METHOD FOR PRODUCING ALKALI METAL HEXAFLUOROPHOSPHATE, ALKALI METAL HEXAFLUOROPHOSPHATE, METHOD FOR PRODUCING ELECTROLYTE CONCENTRATE COMPRISING ALKALI METAL HEXAFLUOROPHOSPHATE, AND METHOD FOR PRODUCING SECONDARY BATTERY

Abstract

Provided are method for producing alkali metal hexafluorophosphate, alkali metal hexafluorophosphate powder, method for producing electrolyte concentrate comprising alkali metal hexafluorophosphate, and method for producing secondary battery. The method for preparing alkali metal hexafluorophosphate includes a step of obtaining an alkali metal hexafluorophosphate by reacting phosphorus pentafluoride with alkali metal fluoride in a haloformate solvent.

Claims

1. A method for preparing alkali metal hexafluorophosphate, the method comprising: obtaining the alkali metal hexafluorophosphate by reacting phosphorus pentafluoride with alkali metal fluoride in a haloformate solvent represented by Formula 1 below: ##STR00003## in Formula 1, X is a halogen group, R is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 5 to 6 ring atoms.

2. The method of claim 1, wherein X is Cl.

3. The method of claim 1, wherein R is an alkyl group having 1 to 3 carbon atoms.

4. The method of claim 3, wherein R is a methyl group or an ethyl group.

5. The method of claim 1, wherein the alkali metal fluoride is LiF, and the alkali metal hexafluorophosphate is LiPF.sub.6.

6. The method of claim 1, further comprising, before reacting the phosphorus pentafluoride with the alkali metal fluoride in the haloformate solvent, obtaining an alkali metal fluoride dispersion by dispersing the alkali metal fluoride in a solid state in the haloformate solvent, wherein the reaction of the phosphorus pentafluoride with the alkali metal fluoride is performed by supplying the phosphorus pentafluoride in a gaseous state into the alkali metal fluoride dispersion.

7. The method of claim 6, wherein obtaining the alkali metal fluoride dispersion and reacting the phosphorus pentafluoride with the alkali metal fluoride is performed in different reactors.

8. The method of claim 1, further comprising, before reacting the phosphorus pentafluoride with the alkali metal fluoride in the haloformate solvent, obtaining the phosphorus pentafluoride by reacting liquid phosphorus trichloride (PCl.sub.3), liquid chlorine (Cl.sub.2), and liquid hydrogen fluoride (HF).

9. The method of claim 8, wherein the phosphorus pentafluoride is obtained in a gas mixture with hydrogen chloride when the phosphorus pentafluoride is obtained by reacting the liquid phosphorus trichloride (PCl.sub.3), the liquid chlorine (Cl.sub.2), and the liquid hydrogen fluoride (HF), and the phosphorus pentafluoride is supplied as the gas mixture with the hydrogen chloride when the alkali metal fluoride is reacted with the phosphorus pentafluoride in the haloformate solvent.

10. The method of claim 9, wherein the hydrogen chloride remaining in the reaction of the phosphorus pentafluoride with the alkali metal fluoride in the haloformate solvent is supplied into a hydrogen chloride absorber and discharged in the form of an aqueous solution of hydrogen chloride.

11. The method of claim 9, further comprising, before reacting the phosphorus pentafluoride with the alkali metal fluoride in the haloformate solvent, obtaining an alkali metal fluoride dispersion by dispersing the alkali metal fluoride in a solid state in the haloformate solvent, wherein obtaining the alkali metal fluoride dispersion and reacting the phosphorus pentafluoride with the alkali metal fluoride is performed in different reactors, the phosphorus pentafluoride and hydrogen chloride mixture remaining in the reaction of the phosphorus pentafluoride and the alkali metal fluoride is fed into the reactor where obtaining the alkali metal fluoride dispersion is performed, the phosphorus pentafluoride in the mixture is reacted with the alkali metal fluoride in the alkali metal fluoride dispersion, and the remaining hydrogen chloride is supplied into the hydrogen chloride absorber and discharged in the form of an aqueous solution of hydrogen chloride.

12. The method of claim 1, wherein the alkali metal hexafluorophosphate is precipitated in a solid state in the haloformate solvent.

13. The method of claim 12, further comprising, filtering the precipitated alkali metal hexafluorophosphate to separate alkali metal hexafluorophosphate, and drying the separated alkali metal hexafluorophosphate under reduced pressure.

14. The method of claim 12, wherein the alkali metal hexafluorophosphate is precipitated as crystal particles in an ellipsoid form.

15. The method of claim 14, wherein at least one of three semiprincipal axes of the crystal particles in the ellipsoid form has different lengths or all of the semiprincipal axes have different lengths.

16. The method of claim 15, wherein the length of the semiprincipal axis is several hundred micrometers in size.

17. A method for preparing an electrolytic concentrate containing an alkali metal hexafluorophosphate, comprising: preparing the alkali metal hexafluorophosphate according to claim 1; dissolving the alkali metal hexafluorophosphate in a non-aqueous organic solvent to obtain an alkali metal hexafluorophosphate solution; concentrating the alkali metal hexafluorophosphate solution into a saturated solution.

18. The method of claim 17, wherein the non-aqueous organic solvent is an acyclic- or cyclic-carbonate ester, a lactone, an acyclic- or a cyclic- ether, or a mixture thereof.

