584,999)

式：3PCl5+5AsF3 → 3PF5+5AsCl3 Formula: 3PCl 5 +5AsF 3 → 3PF 5 +5AsCl 3

2.三氟化磷之氯化(參照美國專利第3584999號說明書) 2. Chlorination of phosphorus trifluoride (refer to the specification of US Pat. No. 3584999)

式：5PF3+3Cl2 → 3PF5+2PCl3 Formula: 5PF 3 +3Cl 2 → 3PF 5 +2PCl 3

3.氟化磷與氟化氫之反應(參照美國專利第3584999號說明書) 3. Reaction of phosphorus fluoride with hydrogen fluoride (refer to the specification of US Pat. No. 3584999)

式：POF3+2HF → PF5+H2O Formula: POF 3 +2HF → PF 5 +H 2 O

4.藉由金屬氟化物、與磷酸或單氟磷酸、與三氧化硫之加熱之反應(參照美國專利第3634034號說明書) 4. Reaction by heating of metal fluoride, phosphoric acid or monofluorophosphoric acid, and sulfur trioxide (refer to US Pat. No. 3,634,304)

式：2H3PO4+6SO3+6CaF2 → PF5+HPF6．2H2O+HF+6CaSO4 Formula: 2H 3 PO 4 +6SO 3 +6CaF 2 → PF 5 +HPF 6 . 2H 2 O+HF+6CaSO 4

5.氯化磷與氟化氫之反應(參照日本專利特開平10-245211號公報) 5. Reaction of phosphorus chloride with hydrogen fluoride (refer to Japanese Patent Laid-Open No. Hei 10-245211)

式：PCl3+5HF+Cl2 → PF5+5HCl Formula: PCl 3 +5HF+Cl 2 → PF 5 +5HCl

6.六氟磷酸與發煙硫酸之反應(參照日本專利特表2005-507849號公報) 6. Reaction of hexafluorophosphoric acid with fuming sulfuric acid (refer to Japanese Patent Laid-Open Publication No. 2005-507849)

式：HPF6+H2SO4(65%SO3) → PF5+H2SO4 Formula: HPF 6 +H 2 SO 4 (65%SO 3 ) → PF 5 +H 2 SO 4

此處，上述1、2及3之製造方法中，必需有將混合鹵化物(例如，PCl4F、PCl2F3)或HCl自五氟化磷中進行分離之大規模之分離步驟。 Here, the manufacturing method of 1, 2 and 3, there must be mixed halides (e.g., PCl 4 F, PCl 2 F 3) or HCl large scale separation step of separating from the phosphorus pentafluoride.

上述4之製造方法中，除五氟化磷以外，亦產生作為副產物之六氟磷酸及硫酸鈣，故而必需有將該等進行分離之大規模之分離步驟及處理硫酸鈣之步驟。 In the production method of the above 4, in addition to phosphorus pentafluoride, hexafluorophosphoric acid and calcium sulfate as by-products are also produced. Therefore, a large-scale separation step for separating the same and a step of treating calcium sulfate are necessary.

上述5之製造方法有於反應中伴隨發熱之傾向，又，於反應用中要求高耐壓容器。 The production method of the above 5 has a tendency to cause heat generation during the reaction, and a high pressure vessel is required for the reaction.

又，任一種製造方法均有產率不充分之傾向。 Moreover, any of the production methods tends to have insufficient yield.

而且，上述6之製造方法中，為了產生五氟化磷，必需有約150℃~180℃之高溫。又，為了將發煙硫酸或五氟化磷等之腐蝕性較高之物質於高溫下進行處理，於設備中必需有高價之耐蝕材料，有成本提高之傾向。 Further, in the above-described production method of 6, it is necessary to have a high temperature of about 150 ° C to 180 ° C in order to produce phosphorus pentafluoride. Further, in order to treat a highly corrosive substance such as fuming sulfuric acid or phosphorus pentafluoride at a high temperature, it is necessary to have a high-priced corrosion-resistant material in the equipment, which tends to increase the cost.

此處，鑒於上文，本發明之目的在於提供一種無需大規模之分離步驟及高耐壓容器，而經歷藉由低溫加熱之反應而高產率地製造五氟化磷之製造方法。 Here, in view of the above, an object of the present invention is to provide a production method for producing phosphorus pentafluoride in a high yield by a reaction of low-temperature heating without requiring a large-scale separation step and a high-pressure container.

又，本發明之目的在於提供一種使用無需大規模之分離步驟及高耐壓容器，而經歷藉由低溫加熱之反應而高產率地製造之五氟化磷之六氟化磷酸鋰之製造方法。 Further, an object of the present invention is to provide a process for producing lithium hexafluorophosphate which is subjected to high-yield production by a low-temperature heating reaction without using a large-scale separation step and a high-pressure container.

進而，本發明之目的在於提供一種氯離子之濃度受到抑制之六氟化磷酸鋰、電池用非水電解液、及鋰二次電池。 Further, an object of the present invention is to provide a lithium hexafluorophosphate, a nonaqueous electrolyte for a battery, and a lithium secondary battery in which the concentration of chlorine ions is suppressed.

再者，於本說明書中，所謂藉由低溫加熱之反應，係指反應溫度為150℃以下之反應。 In the present specification, the reaction by low-temperature heating means a reaction having a reaction temperature of 150 ° C or lower.

本發明者發現：對於上述課題，可藉由具有使下述通式(I)所表示之化合物、與氟磺酸進行反應之步驟之五氟化磷之製造方法，而無需大規模之分離步驟及高耐壓容器，而利用藉由低溫加熱之反應而高產率地製造五氟化磷，從而完成本發明。 The present inventors have found that a method for producing phosphorus pentafluoride having a step of reacting a compound represented by the following formula (I) with a fluorosulfonic acid can be used for the above problem without requiring a large-scale separation step. The present invention has been completed by producing a high-pressure-resistant container and producing phosphorus pentafluoride in a high yield by a reaction of heating at a low temperature.

即，解決本發明之課題之技術手段如下所述。 That is, the technical means for solving the problem of the present invention is as follows.

<1>一種五氟化磷之製造方法，其具有使下述通式(I)所表示之化合物、與藉由水解而產生氟化氫之化合物進行反應之步驟，通式(I)：POFx(OH)y。 <1> A method for producing phosphorus pentafluoride, which comprises the step of reacting a compound represented by the following formula (I) with a compound which generates hydrogen fluoride by hydrolysis, and the formula (I): POF x ( OH) y .

上述通式(I)中，x及y滿足以下之式(1)~式(3)： In the above formula (I), x and y satisfy the following formulas (1) to (3):

(1)0≦x≦3 (1)0≦x≦3

(2)0≦y≦3 (2)0≦y≦3

(3)x+y=3。 (3) x + y = 3.

<2>如<1>之五氟化磷之製造方法，其中，上述產生氟化氫之化合物係含有氟基之硫化合物。 <2> The method for producing phosphorus pentafluoride according to <1>, wherein the hydrogen fluoride-generating compound contains a fluorine-based sulfur compound.

<3>如<1>或<2>之五氟化磷之製造方法，其中，上述產生氟化氫之化合物係分別具有至少1個以上之氟基及磺醯基之化合物。 <3> The method for producing phosphorus pentafluoride according to <1> or <2>, wherein the hydrogen fluoride-generating compound is a compound having at least one or more fluorine groups and sulfonyl groups.

<4>如<1>至<3>中任一項之五氟化磷之製造方法，其中，上述產生氟化氫之化合物係自FSO2OH(氟磺酸)、FS(O)2F、FS(O)2OS(O)2F、FS(O)2OS(O)2OS(O)2F、FS(O)2[OS(O)2]2OS(O)2F、FS(O)2[OS(O)2]3OS(O)2F、FS(O)2[OS(O)2]4OS(O)2F、及FS(O)2[OS(O)2]5OS(O)2F中選擇之至少1種。 The method for producing phosphorus pentafluoride according to any one of <1> to <3> wherein the hydrogen fluoride-generating compound is derived from FSO 2 OH (fluorosulfonic acid), FS(O) 2 F, FS. (O) 2 OS(O) 2 F, FS(O) 2 OS(O) 2 OS(O) 2 F, FS(O) 2 [OS(O) 2 ] 2 OS(O) 2 F, FS( O) 2 [OS(O) 2 ] 3 OS(O) 2 F, FS(O) 2 [OS(O) 2 ] 4 OS(O) 2 F, and FS(O) 2 [OS(O) 2 ] 5 OS(O) 2 F is selected from at least one of them.

<5>如<1>至<4>中任一項之五氟化磷之製造方法，其中，上述產生氟化氫之化合物為氟磺酸。 The method for producing phosphorus pentafluoride according to any one of <1> to <4> wherein the hydrogen fluoride-generating compound is fluorosulfonic acid.

<6>如<1>至<5>中任一項之五氟化磷之製造方法，其中，上述通式(I)所表示之化合物係單氟磷酸及二氟磷酸中之至少一者。 The method for producing phosphorus pentafluoride according to any one of the above-mentioned items, wherein the compound represented by the above formula (I) is at least one of monofluorophosphoric acid and difluorophosphoric acid.

<7>如<6>之五氟化磷之製造方法，其中，上述單氟磷酸及上述二氟磷酸係使自磷酸、聚磷酸、及五氧化二磷中選擇之至少1種磷化合物與無水氟化氫進行反應所獲得之化合物。 <7> The method for producing phosphorus pentafluoride according to <6>, wherein the monofluorophosphate and the difluorophosphate are at least one phosphorus compound selected from the group consisting of phosphoric acid, polyphosphoric acid, and phosphorus pentoxide, and anhydrous A compound obtained by carrying out a reaction of hydrogen fluoride.

<8>如<1>至<7>中任一項之五氟化磷之製造方法，其中，使上述通式(I)所表示之化合物、與上述產生氟化氫之化合物於40℃~150℃之範圍內進行反應。 The method for producing phosphorus pentafluoride according to any one of <1> to <7> wherein the compound represented by the above formula (I) and the hydrogen fluoride-producing compound are at 40 ° C to 150 ° C. The reaction is carried out within the range.

<9>如<2>至<8>中任一項之五氟化磷之製造方法，其中，上述通式(I)所表示之化合物中所含之磷原子、與上述硫化合物中所含之硫原子之莫耳比(硫原子/磷原子)為1~10。 The method for producing phosphorus pentafluoride according to any one of <2> to <8> wherein the phosphorus atom contained in the compound represented by the above formula (I) is contained in the sulfur compound. The molar ratio of the sulfur atom (sulfur atom/phosphorus atom) is 1 to 10.

<10>一種六氟化磷酸鋰之製造方法，其具有：藉由如<1>至<9>中任一項之製造方法而製造五氟化磷之步驟；以及使所製造之五氟化磷與氟化鋰進行反應之步驟。 <10> A method for producing lithium hexafluorophosphate, which comprises the steps of producing a phosphorus pentafluoride by the production method according to any one of <1> to <9>; and the pentafluoride produced A step of reacting phosphorus with lithium fluoride.

<11>一種六氟化磷酸鋰，其係藉由如<10>之製造方法而獲得。 <11> A lithium hexafluorophosphate obtained by a production method such as <10>.

<12>一種電池用非水電解液，其包含非水溶劑、與作為電解質之如<11>之六氟化磷酸鋰。 <12> A nonaqueous electrolytic solution for a battery comprising a nonaqueous solvent and lithium hexafluorophosphate such as <11> as an electrolyte.

<13>一種鋰二次電池，其包含：如<12>之電池用非水電解液、正極、以及負極。 <13> A lithium secondary battery comprising: a nonaqueous electrolyte for a battery such as <12>, a positive electrode, and a negative electrode.

根據本發明之五氟化磷之製造方法，可無需大規模之分離步驟及高耐壓容器，而經歷藉由低溫加熱之反應而高產率地製造五氟化磷。 According to the method for producing phosphorus pentafluoride of the present invention, it is possible to produce phosphorus pentafluoride in a high yield by a reaction of low-temperature heating without requiring a large-scale separation step and a high pressure vessel.

又，本發明可提供一種無需大規模之分離步驟及高耐壓容器，而經歷藉由低溫加熱之反應而高產率地製造之使用五氟化磷之六氟化磷酸鋰之製造方法。 Further, the present invention can provide a process for producing lithium hexafluorophosphate using phosphorus pentafluoride which is produced in a high yield by a reaction of low-temperature heating without requiring a large-scale separation step and a high pressure vessel.

進而，本發明提供一種氯離子之濃度受到抑制之六氟化磷酸鋰、電池用非水電解液、及鋰二次電池。 Further, the present invention provides a lithium hexafluorophosphate, a nonaqueous electrolyte for a battery, and a lithium secondary battery in which the concentration of chlorine ions is suppressed.

[五氟化磷之製造方法] [Manufacturing method of phosphorus pentafluoride]

本發明中之五氟化磷之製造方法係具有使下述通式(I)所表示之化合物、與藉由水解而產生氟化氫之化合物(以下，有稱為「特定化合物」之情形)進行反應之步驟之方法。 The method for producing phosphorus pentafluoride in the present invention has a compound represented by the following formula (I) and a compound which generates hydrogen fluoride by hydrolysis (hereinafter referred to as "specific compound") The method of the steps.

通式(I)：POFx(OH)y Formula (I): POF x (OH) y

上述通式(I)中，x及y滿足以下之式(1)~式(3)： In the above formula (I), x and y satisfy the following formulas (1) to (3):

(1)0≦x≦3 (1)0≦x≦3

(2)0≦y≦3 (2)0≦y≦3

(3)x+y=3。 (3) x + y = 3.

