# Patent

## Title
Method for producing lithium difluorophosphate

## Abstract

A method of producing lithium difluorophosphate, the method including: a step of obtaining a first raw material mixture by mixing lithium hexafluorophosphate, at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B), and a hydrocarbon solvent having from 6 to 12 carbon atoms; a step of obtaining a second raw material mixture by removing at least a part of the hydrocarbon solvent contained in the obtained first raw material mixture; and a step of producing a crude product containing lithium difluorophosphate by reacting the second raw material mixture.

## Background
TECHNICAL FIELD
The present disclosure relates to a method of producing lithium difluorophosphate.
BACKGROUND ART
In recent years, lithium secondary batteries are widely used as power supplies for electronic devices such as mobile phones and laptop computers, electric vehicles, or power storage. In particular, in recent years, the demand for high-capacity, high-power, high-energy density batteries that can be mounted on hybrid vehicles and electric vehicles is rapidly expanding.
The lithium secondary battery includes, for example, a positive electrode and a negative electrode containing a material capable of absorbing and desorbing lithium, and a non-aqueous electrolyte solution for a battery containing a lithium salt and a non-aqueous solvent.
As a positive electrode active material used for the positive electrode, for example, lithium metal oxides such as LiCoO2, LiMnO2, LiNiO2 and LiFePO4 are used.
As the negative electrode active material used for the negative electrode, for example, metallic lithium, metallic compounds capable of absorbing and desorbing lithium (metal alone, oxides, alloys with lithium, etc.) and carbon materials are known, and in particular, coke, artificial graphite and natural graphite are in practical use.
In addition, as a non-aqueous electrolyte solution for a battery, a solution obtained by mixing Li electrolyte such as LiPF6, LiBF4, LiN (SO2CF3)2 or LiN (SO2CF2CF3)2 in a mixed solvent (non-aqueous solvent) of carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, and ethyl methyl carbonate is used.
In order to improve the performance of a battery (for example, a lithium secondary battery) using a non-aqueous electrolyte solution for a battery, various additives are contained in the non-aqueous electrolyte solution for a battery.
For example, as a non-aqueous electrolyte solution for a battery that can improve the storage characteristics of the battery, a non-aqueous electrolyte solution for a battery containing at least one of lithium monofluorophosphate or lithium difluorophosphate as an additive is known (for example, Patent Literature 1).
So far, various methods have been developed as the method of producing lithium difluorophosphate. For example, a method of reacting lithium hexafluorophosphate with silicon dioxide in a non-aqueous solvent (see, for example, Patent Literature 2), and a method of reacting lithium hexafluorophosphate with a compound having a Si—O—Si bond such as hexamethyldisiloxane (see, for example, Patent Literature 3) are disclosed.
Further, as a method of producing lithium difluorophosphate, a method of reacting lithium hexafluorophosphate with a phosphorus oxoacid salt of lithium and an oxo acid anhydride of phosphorus is disclosed (see, for example, Patent Literature 4).
Patent Literature 1: Japanese Patent No. 3439085
Patent Literature 2: Japanese Patent No. 4604505
Patent Literature 3: Japanese Patent No. 5768801
Patent Literature 4: Japanese Patent Application Laid-Open (JP-A) No. 2015-209341
SUMMARY OF INVENTION
Technical Problem
However, in the method of producing lithium difluorophosphate, it may be required to further increase the yield of lithium difluorophosphate.
Therefore, an object of the present disclosure is to provide a method of producing lithium difluorophosphate which can produce lithium difluorophosphate in a high yield.
Solution to Problem
Means for solving the above problem includes the following embodiments.
<1> A method of producing lithium difluorophosphate, the method comprising:
a step of obtaining a first raw material mixture by mixing lithium hexafluorophosphate, at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B), and a hydrocarbon solvent having from 6 to 12 carbon atoms;
a step of obtaining a second raw material mixture by removing at least a part of the hydrocarbon solvent contained in the obtained first raw material mixture; and
a step of producing a crude product containing lithium difluorophosphate by reacting the second raw material mixture.
<2> The method of producing lithium difluorophosphate according to <1>, wherein the hydrocarbon solvent is at least one solvent selected from the group consisting of tetralin, toluene, hexane and cyclohexane.
<3> The method of producing lithium difluorophosphate according to <1> or <2>, wherein a content of the hydrocarbon solvent is 50% by mass or more with respect to an entirety of the first raw material mixture.
<4> The method of producing lithium difluorophosphate according to any one of <1> to <3>, wherein the step of producing the crude product is a step of producing the crude product by reacting lithium hexafluorophosphate with at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B) according to the following reaction formula:

x(LiPF6)+y(oxide of phosphorus (A))+z(lithium salt of phosphoric acid (B))→n(LiPO2F2)  Reaction formula:

wherein, in the reaction formula, x, y, z, and n represent stoichiometric coefficients, each of x and n independently represents an integer of 1 or more, and each of y and z independently represents an integer of 0 or 1 or more, provided that, x, y, z, and n satisfy the following formulae (1) to (4):

x+number of Li atoms in (B)×z=n;  Formula (1):

x+number of P atoms in (A)×y+number of P atoms in (B)×z=n;  Formula (2):

number of O atoms in (A)×y+number of O atoms in (B)×z=2n; and  Formula (3):

6x=2n.  Formula (4):

<5> The method of producing lithium difluorophosphate according to any one of <1> to <4>, wherein the step of producing the crude product is a step of producing the crude product by reacting lithium hexafluorophosphate with at least one selected from the group consisting of lithium metaphosphate, trilithium phosphate, tetralithium pyrophosphate, pentalithium triphosphate, hexalithium tetraphosphate, and diphosphorus pentoxide.
<6> The method of producing lithium difluorophosphate according to any one of <1> to <5>, wherein the step of producing the crude product is a step of producing the crude product by reacting lithium hexafluorophosphate with a compound containing one selected from the group consisting of trilithium phosphate, tetralithium pyrophosphate, pentalithium triphosphate, and hexalithium tetraphosphate, and diphosphorus pentoxide.
<7> The method of producing lithium difluorophosphate according to any one of <1> to <6>, wherein the step of producing the crude product is a step of producing the crude product by reacting lithium hexafluorophosphate with trilithium phosphate and diphosphorus pentoxide.
<8> The method of producing lithium difluorophosphate according to any one of <1> to <5>, wherein the step of producing the crude product is a step of producing the crude product by reacting lithium hexafluorophosphate with lithium metaphosphate.
<9> The method of producing lithium difluorophosphate according to any one of <1> to <8>, further comprising:
a step of obtaining a solution by dissolving the crude product in a purification solvent; and
a step of extracting lithium difluorophosphate from the solution.
<10> The method of producing lithium difluorophosphate according to <9>, wherein the purification solvent is a mixed solvent in which at least one solvent (X) selected from the group consisting of ethyl acetate, acetone, dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether, and at least one solvent (Y) selected from the group consisting of toluene, xylene, hexane, acetonitrile, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate, are mixed at a mass ratio (the solvent (X)/the solvent (Y)) in a range from 70/30 to 95/5.
<11> The method of producing lithium difluorophosphate according to <10>, wherein the purification solvent is a mixed solvent containing at least one of ethyl acetate or dimethoxyethane as the solvent (X) and at least one of toluene or dimethyl carbonate as the solvent (Y).
<12> The method of producing lithium difluorophosphate according to <10> or <11>, wherein a combination of the solvent (X) and the solvent (Y) is a combination of ethyl acetate and toluene, a combination of ethyl acetate and dimethyl carbonate, a combination of dimethoxyethane and toluene, or a combination of dimethoxyethane and dimethyl carbonate.
Advantageous Effects of Invention
According to the present disclosure, a method of producing lithium difluorophosphate which can produce lithium difluorophosphate in a high yield is provided.