19. The method of claim 17, further comprising diluting the saturated solution of the alkali metal hexafluorophosphate by adding the non-aqueous organic solvent.

20. A method for manufacturing a secondary battery, comprising: obtaining an alkali metal hexafluorophosphate solution by dissolving the alkali metal hexafluorophosphate prepared according to claim 1 or by using the electrolytic concentrate containing the alkali metal hexafluorophosphate prepared according to claim 17; and introducing the alkali metal hexafluorophosphate solution as an electrolyte between a negative electrode active material layer and a positive electrode active material layer.

21. The method of claim 20, wherein the non-aqueous organic solvent is an acyclic- or cyclic-carbonate ester, a lactone, an acyclic- or a cyclic- ether, or a mixture thereof.

22. (canceled)

Description

BRIEF DESCRIPTION OF DRAWINGS

[0018] Example embodiments of the present inventive concept will become more apparent by describing in detail example embodiments of the present inventive concept with reference to the accompanying drawings, in which:

[0019] FIG. 1 is a manufacturing process diagram showing a method for preparing a phosphorus pentafluoride (PF.sub.5), hexafluorophosphate salt (MPF.sub.6), and hexafluorophosphate salt (MPF.sub.6)-containing electrolytic concentrate according to an embodiment of the present inventive concept.

[0020] FIG. 2 is a flow chart showing a method for preparing a phosphorus pentafluoride (PF.sub.5) and hexafluorophosphate salt (MPF.sub.6) according to an embodiment of the present inventive concept.

[0021] FIG. 3 is a schematic view showing a secondary battery according to an embodiment of the present inventive concept.

[0022] FIGS. 4 and 5 are electron microscope images taken of the particles according to Preparation Example A1 and Comparative Example A7, respectively.

[0023] FIG. 6A is a graph illustrating a change in capacity according to cycle number of lithium secondary batteries according to Preparation Example and Comparative Example, and FIG. 6B is a graph illustrating a capacity retention ratio according to cycle number of lithium secondary batteries according to Preparation Example and Comparative Example.

DESCRIPTION OF EXAMPLE EMBODIMENTS

[0024] Hereinafter, to more fully explain the present inventive concept, embodiments according to the present inventive concept will be described in further detail with reference to the accompanying drawings. However, the present inventive concept may be embodied in different forms without limitation to the embodiments explained herein. Like reference numerals denote like elements throughout the specification. In the specification, the sentence a first layer is disposed on a second layer means that these layers are in direct contact with each other, and a third layer(s) is/are disposed between these layers. In the present embodiments, first, second, or third is not intended to impose any limitation on the components, but should be understood as a term for distinguishing the components.

[0025] As used herein, unless otherwise defined, alkyl refers to an aliphatic hydrocarbon group and may be saturated alkyl that does not include a double bond or a triple bond.

[0026] As used herein, unless otherwise defined, alkenyl may be a monovalent group of an alkene which is a hydrocarbon having at least one carbon-carbon double bond.

[0027] As used herein, unless otherwise defined, an aryl may refer to an aromatic hydrocarbon group containing 1 to 5 rings which may be linked or fused.

[0028] In the case where the carbon number or the atom number X to Y is described herein, the case having a number corresponding to all integers between X and Y should also be interpreted as being described together.

[0029] In the present specification, when X to Y is described, the number corresponding to all integers between X and Y should be interpreted as being described together.

[0030] The term anhydrous HF means hydrogen fluoride containing 10 wt ppm or less of water, but the method of the present inventive concept can also use HF containing 100 wt ppm or less of water.

[0031] FIG. 1 is a manufacturing process diagram showing a method for preparing a phosphorus pentafluoride (PF.sub.5), hexafluorophosphate salt (MPF.sub.6), and hexafluorophosphate salt (MPF.sub.6)-containing electrolytic concentrate according to an embodiment of the present inventive concept. FIG. 2 is a flow chart showing a method for preparing a phosphorus pentafluoride (PF.sub.5) and hexafluorophosphate salt (MPF.sub.6) according to an embodiment of the present inventive concept.

[0032] Preparing Method of Phosphorus Pentafluoride (PF.sub.5)

[0033] Referring to FIGS. 1 and 2, phosphorus pentafluoride (PF.sub.5) may be produced in the first reactor 10. Specifically, the first reactor 10 may be a reaction distillation apparatus including a reaction unit 10a and a distillation unit 10b. However, the present inventive concept is not limited thereto, and the first reactor 10 may have a structure in which a distillator is connected to the autoclave.

[0034] Phosphorus pentafluoride (PF.sub.5) may be produced by reacting phosphorus trichloride (PCl.sub.3), chlorine (Cl.sub.2), and hydrogen fluoride (HF) (S1). Phosphorus trichloride (PCl.sub.3), chlorine (Cl.sub.2), and hydrogen fluoride (HF) may be supplied to the first reactor 10, specifically the reaction unit 10a. Here, HF may be anhydrous HF. Thereafter, the reaction according to the following Scheme 1 may be performed in the reaction unit 10a to generate phosphorus pentafluoride (PF.sub.5) and hydrogen chloride (HCl).

[0035] [Scheme 1]

PCl.sub.3(l)+Cl.sub.2(l)+5HF(l).fwdarw.PF.sub.5(g)+5HCl(g)

[0036] When PCl.sub.3, Cl.sub.2, and HF are fed, the molar ratio of HF/PCl.sub.3 may be between 5 and 5.5, and the molar ratio of Cl.sub.2/PCl.sub.3 may be between 1 and 1.5. The reaction according to Scheme 1 may proceed until all PCl.sub.3 is consumed.