根據以上，於本發明之五氟化磷之製造方法中，可無需大規模之分離步驟及高耐壓容器，而利用藉由低溫加熱之反應而高產率地製造五氟化磷。 According to the above, in the method for producing phosphorus pentafluoride according to the present invention, it is possible to produce phosphorus pentafluoride in a high yield by a reaction of low-temperature heating without requiring a large-scale separation step and a high-pressure container.

通式(I)所表示之化合物、與特定化合物之反應可藉由分別將該等添加至反應容器中而進行。 The reaction of the compound represented by the formula (I) with a specific compound can be carried out by separately adding the above to the reaction vessel.

添加該等之順序並無特別限制。 There is no particular limitation on the order in which these are added.

又，添加較佳為於惰性氣體環境下進行。 Further, the addition is preferably carried out under an inert gas atmosphere.

作為五氟化磷之製造方法，更佳為舉出：例如如下所述般使於將五氧化二磷溶解於氟磺酸中之溶液中添加無水氟化氫所產生之通式(I)所表示之化合物、與特定化合物進行反應之製造方法。 Further, as a method for producing phosphorus pentafluoride, for example, it is represented by the formula (I) obtained by adding anhydrous hydrogen fluoride to a solution in which phosphorus pentoxide is dissolved in fluorosulfonic acid, as described below. A method of producing a compound or a reaction with a specific compound.

首先，於乾燥環境下(例如，10RH%以下)，製備使五氧化二磷溶解於特定化合物中之溶液(以下，稱為「特定五氧化二磷溶解液」)。 First, a solution in which phosphorus pentoxide is dissolved in a specific compound (hereinafter referred to as "specific phosphorus pentoxide solution") is prepared in a dry environment (for example, 10 RH% or less).

繼而，於該特定五氧化二磷溶解液中，將無水氟化氫一面冷卻保持為0℃~30℃(較佳為0℃~20℃，進而較佳為0℃~10℃)之溫度一面添加，於反應容器內產生通式(I)所表示之化合物。 Then, in the specific phosphorus pentoxide solution, the anhydrous hydrogen fluoride is cooled while being maintained at a temperature of 0 ° C to 30 ° C (preferably 0 ° C to 20 ° C, and more preferably 0 ° C to 10 ° C). A compound represented by the formula (I) is produced in a reaction vessel.

然後，使通式(I)所表示之化合物與特定化合物進行反應而製造五 氟化磷。 Then, a compound represented by the formula (I) is reacted with a specific compound to produce five Phosphorus fluoride.

再者，上述特定五氧化二磷溶解液中，五氧化二磷之含量相對於特定五氧化二磷溶解液總量，較佳為7質量%~40質量%，更佳為9質量%~26質量%，進而較佳為15質量%~26質量%。 Further, in the specific phosphorus pentoxide solution, the content of phosphorus pentoxide is preferably 7 mass% to 40 mass%, more preferably 9 mass% to 26%, based on the total amount of the phosphorus pentoxide solution. The mass% is further preferably 15% by mass to 26% by mass.

通式(I)所表示之化合物與特定化合物之反應溫度可為室溫(20℃~30℃)，亦可一面加熱一面進行，例如較佳為於40℃~150℃之範圍內進行反應，更佳為於80℃~130℃之範圍內進行反應，進而較佳為於90℃~100℃之範圍內進行反應。 The reaction temperature of the compound represented by the formula (I) and the specific compound may be room temperature (20 ° C to 30 ° C), and may be carried out while heating, for example, preferably in the range of 40 ° C to 150 ° C. More preferably, the reaction is carried out in the range of from 80 ° C to 130 ° C, and more preferably in the range of from 90 ° C to 100 ° C.

關於溫度，認為藉由設為40℃以上，而提高五氟化磷之產率，又，藉由設為150℃以下，而提高五氟化磷之產率，並且無需由高價之耐蝕材料所構成之設備。 Regarding the temperature, it is considered that the yield of phosphorus pentafluoride is increased by setting it to 40 ° C or higher, and the yield of phosphorus pentafluoride is increased by setting it to 150 ° C or less, and it is not necessary to use a high-priced corrosion-resistant material. The equipment that constitutes it.

再者，上述溫度表示反應容器內之通式(I)所表示之化合物與特定化合物進行反應之反應液之溫度。 Further, the above temperature indicates the temperature of the reaction liquid in which the compound represented by the formula (I) in the reaction vessel is reacted with a specific compound.

特定化合物及通式(I)所表示之化合物中所含之氟原子相對於通式(I)所表示之化合物中所含之磷原子之莫耳比(F/P)較佳為調整成為5~15，其中，更佳為6~12，進而較佳為7~10。 The molar ratio (F/P) of the specific compound and the fluorine atom contained in the compound represented by the formula (I) to the phosphorus atom contained in the compound represented by the formula (I) is preferably adjusted to 5. ~15, wherein, more preferably, it is 6-12, and further preferably 7-10.

關於莫耳比F/P，藉由設為上述範圍之下限值以上，而抑制五氟化磷之產率下降，故而較佳。 With respect to the molar ratio F/P, it is preferable to set the lower limit of the above range or more to suppress the decrease in the yield of phosphorus pentafluoride.

另一方面，該等莫耳比係藉由設為上述範圍之上限值以下，而實現五氟化磷之產率下降之抑制、或削減用以分離過量之氟化氫與所產生之氣體之勞動力，故而較佳。 On the other hand, the molar ratios are set to be lower than the upper limit of the above range, thereby suppressing the decrease in the yield of phosphorus pentafluoride or reducing the labor for separating excess hydrogen fluoride and the generated gas. Therefore, it is better.

藉由上述製造方法所獲得之五氟化磷有包含微量之氟化氫或氧氟化磷(POF3)等氣體之情況。於氟化氫或氧氟化磷等氣體不成為問題之情形時，可直接使用，於必需有純度較高之五氟化磷之情 形時，亦可以已知之方法將氟化氫及氧氟化磷等氣體去除後使用。 The phosphorus pentafluoride obtained by the above production method may contain a trace amount of a gas such as hydrogen fluoride or phosphorus oxyfluoride (POF 3 ). When a gas such as hydrogen fluoride or phosphorus oxyfluoride is not a problem, it can be used as it is. When it is necessary to have a phosphorus pentafluoride having a high purity, a gas such as hydrogen fluoride or phosphorus oxyfluoride can be removed by a known method. After use.

再者，於本發明之五氟化磷之製造方法中，亦可併用脫水劑。 Further, in the method for producing phosphorus pentafluoride of the present invention, a dehydrating agent may be used in combination.

作為脫水劑，例如可舉出：藉由化學物質具有之化學作用進行脫水之化學脫水劑、或利用多孔質表面容易吸附水分子之情況而進行脫水之物理脫水劑。 Examples of the dehydrating agent include a chemical dehydrating agent which dehydrates by a chemical action of a chemical substance, or a physical dehydrating agent which dehydrates by using a porous surface to easily adsorb water molecules.

作為化學脫水劑，例如可舉出：五氧化磷、過氯酸鎂、濃硫酸、氯化鈣、鈉、硫酸鈉(無水)、或硫酸鈉(無水)、及硫酸銅(無水)。 Examples of the chemical dehydrating agent include phosphorus pentoxide, magnesium perchlorate, concentrated sulfuric acid, calcium chloride, sodium, sodium sulfate (anhydrous), sodium sulfate (anhydrous), and copper sulfate (anhydrous).

作為物理脫水劑，例如可舉出：矽膠、氧化鋁、分子篩、或沸石。 Examples of the physical dehydrating agent include silicone, alumina, molecular sieve, or zeolite.

以下，對於本發明中所使用之通式(I)所表示之化合物及特定化合物詳細地進行說明。 Hereinafter, the compound represented by the formula (I) and the specific compound used in the present invention will be described in detail.

(通式(I)所表示之化合物) (compound represented by the formula (I))

通式(I)所表示之化合物係以POFx(OH)y表示。 The compound represented by the formula (I) is represented by POF x (OH) y .

上述通式(I)中，x及y滿足以下之式(1)~式(3)： In the above formula (I), x and y satisfy the following formulas (1) to (3):

(1)0≦x≦3 (1)0≦x≦3

(2)0≦y≦3 (2)0≦y≦3

(3)x+y=3。 (3) x + y = 3.

作為通式(I)所表示之化合物，具體而言，可舉出以下之化合物。 Specific examples of the compound represented by the formula (I) include the following compounds.

關於通式(I)所表示之化合物，就利用藉由低溫加熱之反應而高產率地製造五氟化磷之觀點而言，上述化合物中，較佳為：磷酸、單氟磷酸、或二氟磷酸，尤佳為單氟磷酸及二氟磷酸中之至少一者。 With respect to the compound represented by the formula (I), in view of producing a phosphorus pentafluoride in a high yield by a reaction of heating at a low temperature, among the above compounds, phosphoric acid, monofluorophosphoric acid or difluoro is preferred. Phosphoric acid is particularly preferably at least one of monofluorophosphate and difluorophosphoric acid.

又，亦可併用該等化合物。 Further, these compounds may be used in combination.

於本發明中作為起始反應物所使用之通式(I)所表示之化合物亦可直接使用市售者。 The compound represented by the formula (I) used as the starting reactant in the present invention can also be used as it is.

又，通式(I)所表示之化合物可藉由公知之方法而製造。 Further, the compound represented by the formula (I) can be produced by a known method.

例如，於單氟磷酸及二氟磷酸之情形時，可藉由使自磷酸、聚磷酸、及五氧化二磷中選擇之至少1種磷化合物、與無水氟化氫進行反應而獲得。 For example, in the case of monofluorophosphoric acid and difluorophosphoric acid, it can be obtained by reacting at least one phosphorus compound selected from the group consisting of phosphoric acid, polyphosphoric acid and phosphorus pentoxide with anhydrous hydrogen fluoride.

(特定化合物) (specific compound)

作為本發明之五氟化磷之製造方法中所使用之特定化合物，例如可舉出：FSO2CF=CF2、FSO2C6H5、FSO2(p-C6H4OCH3)、FSO2(p-C6H4NO2)、FSO2(p-C6H4F)、FSO2CHFCF2OCH3、FSO2CHFCF3、FSO2CHFCF2Br、FSO2CFClCF2Cl、FSO2CFBrCF2Br、FS(O)2N=S=O、FS(O)2N=S(O)F2、FS(O)2N=SF2、FS(O)2N=SCl2、F2S(O)=NS(O)2F、FSO2NH2、(FSO2)2NH、FSO2NF2、(FSO2)2NF、FSO2OH(氟磺酸)、FS(O)2OCF3、FS(O)2OCF2Cl、FS(O)2OCF2CF3、FS(O)2OCF(CF3)CF2CF3、FS(O)2OCF(CF3)CFBrCF3、[FS(O)2O]3CF、[FS(O)2O]2CF2、[FS(O)2O]2CF2CF2、FS(O)2OCF2CF2NF2、FS(O)2OCF2CF(NF2)CF3、FS(O)2OC(O)CF3、FS(O)2OC(O)CF2Cl、FS(O)2OC(O)CF2CF3、FS(O)2OC(O)CF2CF2CF3、FS(O)2OC(O)CF2CF2OS(O)2F、FS(O)2ONF2、 FS(O)2OOCF3、FS(O)2OOSOOF、FS(O)2OOS(O)2F、FS(O)2OOF、FS(O)2OF、[FS(O)2O]3PO、[FS(O)2O]2P(O)F、FS(O)2OP(O)F2、FS(O)2OS(O)2F、FS(O)2OS(O)2OS(O)2F、FS(O)2[OS(O)2]2OS(O)2F、FS(O)2[OS(O)2]3OS(O)2F、FS(O)2[OS(O)2]4OS(O)2F、FS(O)2[OS(O)2]5OS(O)2F、FS(O)2OSOOF、FS(O)2OSF5、FS(O)2OCl、FS(O)2OBr、CF3CF[OS(O)2F]CF2NF2、F(SO3)2SO2F、FS(O)2F、FS(O)2Br、LiPF6、LiBF4、LiAsPF6、LiSbF6、SF4、SiF4、BF3、PF3等。 Specific examples of the compound used in the method for producing phosphorus pentafluoride of the present invention include FSO 2 CF=CF 2 , FSO 2 C 6 H 5 , FSO 2 (pC 6 H 4 OCH 3 ), and FSO 2 . (pC 6 H 4 N O 2 ), FSO 2 (pC 6 H 4 F), FSO 2 CHFCF 2 OCH 3, FSO 2 CHFCF 3, FSO 2 CHFCF 2 Br, FSO 2 CFClCF 2 Cl, FSO 2 CFBrCF 2 Br, FS(O) 2 N=S=O, FS(O) 2 N=S(O)F 2 , FS(O) 2 N=SF 2 , FS(O) 2 N=SCl 2 , F 2 S(O = NS(O) 2 F, FSO 2 NH 2 , (FSO 2 ) 2 NH, FSO 2 NF 2 , (FSO 2 ) 2 NF, FSO 2 OH (fluorosulfonic acid), FS(O) 2 OCF 3 , FS(O) 2 OCF 2 Cl, FS(O) 2 OCF 2 CF 3 , FS(O) 2 OCF(CF 3 )CF 2 CF 3 , FS(O) 2 OCF(CF 3 )CFBrCF 3 , [FS( O) 2 O] 3 CF, [FS(O) 2 O] 2 CF 2 , [FS(O) 2 O] 2 CF 2 CF 2 , FS(O) 2 OCF 2 CF 2 NF 2 , FS(O) 2 OCF 2 CF(NF 2 )CF 3 , FS(O) 2 OC(O)CF 3 , FS(O) 2 OC(O)CF 2 Cl, FS(O) 2 OC(O)CF 2 CF 3 , FS(O) 2 OC(O)CF 2 CF 2 CF 3 , FS(O) 2 OC(O)CF 2 CF 2 OS(O) 2 F, FS(O) 2 ONF 2 , FS(O) 2 OOCF 3 , FS(O) 2 OOSOOF, FS(O) 2 OOS(O) 2 F, FS(O) 2 OOF, FS(O) 2 OF, [FS(O) 2 O] 3 PO, [FS(O) ) 2 O] 2 P (O ) F FS (O) 2 OP (O ) F 2, FS (O) 2 OS (O) 2 F, FS (O) 2 OS (O) 2 OS (O) 2 F, FS (O) 2 [OS (O ) 2 ] 2 OS(O) 2 F, FS(O) 2 [OS(O) 2 ] 3 OS(O) 2 F, FS(O) 2 [OS(O) 2 ] 4 OS(O) 2 F FS(O) 2 [OS(O) 2 ] 5 OS(O) 2 F, FS(O) 2 OSOOF, FS(O) 2 OSF 5 , FS(O) 2 OCl, FS(O) 2 OBr, CF 3 CF[OS(O) 2 F]CF 2 NF 2 , F(SO 3 ) 2 SO 2 F, FS(O) 2 F, FS(O) 2 Br, LiPF 6 , LiBF 4 , LiAsPF 6 , LiSbF 6 , SF 4 , SiF 4 , BF 3 , PF 3, etc.