DESCRIPTION OF EMBODIMENTS
In the present specification, a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
In the present specification, the term “step” encompasses not only an independent step but also a step that cannot be clearly distinguished from other steps if the intended purpose of the step is achieved.
[Method of Producing Lithium Difluorophosphate]
A method of producing lithium difluorophosphate of the present disclosure (hereinafter, also referred to as “the production method of the present disclosure”) includes: a step of obtaining a first raw material mixture by mixing lithium hexafluorophosphate, at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B), and a hydrocarbon solvent having from 6 to 12 carbon atoms (hereinafter, also referred to as “specific hydrocarbon solvent”); a step of obtaining a second raw material mixture by removing at least a part of the hydrocarbon solvent contained in the obtained first raw material mixture; and a step of producing a crude product containing lithium difluorophosphate by reacting the second raw material mixture (hereinafter, also referred to as “reaction step”).
Here, the specific hydrocarbon solvent, that is, the hydrocarbon solvent having from 6 to 12 carbon atoms is a medium for mixing LiPF6, and at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B) (hereinafter, also referred to as “raw material mixed medium”).
Hereinafter, lithium difluorophosphate is also referred to as “LiPO2F2” and lithium hexafluorophosphate is also referred to as “LiPF6”.
According to the production method of the present disclosure, LiPO2F2 can be produced in a high yield.
Although the reason why such an effect is exerted is not clear, it is considered to be because, in the step of obtaining the first raw material mixture, the raw materials are easily mixed uniformly by mixing LiPF6 and at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B) (hereinafter, also referred to simply as “raw materials”) using the specific hydrocarbon solvent, and as a result, the reaction in the reaction step proceeds efficiently.
In contrast, when a solvent having no hydrocarbon structure (for example, acetone, triethylene glycol dimethyl ether, or acetonitrile) is used instead of the specific hydrocarbon solvent, the reaction may be inhibited in the reaction step.
Therefore, it is considered that, according to the production method of the present disclosure, since the reaction proceeds efficiently, the yield of LiPO2F2 is improved.
Hereinafter, each step in the production method of the present disclosure will be described.
<Step of Obtaining First Raw Material Mixture>
The step of obtaining the first raw material mixture is a step of obtaining a first raw material mixture by mixing lithium hexafluorophosphate (LiPF6), at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B), and a hydrocarbon solvent having from 6 to 12 carbon atoms.
A solid (for example, powder) produced by a conventionally known method can be use as LiPF6.
Examples of an oxide of phosphorus (A) include diphosphorus pentoxide (hereinafter, also referred to as “P2O5”). P2O5 encompasses tetraphosphorus decoxide (P4O10) as the same compound.
Solids (for example, powder) produced by a conventionally known method can be used as P2O5.
Examples of a lithium salt of a phosphoric acid (B) include lithium metaphosphate (hereinafter also referred to as “LiPO3”), trilithium phosphate (hereinafter also referred to as “Li3PO4”), tetralithium pyrophosphate (hereinafter also referred to as “Li4P2O7”), pentalithium triphosphate (hereinafter also referred to as “Li5P3O10”), and hexalithium tetraphosphate (hereinafter also referred to as “Li6P4O13”).
Solids (for example, powder) produced by a conventionally known method can be used as a lithium salt of a phosphoric acid (B).
From the viewpoint of reducing by-products, the purity of the raw material (LiPF6, oxide of phosphorus (A), lithium salt of a phosphoric acid (B)) is preferably high, but is not particularly limited.
Examples of the hydrocarbon solvent having from 6 to 12 carbon atoms (specific hydrocarbon solvents) include aliphatic hydrocarbon solvents having from 6 to 12 carbon atoms, aromatic hydrocarbon solvents having from 6 to 12 carbon atoms, and alicyclic hydrocarbon solvents having from 6 to 12 carbon atoms.
Examples of the aliphatic hydrocarbon solvents having from 6 to 12 carbon atoms include hexane, heptane, octane, nonane, and decane. These may be linear or branched.
Examples of the aromatic hydrocarbon solvents having from 6 to 12 carbon atoms include benzene, toluene, xylene (ortho, meta and para), ethylbenzene, butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, propylbenzene, isopropylbenzene (cumene), cyclohexylbenzene, tetralin and mesitylene. The alkyl group of the above-described aromatic hydrocarbon solvents may be linear or branched.
Examples of the alicyclic hydrocarbon solvents having from 6 to 12 carbon atoms include methyl cyclopentane, cyclohexane, methyl cyclohexane, cycloheptane, cyclooctane, cyclononane and the like.
Among others, the specific hydrocarbon solvent is preferably at least one solvent selected from the group consisting of tetralin, toluene, hexane, and cyclohexane from the viewpoint of improving the yield of LiPO2F2.
The method of mixing the raw material (LiPF6 and at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B)) with a specific hydrocarbon solvent is not particularly limited, and known methods can be used. Examples of the method include a method of mixing using a reactor equipped with a stirring mechanism such as a mechanical stirrer or a magnetic stirrer; a method of mixing using a mixer, a blender, a mill or the like; and method of mixing using a slurry mixer, a kneader, a mixing and kneading machine or the like.
The content of the specific hydrocarbon solvent contained in the first raw material mixture is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, with respect to the entirety of the first raw material mixture.
<Step of Obtaining Second Raw Material Mixture>
The step of obtaining the second raw material mixture is a step of obtaining the second raw material mixture by removing at least a part of the specific hydrocarbon solvent contained in the obtained first raw material mixture.
Examples of the method of removing at least a part of the specific hydrocarbon solvent contained in the first raw material mixture include, without specific limitation, a method of heating and concentrating the first raw material mixture and distilling off the specific hydrocarbon solvent; a method of concentrating the first raw material mixture under reduced pressure with an evaporator and distilling off the specific hydrocarbon solvent; a method of filtering the first raw material mixture (for example, filter filtration, filtration under reduced pressure, suction filtration); and the like.
The step of obtaining the second raw material mixture is preferably a step of obtaining the second raw material mixture in the form of a wet cake from the viewpoint of further enhancing the reactivity in the reaction step described later.
In other words, in the step of obtaining the second raw material mixture, the specific hydrocarbon solvent contained in the first raw material mixture is preferably removed to such an extent that the second raw material mixture in a form of a wet cake can be obtained.
<Reaction Step>
In the production method of the present disclosure, the reaction step is a step of producing a crude product containing lithium difluorophosphate (LiPO2F2) by reacting the second raw material mixture.
Here, “reacting the second raw material mixture” refers to reacting lithium hexafluorophosphate (LiPF6) in the second raw material mixture with at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B) in the second raw material mixture.
In the production method of the present disclosure, it is preferable that the reaction step is a step of producing the crude product by reacting lithium hexafluorophosphate (that is, lithium hexafluorophosphate in the second raw material mixture) with at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B) (that is, at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B) in the second raw material mixture) according to the reaction formula given below.

x(LiPF6)+y(oxide of phosphorus (A))+z(lithium salt of phosphoric acid (B))→n(LiPO2F2)  Reaction formula:

In the above reaction formula, x, y, z, and n represent stoichiometric coefficients, each of x and n independently represents an integer of 1 or more, and each of y and z independently represents an integer of 0 or 1 or more, provided that, x, y, z, and n satisfy the following formulae (1) to (4).

x+number of Li atoms in the (B)×z=n  Formula (1):

x+number of P atoms in the (A)×y+number of P atoms in the (B)×z=n  Formula (2):

number of O atoms in the (A)×y+number of O atoms in the (B)×z=2n  Formula (3):

