NL2020683A

NL2020683A - Production of lithium hexafluorophosphate

Info

Publication number: NL2020683A
Application number: NL2020683A
Authority: NL
Inventors: Diphago Stanley Lekgoathi Mpho; John Le Roux Petrus; Sello Mmotong Danny
Original assignee: The South African Nuclear Energy Corporation Soc Ltd
Priority date: 2018-03-29
Filing date: 2018-03-29
Publication date: 2018-07-16
Also published as: SG11202009329RA; WO2019186481A1; EP3774656A1; JP2021519738A; NL2020683B1; AU2019244870A1; US20210024361A1; KR20200136987A; CN111989295A; TW201942051A

Abstract

A method of producing lithium hexafluorophosphate (LiPF6) includes fluorinating lithium phosphate (LiF) by reacting it with a fluorination agent in a liquid medium that is non-reactive with, i.e. is inert to, the fluorination agent, thereby producing LiPF6.

Description

FIELD OF THE INVENTION

THIS IN VENTION relates to the production of lithium hexafluorophosphate. The invention provides a method of producing lithium hexafluorophosphate, and extends to lithium hexafluorophosphate produced in accordance with the method. The invention also extends to a method of producing an electrolyte, and extends to an electrolyte produced in accordance with the method. The invention also provides an electric battery and a method of manufacturing an electric batten^-. Hie invention further provides another method of producing an electrolyte.

BACKGROUND TO THE INVENTION

IT IS KNOWN to use lithium hexafluorophosphate (LiPF,,) as an electrolyte in lithium ion batteries.

Conventional preparation methods of LiPF₆ include wet chemical synthesis methods in aqueous reaction conditions and dry synthesis methods in non-aqueous conditions.

A common method of preparing LiPF« using a wet chemical preparation method involves synthesizing water stable organic complexes such as pyridinium or tetraacetonitrilolithium hexafluorophosphate, and converting the complexes into solvated LiPF,,. The pyridinium cation is preferred to the acetonitrile cation as the latter poorly dissolves the lithium base used in a subsequent reaction to substitute the organic cation. However, tetraacetonitrilolithium hexafluorophosphate complex' produced by a reaction of LiF salt and PF< gas in the presence of acetonitrile allows low temperature decomposition of the complex in vacuum (20 °C) to produce high purity’ LiPF,,.

Various phosphorus halides and a solution of pyridinium poly (hydrogen fluoride) has been used to synthesize the pyridinium hexafluorophosphate complex, and further reacted the complex with alkali metal hydroxides to obtain their corresponding hexafluorophosphate complexes. Although several alkali-PF₆ salts are stable in sulphuric acid, L,iPF₆ is very unstable and cannot be isolated due to the presence of water in the intermediate products. Reaction Equations 1.1 and 1.2 show the chemical reactions involved during the formation of the hexafluorophosphate complex:

PZX3 + Cd LXH f (HL),,' ->

PX₅ + Cd LXH F(HF) / ->

CdLXH PE,' + 11,/ + 3HX Cd LXIL PF,,' + 5HX (Eq. A) (Eq. B) where

-)

Z is oxygen or sulphur; and

X is chlorine or bromine.

It is also known that hexafluorophosphate complexes of ammonia and alkali metals can be prepared by reacting ammonium or alkali metal fluorides with phosphorus pentachloride, however, the subsequent isolation process is tedious and time consuming as the yields are very low.

Another preparation method of LiPF₆ using wet chemical synthesis involves reacting hexafluorophosphoric acid with pyridine to form the complex, and then exchanging the pyridinium cation with a lithium cation from a hydroxide or alkoxide to obtain a LiPF₆ pyridine complex which can be treated further to produce high purity LiPF₆. This is illustrated in Equations 1.3 and 1.4:

HPF₆ + C₅H₅N -► CjH₅NPF₆ (Eq. C)

C₅H₅NHPF₆ + LiOH + CH,OH -* LiPF₆.C₅H₅N (Eq. D)

The lithium base used in this method is dissolved in an alcohol media to avoid a subsequent reaction between the synthesized LiPF₆ and water. This method is based on the fact that alkali metal ions from corresponding hydroxides are easily exchanged with the pyridinium cation. Tire pyridinium hexafluorophosphate yield is approximately 70%, and a further 96% LiPF,, crystalline product is obtained from a subsequent reaction of the complex with a lithium base and drying the product in a partial vacuum at 30 °C.