再者，該等特定化合物亦可併用2種以上。 Further, these specific compounds may be used in combination of two or more kinds.

又，作為特定化合物，例如可舉出以下之聚合物。 Moreover, as a specific compound, the following polymers are mentioned, for example.

特定化合物中之硫原子亦可至少一個或全部為硼原子、矽原子、磷原子、砷原子、硒原子、銻原子或碲原子。 The sulfur atom in the specific compound may also be at least one or all of a boron atom, a germanium atom, a phosphorus atom, an arsenic atom, a selenium atom, a germanium atom or a germanium atom.

關於特定化合物，該等之中，較佳為含有氟基之硫化合物，更佳為分別含有至少1個以上之氟基及磺醯基之化合物。 Among the specific compounds, among these, a sulfur compound containing a fluorine group is preferred, and a compound containing at least one or more fluorine groups and sulfonyl groups, respectively, is more preferred.

作為含有氟基之硫化合物，就藉由上述製造方法所獲得之五氟化磷不易含有雜質之觀點而言，例如可舉出：FS(O)2OOSOOF、FS(O)2OOS(O)2F、FS(O)2OOF、FS(O)2OF、[FS(O)2O]3PO、 [FS(O)2O]2P(O)F、FS(O)2OP(O)F2、FS(O)2OS(O)2F、FS(O)2OS(O)2OS(O)2F、FS(O)2[OS(O)2]2OS(O)2F、FS(O)2[OS(O)2]3OS(O)2F、FS(O)2[OS(O)2]4OS(O)2F、FS(O)2[OS(O)2]5OS(O)2F、FS(O)2OSOOF、FS(O)2OSF5、F(SO3)2SO2F、FS(O)2F、FSO2OH(氟磺酸)。 As a fluorine-containing sulfur compound, the phosphorus pentafluoride obtained by the above production method is less likely to contain impurities, and examples thereof include FS(O) 2 OOSOOF and FS(O) 2 OOS(O). 2 F, FS(O) 2 OOF, FS(O) 2 OF, [FS(O) 2 O] 3 PO, [FS(O) 2 O] 2 P(O)F, FS(O) 2 OP ( O) F 2 , FS(O) 2 OS(O) 2 F, FS(O) 2 OS(O) 2 OS(O) 2 F, FS(O) 2 [OS(O) 2 ] 2 OS(O 2 F, FS(O) 2 [OS(O) 2 ] 3 OS(O) 2 F, FS(O) 2 [OS(O) 2 ] 4 OS(O) 2 F, FS(O) 2 [ OS(O) 2 ] 5 OS(O) 2 F, FS(O) 2 OSOOF, FS(O) 2 OSF 5 , F(SO 3 ) 2 SO 2 F, FS(O) 2 F, FSO 2 OH ( Fluorosulfonic acid).

該等之中，較佳為：FSO2OH(氟磺酸)、FS(O)2F、FS(O)2OS(O)2F、FS(O)2OS(O)2OS(O)2F、FS(O)2[OS(O)2]2OS(O)2F、FS(O)2[OS(O)2]3OS(O)2F、FS(O)2[OS(O)2]4OS(O)2F、及FS(O)2[OS(O)2]5OS(O)2F。 Among these, FSO 2 OH (fluorosulfonic acid), FS(O) 2 F, FS(O) 2 OS(O) 2 F, FS(O) 2 OS(O) 2 OS(O) is preferred. 2 F, FS(O) 2 [OS(O) 2 ] 2 OS(O) 2 F, FS(O) 2 [OS(O) 2 ] 3 OS(O) 2 F, FS(O) 2 [ OS(O) 2 ] 4 OS(O) 2 F, and FS(O) 2 [OS(O) 2 ] 5 OS(O) 2 F.

關於特定化合物，該等之中，尤佳為氟磺酸。 Among the specific compounds, among these, fluorosulfonic acid is particularly preferred.

本發明中所使用之氟磺酸可直接使用市售之氟磺酸(HSO3F)。 As the fluorosulfonic acid used in the present invention, commercially available fluorosulfonic acid (HSO 3 F) can be used as it is.

又，本發明中所使用之氟磺酸亦可為使自硫酸、發煙硫酸或三氧化硫中選擇之至少1種化合物與無水氟化氫進行反應所獲得之氟磺酸。 Further, the fluorosulfonic acid used in the present invention may be a fluorosulfonic acid obtained by reacting at least one compound selected from sulfuric acid, fuming sulfuric acid or sulfur trioxide with anhydrous hydrogen fluoride.

上述發煙硫酸係藉由使三氧化硫溶解於硫酸中而製備。發煙硫酸中，游離三氧化硫之含量較佳為80質量%以下，更佳為5質量%以上且80質量%以下，最佳為60質量%。 The above fuming sulfuric acid is prepared by dissolving sulfur trioxide in sulfuric acid. The content of the free sulfur trioxide in the fuming sulfuric acid is preferably 80% by mass or less, more preferably 5% by mass or more and 80% by mass or less, and most preferably 60% by mass or less.

再者，亦可直接使用純的三氧化硫。 Furthermore, pure sulfur trioxide can also be used directly.

於本發明之五氟化磷之製造方法中，認為例如於應用氟磺酸作為特定化合物之情形時，首先，藉由將氟磺酸進行水解，而產生硫酸及氟化氫，其後，進行藉由硫酸之脫水作用及藉由氟化氫之氟取代。可藉由應用有氟磺酸之該反應，而不經由先前技術所示之六氟磷酸，而高產率地獲得作為目標物之五氟化磷，進而與先前技術相比以低溫且容易地進行反應。 In the method for producing phosphorus pentafluoride according to the present invention, it is considered that, for example, when fluorosulfonic acid is used as a specific compound, first, sulfuric acid and hydrogen fluoride are produced by hydrolyzing fluorosulfonic acid, and then, by using Dehydration of sulfuric acid and substitution by fluorine of hydrogen fluoride. The phosphorus pentafluoride as a target can be obtained in high yield by the reaction using fluorosulfonic acid without the hexafluorophosphoric acid shown in the prior art, and thus can be carried out at a low temperature and easily compared with the prior art. reaction.

其結果為，本發明無需大規模之分離步驟及高耐壓容器，而容易地利用藉由低溫加熱之反應而高產率地製造五氟化磷。 As a result, the present invention can easily produce phosphorus pentafluoride in a high yield by a reaction of low-temperature heating without requiring a large-scale separation step and a high pressure vessel.

再者，於應用氟磺酸作為特定化合物之上述反應中，亦可併用脫水劑。 Further, in the above reaction using fluorosulfonic acid as a specific compound, a dehydrating agent may be used in combination.

作為脫水劑，可舉出上述脫水劑。 The dehydrating agent mentioned above is mentioned above.

於特定化合物為具有硫原子之硫化合物之情形時，關於通式(I)所表示之化合物與特定化合物之添加比，較佳為將特定化合物中所含之硫原子相對於通式(I)所表示之化合物中所含之磷原子之莫耳比(S/P)調整成為1~10，其中，更佳為2~7，進而較佳為2~4。 When the specific compound is a sulfur compound having a sulfur atom, the ratio of the compound represented by the formula (I) to the specific compound is preferably such that the sulfur atom contained in the specific compound is relative to the formula (I). The molar ratio (S/P) of the phosphorus atom contained in the compound represented is adjusted to 1 to 10, more preferably 2 to 7, and still more preferably 2 to 4.

藉由將莫耳比S/P設為上述範圍之下限值以上，而抑制五氟化磷之產率下降，故而較佳。 It is preferable to set the molar ratio S/P to be equal to or higher than the lower limit of the above range, thereby suppressing a decrease in the yield of phosphorus pentafluoride.

另一方面，藉由將該等莫耳比設為上述範圍之上限值以下，而實現五氟化磷之產率下降之抑制、或削減用以將過量之氟化氫與所產生之氣體進行分離之勞動力，故而較佳。 On the other hand, by setting the molar ratio to be equal to or lower than the upper limit of the above range, the suppression of the decrease in the yield of phosphorus pentafluoride or the reduction of the excess hydrogen fluoride from the generated gas is achieved. The labor force is therefore better.

[六氟化磷酸鋰之製造方法] [Manufacturing method of lithium hexafluorophosphate]

本發明中之六氟化磷酸鋰之製造方法係具有製造上述五氟化磷之步驟、與使所獲得之五氟化磷與氟化鋰進行反應之步驟之六氟化磷酸鋰之製造方法。 The method for producing lithium hexafluorophosphate in the present invention is a method for producing lithium hexafluorophosphate which is a step of producing the above phosphorus pentafluoride and a step of reacting the obtained phosphorus pentafluoride with lithium fluoride.

五氟化磷與氟化鋰之反應可適用製造六氟化磷酸鋰時通常進行之公知之方法進行。 The reaction of phosphorus pentafluoride with lithium fluoride can be carried out by a known method generally carried out in the production of lithium hexafluorophosphate.

本發明中之六氟化磷酸鋰之製造方法由於不使用氯化物作為原料，故而可抑制六氟化磷酸鋰中之氯離子之濃度。 In the method for producing lithium hexafluorophosphate in the present invention, since the chloride is not used as a raw material, the concentration of chloride ions in lithium hexafluorophosphate can be suppressed.

因此，本發明中之六氟化磷酸鋰之製造方法例如可獲得氯離子之濃度為2ppm以下之六氟化磷酸鋰，進而，亦可獲得不含氯離子之六氟化磷酸鋰。 Therefore, in the method for producing lithium hexafluorophosphate in the present invention, for example, lithium hexafluorophosphate having a chloride ion concentration of 2 ppm or less can be obtained, and further, lithium hexafluorophosphate containing no chloride ions can be obtained.

[六氟化磷酸鋰] [Lithium hexafluorophosphate]

本發明中之六氟化磷酸鋰可藉由上述六氟化磷酸鋰之製造方法而獲得。 The lithium hexafluorophosphate in the present invention can be obtained by the above-described method for producing lithium hexafluorophosphate.

本發明之六氟化磷酸鋰可藉由不使用氯化物作為原料之本發明之六氟化磷酸鋰之製造方法而獲得，故而氯離子之濃度受到抑制。 The lithium hexafluorophosphate of the present invention can be obtained by the method for producing lithium hexafluorophosphate of the present invention which does not use chloride as a raw material, and thus the concentration of chloride ions is suppressed.

因此，本發明之六氟化磷酸鋰係例如可成為氯離子之濃度為2ppm以下之六氟化磷酸鋰者，進而，亦可成為不含氯離子之六氟化磷酸鋰。 Therefore, the lithium hexafluorophosphate of the present invention may be, for example, lithium hexafluorophosphate having a chloride ion concentration of 2 ppm or less, or may be lithium hexafluorophosphate containing no chloride ions.

再者，於本發明之六氟化磷酸鋰中，藉由五氟化磷產生反應之產率，而可使二氟磷酸鋰包含於產物中。 Further, in the lithium hexafluorophosphate of the present invention, lithium difluorophosphate can be contained in the product by the yield of the reaction by phosphorus pentafluoride.

[電池用非水電解液] [Non-aqueous electrolyte for battery]

本發明中之電池用非水電解液包含非水溶劑、與作為電解質之本發明中之上述六氟化磷酸鋰。 The nonaqueous electrolytic solution for a battery of the present invention comprises a nonaqueous solvent and the above lithium hexafluorophosphate in the present invention as an electrolyte.

再者，本發明中之電池用非水電解液亦可以例如改善電池電阻為目的，以抑制高溫環境下之鋰過渡金屬氧化物之變質、電解液之分解、或形成於負極表面之保護皮膜之破壞等為目的，而含有添加劑等。 Further, the non-aqueous electrolyte solution for a battery of the present invention can also, for example, improve battery resistance for suppressing deterioration of a lithium transition metal oxide in a high-temperature environment, decomposition of an electrolytic solution, or formation of a protective film on a surface of a negative electrode. For the purpose of destruction, etc., it contains additives and the like.

本發明中之上述六氟化磷酸鋰可如上所述般抑制氯離子之濃度，故而本發明中之電池用非水電解液亦成為即便不經歷將氯離子去除之步驟，氯離子之濃度亦受到抑制者。 The lithium hexafluorophosphate in the present invention can suppress the concentration of chloride ions as described above, and therefore the nonaqueous electrolyte for a battery of the present invention is also subjected to a step of removing chloride ions even if the concentration of chloride ions is not subjected to the step of removing the chloride ions. Repressor.