6x=2n  Formula (4):

When the reaction step follows the above-described reaction formula, it is easy to obtain a crude product in which products (that is, by-products) other than the main product LiPO2F2 is further reduced in the above-described reaction. In addition, waste of raw materials is also reduced.
In the reaction according to the above-described reaction formula, fluctuation of the molar number (stoichiometric coefficient) of the raw material can be tolerated according to the purity of the raw material.
Further, in the above-described reaction, it is possible to allow fluctuation of the raw material molar ratio due to measurement error of the purity of the raw material and weighing error in the range where the effects of the present disclosure are exhibited.
In the production method of the present disclosure, it is also preferable that the reaction step is a step of producing the crude product by reacting lithium hexafluorophosphate (LiPF6) with at least one selected from the group consisting of lithium metaphosphate (LiPO3), trilithium phosphate (Li3PO4), tetralithium pyrophosphate (Li4P2O7), pentalithium triphosphate (Li5P3O10), hexalithium tetraphosphate (Li6P4O13), and diphosphorus pentoxide (P2O5).
When the reaction step is this embodiment, “at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B)” in the step of obtaining the first raw material mixture preferably includes at least one selected from the group consisting of LiPO3, Li3PO4, Li4P2O7, Li5P3O10, Li6P4O13, and P2O5.
When the reaction step is the above-described embodiment, the above reaction formula may not be satisfied, but it is more preferable to be satisfied.
Here, P2O5 corresponds to the oxide of phosphorus (A), and LiPO3, Li3PO4, Li4P2O7, Li5P3O10 and Li6P4O13 correspond to a lithium salt of a phosphoric acid (B).
Examples of the modes of the above-described reaction include the following three modes. In modes 1 and 2, a lithium salt of a phosphoric acid (B) other than LiPO3 may be used singly or in combination of two or more.
(Mode 1): Reaction of LiPF6, P2O5, and a lithium salt of a phosphoric acid (B) other than LiPO3 
(Mode 2): Reaction of LiPF6, P2O5, LiPO3, and a lithium salt of a phosphoric acid (B) other than LiPO3.
(Mode 3): Reaction of LiPF6 with LiPO3 
The reaction step is more preferably the following reaction step A or reaction step B.
(Reaction Step A)
The reaction step A is a step of producing the crude product through the reaction of the above-described mode 1 or 2.
In other words, the reaction step A is a step of producing the crude product by reacting lithium hexafluorophosphate (LiPF6) with a compound containing one selected from the group consisting of trilithium phosphate (Li3PO4), tetralithium pyrophosphate (Li4P2O7), pentalithium triphosphate (Li5P3O10), and hexalithium tetraphosphate (Li6P4O13), and diphosphorus pentoxide (P2O5).
Among others, the reaction step A is preferably a step of producing the crude product by reacting lithium hexafluorophosphate (LiPF6) with trilithium phosphate (Li3PO4) and diphosphorus pentoxide (P2O5).
When the reaction step in the production method of the present disclosure is the reaction step A, “at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B)” in the step of obtaining the first raw material mixture preferably includes at least one selected from the group consisting of Li3PO4, Li4P2O7, Li5P3O10, and Li6P4O13, and P2O5, and more preferably includes Li3PO4 and P2O5.
Specifically, the reaction step A is preferably a step of producing the crude product by the reaction of the following modes A1 to A4. Especially, it is more preferable that it is a step of producing the crude product by reaction of the mode A1.

3LiPF6+2P2O5+2Li3PO4→9LiPO2F2  (Mode A1):

2LiPF6+P2O5+Li4P2O7→6LiPO2F2  (Mode A2):

5LiPF6+2P2O5+2Li5P3O10→15LiPO2F2  (Mode A3):

3LiPF6+P2O5+Li6P4O13→9LiPO2F2  (Mode A4):

In the reactions of the modes A1 to A4, one or more lithium salts of a phosphoric acid other than Li3PO4, one or more lithium salts of a phosphoric acid other than Li4P2O7, one or more lithium salts of a phosphoric acid other than Li5P3O10, and one or more lithium salts of a phosphoric acid other than Li6P4O13 can be respectively reacted by adjusting the raw material molar ratio.
(Reaction Step B)
The reaction step B is a step of producing the crude product through the reaction of the above-described Mode 3.
In other words, the reaction step B is a step of producing the crude product by reacting lithium hexafluorophosphate (LiPF6) with lithium metaphosphate (LiPO3).
When the reaction step is reaction step B, “at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B)” in the step of obtaining the first raw material mixture preferably includes LiPO3.
Specifically, the reaction step B is preferably a step of producing the crude product by the reaction of the following mode B.

LiPF6+2LiPO3→3LiPO2F2  (Mode B):