Hexafluorophosphoric acid may also be reacted with lithium hydroxide in water to form LiPF₍„ however, the formed electrolyte quickly hydrolyzes and precipitate in the form of various other species such as PO2F2', PO4’, and HPO₃F. Another disadvantage associated with this preparation method includes the use of hexafluorophosphoric acid which is a mixture of several weak acids resulting from gradual decomposition of the HPF₆ itself. Therefore, the amount of PF₆ ion available to react is not always known. This requires that a preliminary titration be undertaken between the acid and an alkali hydroxide to determine the exact stoichiometry of the PF₆‘ ion in the acid before neutralization with pyridine.

Other w’et chemical synthesis methods involve the reactions of lithium sources and hexafluorophosphate salts in various solvents. The reaction of LiH with NHjPFg in dimethoxyethane (DME) is one such an example as shown in Equation 1.5:

•Λ

NIIiPF, (s)

LiH,

DMÏ

IJPF_&sj + NH_3(b) + Sf, (Eq. E)

In this chemical process, an ether with at least two functionalities and enough spacing to complex a lithium ligand, for example, 1,2-dimethoxyethane is used to dissolve the ammonium hexafluorophosphate salt. The complex 2DME.LiPF₆, ammonia and hydrogen gas are formed as products. The complex is stable and is further dissolved in an electrolyte solvent for applications in batteries, however, the ether is difficult to remove and will feature in the final electrolyte.

To eliminate the ether interference, the reaction between a lithium source, for example LiH, and NH._tPF₆ can be carried out directly in a solvent to be used in the final electrolyte. At least one of the reactants must be soluble and the other should be insoluble in the solvent used so that excess salts can be easily removed via precipitation from the electrolyte. If a. two solvent process is carried out, then the initial solvent used must be non-protic, have high solubility for the lithium compound used and possess a low boiling point. A more viscous, high boiling point solvent, such as ethylene carbonate (EC), can then be added as a co-solvent followed by the evaporation of the initial solvent.

Lithium hexafluorophosphate may also be synthesized using LiF and PCI? in water, however, low yields are obtained with this preparation method. To improve on the yield, a chloride salt such as LiCl or even LiF is dissolved in anhydrous HF, and then PCI? is slowly added to precipitate a lithium hexafluorophosphate salt with a higher yield.

A further method of preparing LiPF₆ involves using PCI? and HF in an anhydrous organic solvent of the type carbonic ethers and esters. The carbonates such as ethyl carbonate and other related solvents react and form adducts with PF? gas. Not only is the reaction of PF? and the solvent a challenge when this preparation method is used, but the introduction of HF is not desirable as it will further react and introduce additional complications.

In light of the above, the following shortcomings associated with using wet chemical synthesis methods for the preparation of LiPF,_:, salt have been identified:

(i) The Li⁺ ion is too small to precipitate with a relatively larger PF,,' ion; hence obtaining LiPFf, crystals directly from the solution is difficult.

(ii) The LiPF,_; salt itself is thermally unstable and will decompose during thermal treatment to remove the solvent used.

A widely used method for the synthesis of LiPF₆ using non-aqueous conditions involves a reaction between LiF and PF₅ gas to form LiPF₆. Various drawbacks are associated with this method, including the difficulty of handling poisonous PF_S gas and low product purity (90-95%) compared to the required purity of at least 99.9% of LiPF« used in battery applications. Excess LiF and LiHF? are also formed as by-products in this preparation method.

This technique has been modified to improve the purity of the LiPF₍, product by reacting acetonitrile with the obtained LiPF₆ to form tetraacetonitrilolithium hexafluorophosphate, which, upon partial heating in vacuum, regenerates a purer LiPF₆ salt.

The LiPF₆ salt may also be synthesized by reacting lithium fluoride and bromine trifluoride in excess phosphorous pentoxide. Other methods for LiPF₆ synthesis involve in situ generation of PF_Sgas and its subsequent reaction with a lithium source to form the LiPF₆ salt. This technique is said to eliminate moisture ingress into the intermediates during the chemical reaction.

Solid state thermal reactions provide alternative dry synthesis methods to the gaseous routes for the preparation of LiPF₆. A lithium source, for an example, may be reacted with a phosphate such as ammonium phosphate at a high temperature (300 °C) in a solid state to form lithium metaphosphate, which is then further reacted with ammonium fluoride at 150 °C to obtain LiPF₆. This is shown in Equations 1.6 and 1.7 below:

(NTL)₂HPO₄ + LbO -> 21Λ PO, + 4NH₃ + 3ELO (Eq. F)

LiPO_?, -t 6NILF -► LiPF(, + 6NH₃ + 3FFO (Eq. G)

Solid state thermal reactions tend to be incomplete if powders are mixed as received and heated at elevated temperatures. This, therefore, presents a challenge to thoroughly grind the reactants together and press them into pellets to facilitate contact between them. Despite the high temperature and pressures needed to facilitate solid state reactions, these types of chemical reactions are still the preferred reaction methods for producing advanced, highly ordered crystal structures such as special ceramics, piezoelectrics and some scintillation crystals, hence the technique may be used to produce highly crystalline LiPF₆.