具體而言，本發明中之電池用非水電解液可製成氯離子之濃度為0.2ppm以下之電池用非水電解液，進而，亦可製成不包含氯離子之電池用非水電解液。 Specifically, the non-aqueous electrolyte solution for a battery of the present invention can be used as a non-aqueous electrolyte for a battery having a chloride ion concentration of 0.2 ppm or less, or a non-aqueous electrolyte for a battery containing no chlorine ion. .

再者，關於電池用非水電解液，就抑制成為電極之金屬之腐蝕之 觀點而言，較佳為氯離子之濃度較低。 Furthermore, regarding the non-aqueous electrolyte for batteries, the corrosion of the metal which becomes the electrode is suppressed. In view of the above, it is preferred that the concentration of chloride ions is low.

(非水溶劑) (non-aqueous solvent)

作為非水溶劑，可適宜選擇各種公知者，較佳為使用環狀之非質子性溶劑及/或鏈狀之非質子性溶劑。 As the nonaqueous solvent, various known ones can be appropriately selected, and a cyclic aprotic solvent and/or a chain aprotic solvent is preferably used.

為了提高電池之安全性，於欲提高溶劑之引火點之情形時，較佳為使用環狀之非質子性溶劑作為非水溶劑。 In order to improve the safety of the battery, in the case where the ignition point of the solvent is to be increased, it is preferred to use a cyclic aprotic solvent as the nonaqueous solvent.

作為環狀之非質子性溶劑，可使用：環狀碳酸酯、環狀羧酸酯、環狀碸、環狀醚。 As the cyclic aprotic solvent, a cyclic carbonate, a cyclic carboxylic acid ester, a cyclic hydrazine, or a cyclic ether can be used.

環狀之非質子性溶劑可單獨使用，亦可混合複數種使用。 The cyclic aprotic solvent may be used singly or in combination of plural kinds.

環狀之非質子性溶劑之非水溶劑中之混合比率為10質量%~100質量%，進而較佳為20質量%~90質量%，尤佳為30質量%~80質量%。可藉由設為此種比率，而提高有關電池之充放電特性之電解液之導電率。 The mixing ratio in the nonaqueous solvent of the cyclic aprotic solvent is from 10% by mass to 100% by mass, more preferably from 20% by mass to 90% by mass, even more preferably from 30% by mass to 80% by mass. By setting such a ratio, the conductivity of the electrolytic solution relating to the charge and discharge characteristics of the battery can be improved.

作為環狀碳酸酯之例，具體而言，可舉出：碳酸伸乙酯、碳酸丙烯酯、碳酸1,2-伸丁酯、碳酸2,3-伸丁酯、碳酸1,2-伸戊酯、碳酸2,3-伸戊酯等。其中，可較佳地使用介電常數較高之碳酸伸乙酯與碳酸丙烯酯。於使用石墨作為負極活性物質之電池之情形時，更佳為碳酸伸乙酯。又，該等環狀碳酸酯亦可混合2種以上使用。 Specific examples of the cyclic carbonate include ethyl carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, and 1,2-carbonate. Ester, 2,3-amyl acetate, and the like. Among them, ethyl carbonate and propylene carbonate having a high dielectric constant can be preferably used. In the case of a battery using graphite as the negative electrode active material, it is more preferably ethyl carbonate. Further, these cyclic carbonates may be used in combination of two or more kinds.

作為環狀羧酸酯，具體而言，可例示：γ-丁內酯、δ-戊內酯、或甲基γ-丁內酯、乙基γ-丁內酯、乙基δ-戊內酯等烷基取代體等。 Specific examples of the cyclic carboxylic acid ester include γ-butyrolactone, δ-valerolactone, or methyl γ-butyrolactone, ethyl γ-butyrolactone, and ethyl δ-valerolactone. An alkyl substituent or the like.

環狀羧酸酯之蒸氣壓較低、黏度較低、且介電常數較高，可不降低電解液之引火點與電解質之解離度而降低電解液之黏度。因此，具 有可不提高電解液之易燃性而提高作為有關電池之放電特性指標之電解液之導電率的特徵，故而於指向溶劑之引火點之提高之情形時，較佳為使用環狀羧酸酯作為上述環狀之非質子性溶劑。環狀羧酸酯之中，最佳為γ-丁內酯。 The cyclic carboxylic acid ester has a low vapor pressure, a low viscosity, and a high dielectric constant, and can lower the viscosity of the electrolyte without lowering the dissociation degree of the ignition point of the electrolyte and the electrolyte. Therefore, with It is possible to improve the conductivity of the electrolyte as an indicator of the discharge characteristics of the battery without increasing the flammability of the electrolyte. Therefore, when the ignition point of the solvent is raised, it is preferred to use a cyclic carboxylic acid ester as the carboxylic acid ester. The above cyclic aprotic solvent. Among the cyclic carboxylic acid esters, γ-butyrolactone is preferred.

又，環狀羧酸酯較佳為與其他環狀之非質子性溶劑混合使用。例如可舉出：環狀羧酸酯、與環狀碳酸酯及/或鏈狀碳酸酯之混合物。 Further, the cyclic carboxylic acid ester is preferably used in combination with another cyclic aprotic solvent. For example, a mixture of a cyclic carboxylic acid ester and a cyclic carbonate and/or a chain carbonate can be mentioned.

作為環狀碸之例，可舉出：環丁碸、2-甲基環丁碸、3-甲基環丁碸、二甲基碸、二乙基碸、二丙基碸、甲基乙基碸、甲基丙基碸等。 Examples of the cyclic oxime include cyclobutyl hydrazine, 2-methylcyclobutyl fluorene, 3-methylcyclobutyl hydrazine, dimethyl hydrazine, diethyl hydrazine, dipropyl hydrazine, and methyl ethyl group.碸, methyl propyl hydrazine, and the like.

作為環狀醚之例，可舉出二氧雜環戊烷。 As an example of a cyclic ether, a dioxolane is mentioned.

作為本發明之鏈狀之非質子性溶劑，可使用：鏈狀碳酸酯、鏈狀羧酸酯、鏈狀醚、鏈狀磷酸酯等。 As the chain-like aprotic solvent of the present invention, a chain carbonate, a chain carboxylate, a chain ether, a chain phosphate or the like can be used.

鏈狀之非質子性溶劑之非水溶劑中之混合比率為10質量%~100質量%，進而較佳為20質量%~90質量%，尤佳為30質量%~80質量%。 The mixing ratio in the nonaqueous solvent of the chain aprotic solvent is from 10% by mass to 100% by mass, more preferably from 20% by mass to 90% by mass, even more preferably from 30% by mass to 80% by mass.

作為鏈狀碳酸酯，具體而言，可舉出：碳酸二甲酯、碳酸甲基乙基酯、碳酸二乙酯、碳酸甲基丙基酯、碳酸甲基異丙基酯、碳酸乙基丙基酯、碳酸二丙酯、碳酸甲基丁基酯、碳酸乙基丁基酯、碳酸二丁酯、碳酸甲基戊基酯、碳酸乙基戊基酯、碳酸二戊酯、碳酸甲基庚基酯、碳酸乙基庚基酯、碳酸二庚酯、碳酸甲基己基酯、碳酸乙基己基酯、碳酸二己酯、碳酸甲基辛基酯、碳酸乙基辛基酯、碳酸二辛酯、碳酸甲基三氟乙酯等。該等鏈狀碳酸酯亦可混合2種以上使用。 Specific examples of the chain carbonate include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, and ethyl propyl carbonate. Base ester, dipropyl carbonate, methyl butyl carbonate, ethyl butyl carbonate, dibutyl carbonate, methyl amyl carbonate, ethyl amyl carbonate, diamyl carbonate, methyl glycolate Base ester, ethyl heptyl carbonate, diheptyl carbonate, methylhexyl carbonate, ethylhexyl carbonate, dihexyl carbonate, methyl octyl carbonate, ethyl octyl carbonate, dioctyl carbonate , methyl trifluoroethyl carbonate, and the like. These chain carbonates may be used in combination of two or more kinds.

作為鏈狀羧酸酯，具體而言，可舉出三甲基乙酸甲酯等。 Specific examples of the chain carboxylic acid ester include methyl trimethylacetate.

作為鏈狀醚，具體而言，可舉出二甲氧基乙烷等。 Specific examples of the chain ether include dimethoxyethane and the like.

作為鏈狀磷酸酯，具體而言，可舉出磷酸三甲酯等。 Specific examples of the chain phosphate include trimethyl phosphate.

(溶劑之組合) (combination of solvents)

本發明之非水電解液中所使用之非水溶劑可使用1種亦可混合複數種使用。又，可僅使用1種或複數種環狀之非質子性溶劑，亦可僅使用1種或複數種鏈狀之非質子性溶劑，或亦可混合環狀之非質子性溶劑及鏈狀之質子性溶劑使用。於尤其謀求電池之負載特性、低溫特性之提高之情形時，較佳為組合環狀之非質子性溶劑與鏈狀之非質子性溶劑作為非水溶劑而使用。 The nonaqueous solvent used in the nonaqueous electrolytic solution of the present invention may be used alone or in combination of plural kinds. Further, only one or a plurality of cyclic aprotic solvents may be used, or only one or a plurality of chain aprotic solvents may be used, or a cyclic aprotic solvent and a chain may be mixed. Use as a protic solvent. In particular, in the case where the load characteristics and low-temperature characteristics of the battery are improved, it is preferred to use a combination of a cyclic aprotic solvent and a chain aprotic solvent as a nonaqueous solvent.

進而，就電解液之電化學穩定性之方面而言，最佳為應用環狀碳酸酯作為環狀之非質子性溶劑、鏈狀碳酸酯作為鏈狀之非質子性溶劑。又，亦可藉由環狀羧酸酯與環狀碳酸酯及/或鏈狀碳酸酯之組合，而提高有關電池之充放電特性之電解液之導電率。 Further, in terms of electrochemical stability of the electrolytic solution, it is preferred to use a cyclic carbonate as a cyclic aprotic solvent or a chain carbonate as a chain aprotic solvent. Further, the conductivity of the electrolyte solution relating to the charge and discharge characteristics of the battery can be improved by a combination of a cyclic carboxylic acid ester and a cyclic carbonate and/or a chain carbonate.

作為環狀碳酸酯與鏈狀碳酸酯之組合，具體而言，可舉出：碳酸伸乙酯與碳酸二甲酯、碳酸伸乙酯與碳酸甲基乙基酯、碳酸伸乙酯與碳酸二乙酯、碳酸丙烯酯與碳酸二甲酯、碳酸丙烯酯與碳酸甲基乙基酯、碳酸丙烯酯與碳酸二乙酯、碳酸伸乙酯與碳酸丙烯酯與碳酸甲基乙基酯、碳酸伸乙酯與碳酸丙烯酯與碳酸二乙酯、碳酸伸乙酯與碳酸二甲酯與碳酸甲基乙基酯、碳酸伸乙酯與碳酸二甲酯與碳酸二乙酯、碳酸二乙酯與碳酸甲基乙基酯與碳酸二乙酯、碳酸伸乙酯與碳酸二甲酯與碳酸甲基乙基酯與碳酸二乙酯、碳酸伸乙酯與碳酸丙烯酯與碳酸二甲酯與碳酸甲基乙基酯、碳酸伸乙酯與碳酸丙烯酯與碳酸二甲酯與碳酸二乙酯、碳酸伸乙酯與碳酸丙烯酯與碳酸甲基乙基酯與碳酸二乙酯、碳酸伸乙酯與碳酸丙烯酯與碳酸二甲酯與碳酸甲基乙基 酯與碳酸二乙酯等。 Specific examples of the combination of the cyclic carbonate and the chain carbonate include ethyl carbonate and dimethyl carbonate, ethyl carbonate and methyl ethyl carbonate, ethyl carbonate and carbonic acid. Ethyl ester, propylene carbonate and dimethyl carbonate, propylene carbonate and methyl ethyl carbonate, propylene carbonate and diethyl carbonate, ethyl carbonate and propylene carbonate and methyl ethyl carbonate, carbonic acid Ethyl ester and propylene carbonate with diethyl carbonate, ethyl carbonate and ethyl dimethyl carbonate and methyl ethyl carbonate, ethyl carbonate and diethyl carbonate and diethyl carbonate, diethyl carbonate and carbonic acid Methyl ethyl ester and diethyl carbonate, ethyl carbonate and diethyl carbonate and methyl ethyl carbonate and diethyl carbonate, ethyl carbonate and propylene carbonate and dimethyl carbonate and methyl carbonate Ethyl ester, ethyl carbonate and propylene carbonate with dimethyl carbonate and diethyl carbonate, ethyl carbonate and ethyl acrylate and methyl ethyl carbonate and diethyl carbonate, ethyl carbonate and carbonic acid Propylene ester with dimethyl carbonate and methyl ethyl carbonate Ester and diethyl carbonate, and the like.

關於環狀碳酸酯與鏈狀碳酸酯之混合比率，以質量比表示，環狀碳酸酯：鏈狀碳酸酯為5：95~80：20，進而較佳為10：90~70：30，尤佳為15：85~55：45。藉由設為此種比率，而可抑制電解液之黏度上升，提高電解質之解離度，故而可提高有關電池之充放電特性之電解液之導電率。又，可進而提高電解質之溶解度。因此，可製成於常溫或低溫下之導電性優異之電解液，故而可改善常溫至低溫下之電池之負載特性。 The mixing ratio of the cyclic carbonate to the chain carbonate is represented by a mass ratio, and the cyclic carbonate: the chain carbonate is 5:95 to 80:20, and more preferably 10:90 to 70:30. Good for 15:85~55:45. By setting such a ratio, the viscosity of the electrolytic solution can be suppressed from increasing, and the degree of dissociation of the electrolyte can be improved, so that the conductivity of the electrolytic solution with respect to the charge and discharge characteristics of the battery can be improved. Moreover, the solubility of the electrolyte can be further increased. Therefore, it is possible to produce an electrolytic solution excellent in conductivity at normal temperature or low temperature, so that the load characteristics of the battery at normal temperature to low temperature can be improved.