In the reaction step, the reaction when reacting LiPF6 with at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B) is preferably a solid phase reaction. When the second raw material mixture is in a form of a wet cake, this solid phase reaction can be realized.
In the reaction step, the second raw material mixture is preferably heated and reacted in a sealed reaction system to a desired temperature condition.
In the reaction step, the second raw material mixture may be reacted while being mixed, for example, using a reactor equipped with a stirring mechanism.
The reaction in the reaction step may be carried out under normal pressure or under reduced pressure, but from the viewpoint of obtaining LiPO2F2 in a high yield, it is preferable to carry out in a sealed reaction system from the start of the reaction to the end.
When the above-described reaction is carried out in a sealed reaction system, the reaction may be conducted under an inert atmosphere such as nitrogen or argon or under reduced pressure in the reaction system.
When the above-described reaction is carried out in the sealed reaction system, the reaction may be carried out in a sealed system containing oxygen. For the sealed system containing oxygen, reference can be made to a reference mode described later.
In the reaction step, the temperature when reacting LiPF6 with at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B) (hereinafter also referred to as “reaction temperature”) is preferably from 100° C. to 350° C., more preferably from 150° C. to 300° C., and still more preferably from 180° C. to 250° C.
When the reaction temperature is 100° C. or higher, the reaction tends to proceed efficiently.
When the reaction temperature is 350° C. or lower, LiPO2F2 is difficult to be decomposed, and the formation of products (that is, by-products) other than LiPO2F2 which is a main product is easily suppressed.
In the reaction step, from the viewpoint of efficiently advancing the reaction, the time for reacting LiPF6 with at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B) is preferably from 4 hours to 16 hours, more preferably from 5 hours to 14 hours, and still more preferably from 6 hours to 12 hours.
The production method of the present disclosure preferably includes a step of obtaining a solution by dissolving the above-described crude product in a purification solvent (hereinafter also referred to as “dissolution step”) and a step of extracting lithium difluorophosphate from this solution (hereinafter also referred to as “extracting step”).
When the production method of the present disclosure includes the dissolution step and the extracting step, the crude product (LiPO2F2 containing impurities) can be effectively purified, and LiPO2F2 with an increased purity can be extracted.
The dissolution step and the extracting step will be described below.
<Dissolution Step>
The above-described dissolution step is a step of obtaining a solution by dissolving a crude product in a purification solvent.
The purification solvent is not particularly limited as long as it can dissolve the crude product, and a mixed solvent of a good solvent for LiPO2F2 (hereinafter referred to as “solvent (X)”) and a poor solvent for LiPO2F2 (hereinafter referred to as “solvent (Y)”) is preferably used. Accordingly, LiPO2F2 is easily dissolved in the purification solvent, and LiPO2F2 can be easily extracted from the solution in which the crude product is dissolved.
Examples of the good solvent (solvent (X)) include ethyl acetate, acetone, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and the like. A solvent (X) may be used singly, or in combination of two or more.
Examples of the poor solvent (solvent (Y)) include toluene, xylene, hexane, acetonitrile, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate and the like. The solvent (Y) may be used singly or in combination of two or more.
The mass ratio (solvent (X)/solvent (Y)) of the purification solvent (mixed solvent) is preferably from 70/30 to 95/5, more preferably from 75/25 to 95/5, still more preferably from 80/20 to 95/5, and particularly preferably from 85/15 to 95/5.
By setting the mass ratio of the purification solvent (solvent (X)/solvent (Y)) to 70/30 or more, LiPO2F2 is more easily dissolved in the purification solvent. On the other hand, it is considered that solubility of the solvent (Y) is low not only for LiPO2F2 but also for impurities contained in the crude product.
By setting the mass ratio of the purification solvent (solvent (X) and solvent (Y)) to 95/5 or less, dissolution of impurities in the purification solvent is easily suppressed.
Therefore, by setting the mass ratio of the purification solvent to the above-described range, LiPO2F2 can be easily extracted from the solution in which the crude product is dissolved. In other words, it is easy to extract high purity LiPO2F2 in a high yield.
In other words, the above-described purification solvent is preferably a mixed solvent in which at least one solvent (X) selected from the group consisting of ethyl acetate, acetone, dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether, and at least one solvent (Y) selected from the group consisting of toluene, xylene, hexane, acetonitrile, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate, are mixed at a mass ratio (the solvent (X)/the solvent (Y)) in the range from 70/30 to 95/5.
When the purification solvent is a mixed solvent of solvent (X) and solvent (Y), the purification solvent is preferably a mixed solvent containing at least one of ethyl acetate or dimethoxyethane as the solvent (X) and at least one of toluene or dimethyl carbonate as the solvent (Y).
A combination of the solvent (X) and the solvent (Y) is preferably a combination of ethyl acetate and toluene, a combination of ethyl acetate and dimethyl carbonate, a combination of dimethoxyethane and toluene, or a combination of dimethoxyethane and dimethyl carbonate.
When dissolving the crude product in the purification solvent (preferably, a mixed solvent of solvent (X) and solvent (Y)) in the dissolution step, the crude product is preferably cooled to 60° C. or lower (preferably 50° C. or lower) and injected or circulated in the purification solvent. Accordingly, when LiPO2F2 is extracted in the extracting step described later, the purity of LiPO2F2 tends to increase.
The method of dissolving the crude product containing LiPO2F2 in a purification solvent is not particularly limited, and known methods (stirring method, ultrasonic irradiation method, and the like) can be used.
<Extracting Step>
The extracting step is a step of extracting LiPO2F2 from the solution obtained in the dissolution step.
There is no particular limitation on the method of extracting LiPO2F2 from the solution (the solution in which the crude product is dissolved in the purification solvent) obtained in the dissolution step, and the conventionally known methods can be arbitrarily selected and carried out. Examples of the method include: a method of heating and concentrating the solution and distilling off the purification solvent; a method of concentrating the solution under reduced pressure using an evaporator and distilling off the purification solvent; a method of filtering the solution (for example, filter filtration, filtration under reduced pressure, and suction filtration), a method of precipitating LiPO2F2 by further adding another purification solvent different from the purification solvent in which the crude product is dissolved to the solution, and the like. By the above-described method, LiPO2F2 as a solid can be extracted.
As a method drying LiPO2F2 extracted as a solid, conventionally known methods can be arbitrarily selected and implemented. For example, a stationary drying method in tray type dryer; a fluid drying method in conical dryer; method of drying using apparatus such as hot plate or oven; a method of supplying warm air or hot air with drying apparatus such as a dryer; and the like. Accordingly, removal of the residual solvent of extracted LiPO2F2 can be performed.
The method of producing LiPO2F2 of the present disclosure described above is particularly suitable for producing LiPO2F2 as an additive to be added to a non-aqueous electrolyte solution for a lithium ion battery (preferably a lithium ion secondary battery).
In other words, according to the production method of the present disclosure, since LiPO2F2 can be produced with a high yield, productivity of LiPO2F2 is improved.
The LiPO2F2 produced by the production method of the present disclosure is expected to contribute to the improvement of battery characteristics when added to the non-aqueous electrolyte solution.
[Reference Mode of Method of Producing Lithium Difluorophosphate]
The reference mode of the method of producing lithium difluorophosphate is shown below.
According to the reference mode, lithium difluorophosphate can be produced in a high yield.
The method of producing lithium difluorophosphate according to the reference mode includes the following modes <1A> to <9A>.
<1A> A method of producing lithium difluorophosphate, including a step of producing a crude product containing lithium difluorophosphate by reacting lithium hexafluorophosphate with at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B) in a sealed system containing oxygen.
<2A> The method of producing lithium difluorophosphate according to <1A>, wherein the step of producing the crude product is a step of producing the crude product according to the following reaction formula:

x(LiPF6)+y(oxide of phosphorus (A))+z(lithium salt of phosphoric acid (B))→n(LiPO2F2)  Reaction formula:

    
    
        wherein, in the above reaction formula, x, y, z, and n represent stoichiometric coefficients, each of x and n independently represents an integer of 1 or more, and each of y and z independently represents an integer of 0 or 1 or more, provided that, x, y, z, and n satisfy the following formulae (1) to (4):

x+number of Li atoms in the (B)×z=n;  Formula (1):

x+number of P atoms in the (A)×y+number of P atoms in the (B)×z=n;  Formula (2):

number of O atoms in the (A)×y+number of O atoms in the (B)×z=2n; and  Formula (3):

6x=2n.  Formula (4):

    
    


<3A> The method of producing lithium difluorophosphate according to <1A> or <2A>, wherein the step of producing the crude product is a step of producing the crude product by reacting lithium hexafluorophosphate with at least one selected from the group consisting of lithium metaphosphate, trilithium phosphate, tetralithium pyrophosphate, pentalithium triphosphate, hexalithium tetraphosphate, and diphosphorus pentoxide.
<4A> The method of producing lithium difluorophosphate according to any one of <1A> to <3A>, wherein the step of producing the crude product is a step of producing the crude product by reacting lithium hexafluorophosphate with a compound containing one selected from the group consisting of trilithium phosphate, tetralithium pyrophosphate, pentalithium triphosphate, and hexalithium tetraphosphate, and diphosphorus pentoxide.
<5A> The method of producing lithium difluorophosphate according to any one of <1A> to <4A>, wherein the step of producing the crude product is a step of producing the crude product by reacting lithium hexafluorophosphate with trilithium phosphate and diphosphorus pentoxide.
<6A> The method of producing lithium difluorophosphate according to any one of <1A> to <3A>, wherein the step of producing the crude product is a step of producing the crude product by reacting lithium hexafluorophosphate with lithium metaphosphate.
<7A> The method of producing lithium difluorophosphate according to any one of <1A> to <6A>, further including:
a step of obtaining a solution by dissolving the crude product in a purification solvent; and
a step of extracting lithium difluorophosphate from the solution.
<8A> The method of producing lithium difluorophosphate according to <7A>, wherein the purification solvent is a mixed solvent in which at least one solvent (X) selected from the group consisting of ethyl acetate, acetone, dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether, and at least one solvent (Y) selected from the group consisting of toluene, xylene, hexane, acetonitrile, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate, are mixed at a mass ratio (the solvent (X)/the solvent (Y)) in the range from 70/30 to 95/5.
<9A> The method of producing lithium difluorophosphate according to <7A> or <8A>, wherein the purification solvent is a mixed solvent containing at least one of ethyl acetate or dimethoxyethane as the solvent (X) and at least one of toluene or dimethyl carbonate as the solvent (Y).
<10A> The method of producing lithium difluorophosphate according to any one of <7A> to <9A>, wherein a combination of the solvent (X) and the solvent (Y) is a combination of ethyl acetate and toluene, a combination of ethyl acetate and dimethyl carbonate, a combination of dimethoxyethane and toluene, or a combination of dimethoxyethane and dimethyl carbonate.
The method of producing lithium difluorophosphate of the reference mode (hereinafter also referred to as “production method of the reference mode”) includes a step of producing a crude product containing lithium difluorophosphate by reacting lithium hexafluorophosphate with at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B) in the sealed system containing oxygen (hereinafter also referred to as “reaction step”).
Here, the sealed system means a sealed reaction system. Specifically, it refers to a system without substantial gas leakage out of the atmosphere in which the reaction takes place. Without substantial gas leakage means that the design may include unavoidable gas leakage.
According to the production method of the reference mode, LiPO2F2 can be manufactured in a high yield.
Although the reason why such an effect is exerted is not clear, it is considered to be because, in the above-described reaction step, the reaction proceeds efficiently by reacting LiPF6 with at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B) in the sealed system containing oxygen.
In contrast, when the above-described reaction step is performed in a sealed system containing no oxygen or in an open system containing oxygen, the target reaction is likely to be inhibited.
Therefore, it is considered that, according to the production method of the reference mode, the reaction in the sealed system containing oxygen contributes to the improvement of the yield of LiPO2F2.
For example, when the above-described reaction step is a step of producing a crude product containing LiPO2F2 by reacting LiPF6 with P2O5 as an oxide of phosphorus (A) and Li3PO4 as a lithium salt of a phosphoric acid (B), a crude product containing LiPO2F2 can be produced through the reaction 1 and reaction 2 described below.
In this case, volatilization of the POF3 gas generated by the reaction 1 is suppressed by performing the reaction 1 and the reaction 2 in a sealed system containing oxygen. As a result, the POF3 gas easily reacts with Li3PO4 and is easily converted to LiPO2F2. That is, it is considered that the reaction of reaction 2 proceeds efficiently.