[0037] In this case, the first reactor 10 may be in a temperature and pressure range such that the reactants PCl.sub.3, Cl.sub.2, and HF maintain a liquid state, and the products PF.sub.5 and HCl may have a gaseous state. Specifically, the first reactor 10 may be within a temperature range of 20 to 30 C. and a pressure range of 5.0 to 30 kg/cm.sup.2g. Cl.sub.2 may be supplied in a gaseous state or a liquid state.

[0038] The mixture of gaseous PF.sub.5 and HCl, the product of the reaction, may additionally include vaporized Cl.sub.2 and vaporized HF from the remaining reactants and include POF.sub.3, which may be produced when water is incorporated into the reactants. These reaction products may pass through the distillation unit (10b), and then may flow into a condenser 11 through line 101, the mixture of Cl.sub.2, HF, and POF.sub.3 liquefied in the condenser 11 may be refluxed into the first reactor 10 through line 112, and PF.sub.5 and HCl mixture having improved purity may be discharged from the condenser 11 through line 113 in gaseous state.

[0039] Preparing Method of Hexafluorophosphate Salt (MPF.sub.6)

[0040] Hexafluorophosphate salt may be prepared through the following Scheme 2.

[0041] [Scheme 2]

MF(s)+PF.sub.5(g).fwdarw.MPF.sub.6 (s)

[0042] In Scheme 2, M may be an alkali metal, specifically Li, Na, or K. As an example, the MF (alkali metal fluoride) may be LiF, NaF, or KR In addition, the reaction of Scheme 2 may be performed in an organic solvent represented by Formula 1, that is, a haloformate-based solvent. In other words, the hexafluorophosphate salt specifically, the alkali metal hexafluorophosphate may be produced by reacting the phosphorus pentafluoride with the alkali metal fluoride in the haloformate solvent (S3).

##STR00002##

[0043] In Formula 1, X may be a halogen group, specifically, F, Cl, Br, or I. In one example, X may be Cl. R may be an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 5 to 6 ring atoms. The alkyl group may be a linear alkyl group. Furthermore, the alkyl group may be an alkyl group having 1 to 3 carbon atoms. More specifically, the alkyl group may be an alkyl group having 1 to 2 carbon atoms, that is, a methyl group or an ethyl group. The alkenyl group may also be a linear alkenyl group. Furthermore, the alkenyl group may be an alkenyl group having 2 to 3 carbon atoms, specifically vinyl group or an allyl group. The aryl group may be a phenyl group.

[0044] The organic solvent may be methyl chloroformate, ethyl chloroformate, vinyl chloroformate, n-propyl chloroformate, allyl chloroformate, n-butyl chloroformate, n-hexyl chloroformate, phenyl chloroformate, or a mixture thereof.

[0045] Before reacting the phosphorus pentafluoride with the alkali metal fluoride in the haloformate solvent, an alkali metal fluoride (MF) dispersion may be obtained by dispersing alkali metal fluoride (MF) in a solid state in the haloformate solvent (S2). Specifically, after supplying the haloformate-based solvent represented by the Formula 1 through line 31 in a second reactor 30 equipped with a stirrer, the solid state MF is supplied through a line 32, and MF dispersion in the form of a slurry may be obtained by uniformly dispersing the solid MF in the haloformate solvent. The MF dispersion may contain about 15 to 40 wt % MF, for example 25 to 30 wt % MF.

[0046] Thereafter, in one example, after introducing PF.sub.5 in a gaseous state into the same reactor 30, the reaction of Scheme 2 may be performed. In another example, the MF dispersion may be supplied to a third reactor 20 through line 301, and the reaction of Scheme 2 may be performed after introducing the gaseous PF.sub.5 into the third reactor 20. In the reaction, MF may be introduced at a chemical equivalent and PF.sub.5 may be introduced at a chemical equivalent or in excess. Specifically, the molar ratio of PF.sub.5/MF may be 1 to 1.5. In one example, the PF.sub.5 may be supplied as a gas mixture of PF.sub.5 and HCl fed from the condenser 11 via line 113.

[0047] In the third reactor 20, PF.sub.5 is rapidly reacted with MF in the dispersion, and hexafluorophosphate salt or alkali metal hexafluorophosphate (MPF.sub.6) may be precipitated as a solid, for example, as a crystal. The hexafluorophosphate salt has very low or little solubility in the haloformate-based solvent represented by Formula 1, and may be precipitated as crystals in the haloformate-based solvent represented by Formula 1. The above method does not require any concentration process to obtain the hexafluorophosphate salt as a crystal. This can result in a cost reduction and yield improvement as compared to the conventional method of preparing hexafluorophosphate salt which uses a solvent in which hexafluorophosphate salt is easy to dissolve, therefore requires an additional concentration process at a relatively high temperature to obtain hexafluorophosphate salt as a crystal. Furthermore, free hydrofluoric acid, which is an impurity, may be generated as the hexafluorophosphate salt is thermally decomposed due to the high temperature in the concentration process in the conventional method. As the concentration process is omitted in this embodiment, the content of impurities such as free hydrofluoric acid may be reduced. It can improve the purity of hexafluorophosphate salt.