作為環狀羧酸酯與環狀碳酸酯及/或鏈狀碳酸酯之組合之例，具體而言，可舉出：γ-丁內酯與碳酸伸乙酯、γ-丁內酯與碳酸伸乙酯與碳酸二甲酯、γ-丁內酯與碳酸伸乙酯與碳酸甲基乙基酯、γ-丁內酯與碳酸伸乙酯與碳酸二乙酯、γ-丁內酯與碳酸丙烯酯、γ-丁內酯與碳酸丙烯酯與碳酸二甲酯、γ-丁內酯與碳酸丙烯酯與碳酸甲基乙基酯、γ-丁內酯與碳酸丙烯酯與碳酸二乙酯、γ-丁內酯與碳酸伸乙酯與碳酸丙烯酯、γ-丁內酯與碳酸伸乙酯與碳酸丙烯酯與碳酸二甲酯、γ-丁內酯與碳酸伸乙酯與碳酸丙烯酯與碳酸甲基乙基酯、γ-丁內酯與碳酸伸乙酯與碳酸丙烯酯與碳酸二乙酯、γ-丁內酯與碳酸伸乙酯與碳酸二甲酯與碳酸甲基乙基酯、γ-丁內酯與碳酸伸乙酯與碳酸二甲酯與碳酸二乙酯、γ-丁內酯與碳酸伸乙酯與碳酸甲基乙基酯與碳酸二乙酯、γ-丁內酯與碳酸伸乙酯與碳酸二甲酯與碳酸甲基乙基酯與碳酸二乙酯、γ-丁內酯與碳酸伸乙酯與碳酸丙烯酯與碳酸二甲酯與碳酸甲基乙基酯、γ-丁內酯與碳酸伸乙酯與碳酸丙烯酯與碳酸二甲酯與碳酸二乙酯、γ-丁內酯與碳酸伸乙酯與碳酸丙烯酯與碳酸甲基乙基酯與碳酸二乙酯、γ-丁內酯與碳酸伸乙酯與碳酸丙烯酯與碳酸二甲酯與碳酸甲基乙基酯與碳酸二乙酯、γ-丁內酯與 環丁碸、γ-丁內酯與碳酸伸乙酯與環丁碸、γ-丁內酯與碳酸丙烯酯與環丁碸、γ-丁內酯與碳酸伸乙酯與碳酸丙烯酯與環丁碸、γ-丁內酯與環丁碸與碳酸二甲酯等。 Specific examples of the combination of the cyclic carboxylic acid ester and the cyclic carbonate and/or the chain carbonate include γ-butyrolactone and ethyl carbonate, γ-butyrolactone and carbonic acid extension. Ethyl ester with dimethyl carbonate, γ-butyrolactone and ethyl carbonate and methyl ethyl carbonate, γ-butyrolactone and ethyl carbonate and diethyl carbonate, γ-butyrolactone and propylene carbonate Ester, γ-butyrolactone and propylene carbonate with dimethyl carbonate, γ-butyrolactone and propylene carbonate with methyl ethyl carbonate, γ-butyrolactone and propylene carbonate with diethyl carbonate, γ -butyrolactone and ethyl carbonate and propylene carbonate, γ-butyrolactone and ethyl carbonate and propylene carbonate and dimethyl carbonate, γ-butyrolactone and ethyl carbonate and propylene carbonate and carbonic acid Methyl ethyl ester, γ-butyrolactone and ethyl carbonate and propylene carbonate and diethyl carbonate, γ-butyrolactone and ethyl carbonate and dimethyl carbonate and methyl ethyl carbonate, γ -butyrolactone and ethyl carbonate and diethyl carbonate and diethyl carbonate, γ-butyrolactone and ethyl carbonate and methyl ethyl carbonate and diethyl carbonate, γ-butyrolactone and carbonic acid Yan B Ester and dimethyl carbonate and methyl ethyl carbonate and diethyl carbonate, γ-butyrolactone and ethyl carbonate and propylene carbonate with dimethyl carbonate and methyl ethyl carbonate, γ-butane Ester and ethyl carbonate and propylene carbonate with dimethyl carbonate and diethyl carbonate, γ-butyrolactone and ethyl carbonate and propylene carbonate and methyl ethyl carbonate and diethyl carbonate, γ- Butyrolactone and ethyl carbonate and propylene carbonate with dimethyl carbonate and methyl ethyl carbonate and diethyl carbonate, γ-butyrolactone Cyclobutane, γ-butyrolactone and ethyl carbonate and cyclobutyl hydrazine, γ-butyrolactone and propylene carbonate and cyclobutyl hydrazine, γ-butyrolactone and ethyl carbonate and propylene carbonate and cyclohexane碸, γ-butyrolactone and cyclobutyl hydrazine and dimethyl carbonate.

(其他溶劑) (other solvents)

本發明之非水電解液中，作為非水溶劑，亦可包含上述以外之其他溶劑。作為其他溶劑，具體而言，可舉出：二甲基甲醯胺等醯胺、甲基-N,N-胺基甲酸二甲酯等鏈狀胺基甲酸酯、N-甲基吡咯啶酮等環狀醯胺、N,N-二甲基咪唑啶酮等環狀脲、硼酸三甲酯、硼酸三乙酯、硼酸三丁酯、硼酸三辛酯、硼酸三甲基矽烷酯等硼化合物、及下述通式所表示之聚乙二醇衍生物等。 In the nonaqueous electrolytic solution of the present invention, other solvents than the above may be contained as the nonaqueous solvent. Specific examples of the other solvent include a chain urethane such as decylamine such as dimethylformamide or a dimethylamino-N,N-aminocarbamic acid dimethyl ester or N-methylpyrrolidine. Cyclic urea such as ketone or cyclic urea such as N,N-dimethylimidazolidone, trimethyl borate, triethyl borate, tributyl borate, trioctyl borate, trimethyldecyl borate, etc. A compound, a polyethylene glycol derivative represented by the following formula, and the like.

HO(CH2CH2O)aH HO(CH 2 CH 2 O) a H

HO[CH2CH(CH3)O]bH HO[CH 2 CH(CH 3 )O] b H

CH3O(CH2CH2O)cH CH 3 O(CH 2 CH 2 O) c H

CH3O[CH2CH(CH3)O]dH CH 3 O[CH 2 CH(CH 3 )O] d H

CH3O(CH2CH2O)eCH3 CH 3 O(CH 2 CH 2 O) e CH 3

CH3O[CH2CH(CH3)O]fCH3 CH 3 O[CH 2 CH(CH 3 )O] f CH 3

C9H19PhO(CH2CH2O)g[CH(CH3)O]hCH3 C 9 H 19 PhO(CH 2 CH 2 O) g [CH(CH 3 )O] h CH 3

(Ph為苯基) (Ph is phenyl)

CH3O[CH2CH(CH3)O]iCO[OCH(CH3)CH2]jOCH3 CH 3 O[CH 2 CH(CH 3 )O] i CO[OCH(CH 3 )CH 2 ] j OCH 3

上述式中，a~f為5~250之整數，g~j為2~249之整數，5≦g+h≦250，5≦i+j≦250。 In the above formula, a~f is an integer of 5 to 250, and g~j is an integer of 2 to 249, 5≦g+h≦250, 5≦i+j≦250.

[鋰二次電池] [Lithium secondary battery]

本發明中之鋰二次電池包含：本發明中之上述電池用非水電解液、正極、以及負極。通常，於負極與正極之間設置分隔件。 The lithium secondary battery of the present invention comprises the above-mentioned nonaqueous electrolyte for a battery, a positive electrode, and a negative electrode in the present invention. Usually, a separator is provided between the negative electrode and the positive electrode.

以下，對於鋰二次電池之構成進行說明。 Hereinafter, the configuration of the lithium secondary battery will be described.

(正極) (positive electrode)

作為構成上述正極之正極活性物質，可舉出：MoS2、TiS2、MnO2、V2O5等過渡金屬氧化物或過渡金屬硫化物、LiCoO2、LiMnO2、LiMn2O4、LiNiO2、LiNixCo(1-x)O2[0<X<1]、LiFePO4等包含鋰與過渡金屬之複合氧化物、聚苯胺、聚噻吩、聚吡咯、聚乙炔、多并苯(polyacene)、二巰基噻二唑、聚苯胺複合體等導電性高分子材料等。該等之中，尤佳為包含鋰與過渡金屬之複合氧化物。於負極為鋰金屬或鋰合金之情形時，亦可使用碳材料作為正極。又，作為正極，亦可使用鋰與過渡金屬之複合氧化物、與碳材料之混合物。 Examples of the positive electrode active material constituting the positive electrode include a transition metal oxide such as MoS 2 , TiS 2 , MnO 2 , and V 2 O 5 or a transition metal sulfide, LiCoO 2 , LiMnO 2 , LiMn 2 O 4 , and LiNiO 2 . , LiNi x Co (1 - x) O 2 [0<X<1], LiFePO 4 and the like, a composite oxide containing lithium and a transition metal, polyaniline, polythiophene, polypyrrole, polyacetylene, polyacene Conductive polymer materials such as dimercaptothiadiazole and polyaniline composite. Among these, a composite oxide containing lithium and a transition metal is particularly preferable. In the case where the negative electrode is a lithium metal or a lithium alloy, a carbon material may also be used as the positive electrode. Further, as the positive electrode, a mixture of a composite oxide of lithium and a transition metal and a carbon material may be used.

上述正極活性物質可使用1種，亦可混合2種以上使用。於正極活性物質之導電性不充分之情形時，可與導電性助劑一併使用而構成正極。作為導電性助劑，可例示：碳黑、非晶晶鬚、石墨等碳材料。 One type of the above-mentioned positive electrode active material may be used, or two or more types may be used in combination. When the conductivity of the positive electrode active material is insufficient, it can be used together with a conductive auxiliary agent to constitute a positive electrode. Examples of the conductive auxiliary agent include carbon materials such as carbon black, amorphous whiskers, and graphite.

(負極) (negative electrode)

構成上述負極之負極活性物質可使用自由金屬鋰、含鋰合金、可與鋰合金化之金屬或合金、可摻雜-脫摻雜鋰離子之氧化物、可摻雜-脫摻雜鋰離子之過渡金屬氮化物、及可摻雜-脫摻雜鋰離子之碳材料所組成之群組中選擇之至少1種(可單獨使用亦可使用包含該等2種以上之混合物)。 The negative electrode active material constituting the above negative electrode may be a free metal lithium, a lithium-containing alloy, a metal or alloy which can be alloyed with lithium, an oxide capable of doping-dedoping lithium ions, and a doping-de-doping lithium ion. At least one selected from the group consisting of a transition metal nitride and a carbon material capable of doping-dedoping lithium ions (may be used alone or in combination of two or more kinds thereof).

作為可與鋰(或鋰離子)合金化之金屬或合金，可舉出：矽、矽合金、 錫、錫合金等。又，亦可為鈦酸鋰。 Examples of the metal or alloy that can be alloyed with lithium (or lithium ion) include ruthenium and osmium alloys. Tin, tin alloy, etc. Further, it may be lithium titanate.

其中，較佳為可摻雜-脫摻雜鋰離子之碳材料。作為此種碳材料，可舉出：碳黑、活性碳、石墨材料(人造石墨、天然石墨)、非晶質碳材料等。上述碳材料之形態亦可為纖維狀、球狀、馬鈴薯狀、小片狀(flake)中任一種之形態。 Among them, a carbon material which can be doped-dedoped with lithium ions is preferred. Examples of such a carbon material include carbon black, activated carbon, graphite material (artificial graphite, natural graphite), and amorphous carbon material. The form of the carbon material may be in the form of any of a fibrous shape, a spherical shape, a potato shape, and a flake shape.

作為上述非晶質碳材料，具體而言，可例示：硬碳、焦炭、於1500℃以下煅燒之中間相碳微球(MCMB)、中間相瀝青碳纖維(MCF)等。 Specific examples of the amorphous carbon material include hard carbon, coke, mesocarbon microbeads (MCMB) calcined at 1500 ° C or lower, mesophase pitch carbon fibers (MCF), and the like.

作為上述石墨材料，可舉出：天然石墨、人造石墨。作為人造石墨，可使用：石墨化MCMB(Mesophase Carbon Micro Beads，中間相碳微球)、石墨化MCF(Mesophase pitch-based Carbon Fiber，中間相瀝青碳纖維)等。又，作為石墨材料，亦可使用含有硼者等。又，作為石墨材料，亦可使用：以金、鉑、銀、銅、錫等金屬被覆者、以非晶質碳被覆者、混合有非晶質碳與石墨者。 Examples of the graphite material include natural graphite and artificial graphite. As the artificial graphite, graphitized MCMB (Mesophase Carbon Micro Beads), graphitized MCF (Mesophase pitch-based Carbon Fiber), or the like can be used. Further, as the graphite material, those containing boron or the like can also be used. Further, as the graphite material, those coated with a metal such as gold, platinum, silver, copper or tin, those coated with amorphous carbon, and amorphous carbon and graphite may be used.