3LiPF6+2P2O5→3LiPO2F2+4POF3 (gas)  Reaction 1:

4POF3 (gas)+2Li3PO4→6LiPO2F2  Reaction 2:

Hereinafter, each step of the production method of the reference mode is demonstrated.
<Reaction Step>
In the production method of the reference mode, the reaction step is a step of producing a crude product containing lithium difluorophosphate (LiPO2F2) by reacting lithium hexafluorophosphate (LiPF6) with at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B) in a sealed system containing oxygen.
The reaction step in the production method of the reference mode is the same as the reaction step in the production method of the present disclosure except for being limited to reacting lithium hexafluorophosphate (LiPF6) with at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B) in a sealed system containing oxygen, and a preferable mode is also the same.
Examples of the sealed system (sealed reaction system) in a reaction step include a sealable reaction vessel. The sealable reaction vessel is not particularly limited, but is preferably a reaction vessel which can stir so that the raw materials (LiPF6 and at least one of oxide of phosphorus (A) or lithium salt of a phosphoric acid (B)) are sufficiently mixed.
Examples of the oxygen include, without specific limitation, air (dry air or the like), oxygen and air diluted with an inert gas (nitrogen, helium, argon, or the like).
The oxygen concentration in the sealed system is preferably from 3 volume percent to 50 volume percent, more preferably from 5 volume percent to 40 volume percent, and still more preferably from 8 volume percent to 30 volume percent.
When the oxygen concentration is 3 volume percent or more, consumption of P2O5 due to side reaction (for example, decomposition of P2O5 by water) is likely to be suppressed.
When the oxygen concentration is 50 volume percent or less, excessive oxidation of LiPF6 is likely to be suppressed.
Therefore, when the oxygen concentration is from 3 volume percent to 50 volume percent, by-products in the reaction step are reduced, and LiPO2F2 is easily obtained in a high yield.
The production method of the reference mode preferably includes a step of obtaining a solution by dissolving the above-described crude product in a purification solvent (hereinafter also referred to as “dissolution step”) and a step of extracting lithium difluorophosphate from this solution (hereinafter also referred to as “extracting step”).
When the production method of the present disclosure includes the dissolution step and the extracting step, the crude product (LiPO2F2 containing impurities) can be effectively purified, and LiPO2F2 with an increased purity can be extracted.
The dissolution step and the extracting step which may be included in the production method of the reference mode are respectively the same as the dissolution step and the extracting step which may be included in the production method of the present disclosure, and the preferred embodiments are also the same.
The production method of the reference mode is also particularly suitable for producing LiPO2F2 as an additive to be added to a non-aqueous electrolyte solution for a lithium ion battery (preferably a lithium ion secondary battery).
In other words, according to the production method of the reference mode, since LiPO2F2 can be produced with a high yield, productivity of LiPO2F2 is improved.
The LiPO2F2 produced by the production method of the reference mode is expected to contribute to the improvement of battery characteristics when added to the non-aqueous electrolyte solution.
EXAMPLES
Examples of the present disclosure will be shown below, but the present disclosure is not limited to the following examples.
In the following, “%” refers to “% by mass” unless otherwise noted.
Example 1
A crude product containing LiPO2F2 was prepared in the following manner.
In a glove box purged with dry nitrogen gas, respective powders of 5.0 g of lithium hexafluorophosphate, 3.1 g of diphosphorus pentoxide, and 2.5 g of trilithium phosphate as raw materials, and 100 mL of tetralin as a raw material mixed medium were put into a beaker of 200 mL together with a stirring bar of a magnetic stirrer, and were stirred and mixed at 300 rpm for one hour (the step of obtaining the first raw material mixture) by the stirrer.
Subsequently, the mixed slurry liquid was filtered to remove at least a part of the raw material mixed medium (tetralin) so that a wet cake of raw material powder was obtained (the step of obtaining the second raw material mixture).
Next, a 200 mL Hastelloy C sealed reaction vessel (hereinafter, also simply referred to as a “reaction vessel”) equipped with a thermometer, a pressure gauge, and gas introduction and exhaust lines is placed in the same glove box, the wet cake of the raw material powder mixed in advance was put in the reaction vessel together with a stirring bar, covered with a lid, and sealed. The reaction vessel was taken out of the glove box, heated, and reacted at a temperature of 200° C. for 8 hours (the reaction step).
Next, the reaction vessel was cooled to room temperature (25° C.), the inside of the reaction vessel was purged with nitrogen gas, and then the reaction vessel was again put into a glove box purged with dry nitrogen gas, and the lid of the reaction vessel was opened. 150 g of a purification solvent (ethyl acetate/toluene (mass ratio)=95/5) prepared in advance by mixing ethyl acetate as a solvent (X) and toluene as a solvent (Y) was added thereinto, then, the reaction vessel was covered with the lid and was taken out of the glove box, heated to 60° C. and stirred at 300 rpm for 1 hour, so that a solution in which the crude product was dissolved was obtained (the dissolution step).
After that, the lid of the reaction vessel was opened immediately, the solution in the reaction vessel (solution in which the crude product was dissolved) was poured into a filter unit equipped with a filter to filter out solvent insoluble solid (impurities) by filtration under reduced pressure, and then the solution was collected. The collected solution was subjected to solvent removal by an evaporator and thus was concentrated, then the operation was stopped at a timing when the solvent was removed by approximately 100 g, the obtained slurry liquid was filtered at a room temperature (25° C.), and consequently, a wet cake containing LiPO2F2 was obtained (the extracting step). Then, it was dried under reduced pressure at 50° C. and 1000 Pa or less, and a solid having a weight of 9.4 g after drying was obtained.
As a result of analysis of the obtained solid to determine the purity, 99.9% of lithium difluorophosphate (LiPO2F2) and 0.1% of the other components were identified. The yield was 88.2% (see Table 1).
The purity and yield of LiPO2F2 were determined as follows.
(Purity of LiPO2F2)
The obtained solid was dissolved in a heavy water solvent. 19F-NMR analysis was conducted, and the purity of LiPO2F2 was calculated by the percentage method on a mass basis based on the integral value of the obtained spectrum.
The assignment of the 19F-NMR spectrum was as follows.
LiPF6: −71.4 ppm, −73.3 ppm (molecular weight: 151.9, F number: 6)
Li2PO3F: −75.0 ppm, −77.5 ppm (molecular weight: 111.9, F number: 1)
LiPO2F2: −81.0 ppm, −83.5 ppm (molecular weight: 107.9, F number: 2)
LiF: −120.0 ppm (molecular weight: 25.9, F number: 1)
Other components: other peaks (molecular weight and F number were assumed to be the same as LiPF6)
From the spectrum obtained by the analysis, the mass fraction of each compound was determined by the above-described assignment and the following formula, and the mass fraction of LiPO2F2 was taken as the purity.