[0048] In the reactor performing the reaction according to Scheme 2, temperature may be maintained at 15 to C. and pressure may be maintained at 0 to 5kg/cm.sup.2g. In the temperature and pressure range of the reactor, a high purity hexafluorophosphate salt may be obtained, the color change of the solvent by heat may be prevented, and the formation of free hydrofluoric acid may be suppressed in the reactor.

[0049] The remaining PF.sub.5 after the reaction may be discharged through line 201 from the reactor 20. When PF5 is supplied via line 113 as a gas mixture with HCl to the third reactor 20, the content of PF.sub.5 in the gas mixture exiting through line 201 after the reaction can be significantly reduced.

[0050] The reaction solution containing hexafluorophosphate salt precipitated as crystals in the third reactor 20 may be supplied to a filter 21 through line 202 and filtered through the filter 21 to separate the hexafluorophosphate salt crystals from a filtrate (S4). The separated crystals may be dried under reduced pressure (S5), for example, by vacuum drying at 20 to 90 C. to obtain hexafluorophosphate salt as crystal particles. Here, the hexafluorophosphate salt crystal particles may have an ellipsoid shape. In this embodiment, the ellipsoid shape in this embodiment, even if it does not completely conform to the definition of the ellipsoid, but may have a surface that is curved and at least one of the three semiprincipal axes has a different length from the others or all three semiprincipal axes have different lengths. The length of these semiprincipal axes may be several hundred micrometer, for example, about 100 to 500 um in size.

[0051] The hexafluorophosphate salt may have a purity of 98 to 99.999 wt %, for example, 99 to 99.999 wt %, specifically 99.9 to 99.999 wt %. The hexafluorophosphate salt may contain 20 to 100 wt ppm, for example 25 to 65 wt ppm, specifically 25 to 35 wt ppm of free hydrofluoric acid, and may contain 5 to 10 wt ppm of water.

[0052] The filtrate obtained from the filter 21 may be in a state in which PF.sub.5 is partially dissolved in the organic solvent of Formula 1. This filtrate may be fed back to the second reactor 30 via line 212. Thereafter, MF may be additionally supplied into the second reactor 30 through the line 32, and the supplied MF may be dispersed in the filtrate fed through the line 212, that is, the PF.sub.5-containing haloformate-based solvent and haloformate-based solvent additionally supplied through the line 31. The dispersed MF may react with PF.sub.5 contained in the filtrate and PF5 or PF.sub.5/HCl mixture discharged from the third reactor 20 via line 201. As a result, a small amount of hexafluorophosphate salt may be generated even in the second reactor 30. Thereafter, the MF dispersion containing a small amount of hexafluorophosphate salt may be fed into the third reactor 20 to perform the reaction as described above.

[0053] Meanwhile, PF.sub.5 in the second reactor 30 may be almost consumed, and the gaseous product exiting the second reactor 30 may contain little or no PF.sub.5 or some PF.sub.5 at a very low content. The gaseous product exiting the second reactor 30 can be fed to the HCl absorber 40 via line 302, and HCl absorbed by water in the HCl absorber 40 may be discharged through line 401 as an aqueous HCl solution. In other example, wherein the HCl remaining in the reaction of the phosphorus pentafluoride with the alkali metal fluoride in the haloformate solvent in the third reactor 20 may be supplied into a HCl absorber 40 and may be discharged in the form of an aqueous solution of HCl through line 401.

[0054] Preparing Method of Hexafluorophosphate Salt (MPF.sub.6)-Containing Electrolytic Concentrate

[0055] The hexafluorophosphate salt crystal particles may be fed into a fourth reactor 22 via line 211. The fourth reactor 22 may be supplied with a non-aqueous organic solvent through line 221, and in the the fourth reactor 22, hexafluorophosphate salt crystal particles are dissolved in the non-aqueous organic solvent while stirring to obtain a hexafluorophosphate salt solution. Here, dissolution may be performed at a temperature of 40 C. or lower to prevent decomposition of the hexafluorophosphate salt, thereby inhibiting free hydrofluoric acid generation.

[0056] The hexafluorophosphate salt solution can be concentrated to obtain a concentrated solution as a saturated solution. The concentration can be carried out in a vacuum of about 40 C. while bubbling nitrogen gas in the solution. In the process, the non-aqueous organic solvent may be evaporated, at the same time, the concentration of halo ions for example, chlorine ions derived from free hydrofluoric acid and the solvent represented by the Formula 1 may be reduced. The hexafluorophosphate salt in the obtained hexafluorophosphate salt concentrate may be contained at a concentration of about 35 to 70 wt %, for example, 40 to 55 wt %, specifically 45 to 50 wt %.

[0057] The non-aqueous organic solvent may be additionally supplied through the line 221 in the concentrate to prepare an electrolytic concentrate of about 25 to 34 wt %, for example, 29 to 33 wt %, specifically, 30 to 32 wt %. Thereafter, the concentrate may be supplied to a filter 23 through line 223 and filtered through the filter 23 to remove a trace solid metal fluoride salt, thereby obtaining a concentrate 231 having improved purity.

[0058] As an example, a solution obtained by dissolving LiPF.sub.6 crystals in ethyl methyl carbonate may be concentrated to obtain a concentrate as a saturated solution. This concentrate may be at a concentration of about 45 to 50 wt %. Ethyl methyl carbonate may be further added to the concentrate to obtain an electrolytic concentrate having a concentration of 29.5 to 32.5 wt %.