The quest for water free and pure LiPF₆ electrolyte salt has also prompted the use of fluorine gas at room temperature to make the salt. In contrast to using anhydrous hydrogen fluoride as a solvent during fluorination of LiF by PF₅ gas, the use of pure fluorine does not produce oxyfluorides of the form LiPO_xF_v as impurities. These oxyfluorides are partially dissolved in HF and therefore remain as impurities in the final product.

It has been shown that LiPF₆ can be produced by reacting phosphorus with fluorine gas at a temperature of 23°C to generate PF_S gas, which, is then reacted in situ with LiF to produce LiPF₀. The fluorine gas is first liquefied at -196 °C using liquid nitrogen, and then the temperature is increased stepwise to -80 °C, where the reaction commenced. The reaction is allowed to occur slowly until a temperature of 23 °C where the LiPF,, production rate is high. The temperature is further elevated to 150 °C to obtain a purer product. This technique is time consuming, and the reaction is expected to be completed after 10 hr, which is expensive in terms of production time.

It is an object of the invention to at least alleviate the drawbacks mentioned above, and particularly to minimize and more preferably to avoid completely the formation of HF.

IN ACCORDANCE WITH A FIRST ASPECT OF THE INVENTION IS PROVIDED a method of producing lithium hexafluorophosphate (LiPF₆), the method including fluorinating lithium fluoride (LiF) by reacting it with a fluorination agent in a liquid medium that is non-reactive with, i.e. is inert to, the fluorination agent, thereby producing LiPF₆.

The reaction is therefore performed in the liquid medium.

The liquid medium may, in particular, be a perhalogenated organic compound.

In this specification “jperWogenataf’ means, as is conventionally understood in the art of the invention, a fully halogenated version of an organic compound, in that all of the hydrogen atoms of the organic compound have been substituted with halogen atoms, thus providing the perhalogenated organic compound. For example, if the organic compound is decalin (CioH_ls), the perhalogenated organic compound is perfluorodecalin (C_i0Fi_K).

However, the above meaning of ‘'‘’perhalogenated'' does not exclude that the perhalogenated organic compound may be a virtually fully halogenated version of the organic compound, in which case the perhalogenated organic compound may still include some hydrogen atoms; and/or that the perhalogenated organic compound is not a saturated organic compound, e.g. that it is an alkene or an alkyne.

and the meaning afforded to ‘perhalogencitecf ' in this specification is therefore broader in scope than the conventional meaning.

In any event, the extent of halogenation of the organic compound, as embodied in the perhalogenated organic compound when it provides the liquid medium, is preferably such that the perhaiogenated organic compound is inert to the fluorination agent, i.e. is non-reactive with the fluorination agent, and is preferably a solvent for the fluorination agent.

The LiF may be in solid, e.g. granular, form.

The fluorination agent may, in particular, be phosphorous pentafluoride (PF₅). Thus, fluorinating the LiF may include reacting the LiF withPF,.

The PF? may, in particular, be gaseous PF₅.

More particularly, reacting the LiF with gaseous PF₅ may include providing the LiF in the liquid medium, e.g. by dispersing it in the liquid medium when the

LiF is in solid form; and dissolving PF₅ in the liquid medium containing the LiF.

It will be appreciated that reacting the LiF with gaseous PF₅ therefore does not necessarily include directly contacting the LiF with gaseous PF₅. Instead, reacting the LiF with gaseous PF₅ would include contacting the liquid medium that contains the LiF with gaseous PF₅.

Typically, the liquid medium would consist of the perhalogenated organic compound, or conceivably mixtures of two or more perhalogenated organic compounds.

As alluded to above, the perhalogenated organic compound is preferably inert to the PF₅. In other words, the perhalogenated organic compound may be non-reactive with the PF_S.