(Integral value/F number of compound)×(molecular weight of compound)=(mass part of compound)

(Mass part of compound)/(sum of mass parts of compounds)×100=mass fraction of compound (%)

(Yield of LiPO2F2)
The mass of LiPO2F2 was determined by multiplying the mass of the obtained solid by the purity calculated above. From this mass, the number of moles of F atoms contained in LiPO2F2 was calculated, and the result was defined as the number of moles 1. Next, from the mass of LiPF6 as a raw material, the number of moles of F atom contained in this LiPF6 was calculated, and the result was defined as the number of moles 2. The yield of LiPO2F2 was determined as the ratio of the number of moles 1 to the number of moles 2 ((number of moles 1/number of moles 2)×100). In other words, the yield of LiPO2F2 was taken as the yield based on F atoms.
Examples 2 to 16
According to Table 1, a solid was obtained in the same manner as in Example 1 except that the combination of the types of the raw material mixed medium and the purification solvent was changed, and the same measurement as in Example 1 was performed. The results are shown in Table 1. In Table 1, “wt ratio” represents a mass ratio. Table 2 is also the same.
Comparative Example 11
A crude product containing LiPO2F2 was prepared in the following manner.
A 200 mL Hastelloy C sealed reaction vessel equipped with a thermometer, pressure gauge, and gas introduction and exhaust lines was placed into a dry nitrogen gas purged glove box. In the glove box, respective powders of 5.0 g of lithium hexafluorophosphate, 3.1 g of diphosphorus pentoxide, and 2.5 g of trilithium phosphate were placed in the reaction vessel together with a stirring bar of a magnetic stirrer, covered with a lid, and sealed. The reaction vessel was taken out of the glove box, and stirred and mixed at 300 rpm for 1 hour with the stirrer.
Next, the reaction vessel in which the raw materials had been charged and mixed was heated, and the reaction was carried out by treatment at 200° C. for 8 hours to obtain a crude product containing LiPO2F2.
Next, the reaction vessel was cooled to room temperature (25° C.), the inside of the reaction vessel was purged with nitrogen gas, and then the reaction vessel was again put into a glove box purged with dry nitrogen gas, and the lid of the reaction vessel was opened. 150 g of a purification solvent (ethyl acetate/toluene (mass ratio)=95/5) prepared in advance by mixing ethyl acetate as a solvent (X) and toluene as a solvent (Y) was added thereinto, then, the reaction vessel was covered with the lid and was taken out of the glove box, and stirred at 300 rpm for one hour with a stirrer while heating to 60° C. to obtain a solution in which the crude product was dissolved.
After that, the lid of the reaction vessel was opened immediately, the solution in the reaction vessel (solution in which the crude product was dissolved) was poured into a filter unit equipped with a filter to filter out solvent insoluble solid (impurities) by filtration under reduced pressure and then the solution was collected. The collected solution was subjected to solvent removal with an evaporator and thus was concentrated, then the operation was stopped at a timing when the solvent was removed by approximately 100 g, the obtained slurry liquid was filtered at a room temperature (25° C.), and consequently, a wet cake containing LiPO2F2 was obtained. Then, it was dried under reduced pressure at 50° C. and 1000 Pa or less, and a solid having a mass of 8.6 g after drying was obtained.
As a result of analysis of the obtained solid to determine the purity, 99.9% of lithium difluorophosphate (LiPO2F2) and 0.1% of the other components were identified. The yield was 80.7% (see Table 2).
Comparative Examples 2 to 4
According to Table 2, a solid was obtained in the same manner as in Comparative Example 1 except that the combination of the types of the purification solvent was changed, and the same measurement as in Comparative Example 1 was performed. The results are shown in Table 2.
Comparative Examples 5 to 7
According to Table 2, a solid was obtained in the same manner as in Example 1 except that the raw material mixed medium was changed, and the same measurement as in Example 1 was performed. The results are shown in Table 2.













TABLE 1










Reaction






Raw
Conditions

yield
















Reaction Raw
Material
temper-

Purification Solvent
yield
(%)




Material (g/mol)
Mixed
ature
time
Composition (wt ratio)
amount
F atom
Purity (%) [19F-NMR]






















LiPF6
P2O5
Li3PO4
Medium
(° C.)
(h)
solvent (X)
solvent (Y)
(g)
yield
LiPO2F2
Li2PO3F
LiF
others

























Example 1
5.0/
3.1/
2.5/
tetralin
200
8
ethyl acetate
toluene 5
9.4
88.2
99.9
0
0
0.1



0.033
0.022
0.022



95


Example 2






ethyl acetate
dimethyl
9.5
89.2
99.9
0
0
0.1









95
carbonate 5


Example 3






dimethoxy
toluene 5
9.3
87.3
99.9
0
0
0.1









ethane









95


Example 4






dimethoxy
dimethyl
9.3
87.3
99.9
0
0
0.1









ethane
carbonate 5









95


Example 5



toluene


ethyl acetate
toluene 5
9.4
88.2
99.9
0
0
0.1









95


Example 6






ethyl acetate
dimethyl
9.5
89.2
99.9
0
0
0.1









95
carbonate 5


Example 7






dimethoxy
toluene 5
9.3
87.3
99.9
0
0
0.1









ethane









95


Example 8






dimethoxy
dimethyl
9.2
86.3
99.9
0
0
0.1









ethane
carbonate 5









95


Example 9



hexane


ethyl acetate
toluene 5
9.3
87.3
99.9
0
0
0.1









95


Example






ethyl acetate
dimethyl
9.2
86.3
99.9
0
0
0.1


10






95
carbonate 5


Example






dimethoxy
toluene 5
9.2
86.3
99.9
0
0
0.1


11






ethane









95


Example






dimethoxy
dimethyl
9.0
84.5
99.9
0
0
0.1


12






ethane
carbonate 5









95


Example



cyclo


ethyl acetate
toluene 5
9.2
86.3
99.9
0
0
0.1


13



hexane


95


Example






ethyl acetate
dimethyl
9.2
86.3
99.9
0
0
0.1


14






95
carbonate 5


Example






dimethoxy
toluene 5
9.3
87.3
99.9
0
0
0.1


15






ethane









95


Example






dimethoxy
dimethyl
9.0
84.5
99.9
0
0
0.1


16






ethane
carbonate 5









95





















TABLE 2










Raw
Reaction




Reaction Raw
Material
Conditions
Purification Solvent













Material (g/mol)
Mixed
temperature
time
Composition (wt ratio)
