[0059] Energy Storage Devices

[0060] FIG. 3 is a schematic view showing a secondary battery according to an embodiment of the present inventive concept. In the present embodiment, the secondary battery may be an alkali ion secondary battery, for example, a lithium secondary battery, a sodium secondary battery, or a potassium secondary battery. However, it is not limited to this.

[0061] Referring to FIG. 3, the energy storage device includes the negative electrode active material layer 120, the positive electrode active material layer 140, and a separator 130 interposed therebetween. The electrolyte solution 160 may be disposed or introduced between the anode active material layer 120 and the cathode active material layer 140. The negative electrode active material layer 120 may be disposed on the negative electrode current collector 110, and the positive electrode active material layer 140 may be disposed on the positive electrode current collector 150.

[0062] The separator 130 may be a porous insulator, for example, a film laminate containing polyethylene or polypropylene, or a nonwoven fabric containing cellulose, polyester, or polypropylene.

[0063] The electrolyte solution 160 may be a non-aqueous electrolyte solution, including an electrolyte and a non-aqueous organic solvent, and the electrolyte may be LiPF.sub.6 for the lithium secondary battery, NaPF.sub.6 for the sodium secondary battery, or KPF.sub.6 for the potassium secondary battery. For example, the electrolyte solution 160 may be obtained by diluting the aforementioned hexafluorophosphate salt (MPF.sub.6)-containing electrolytic concentrate using a non-aqueous organic solvent and adding various additives thereto. As another example, the electrolyte solution 160 may be obtained by dissolving the hexafluorophosphate salt (MPF.sub.6) crystal powder described above in a non-aqueous organic solvent and adding various additives thereto. The non-aqueous organic solvent may be an acyclic or cyclic carbonate ester, a lactone, an acyclic or a cyclic ether, or a mixture thereof. The acyclic carbonate ester may be dimethyl carbonate, diethyl carbonate, or methyl ethyl carbonate, and the cyclic carbonate ester may be ethylene carbonate, propylene carbonate, or butylene carbonate. The lactone may be gamma-butyrolactone or gamma-valerolactone. The ether may be an acyclic ether such as dimethoxy ethane, diethyl ether, or a cyclic ether such as tetrahydrofuran, methyl terahydrofuran or dioxane. However, the present inventive concept is not limited thereto, and the non-aqueous organic solvent may be any of the solvents in electrolyte solutions used in the secondary battery.

[0064] The negative electrode active material layer 120 includes a negative electrode active material which can intercalate/decalate alkali metal ions or causing a conversion reaction, such as metal, a metal alloy, a metal oxide, a metal fluoride, a metal sulfide, and carbon material such as natural graphite, artificial graphite, cokes, carbon black, carbon nanotubes, and graphene. The negative electrode active material layer 120 may further include a conductive material and/or a binder.

[0065] The positive electrode active material layer 140 may contain a composite oxide or a composite phosphate of an alkali metal and at least one of cobalt, manganese, nickel, aluminum, or a combination thereof. As an example, for the lithium secondary battery, the positive electrode active material may be LiCoO.sub.2, LiNiO.sub.2, Li(Co.sub.xNi.sub.1-x)O.sub.2 (0.5x<1), Li(Ni.sub.1-x-yCo.sub.yMn.sub.z)O.sub.2 (0.1y0.5, 0.1z0.5, 0<y+z<1), Li(Ni.sub.1-x-yCo.sub.xAl.sub.y)O.sub.2 (0.05y0.5, 0.05z0.5, 0<y+z<1), LiMn.sub.2O.sub.4, LiFePO.sub.4, or a combination of two or more thereof. The cathode active material layer 140 may further include a conductive material and/or a binder.

[0066] The positive electrode current collector 150 and the negative electrode current collector 110 may be metal having heat resistance, for example, iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, platinum, and the like irrespective of each other.

[0067] Hereinafter, examples are provided to help in understanding the present inventive concept. However, the following examples are merely provided to help in understanding of the present inventive concept, and the present inventive concept is not limited to the following examples.

[0068] Preparation Example of PF.sub.5

[0069] 30 kg Cl.sub.2 (g), 42.32 kg anhydrous HF (l), and 58.1 kg PCl.sub.3 (l) were quantitatively injected into a 500 L high pressure reactor cooled to 25 C. or lower, and reacted at a pressure of 9 kg/cm.sup.2g until all of the injected PCl.sub.3 (l) was consumed to obtain a gas containing PF.sub.5 as a product.

[0070] Preparation Example of LiPF.sub.6

Preparation Example A1

[0071] As a reaction solvent, 188 kg of methyl chloroformate (ClCOOR, R: CH.sub.3) (l) was added to a PTFE-lined reactor equipped with an agitator, and then 10.7 kg of lithium fluoride (LiF) (s) was added and then stirred to disperse in the reaction solvent. When a uniform dispersion was obtained, PF.sub.5 gas was introduced through the inlet tube while the reactor temperature was cooled to 0 C. or lower, and the reaction proceeded. The reaction temperature was maintained at 20 C. or lower, the pressure was maintained at 1.2 kg/cm.sup.2g or lower. As LiF was consumed, lithium hexafluorophosphate (LiPF.sub.6) was produced and precipitated as crystals in methyl chloroformate. The reaction was terminated when the LiF was exhausted, and the reaction solution containing LiPF.sub.6 precipitated as a crystal was filtered using a filter to separate the crystals and the filtrate. The filtrate was reused in the next reaction, and the separated crystals were vacuum dried at 50 to 80 C. to obtain LiPF.sub.6 as crystals.