該等碳材料可使用1種，亦可混合2種以上使用。作為上述碳材料，尤佳為以X射線分析所測定之(002)面之面間隔d(002)為0.340nm以下之碳材料。又，作為碳材料，亦較佳為真密度為1.70g/cm3以上之石墨或具有接近其之性質之高結晶性碳材料。若使用如上之碳材料，則可進一步提高電池之能量密度。 These carbon materials may be used alone or in combination of two or more. As the carbon material, a carbon material having a surface spacing d (002) of (002) plane measured by X-ray analysis of 0.340 nm or less is particularly preferable. Further, as the carbon material, graphite having a true density of 1.70 g/cm 3 or more or a highly crystalline carbon material having properties close to the same is preferable. If the above carbon material is used, the energy density of the battery can be further increased.

(分隔件) (separator)

分隔件係將正極與負極電氣絕緣且穿透鋰離子之膜，例示有多孔性膜或高分子電解質。 The separator is a film that electrically insulates the positive electrode from the negative electrode and penetrates lithium ions, and is exemplified by a porous film or a polymer electrolyte.

作為上述多孔性膜，可較佳地使用微多孔性高分子薄膜，作為材 質，可例示：聚烯烴、聚醯亞胺、聚偏二氟乙烯、聚酯等。 As the porous film, a microporous polymer film can be preferably used as the material. The quality can be exemplified by polyolefin, polyimine, polyvinylidene fluoride, polyester, and the like.

尤佳為多孔性聚烯烴，具體而言，可例示：多孔性聚乙烯薄膜、多孔性聚丙烯薄膜、或多孔性之聚乙烯薄膜與聚丙烯薄膜之多層薄膜。亦可於多孔性聚烯烴薄膜上，塗佈熱穩定性優異之其他樹脂。 More preferably, it is a porous polyolefin, and specifically, a porous polyethylene film, a porous polypropylene film, or a multilayer film of a porous polyethylene film and a polypropylene film. Other resins excellent in thermal stability can also be applied to the porous polyolefin film.

作為上述高分子電解質，可舉出：將鋰鹽溶解之高分子、或以電解液膨潤之高分子等。 Examples of the polymer electrolyte include a polymer in which a lithium salt is dissolved, or a polymer which is swollen with an electrolytic solution.

本發明之非水電解液亦可以使高分子膨潤而獲得高分子電解質為目的而使用。 The nonaqueous electrolytic solution of the present invention can also be used for the purpose of swelling a polymer to obtain a polymer electrolyte.

(電池之構成) (Battery composition)

本發明之實施形態之鋰二次電池包含：上述負極活性物質、正極活性物質及分隔件。 A lithium secondary battery according to an embodiment of the present invention includes the negative electrode active material, a positive electrode active material, and a separator.

本發明之鋰二次電池可採用各種公知之形狀，可形成為圓筒型、硬幣型、方型、薄膜型及其他任意之形狀。然而，電池之基本構造係無論形狀均相同，可視目的而實施設計變更。 The lithium secondary battery of the present invention can be formed into various known shapes, and can be formed into a cylindrical shape, a coin shape, a square shape, a film type, and any other shape. However, the basic structure of the battery is the same as the shape, and the design change can be implemented for the purpose.

再者，本發明之鋰二次電池亦可為將包含負極、正極、以及上述本發明之非水電解液之鋰二次電池(充放電前之鋰二次電池)進行充放電所獲得之鋰二次電池。 In addition, the lithium secondary battery of the present invention may be a lithium obtained by charging and discharging a lithium secondary battery (a lithium secondary battery before charging and discharging) including a negative electrode, a positive electrode, and the above-described nonaqueous electrolytic solution of the present invention. Secondary battery.

即，本發明之鋰二次電池亦可為藉由首先製作包含負極、正極、以及上述本發明之非水電解液之充放電前之鋰二次電池，繼而，將該充放電前之鋰二次電池進行1次以上充放電所製作之鋰二次電池(經充放電之鋰二次電池)。 That is, the lithium secondary battery of the present invention may be formed by first preparing a lithium secondary battery including a negative electrode, a positive electrode, and the above-described nonaqueous electrolytic solution of the present invention, and then charging and discharging the lithium secondary battery. A lithium secondary battery (charged and discharged lithium secondary battery) produced by charging and discharging the secondary battery one time or more.

本發明之鋰二次電池之用途並無特別限定，可用於各種公知之用途。例如無論筆記型電腦、移動式電腦、行動電話、耳機式 音響、視訊攝影機、液晶電視、攜帶式清潔器、電子記事本、計算器、收音機、備用電源用途、馬達、汽車、電動汽車、機車、電動機車、腳踏車、電動腳踏車、照明器具、遊戲機、時鐘、電動工具、相機等小型行動機器、大型機器，均可廣泛地應用。 The use of the lithium secondary battery of the present invention is not particularly limited and can be used in various known applications. For example, whether it is a notebook computer, a mobile computer, a mobile phone, or a headset. Audio, video camera, LCD TV, portable cleaner, electronic notebook, calculator, radio, backup power supply, motor, car, electric car, locomotive, electric car, bicycle, electric bicycle, lighting, game console, clock Small mobile devices such as power tools and cameras, and large machines can be widely used.

[實施例] [Examples]

以下，根據實施例更具體地說明本發明，但本發明並不受該等實施例限制。再者，於以下之實施例中，「%」表示質量%。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited by the examples. Further, in the following examples, "%" means mass%.

[實施例1] [Example 1]

向具備熱電偶、回流冷卻器、及以液態氮所冷卻之氣體收集用捕集器之內容量250ml之Teflon(註冊商標)製反應容器中，於惰性氣體環境下，添加二氟磷酸-半水合物13.6g(0.12莫耳)，繼而，一面攪拌一面添加氟磺酸50.4g(0.49莫耳)。 To a Teflon (registered trademark) reaction vessel containing a thermocouple, a reflux condenser, and a gas collection trap cooled by liquid nitrogen, 250 ml of a Teflon (registered trademark) reaction vessel was added with difluorophosphoric acid-hemihydrate in an inert gas atmosphere. 13.6 g (0.12 mol) was added, and then 50.4 g (0.49 mol) of fluorosulfonic acid was added while stirring.

於一面將溫度保持為室溫(20℃~30℃)一面進行24小時該反應時，產生4.83g之氣體。將所產生之氣體藉由FT-IR(Fourier Transform-Infrared Radiation，傅立葉轉換紅外線光譜)(製品名FTIR8000，島津製作所製造)進行分析，結果可知其為五氟化磷。產率為(以磷含量基準計)31%。 When the reaction was carried out for 24 hours while maintaining the temperature at room temperature (20 ° C to 30 ° C), 4.83 g of a gas was produced. The generated gas was analyzed by FT-IR (Fourier Transform-Infrared Radiation) (product name: FTIR 8000, manufactured by Shimadzu Corporation), and it was found to be phosphorus pentafluoride. The yield was 31% based on the phosphorus content.

[實施例2] [Embodiment 2]

向具備熱電偶、回流冷卻器、及以液態氮所冷卻之氣體收集用捕集器之內容量250ml之Teflon(註冊商標)製反應容器中，於惰性氣體環境下，添加氟磺酸35.2g(0.35莫耳)，進而，一面攪拌一面添加五氧化二磷9.87g(0.07莫耳)，進行溶解。繼而，將氣體之無水氟化氫7.0 g(0.35莫耳)進行攪拌及冷卻，同時將溫度保持為0℃~30℃之範圍，並且花費40分鐘進行添加。 To a reaction vessel made of Teflon (registered trademark) having a content of 250 ml containing a thermocouple, a reflux condenser, and a gas collection trap cooled by liquid nitrogen, 35.2 g of fluorosulfonic acid was added under an inert gas atmosphere. Further, 0.37 g (0.07 mol) of phosphorus pentoxide was added while stirring, and the solution was dissolved. Then, the gas is anhydrous hydrogen fluoride 7.0 G (0.35 mol) was stirred and cooled while maintaining the temperature in the range of 0 ° C to 30 ° C, and it took 40 minutes to add.

將所獲得之反應液藉由31PNMR(製品名ECX-400P，日本電子製造)及19FNMR(製品名ECX-400P，日本電子製造)進行分析，結果含有：氟磺酸47.7質量%、二氟磷酸9.0質量%、氧氟化磷6.3質量%、磷酸1.7質量%、單氟磷酸0.54質量%。 The obtained reaction liquid was analyzed by 31 P NMR (product name ECX-400P, manufactured by JEOL Ltd.) and 19 F NMR (product name ECX-400P, manufactured by JEOL Ltd.), and the result contained: fluorosulfonic acid 47.7 mass%, difluoro 9.0 mass% of phosphoric acid, 6.3 mass% of phosphorus oxyfluoride, 1.7% by mass of phosphoric acid, and 0.54% by mass of monofluorophosphoric acid.

將該反應液緩緩加熱至130℃，產生五氟化磷，並捕捉至以液態氮所冷卻之捕集器中。所捕捉之五氟化磷之重量為11.6g，藉由FT-IR進行分析，結果含有：作為雜質之氧氟化磷4.8質量%、氟化氫3000wtppm。五氟化磷之產率為(以磷含量基準計)62%。 The reaction solution was slowly heated to 130 ° C to produce phosphorus pentafluoride and captured into a trap cooled with liquid nitrogen. The weight of the phosphorus pentafluoride captured was 11.6 g, and analysis by FT-IR revealed that 4.8 mass% of phosphorus oxyfluoride as an impurity and 3000 wtppm of hydrogen fluoride. The yield of phosphorus pentafluoride was 62% based on the phosphorus content.

[實施例3] [Example 3]

向具備熱電偶、回流冷卻器、及以液態氮所冷卻之氣體收集用捕集器之內容量250ml之Teflon(註冊商標)製反應容器中，於惰性氣體環境下，添加氟磺酸34.9g(0.35莫耳)，進而，一面攪拌一面添加五氧化二磷9.95g(0.07莫耳)，進行溶解。繼而，將氣體之無水氟化氫13.0g(0.65莫耳)進行攪拌及冷卻，同時將溫度保持為0℃~30℃之範圍，並且花費70分鐘進行添加。 To a reaction vessel made of Teflon (registered trademark) having a content of 250 ml containing a thermocouple, a reflux condenser, and a gas collection trap cooled by liquid nitrogen, 34.9 g of fluorosulfonic acid was added under an inert gas atmosphere ( 0.35 mol. Further, 9.95 g (0.07 mol) of phosphorus pentoxide was added while stirring, and the solution was dissolved. Then, 13.0 g (0.65 mol) of anhydrous hydrogen fluoride of the gas was stirred and cooled while maintaining the temperature in the range of 0 ° C to 30 ° C, and it took 70 minutes to carry out the addition.

將所獲得之反應液藉由31PNMR(製品名ECX-400P，日本電子製造)及19FNMR(製品名ECX-400P，日本電子製造)進行分析，結果含有：氟磺酸61.3質量%、二氟磷酸7.4質量%、氧氟化磷7.2質量%、單氟磷酸0.57質量%。 The obtained reaction liquid was analyzed by 31 P NMR (product name ECX-400P, manufactured by JEOL Ltd.) and 19 F NMR (product name ECX-400P, manufactured by JEOL Ltd.), and the result contained: fluorosulfonic acid 61.3% by mass, difluoro 7.4 mass% of phosphoric acid, 7.2 mass% of phosphorus oxyfluoride, and 0.57 mass% of monofluorophosphate.

將該反應液緩緩加熱至130℃，產生五氟化磷，並捕捉至以液態氮所冷卻之捕集器中。所捕捉之五氟化磷之重量為17.9g，藉由FT-IR(製 品名FTIR8000，島津製作所製造)進行分析，結果含有：作為雜質之氧氟化磷0.87質量%、氟化氫2400wtppm。五氟化磷之產率為(以磷含量基準計)99%以上。 The reaction solution was slowly heated to 130 ° C to produce phosphorus pentafluoride and captured into a trap cooled with liquid nitrogen. The weight of the captured phosphorus pentafluoride is 17.9g, by FT-IR The product name FTIR 8000 (manufactured by Shimadzu Corporation) was analyzed and found to contain 0.87 mass% of phosphorus oxyfluoride as an impurity and 2400 wtppm of hydrogen fluoride. The yield of phosphorus pentafluoride is (more than 99% based on the phosphorus content).

[實施例4] [Example 4]

向具備熱電偶、回流冷卻器、及以液態氮所冷卻之氣體收集用捕集器之內容量250ml之Teflon(註冊商標)製反應容器中，於惰性氣體環境下，添加氟磺酸35.7g(0.36莫耳)，進而，一面攪拌一面添加五氧化二磷5.02g(0.035莫耳)，進行溶解。繼而，將氣體之無水氟化氫7.0g(0.36莫耳)進行攪拌並冷卻，同時將溫度保持為0℃~30℃之範圍，並且花費70分鐘進行添加。 To a reaction vessel made of Teflon (registered trademark) having a content of 250 ml containing a thermocouple, a reflux condenser, and a gas collection trap cooled by liquid nitrogen, 35.7 g of fluorosulfonic acid was added under an inert gas atmosphere ( 0.36 mol. Further, 5.02 g (0.035 mol) of phosphorus pentoxide was added while stirring, and the solution was dissolved. Then, 7.0 g (0.36 mol) of anhydrous hydrogen fluoride of the gas was stirred and cooled while maintaining the temperature in the range of 0 ° C to 30 ° C, and it took 70 minutes for the addition.

將所獲得之反應液藉由31PNMR(製品名ECX-400P，日本電子製造)及19FNMR(製品名ECX-400P，日本電子製造)進行分析，結果含有：氟磺酸74.8質量%、二氟磷酸4.1質量%、氧氟化磷8.0質量%、單氟磷酸0.60質量%。 The obtained reaction liquid was analyzed by 31 P NMR (product name ECX-400P, manufactured by JEOL Ltd.) and 19 F NMR (product name ECX-400P, manufactured by JEOL Ltd.), and the result contained: fluorosulfonic acid 74.8% by mass, difluoro 4.1% by mass of phosphoric acid, 8.0% by mass of phosphorus oxyfluoride, and 0.60% by mass of monofluorophosphoric acid.