LiPF6
P2O5
Li3PO4
Medium
(° C.)
(h)
solvent (X)
solvent (Y)





Comparative
5.0/
3.1/
2.5/
nil
200
8
ethyl acetate
toluene 5


Example 1
0.033
0.022
0.022
(powder


95


Comparative



mixture)


ethyl acetate
dimethyl


Example 2






95
carbonate 5


Comparative






dimethoxyethane
toluene 5


Example 3






95


Comparative






dimethoxyethane
dimethyl


Example 4






95
carbonate 5


Comparative



acetone


ethyl acetate
toluene 5


Example 5






95


Comparative



triethylene


ethyl acetate
toluene 5


Example 6



glycol


95






dimethyl






ether


Comparative



acetonitrile


ethyl acetate
toluene 5


Example 7






95














yield
yield (%)




amount
F atom
Purity (%) [19F-NMR]
















(g)
yield
LiPO2F2
Li2PO3F
LiF
others







Comparative
8.6
80.7
99.9
0
0
0.1



Example 1



Comparative
8.7
81.7
99.9
0
0
0.1



Example 2



Comparative
8.1
76.0
99.9
0
0
0.1



Example 3



Comparative
8.2
77.0
99.9
0
0
0.1



Example 4



Comparative
7.5
69.9
99.3
0.5
0
0.2



Example 5



Comparative
4.3
38.9
96.4
2.7
0.1
0.8



Example 6



Comparative
6.6
60.0
97.0
2.1
0
0.9



Example 7










As shown in Tables 1 and 2, it is found that each of the Examples in which the raw material powder was mixed using a hydrocarbon solvent having from 6 to 12 carbon atoms (raw material mixed medium) achieves LiPO2F2 in a high yield compared with Comparative Examples 1 to 4 in which only the raw material powder was mixed, and Comparative Examples 5 to 7 in which the raw material powder was mixed using a solvent other than the above-described hydrocarbon solvent (acetone, triethylene glycol dimethyl ether or acetonitrile). Moreover, the purity of LiPO2F2 obtained in each Example was also high.
Hereinafter, the specific example of the above-mentioned reference mode is shown as a “Reference Example”, and Comparative Example with respect to a Reference Example is shown as a “Reference Comparative Example.”
Reference Example 1
A crude product containing LiPO2F2 was prepared in the following manner.
A 200 mL Hastelloy C sealed reaction vessel (hereinafter, also referred to simply as “reaction vessel”) equipped with a thermometer, pressure gauge, and gas introduction and exhaust lines was placed into a dry nitrogen gas purged glove box. In the glove box, respective powders of 5.0 g of lithium hexafluorophosphate, 3.1 g of diphosphorus pentoxide, and 2.5 g of trilithium phosphate as the raw materials were placed in the reaction vessel together with a stirring bar of a magnetic stirrer, covered with a lid, and sealed. The reaction vessel was taken out of the glove box, and stirred and mixed at 300 rpm for 1 hour with a stirrer.
Next, an operation was repeated twice in which an exhaust line of the reaction vessel in which the raw materials had been charged and mixed was opened, the reaction vessel was depressurized to 1000 Pa or less, dry air was introduced from the gas introduction line, and the inside of the reaction vessel was replaced with dry air. Next, the exhaust line was closed, the reaction vessel was sealed, heating was started, and reaction was carried out by treatment at 200° C. for 8 hours (the reaction step).
Next, the reaction vessel was cooled to room temperature (25° C.), the inside of the reaction vessel was purged with nitrogen gas, and then the reaction vessel was again put into a glove box purged with dry nitrogen gas, and the lid of the reaction vessel was opened. 150 g of a purification solvent (ethyl acetate/toluene (mass ratio)=95/5) prepared in advance by mixing ethyl acetate as a solvent (X) and toluene as a solvent (Y) was added thereinto, then, the reaction vessel was covered with the lid and was taken out of the glove box, and stirred by the stirrer at 300 rpm for 1 hour while heating to 60° C., so that a solution in which the crude product was dissolved was obtained (the dissolution step).
After that, the lid of the reaction vessel was opened immediately, the solution in the reaction vessel (solution in which the crude product was dissolved) was poured into a filter unit equipped with a filter to filter out solvent insoluble solid (impurities) by filtration under reduced pressure and then the solution was collected. The collected solution was subjected to solvent removal by an evaporator and thus was concentrated, then the operation was stopped at a timing when the solvent was removed by approximately 100 g, the obtained slurry liquid was filtered at a room temperature (25° C.), and consequently, a wet cake containing LiPO2F2 was obtained (the extracting step). Then, it was dried under reduced pressure at 50° C. and 1000 Pa or less, and a solid having a mass of 9.4 g after drying was obtained.
As a result of analysis of the obtained solid to determine the purity, 99.9% of lithium difluorophosphate (LiPO2F2) and 0.1% of the other components were identified. The yield was 88.2% (see Table 1).
The purity and yield of LiPO2F2 were determined as follows.
(Purity of LiPO2F2)
The obtained solid was dissolved in a heavy water solvent, 19F-NMR analysis was conducted, and the purity of LiPO2F2 was calculated by the percentage method on a mass basis based on the integral value of the obtained spectrum.
The assignment of the 19F-NMR spectrum was as follows.
LiPF6: −71.4 ppm, −73.3 ppm (molecular weight: 151.9, F number: 6)
Li2PO3F: −75.0 ppm, −77.5 ppm (molecular weight: 111.9, F number: 1)
LiPO2F2: −81.0 ppm, −83.5 ppm (molecular weight: 107.9, F number: 2)
LiF: −120.0 ppm (molecular weight: 25.9, F number: 1)
Other components: other peaks (molecular weight and F number were assumed to be the same as LiPF6)
From the spectrum obtained by the analysis, the mass fraction of each compound was determined by the above-described assignment and the following formula, and the mass fraction of LiPO2F2 was taken as the purity.

(Integral value/F number of compound)×(molecular weight of compound)=(mass part of compound)

(Mass part of compound)/(sum of mass parts of compounds)×100=mass fraction of compound (%)

(Yield of LiPO2F2)
The mass of LiPO2F2 was determined by multiplying the mass of the obtained solid by the purity calculated above. From this mass, the number of moles of F atoms contained in LiPO2F2 was calculated, and the result was defined as the number of moles 1. Next, from the mass of LiPF6 as a raw material, the number of moles of F atom contained in this LiPF6 was calculated, and the result was defined as the number of moles 2. The yield of LiPO2F2 was determined as the ratio of the number of moles 1 to the number of moles 2 ((number of moles 1/number of moles 2)×100). In other words, the yield of LiPO2F2 was taken as the yield based on F atoms.
Reference Example 2 to Reference Example 4
According to Table 3, a solid was obtained in the same manner as in Reference Example 1 except that the combination of the types of the purification solvent was changed, and the same measurement as in Reference Example 1 was performed. The results are shown in Table 3.
Reference Comparative Example 1
A solid was obtained in the same manner as in Reference Example 1 except that nitrogen was introduced from the gas introduction line in the reaction step of Reference Example 1, and the same measurement as in Reference Example 1 was performed. The results are shown in Table 3.
Reference Comparative Examples 2 to 4
According to Table 3, a solid was obtained in the same manner as in Reference Comparative Example 1 except that the combination of the types of the purification solvent was changed, and the same measurement as in Reference Comparative Example 1 was performed. The results are shown in Table 3.