[0072] The production of standard LiPF.sub.6 was confirmed by .sup.19F NMR spectrum ((470.40 MHz, CD.sub.3CN): d 71.48 (d, J=705.6)) and the yield was 99.9%. The purity was 99.985%, the concentration of free hydrofluoric acid was 30 ppm by weight, and the moisture was 8 ppm by weight.

Preparation Example A2

[0073] LiPF.sub.6 was obtained as crystals in the same manner as in Preparation Example A1, except that 188 kg of ethyl chloroformate (ClCOOR, R: CH.sub.2CH.sub.3) was added as a reaction solvent.

[0074] The production of standard LiPF6 was confirmed by .sup.19F NMR spectrum ((470.40 MHz, CD.sub.3CN): d 71.48 (d, J=705.6)) and the yield was 99.9%. The purity was 99.985%, the concentration of free hydrofluoric acid was 30 ppm by weight, and the moisture was 9 ppm by weight.

Preparation Example A3

[0075] LiPF.sub.6 was obtained as crystals in the same manner as in Preparation Example A1, except that 188 kg of vinyl chloroformate (ClCOOR, R: CHCH.sub.2) was added as a reaction solvent.

[0076] The production of standard LiPF.sub.6 was confirmed by .sup.19F NMR spectrum ((470.40 MHz, CD.sub.3CN): d 71.48 (d, J=705.6)) and the yield was 99%. The purity was 99.9%, the concentration of free hydrofluoric acid was 55 ppm by weight, and the moisture was 9 ppm by weight.

Preparation Example A4

[0077] LiPF.sub.6 was obtained as crystals in the same manner as in Preparation Example A1, except that 188 kg of n-propyl chloroformate (ClCOOR, R: (CH.sub.2).sub.2CH.sub.3) was added as a reaction solvent.

[0078] The production of standard LiPF.sub.6 was confirmed by .sup.19F NMR spectrum ((470.40 MHz, CD.sub.3CN): d 71.48 (d, J=705.6)) and the yield was 99%. The purity was 99.8%, the concentration of free hydrofluoric acid was 62 ppm by weight, and the moisture was 9 ppm by weight.

Preparation Example A5

[0079] LiPF.sub.6 was obtained as crystals in the same manner as in Preparation Example A1, except that 188 kg of allyl chloroformate (ClCOOR, R: CH.sub.2CHCH.sub.2) was added as a reaction solvent.

[0080] The production of standard LiPF.sub.6 was confirmed by .sup.19F NMR spectrum ((470.40 MHz, CD.sub.3CN): d 71.48 (d, J=705.6)) and the yield was 99%. The purity was 99.1%, the concentration of free hydrofluoric acid was 60 ppm by weight, and the moisture was 10 ppm by weight.

Preparation Example A6

[0081] LiPF.sub.6 was obtained as crystals in the same manner as in Preparation Example A1, except that 188 kg of n-butyl chloroformate (ClCOOR, R: (CH.sub.2).sub.3CH.sub.3) was added as a reaction solvent.

[0082] The production of standard LiPF.sub.6 was confirmed by .sup.19F NMR spectrum ((470.40 MHz, CD.sub.3CN): d 71.48 (d, J=705.6)) and the yield was 99%. The purity was 98.9%, the concentration of free hydrofluoric acid was 85 ppm by weight, and the moisture was 9 ppm by weight.

Preparation Example A7

[0083] LiPF.sub.6 was obtained as crystals in the same manner as in Preparation Example A1, except that 188 kg of n-hexyl chloroformate (ClCOOR, R: (CH.sub.2).sub.5CH.sub.3) was added as a reaction solvent.

[0084] The production of standard LiPF.sub.6 was confirmed by .sup.19F NMR spectrum ((470.40 MHz, CD.sub.3CN): d 71.48 (d, J=705.6)) and the yield was 98%. The purity was 98.4%, the concentration of free hydrofluoric acid was 67 ppm by weight, and the moisture was 9 ppm by weight.

Preparation Example A8

[0085] LiPF.sub.6 was obtained as crystals in the same manner as in Preparation Example A1, except that 188 kg of phenyl chloroformate (ClCOOR, R: phenyl) was added as a reaction solvent.

[0086] The production of standard LiPF.sub.6 was confirmed by .sup.19F NMR spectrum ((470.40 MHz, CD.sub.3CN): d 71.48 (d, J=705.6)) and the yield was 98%. The purity was 98.2%, the concentration of free hydrofluoric acid was 95 ppm by weight, and the moisture was 9 ppm by weight.

Comparative Example A1

[0087] As a reaction solvent, 188 g of dimethyl carbonate (R.sub.1OCOOR.sub.2, R.sub.1 & R.sub.2: CH.sub.3) was added to a PTFE-lined reactor, and then 10.7 g of lithium fluoride (LiF) (s) was added and then stirred to disperse in the reaction solvent. When a uniform dispersion was obtained, PF.sub.5 gas was slowly introduced through the inlet tube while the reactor temperature was cooled to 10 C. or lower and the reactor pressure was maintained at 1.2 kg/cm.sup.2g, and the reaction proceeded. As LiF was consumed, LiPF.sub.6 dissolved in the solvent was produced. The reaction was terminated when all of the LiF was consumed, and the reaction solution was concentrated in vacuum at 0 to 50 C. to obtain LiPF.sub.6 as crystals.