將該反應液緩緩加熱至130℃，產生五氟化磷，並捕捉至以液態氮所冷卻之捕集器中。所捕捉之五氟化磷之重量為8.9g，藉由FT-IR進行分析，結果含有：作為雜質之氧氟化磷0.34質量%、氟化氫900wtppm。五氟化磷之產率為(以磷含量基準計)99%以上。 The reaction solution was slowly heated to 130 ° C to produce phosphorus pentafluoride and captured into a trap cooled with liquid nitrogen. The weight of the phosphorus pentafluoride trapped was 8.9 g, and analysis by FT-IR revealed that the phosphorus oxyfluoride as an impurity was 0.34% by mass and the hydrogen fluoride was 900 wtppm. The yield of phosphorus pentafluoride is (more than 99% based on the phosphorus content).

[實施例5] [Example 5]

向具備熱電偶、回流冷卻器、及以液態氮所冷卻之氣體收集用捕集器之內容量250ml之Teflon(註冊商標)製反應容器中，於惰性氣體環境下，添加氟磺酸35.2g(0.35莫耳)，進而，一面攪拌一面添加五氧 化二磷5.05g(0.036莫耳)，進行溶解。繼而，將氣體之無水氟化氫7.1g(0.35莫耳)進行攪拌並冷卻，同時將溫度保持於0~30℃之範圍，並且花費70分鐘進行添加。 To a reaction vessel made of Teflon (registered trademark) having a content of 250 ml containing a thermocouple, a reflux condenser, and a gas collection trap cooled by liquid nitrogen, 35.2 g of fluorosulfonic acid was added under an inert gas atmosphere. 0.35 mol), and further, add five oxygen while stirring Diammonium phosphate 5.05 g (0.036 mol) was dissolved. Then, 7.1 g (0.35 mol) of anhydrous hydrogen fluoride of the gas was stirred and cooled while maintaining the temperature in the range of 0 to 30 ° C, and it took 70 minutes to carry out the addition.

將所獲得之反應液藉由31PNMR(製品名ECX-400P，日本電子製造)及19FNMR(製品名ECX-400P，日本電子製造)進行分析，結果含有：氟磺酸74.4質量%、二氟磷酸4.4質量%、氧氟化磷8.2質量%、單氟磷酸0.50質量%。 The obtained reaction liquid was analyzed by 31 P NMR (product name ECX-400P, manufactured by JEOL Ltd.) and 19 F NMR (product name ECX-400P, manufactured by JEOL Ltd.), and the result contained: fluorosulfonic acid 74.4% by mass, difluoro 4.4 mass% of phosphoric acid, 8.2 mass% of phosphorus oxyfluoride, and 0.50 mass% of monofluorophosphate.

將該反應液緩緩加熱至100℃，產生五氟化磷，並捕捉至以液態氮所冷卻之捕集器中。所捕捉之五氟化磷之重量為8.9g，藉由FT-IR進行分析，結果含有：作為雜質之氧氟化磷0.2質量%、氟化氫1500wtppm。五氟化磷之產率為(以磷含量基準計)99%。 The reaction solution was slowly heated to 100 ° C to produce phosphorus pentafluoride and captured into a trap cooled with liquid nitrogen. The weight of the phosphorus pentafluoride captured was 8.9 g, and analysis by FT-IR revealed that 0.2% by mass of phosphorus oxyfluoride as an impurity and 1,500 wtppm of hydrogen fluoride. The yield of phosphorus pentafluoride is (based on the phosphorus content) 99%.

[實施例6] [Embodiment 6]

向具備熱電偶、回流冷卻器、及以液態氮所冷卻之氣體收集用捕集器之內容量250ml之Teflon(註冊商標)製反應容器中，於惰性氣體環境下，添加氟磺酸35.1g(0.35莫耳)，進而，一面攪拌一面添加五氧化二磷5.09g(0.036莫耳)，進行溶解。繼而，將氣體之無水氟化氫7.0g(0.35莫耳)進行攪拌及冷卻，同時將溫度保持為0℃~30℃之範圍，並且花費70分鐘進行添加。 To a reaction vessel made of Teflon (registered trademark) having a content of 250 ml containing a thermocouple, a reflux condenser, and a gas collection trap cooled by liquid nitrogen, 35.1 g of fluorosulfonic acid was added under an inert gas atmosphere. 0.35 mol. Further, 5.09 g (0.036 mol) of phosphorus pentoxide was added while stirring, and the solution was dissolved. Then, 7.0 g (0.35 mol) of anhydrous hydrogen fluoride gas was stirred and cooled while maintaining the temperature in the range of 0 ° C to 30 ° C, and it took 70 minutes to carry out the addition.

將所獲得之反應液藉由31PNMR(製品名ECX-400P，日本電子製造)及19FNMR(製品名ECX-400P，日本電子製造)進行分析，結果含有：氟磺酸75.0質量%、二氟磷酸4.0質量%、氧氟化磷7.8質量%、單氟磷酸0.66質量%。 The obtained reaction liquid was analyzed by 31 P NMR (product name ECX-400P, manufactured by JEOL Ltd.) and 19 F NMR (product name ECX-400P, manufactured by JEOL Ltd.), and the result contained: fluorosulfonic acid 75.0% by mass, difluoro 4.0% by mass of phosphoric acid, 7.8% by mass of phosphorus oxyfluoride, and 0.66% by mass of monofluorophosphate.

將該反應液緩緩加熱至80℃，產生五氟化磷，並捕捉至以液態氮 所冷卻之捕集器中。所捕捉之五氟化磷之重量為7.4g，藉由FT-IR進行分析，結果含有：作為雜質之氧氟化磷1.0質量%、氟化氫900wtppm。五氟化磷之產率為(以磷含量基準計)81%。 The reaction solution was slowly heated to 80 ° C to produce phosphorus pentafluoride and captured to liquid nitrogen. Cooled in the trap. The weight of the phosphorus pentafluoride trapped was 7.4 g, and analysis by FT-IR revealed that 1.0 mass% of phosphorus oxyfluoride as an impurity and 900 wtppm of hydrogen fluoride. The yield of phosphorus pentafluoride was 81% based on the phosphorus content.

[實施例7] [Embodiment 7]

向具備熱電偶、回流冷卻器、及以液態氮所冷卻之氣體收集用捕集器之內容量250ml之Teflon(註冊商標)製反應容器中，於惰性氣體環境下，添加氟磺酸35.7g(0.35莫耳)，進而，一面攪拌一面添加五氧化二磷5.02g(0.036莫耳)，進行溶解。繼而，將氣體之無水氟化氫7.0g(0.35莫耳)進行攪拌及冷卻，同時將溫度保持為0℃~30℃之範圍，並且花費70分鐘進行添加。 To a reaction vessel made of Teflon (registered trademark) having a content of 250 ml containing a thermocouple, a reflux condenser, and a gas collection trap cooled by liquid nitrogen, 35.7 g of fluorosulfonic acid was added under an inert gas atmosphere ( 0.35 mol. Further, 5.02 g (0.036 mol) of phosphorus pentoxide was added while stirring, and the solution was dissolved. Then, 7.0 g (0.35 mol) of anhydrous hydrogen fluoride gas was stirred and cooled while maintaining the temperature in the range of 0 ° C to 30 ° C, and it took 70 minutes to carry out the addition.

將所獲得之反應液藉由31PNMR(製品名ECX-400P，日本電子製造)及19FNMR(製品名ECX-400P，日本電子製造)進行分析，結果含有：氟磺酸74.8質量%、二氟磷酸4.1質量%、氧氟化磷8.0質量%、單氟磷酸0.60質量%。 The obtained reaction liquid was analyzed by 31 P NMR (product name ECX-400P, manufactured by JEOL Ltd.) and 19 F NMR (product name ECX-400P, manufactured by JEOL Ltd.), and the result contained: fluorosulfonic acid 74.8% by mass, difluoro 4.1% by mass of phosphoric acid, 8.0% by mass of phosphorus oxyfluoride, and 0.60% by mass of monofluorophosphoric acid.

將該反應液緩緩加熱至40℃，產生五氟化磷，並捕捉至以液態氮所冷卻之捕集器中。所捕捉之五氟化磷之重量為6.6g，藉由FT-IR進行分析，結果含有：作為雜質之氧氟化磷1.2質量%、氟化氫530wtppm。五氟化磷之產率為(以磷含量基準計)73%。 The reaction solution was slowly heated to 40 ° C to produce phosphorus pentafluoride and captured into a trap cooled with liquid nitrogen. The weight of the phosphorus pentafluoride trapped was 6.6 g, and analysis by FT-IR revealed that 1.2% by mass of phosphorus oxyfluoride as an impurity and 530 wtppm of hydrogen fluoride. The yield of phosphorus pentafluoride was 73% based on the phosphorus content.

[實施例8] [Embodiment 8]

向具備熱電偶、回流冷卻器、及以液態氮所冷卻之氣體收集用捕集器之內容量250ml之Teflon(註冊商標)製反應容器中，於惰性氣體環境下，添加85%磷酸8.07g(0.07莫耳)，繼而，一面攪拌一面添加氟 磺酸56.0g(0.56莫耳)。 To a reaction vessel made of Teflon (registered trademark) containing 250 ml of a gas trap, which is equipped with a thermocouple, a reflux condenser, and a gas collection trap cooled by liquid nitrogen, 80.7 g of 85% phosphoric acid was added under an inert gas atmosphere ( 0.07 mol), then add fluorine while stirring The sulfonic acid was 56.0 g (0.56 mol).

將該反應液緩緩加熱至130℃，產生五氟化磷，並捕捉至以液態氮所冷卻之捕集器中。所捕捉之五氟化磷之重量為6.6g，藉由FT-IR進行分析，結果含有：作為雜質之氧氟化磷1.4質量%、氟化氫230wtppm。五氟化磷之產率為(以磷含量基準計)75%。 The reaction solution was slowly heated to 130 ° C to produce phosphorus pentafluoride and captured into a trap cooled with liquid nitrogen. The weight of the phosphorus pentafluoride trapped was 6.6 g, and analysis by FT-IR revealed that 1.4% by mass of phosphorus oxyfluoride as an impurity and 230 wtppm of hydrogen fluoride. The yield of phosphorus pentafluoride is 75% (based on the phosphorus content).

[實施例9] [Embodiment 9]

向具備熱電偶、回流冷卻器、及以液態氮所冷卻之氣體收集用捕集器之內容量250ml之Teflon(註冊商標)製反應容器中，於惰性氣體環境下，添加單氟磷酸7.00g(0.07莫耳)，繼而，一面攪拌一面添加氟磺酸49.0g(0.49莫耳)。 To a reaction vessel made of Teflon (registered trademark) having a content of 250 ml containing a thermocouple, a reflux condenser, and a gas collection trap cooled by liquid nitrogen, 7.00 g of monofluorophosphate was added under an inert gas atmosphere ( 0.07 mol. Then, 49.0 g (0.49 mol) of fluorosulfonic acid was added while stirring.

將該反應液緩緩加熱至130℃，產生五氟化磷，並捕捉至以液態氮所冷卻之捕集器中。所捕捉之五氟化磷之重量為6.8g，藉由FT-IR進行分析，結果含有：作為雜質之氧氟化磷1.3質量%、氟化氫250wtppm。五氟化磷之產率為(以磷含量基準計)77%。 The reaction solution was slowly heated to 130 ° C to produce phosphorus pentafluoride and captured into a trap cooled with liquid nitrogen. The weight of the phosphorus pentafluoride trapped was 6.8 g, and analysis by FT-IR revealed that: 1.3 mass% of phosphorus oxyfluoride as an impurity and 250 wtppm of hydrogen fluoride. The yield of phosphorus pentafluoride was 77% based on the phosphorus content.

[實施例10] [Embodiment 10]

向具備熱電偶、回流冷卻器、及以液態氮所冷卻之氣體收集用捕集器之內容量250ml之Teflon(註冊商標)製反應容器中，於惰性氣體環境下，添加二氟磷酸-半水合物7.77g(0.07莫耳)，繼而，一面攪拌一面添加氟磺酸42.0g(0.42莫耳)。 To a Teflon (registered trademark) reaction vessel containing a thermocouple, a reflux condenser, and a gas collection trap cooled by liquid nitrogen, 250 ml of a Teflon (registered trademark) reaction vessel was added with difluorophosphoric acid-hemihydrate in an inert gas atmosphere. 7.77 g (0.07 mol) was added, and then 42.0 g (0.42 mol) of fluorosulfonic acid was added while stirring.

將該反應液緩緩加熱至130℃，產生五氟化磷，並捕捉至以液態氮所冷卻之捕集器中。所捕捉之五氟化磷之重量為7.1g，藉由FT-IR進行分析，結果含有：作為雜質之氧氟化磷1.2質量%、氟化氫300 wtppm。五氟化磷之產率為(以磷含量基準計)80%。 The reaction solution was slowly heated to 130 ° C to produce phosphorus pentafluoride and captured into a trap cooled with liquid nitrogen. The weight of the phosphorus pentafluoride captured was 7.1 g, and analyzed by FT-IR, and the result contained: 1.2% by mass of phosphorus oxyfluoride as an impurity, and 300 ppm of hydrogen fluoride. Wtppm. The yield of phosphorus pentafluoride is 80% based on the phosphorus content.