TABLE 3











O2





Reaction Raw Material
Atmosphere
concentration
Reaction Conditions
Purification Solvent














(g/mol)
in reaction
in reaction
temperature
time
Composition (wt ratio)

















LiPF6
P2O5
Li3PO4
system
system (vol %)
(° C.)
(h)
solvent (X)
solvent (Y)





Reference
5.0/
3.1/
2.5/
dried air
21
200
8
ethyl
toluene 5


Example 1
0.033
0.022
0.022




acetate










95


Reference




21


ethyl
dimethyl


Example 2







acetate
carbonate 5










95


Reference




21


dimethoxy
toluene 5


Example 3







ethane










95


Reference




21


dimethoxy
dimethyl


Example 4







ethane
carbonate 5










95


Reference



nitrogen
0


ethyl
toluene 5


Comparative







acetate


Example 1







95


Reference




0


ethyl
dimethyl


Comparative







acetate
carbonate 5


Example 2







95


Reference




0


dimethoxy
toluene 5


Comparative







ethane


Example 3







95


Reference




0


dimethoxy
dimethyl


Comparative







ethane
carbonate 5


Example 4







95















yield




yield
(%)



amount
F atom
Purity (%) [19F-NMR]
















(g)
yield
LiPO2F2
Li2PO3F
LiF
others







Reference
9.4
88.2
99.9
0
0
0.1



Example 1



Reference
9.2
86.3
99.9
0
0
0.1



Example 2



Reference
9.4
88.2
99.9
0
0
0.1



Example 3



Reference
9.2
86.3
99.9
0
0
0.1



Example 4



Reference
8.6
80.7
99.9
0
0
0.1



Comparative



Example 1



Reference
8.7
81.7
99.9
0
0
0.1



Comparative



Example 2



Reference
8.1
76.0
99.9
0
0
0.1



Comparative



Example 3



Reference
8.2
77.0
99.9
0
0
0.1



Comparative



Example 4










—Description of Table 3—
“wt ratio” represents a mass ratio.
“vol %” represents volume percent.
The “reaction system” is a reaction vessel which is an example of a sealed system containing oxygen.
As shown in Table 3, it is found that, in the reaction step, when reacting LiPF6 with P2O5 (oxide of phosphorus (A)) and Li3PO4 (lithium salt of phosphoric acid (B)), LiPO2F2 was obtained with a higher yield in each Reference Example in which the reaction was performed in the sealed system (reaction vessel) containing oxygen, compared with each Reference Comparative Example in which the reaction was performed in the sealed system of a nitrogen atmosphere. In addition, the obtained LiPO2F2 was also high in purity.
The disclosures of Japanese Patent Application No. 2017-015855 and Japanese Patent Application No. 2017-015856 are incorporated herein by reference in their entirety.
All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each individual document, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

## Claims

1. A method of producing lithium difluorophosphate, the method comprising:
obtaining a first raw material mixture by mixing lithium hexafluorophosphate, at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B), and at least one hydrocarbon solvent selected from the group consisting of tetralin, toluene, hexane and cyclohexane, a content of the hydrocarbon solvent contained in the first raw material mixture being 50% by mass or more with respect to an entirety of the first raw material mixture;
obtaining a second raw material mixture in a form of a wet cake by removing at least a part of the hydrocarbon solvent contained in the obtained first raw material mixture; and
producing a crude product containing lithium difluorophosphate by reacting the second raw material mixture at a temperature of from 100° C. to 350° C.

2. The A method of producing lithium difluorophosphate, the method comprising:
obtaining a first raw material mixture by mixing lithium hexafluorophosphate, at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B), and at least one hydrocarbon solvent selected from the group consisting of tetralin, toluene, hexane and cyclohexane, a content of the hydrocarbon solvent contained in the first raw material mixture being 50% by mass or more with respect to an entirety of the first raw material mixture;
obtaining a second raw material mixture in a form of a wet cake by removing at least a part of the hydrocarbon solvent contained in the obtained first raw material mixture; and
producing a crude product containing lithium difluorophosphate by reacting the second raw material mixture at a temperature of from 100° C. to 350° C., wherein producing the crude product includes producing the crude product by reacting lithium hexafluorophosphate with at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B) according to the following reaction formula:
Reaction formula: x(LiPF6)+y(oxide of phosphorus (A))+z(lithium salt of phosphoric acid (B)) n(LiPO2F2)
wherein, in the reaction formula, x, y, z, and n represent stoichiometric coefficients, each of x and n independently represents an integer of 1 or more, and each of y and z independently represents an integer of 0 or 1 or more, provided that, x, y, z, and n satisfy the following formulae (1) to (4):


x+number of Li atoms in (B)×z=n;  Formula (1):



x+number of P atoms in (A)×y+number of P atoms in (B)×z=n;  Formula (2):



number of O atoms in (A)×y+number of O atoms in (B)×z=2n; and  Formula (3):



6x=2n.  Formula (4):

3. The method of producing lithium difluorophosphate according to claim 1, wherein producing the crude product includes producing the crude product by reacting lithium hexafluorophosphate with at least one selected from the group consisting of lithium metaphosphate, trilithium phosphate, tetralithium pyrophosphate, pentalithium triphosphate, hexalithium tetraphosphate, and diphosphorus pentoxide.

4. The method of producing lithium difluorophosphate according to claim 1, wherein producing the crude product includes producing the crude product by reacting lithium hexafluorophosphate with a compound containing one selected from the group consisting of trilithium phosphate, tetralithium pyrophosphate, pentalithium triphosphate, and hexalithium tetraphosphate, and diphosphorus pentoxide.

5. The method of producing lithium difluorophosphate according to claim 1, wherein producing the crude product includes producing the crude product by reacting lithium hexafluorophosphate with trilithium phosphate and diphosphorus pentoxide.

6. The method of producing lithium difluorophosphate according to claim 1, wherein producing the crude product includes producing the crude product by reacting lithium hexafluorophosphate with lithium metaphosphate.

7. The method of producing lithium difluorophosphate according to claim 1, further comprising:
obtaining a solution by dissolving the crude product in a purification solvent; and
extracting lithium difluorophosphate from the solution.

8. The method of producing lithium difluorophosphate according to claim 7, wherein the purification solvent is a mixed solvent in which at least one solvent (X) selected from the group consisting of ethyl acetate, acetone, dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether, and at least one solvent (Y) selected from the group consisting of toluene, xylene, hexane, acetonitrile, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate, are mixed at a mass ratio (the solvent (X)/the solvent (Y)) in a range from 70/30 to 95/5.

9. The method of producing lithium difluorophosphate according to claim 8, wherein the purification solvent is a mixed solvent containing at least one of ethyl acetate or dimethoxyethane as the solvent (X) and at least one of toluene or dimethyl carbonate as the solvent (Y).

10. The method of producing lithium difluorophosphate according to claim 8, wherein a combination of the solvent (X) and the solvent (Y) is a combination of ethyl acetate and toluene, a combination of ethyl acetate and dimethyl carbonate, a combination of dimethoxyethane and toluene, or a combination of dimethoxyethane and dimethyl carbonate.

11. A method of producing lithium difluorophosphate, the method comprising:
obtaining a first raw material mixture by mixing lithium hexafluorophosphate, at least one selected from the group consisting of an oxide of phosphorus (A) and a lithium salt of a phosphoric acid (B), and a hydrocarbon solvent having from 6 to 12 carbon atoms, a content of the hydrocarbon solvent contained in the first raw material mixture being 50% by mass or more with respect to an entirety of the first raw material mixture;
obtaining a second raw material mixture in a form of a wet cake by removing at least a part of the hydrocarbon solvent contained in the obtained first raw material mixture;
producing a crude product containing lithium difluorophosphate by reacting the second raw material mixture at a temperature of from 100° C. to 350° C.;
obtaining a solution by dissolving the crude product in a purification solvent; and
extracting lithium difluorophosphate from the solution.