[0088] The production of standard LiPF.sub.6 was confirmed by .sup.19F NMR spectrum ((470.40 MHz, CD.sub.3CN): d 71.48 (d, J=705.6)) and the yield was 98%. The purity was 98.1%, the concentration of free hydrofluoric acid was 186 ppm by weight, and the moisture was 8 ppm by weight.

Comparative Example A2

[0089] LiPF.sub.6 was obtained as crystals in the same manner as in Comparative Example A1, except that 188 g of ethyl methyl carbonate (R.sub.1OCOOR.sub.2, R.sub.1: CH.sub.2CH.sub.3 & R.sub.2: CH.sub.3) was added as a reaction solvent.

[0090] The production of standard LiPF.sub.6 was confirmed by .sup.19F NMR spectrum ((470.40 MHz, CD.sub.3CN): d 71.48 (d, J=705.6)) and the yield was 98%. The purity was 98.8%, the concentration of free hydrofluoric acid was 212 ppm by weight, and the moisture was 8 ppm by weight.

Comparative Example A3

[0091] LiPF.sub.6 was obtained as crystals in the same manner as in Comparative Example A1, except that 188 g of diethyl carbonate (R.sub.1OCOOR.sub.2, R.sub.1 & R.sub.2: CH.sub.2CH.sub.3) was added as a reaction solvent.

[0092] The production of standard LiPF.sub.6 was confirmed by .sup.19F NMR spectrum ((470.40 MHz, CD.sub.3CN): d 71.48 (d, J=705.6)) and the yield was 98%. The purity was 98.1%, the concentration of free hydrofluoric acid was 209 ppm by weight, and the moisture was 9 ppm by weight.

Comparative Example A4

[0093] LiPF.sub.6 was obtained as crystals in the same manner as in Comparative Example A1, except that 188 g of methyl formate (HCOOR, R: CH.sub.3) was added as a reaction solvent.

[0094] The production of standard LiPF.sub.6 was confirmed by .sup.19F NMR spectrum ((470.40 MHz, CD.sub.3CN): d 71.48 (d, J=705.6)) and the yield was 98%. The purity was 97.6%, the concentration of free hydrofluoric acid was 266 ppm by weight, and the moisture was 8 ppm by weight.

Comparative Example A5

[0095] LiPF.sub.6 was obtained as crystals in the same manner as in Comparative Example A1, except that 188 g of ethyl formate (HCOOR, R: CH.sub.2CH.sub.3) was added as a reaction solvent.

[0096] The production of standard LiPF.sub.6 was confirmed by .sup.19F NMR spectrum ((470.40 MHz, CD.sub.3CN): d 71.48 (d, J=705.6)) and the yield was 98%. The purity was 97.5%, the concentration of free hydrofluoric acid was 281 ppm by weight, and the moisture was 8 ppm by weight.

Comparative Example A6

[0097] LiPF6 was obtained as crystals in the same manner as in Comparative Example A1, except that 188 g of acetonitrile (CH.sub.3CN) was added as a reaction solvent.

[0098] The production of standard LiPF.sub.6 was confirmed by .sup.19F NMR spectrum ((470.40 MHz, CD.sub.3CN): d 71.48 (d, J=705.6)) and the yield was 98%. The purity was 98.1%, the concentration of free hydrofluoric acid was 254 ppm by weight, and the moisture was 10 ppm by weight.

Comparative Example A7

[0099] LiPF.sub.6 was obtained as crystals in the same manner as in Comparative Example A1, except that 340 g of anhydrous HF was added as a reaction solvent.

[0100] The production of standard LiPF.sub.6 was confirmed by .sup.19F NMR spectrum ((470.40 MHz, CD.sub.3CN): d 71.48 (d, J=705.6)) and the yield was 88%. The purity was 99.985%, the concentration of free hydrofluoric acid was 28 ppm by weight, and the moisture was 8 ppm by weight.

TABLE-US-00001 TABLE 1 LiPF.sub.6 LiPF.sub.6 yield purity Free HF moisture reaction solvent (%) (wt %) (wt ppm) (wt ppm) Preparation ClCOOR R:CH.sub.3 99.9 99.985 30 8 Example A1 Preparation R:CH.sub.2CH.sub.3 99.9 99.985 30 9 Example A2 Preparation R:CHCH.sub.2 99 99.9 55 9 Example A3 Preparation R:(CH.sub.2).sub.2CH.sub.3 99 99.8 62 9 Example A4 Preparation R:CH.sub.2CHCH.sub.2 99 99.1 60 10 Example A5 Preparation R:(CH.sub.2).sub.3CH.sub.3 99 98.9 85 9 Example A6 Preparation R:(CH.sub.2).sub.5CH.sub.3 98 98.4 67 9 Example A7 Preparation R:phenyl 98 98.2 95 9 Example A8 Comparative R.sub.1OCOOR.sub.2 R.sub.1 & R.sub.2:CH.sub.3 98 98.1 186 8 Example A1 Comparative R.sub.1:CH.sub.2CH.sub.3 & 98 98.8 212 8 Example A2 R.sub.2:CH.sub.3 Comparative R.sub.1 & R.sub.2:CH.sub.2CH.sub.3 98 98.1 209 9 Example A3 Comparative HCOOR R:CH.sub.3 98 97.6 266 8 Example A4 Comparative R:CH.sub.2CH.sub.3 98 97.5 281 8 Example A5 Comparative CH.sub.3CN 98 98.1 254 10 Example A6 Comparative anhydrous HF 88 99.985 28 8 Example A7