[實施例11] [Example 11]

向具備熱電偶、回流冷卻器、及以液態氮所冷卻之氣體收集用捕集器之內容量250ml之Teflon(註冊商標)製反應容器中，於惰性氣體環境下，添加氟磺酸84.1g(0.84莫耳)，進而，一面攪拌一面添加五氧化二磷4.97g(0.035莫耳)，進行溶解。繼而，將氣體之無水氟化氫1.4g(0.07莫耳)進行攪拌及冷卻，同時將溫度保持為0℃~30℃之範圍，並且花費10分鐘進行添加。 To a reaction vessel made of Teflon (registered trademark) having a content of 250 ml containing a thermocouple, a reflux condenser, and a gas collection trap cooled by liquid nitrogen, 84.1 g of fluorosulfonic acid was added under an inert gas atmosphere. 0.84 mol, and further, 4.97 g (0.035 mol) of phosphorus pentoxide was added while stirring, and the solution was dissolved. Then, 1.4 g (0.07 mol) of anhydrous hydrogen fluoride of the gas was stirred and cooled while maintaining the temperature in the range of 0 ° C to 30 ° C, and it took 10 minutes to carry out the addition.

將所獲得之反應液藉由31PNMR(製品名ECX-400P，日本電子製造)及19FNMR(製品名ECX-400P，日本電子製造)進行分析，結果含有：氟磺酸83.4質量%、氧氟化磷7.7質量%、單氟磷酸0.50質量%。 The obtained reaction liquid was analyzed by 31 P NMR (product name ECX-400P, manufactured by JEOL Ltd.) and 19 F NMR (product name ECX-400P, manufactured by JEOL Ltd.), and the result contained: fluorosulfonic acid 83.4% by mass, oxygen fluoride Phosphorus was 7.7% by mass and monofluorophosphate was 0.50% by mass.

將該反應液緩緩加熱至130℃，產生五氟化磷，並捕捉至以液態氮所冷卻之捕集器中。所捕捉之五氟化磷之重量為0.4g，藉由FT-IR進行分析，結果含有：作為雜質之氧氟化磷2質量%、氟化氫200wtppm。五氟化磷之產率為(以磷含量基準計)9%。 The reaction solution was slowly heated to 130 ° C to produce phosphorus pentafluoride and captured into a trap cooled with liquid nitrogen. The weight of the phosphorus pentafluoride captured was 0.4 g, and analysis by FT-IR revealed that 2% by mass of phosphorus oxyfluoride as an impurity and 200 ppm by weight of hydrogen fluoride. The yield of phosphorus pentafluoride was 9% (based on the phosphorus content).

[實施例12] [Embodiment 12]

向具備熱電偶、回流冷卻器、及以液態氮所冷卻之氣體收集用捕集器之內容量250ml之Teflon(註冊商標)製反應容器中，於惰性氣體環境下，添加氟磺酸10.5g(0.11莫耳)，進而，一面攪拌一面添加五氧化二磷4.97g(0.035莫耳)，進行溶解。繼而，將氣體之無水氟化氫9.1g(0.46莫耳)進行攪拌及冷卻，同時將溫度保持為0℃~30℃之範圍，並且花費90分鐘進行添加。 To a reaction vessel made of Teflon (registered trademark) having a content of 250 ml containing a thermocouple, a reflux condenser, and a gas collection trap cooled by liquid nitrogen, 10.5 g of fluorosulfonic acid was added under an inert gas atmosphere. 0.11 mol. Further, 4.97 g (0.035 mol) of phosphorus pentoxide was added while stirring, and the solution was dissolved. Then, 9.1 g (0.46 mol) of anhydrous hydrogen fluoride of the gas was stirred and cooled while maintaining the temperature in the range of 0 ° C to 30 ° C, and it took 90 minutes to carry out the addition.

將所獲得之反應液藉由31PNMR(製品名ECX-400P，日本電子製造)及19FNMR(製品名ECX-400P，日本電子製造)進行分析，結果含有：氟磺酸55.8質量%、二氟磷酸8.7質量%、氧氟化磷6.8質量%、單氟磷酸0.60質量%。 The obtained reaction liquid was analyzed by 31 P NMR (product name ECX-400P, manufactured by JEOL Ltd.) and 19 F NMR (product name ECX-400P, manufactured by JEOL Ltd.), and the result contained: fluorosulfonic acid 55.8 mass%, difluoro 8.7% by mass of phosphoric acid, 6.8% by mass of phosphorus oxyfluoride, and 0.60% by mass of monofluorophosphoric acid.

將該反應液緩緩加熱至130℃，產生五氟化磷，並捕捉至以液態氮所冷卻之捕集器中。所捕捉之五氟化磷之重量為3.1g，藉由FT-IR進行分析，結果含有：作為雜質之氧氟化磷1.2質量%、氟化氫550wtppm。五氟化磷之產率為(以磷含量基準計)70%。 The reaction solution was slowly heated to 130 ° C to produce phosphorus pentafluoride and captured into a trap cooled with liquid nitrogen. The weight of the phosphorus pentafluoride trapped was 3.1 g, and analysis by FT-IR revealed that 1.2% by mass of phosphorus oxyfluoride as an impurity and 550 wtppm of hydrogen fluoride. The yield of phosphorus pentafluoride is 70% (based on the phosphorus content).

[比較例1] [Comparative Example 1]

向具備熱電偶、回流冷卻器、及以液態氮所冷卻之氣體收集用捕集器之內容量250ml之Teflon(註冊商標)製反應容器中，於惰性氣體環境下，僅添加二氟磷酸-半水合物45.1g(0.41莫耳)。 In a reaction vessel made of Teflon (registered trademark) containing 250 ml of a gas trap, which is equipped with a thermocouple, a reflux condenser, and a gas collection trap cooled by liquid nitrogen, only difluorophosphate-half is added in an inert gas atmosphere. Hydrate 45.1 g (0.41 mol).

將該反應液緩緩加熱至130℃，將所產生之氣體捕捉至以液態氮所冷卻之捕集器中。所捕捉之氣體之重量為7.2g，藉由FT-IR進行分析，結果，主成分為氟化氫，未檢測出五氟化磷。 The reaction solution was slowly heated to 130 ° C, and the generated gas was captured into a trap cooled with liquid nitrogen. The weight of the trapped gas was 7.2 g, and analysis by FT-IR revealed that the main component was hydrogen fluoride, and phosphorus pentafluoride was not detected.

[比較例2] [Comparative Example 2]

向具備熱電偶、回流冷卻器、及以液態氮所冷卻之氣體收集用捕集器之內容量250ml之Teflon(註冊商標)製反應容器中，於惰性氣體環境下，添加過量之氟磺酸43.6g(0.42莫耳)，進而，一面攪拌一面添加五氧化二磷1.69g(0.012莫耳)。繼而，將該反應液緩緩加熱至130℃，但以液態氮所冷卻之捕集器中未捕捉到任何氣體。 To a reaction vessel made of Teflon (registered trademark) containing 250 ml of a gas trap, which is equipped with a thermocouple, a reflux condenser, and a gas collection trap cooled with liquid nitrogen, an excess of fluorosulfonic acid 43.6 was added under an inert gas atmosphere. g (0.42 mol), and further, 1.69 g (0.012 mol) of phosphorus pentoxide was added while stirring. Then, the reaction liquid was slowly heated to 130 ° C, but no gas was trapped in the trap cooled by liquid nitrogen.

[比較例3] [Comparative Example 3]

向具備熱電偶、回流冷卻器、及以液態氮所冷卻之氣體收集用捕集器之內容量250ml之Teflon(註冊商標)製反應容器中，於惰性氣體環境下，添加85%磷酸8.07g(0.07莫耳)，繼而，一面攪拌一面添加氟化氫酸11.21g(0.56莫耳)。 To a reaction vessel made of Teflon (registered trademark) containing 250 ml of a gas trap, which is equipped with a thermocouple, a reflux condenser, and a gas collection trap cooled by liquid nitrogen, 80.7 g of 85% phosphoric acid was added under an inert gas atmosphere ( 0.07 mol. Then, 11.21 g (0.56 mol) of hydrogen fluoride was added while stirring.

將該反應液緩緩加熱至130℃，但於以液態氮所冷卻之捕集器中未捕捉到任何氣體。 The reaction solution was slowly heated to 130 ° C, but no gas was trapped in the trap cooled with liquid nitrogen.

由上述結果可明瞭，根據本發明之五氟化磷之製造方法，與比較例之製造方法相比，可利用藉由低溫加熱之反應而高產率地製造五氟化磷。 From the above results, it is understood that, according to the method for producing phosphorus pentafluoride of the present invention, phosphorus pentafluoride can be produced in a high yield by a reaction of low-temperature heating as compared with the production method of the comparative example.

2013年3月25日提出申請之日本專利申請2013-062613號之揭示中，將其整體內容藉由參照而併入本說明書中。 The disclosure of Japanese Patent Application No. 2013-062613, filed on March 25, 2013, is hereby incorporated by reference.

本說明書中記載之所有文獻、專利申請、及技術標準係與具體且 分別記載有將每個文獻、專利申請、及技術標準藉由參照而併入之情形相同程度地藉由參照而併入本說明書中。 All documents, patent applications, and technical standards described in this specification are specific and specific The disclosure of each of the documents, patent applications, and technical standards by reference is hereby incorporated by reference in its entirety to the extent of the disclosure.

Claims (6)

一種五氟化磷之製造方法，其具有：使下述通式(I)所表示之化合物、與藉由水解而產生氟化氫之化合物進行反應之步驟；上述產生氟化氫之化合物係自FSO2OH(氟磺酸)、FS(O)2F、FS(O)2OS(O)2F、FS(O)2OS(O)2OS(O)2F、FS(O)2[OS(O)2]2OS(O)2F、FS(O)2[OS(O)2]3OS(O)2F、FS(O)2[OS(O)2]4OS(O)2F、及FS(O)2[OS(O)2]5OS(O)2F中選擇之至少1種；上述通式(I)所表示之化合物中所含之磷原子、與上述產生氟化氫之化合物中所含之硫原子之莫耳比(硫原子/磷原子)為1~10；通式(I)：POFx(OH)y[上述通式(I)中，x及y滿足以下之式(1)~式(3)：(1)0≦x≦3(2)0≦y≦3(3)x+y=3]。 A method for producing phosphorus pentafluoride, comprising: a step of reacting a compound represented by the following formula (I) with a compound which generates hydrogen fluoride by hydrolysis; and the above compound for producing hydrogen fluoride is derived from FSO 2 OH ( Fluorosulfonic acid), FS(O) 2 F, FS(O) 2 OS(O) 2 F, FS(O) 2 OS(O) 2 OS(O) 2 F, FS(O) 2 [OS(O ) 2 ] 2 OS(O) 2 F, FS(O) 2 [OS(O) 2 ] 3 OS(O) 2 F, FS(O) 2 [OS(O) 2 ] 4 OS(O) 2 F And at least one selected from the group consisting of FS(O) 2 [OS(O) 2 ] 5 OS(O) 2 F; a phosphorus atom contained in the compound represented by the above formula (I), and the above-mentioned hydrogen fluoride generation The molar ratio (sulfur atom/phosphorus atom) of the sulfur atom contained in the compound is 1 to 10; and the general formula (I): POF x (OH) y [in the above formula (I), x and y satisfy the following Equation (1)~Formula (3): (1) 0≦x≦3(2)0≦y≦3(3)x+y=3]. 如申請專利範圍第1項之五氟化磷之製造方法，其中，上述產生氟化氫之化合物為氟磺酸。 A method for producing phosphorus pentafluoride according to the first aspect of the invention, wherein the hydrogen fluoride-generating compound is fluorosulfonic acid. 如申請專利範圍第1或2項之五氟化磷之製造方法，其中，上述通式(I)所表示之化合物係單氟磷酸及二氟磷酸中之至少一者。 The method for producing phosphorus pentafluoride according to the first or second aspect of the invention, wherein the compound represented by the above formula (I) is at least one of monofluorophosphoric acid and difluorophosphoric acid. 如申請專利範圍第3項之五氟化磷之製造方法，其中，上述單氟磷酸及上述二氟磷酸係使自磷酸、聚磷酸、及五氧化二磷中選擇之至少1種磷化合物與無水氟化氫進行反應所獲得之化合物。 The method for producing a phosphorus pentafluoride according to the third aspect of the invention, wherein the monofluorophosphoric acid and the difluorophosphoric acid are at least one phosphorus compound selected from the group consisting of phosphoric acid, polyphosphoric acid, and phosphorus pentoxide, and anhydrous A compound obtained by carrying out a reaction of hydrogen fluoride. 如申請專利範圍第1或2項之五氟化磷之製造方法，其中，使上述通式(I)所表示之化合物、與上述產生氟化氫之化合物於40℃~ 150℃之範圍內進行反應。 The method for producing phosphorus pentafluoride according to the first or second aspect of the invention, wherein the compound represented by the above formula (I) and the hydrogen fluoride-producing compound are at 40 ° C. The reaction was carried out in the range of 150 °C. 一種六氟化磷酸鋰之製造方法，其具備：藉由申請專利範圍第1至5項中任一項之製造方法而製造五氟化磷之步驟；以及使所製造之五氟化磷與氟化鋰進行反應之步驟。 A method for producing lithium hexafluorophosphate, comprising: a step of producing phosphorus pentafluoride by the production method according to any one of claims 1 to 5; and preparing the phosphorus pentafluoride and fluorine The step of reacting lithium.
TW103110863A 2013-03-25 2014-03-24 Method of producing phosphorus pentafluoride, method of producing lithium hexafluorophosphate, lithium hexafluorophosphate, non-aqueous electrolyte solution for battery, and lithium secondary battery TWI598292B (en)

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