[0101] Referring to Table 1, in the case of the method according to each of Comparative Examples A1 to A7, lithium hexafluorophosphate was obtained as a solution because lithium hexafluorophosphate has a high solubility in the solvent used, and the solution was concentrated to obtain lithium hexafluorophosphate as a crystal. On the other hand, in the methods according to each of Preparation Examples A1 to A8, the lithium hexafluorophosphate has low solubility in the haloformate-based solvent used, and thus the produced lithium hexafluorophosphate could be precipitated as crystals in the solvent without a concentration process. Therefore, no additional concentration process is necessary to obtain lithium hexafluorophosphate as crystals, so that the cost can be reduced and the yield is also improved.

[0102] In addition, in the methods according to each of Comparative Examples A1 to A7, it can be seen that during the concentration process, lithium hexafluorophosphate is decomposed by heat to generate free hydrofluoric acid. In addition, the concentration process also has the disadvantage that can cause a color change of the solution. As a result, the purity of the obtained lithium hexafluorophosphate may be low. On the other hand, in the method according to each of Preparation Examples Al to A8, it can be seen that the content of free hydrofluoric acid as an impurity is very low and the purity is very excellent.

[0103] In addition, in the case of the method according to each of Preparation Examples A1 to A5 using an alkyl or alkenyl group having 1 to 3 carbon atoms as the reaction solvent, it can be seen that the purity of lithium hexafluorophosphate is improved compared to the method according to each of Preparation Examples A6 to A8. Further, in the case of the method according to each of Preparation Examples Al to A2 using an alkyl group having 1 to 2 carbon atoms as the reaction solvent, it can be seen that the purity is further improved and the yield is also improved.

[0104] FIGS. 4 and 5 are electron microscope images taken of the particles according to Preparation Example Al and Comparative Example A7, respectively.

[0105] Referring to FIGS. 4 and 5, it can be seen that the particles according to Preparation Example A1 have an ellipsoid-like form. On the other hand, it can be seen that the particles according to Comparative Example A7 have a cuboid shape.

Preparation Example of LiPF.SUB.6 .Solution

Preparation Examples B11

[0106] 74 kg of diethyl carbonate was added to a reactor, followed by stirring while maintaining the temperature at 20 C. or lower. 60 kg of lithium hexafluorophosphate obtained through Preparation Example A1 was added to the stirred diethyl carbonate, but slowly added to prevent the internal temperature from rising above 40 C. After the addition, the mixture was stirred for about 1 hour to completely dissolve lithium hexafluorophosphate, and the temperature of the reactor was increased to 40 C., and vacuum concentration was performed while passing nitrogen gas at the bottom of the reactor. Diethyl carbonate was evaporated during the concentration and free fluoric acid and chlorine ions were also removed. Diethyl carbonate was added to the concentrated product to make the concentration 30-320.5 wt %, and the purity of the solution was improved by removing a small amount of lithium fluoride through a filter.

Preparation Examples B2

[0107] A lithium hexafluorophosphate solution was prepared in the same manner as in Preparation Example B1 except that ethyl methyl carbonate was added as the reaction solvent.

Preparation Examples B3

[0108] A lithium hexafluorophosphate solution was prepared in the same manner as in Preparation Example B1 except that diethyl carbonate was added as the reaction solvent.

Preparation Example of Lithium Secondary Battery

Preparation Example

[0109] A lithium secondary battery was manufactured by forming a positive electrode active material layer using mixed LiCoO.sub.2 and Li (Ni.sub.0.8Co.sub.0.15Al.sub.0.05)O.sub.2, forming a negative electrode active material layer using graphite, disposing a glass filter separator, and injecting an electrolyte solution in which LiPF.sub.6 crystals according to LiPF.sub.6 Preparation Example A1 were dissolved in diethyl carbonate at a concentration of 1 M between the positive active material layer and the negative electrode active material layer.

Comparative Example

[0110] A lithium secondary battery was manufactured in the same manner as in Preparation Example, except that an electrolyte solution in which LiPF.sub.6 crystals according to Comparative Example A7 were dissolved in diethyl carbonate at a concentration of 1 M was used.

[0111] FIG. 5A is a graph illustrating a change in capacity according to cycle number of lithium secondary batteries according to Preparation Example and Comparative Example, and FIG. 5B is a graph illustrating a capacity retention ratio according to cycle number of lithium secondary batteries according to Preparation Example and Comparative Example.

[0112] Referring to FIGS. 5A and 5B, it can be seen that the lithium secondary battery according to Preparation Example exhibits a better capacity retention ratio than the lithium secondary battery according to Comparative Example.

[0113] As described above, according to the present inventive concept, by eliminating the crystallization step and/or concentration step for the precipitation of crystals of hexafluorophosphate salt, the process cost can be lowered, while the high purity hexafluorophosphate salt with improved yield and reduced impurities such as free hydrofluoric acid can be provided.

[0114] While the exemplary embodiments of the present inventive concept have been described above, those of ordinary skill in the art should understood that various changes, substitutions and alterations may be made herein without departing from the spirit and scope of the present inventive concept as defined by the following claims.