In one embodiment of the invention, the perhaiogenated organic compound may he a perhalogenated alkane. For example, the perhalogenated alkane may be a cyclic or non-cvclic perfluorocarbon, preferably of the formula C_XF_V where x is an integer selected from 1 to 10 and y is an integer selected from 4 to 20, such as perfluorodecalin or perfluoroheptane or a non-cvclic perfluorocarbon selected from C1F4 and Ο,Τμ to C9F20.

In another embodiment of the invention, the perhalogenated organic compound may be a perfluoroalkene. For example., the perfluoroalkene may be a perfluoroaromatic compound such as hexafluorobenzene or a perfluoroaromatic compound selected from (Τ,Ρ,, to Ci₀F_g, or tetrafluoroethylene or a perfluoroalkene selected from C₅F₆ or C4F3.

It is envisaged that the perhalogenated organic compound may further be an ether, and particularly a perfluoroalkene ether. A ty pical generic formula may be R-O-R.

When the LiF is in solid form and provided that the liquid medium is not a solvent for LiPF„, the produced LiPF₆ would also typically be in solid form. Thus, the fluorination would convert the LiF in solid fonn into Li PF,_; in solid form.

Typically, the method may in such a ease typically produce a mixture of L.iPF₆ in solid form and unreacted LiF in solid form, in residual liquid medium. The method may then include recovering LiPF₆ in solid form and unreacted LiF in solid form from the residual liquid medium, e.g. by filtration.

When the produced LiPF₆ is in solid fonn, the method may include dissolving produced LiPF₆ in solid form in a solvent therefor, thus providing a solution of produced LiPF₆, typically after recovering LiPF₍, in solid fonn and unreacted LiF in solid fonn.

Providing the solution of produced LiPF₆ may therefore be particularly applicable when the method produces the mixture of LiPF₍, in solid form and unreacted LiF in solid form as hereinbefore described, to recover LiPF₍, from the mixture of LiPF₆ in solid form and unreacted LiF in solid form. Thus, the method may include treating the mixture of LiPF,_:, in solid form and unreacted LiF in solid form with a solvent for LiPF₆ in solid fonn. It will be appreciated in this regard that the solvent for LiPF₆ in solid form would not be a solvent for LiF in solid form.

The solvent for LiPF,, in solid form may be an electrolyte solvent, suitable for use in an electric battery. For example, the solvent may be selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, dimethyl ether, and mixtures thereof.

Temperature conditions for the reaction would preferably be selected such that the perhalogenated organic compound would be in the liquid phase.

It is noted that the invention does not exclude the possibility that the liquid medium may be a solvent for LiPF₆, in the case of which the produced LiPF₆ would be in dissolved form in the liquid medium, and not in solid form as hereinbefore described, hi such an embodiment, no subsequent dilution of produced LiPF₆ would be required and LiPF₀ in solution can then merely be separated from unreacted LiF through filtration, thus directly obtaining dissolved LiPF₆.

THE INVENTION EXTENDS, AS A SECOND ASPECT THEREOF, to LiPF₍, produced in accordance with the method of the invention as hereinbefore described, in solid form or in solution.

IN ACCORDANCE WITH A THIRD ASPECT OF THE INVENTION IS PROVIDED a method of producing an electrolyte, the method including producing LiPF,, in solid form, in accordance with the method of the first aspect of the invention; and dissolving the LiPF₆ in solid form in a solvent therefor.

The solvent for LiPF₍. in solid form may be an electrolyte solvent, suitable for use in an electric battery. For example, the solvent may be selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, dimethyl ether, and mixtures thereof.

THE INVENTION EXTENDS, AS A FOURTH ASPECT THEREOF, to an electrolyte produced in accordance with the method of the third aspect of the invention.

The electrolyte may be an electrolyte for an electric battery.

IN ACCORDANCE WITH A FIFTH ASPECT OF THE INVENTION IS PROVIDED an electric battery' including an electrolyte produced using LiPF,, produced in accordance with the method of the first aspect of the invention.

The electrolyte may be an electrolyte produced in accordance with the method of the third aspect of the invention.

IN ACCORDANCE WITH A SIXTH ASPECT OF THE INVENTION IS PROVIDED a method of manufacturing an electric battery, the method including producing an electrolyte in accordance with the method of the thi rd aspect of the invention; and including the electrolyte in an electric batten .

IN ACCORDANCE WITH A SEVENTH ASPECT OF THE INVENTION IS PROVIDED a method of producing an electrolyte, the method including producing LiPF₆ dissolved in a liquid medium in accordance with the method of the first aspect of the invention, by performing the method of the first aspect of the invention in a liquid medium that is a solvent for LiPF₀.

EXAMPLES

EMBODIMENTS OF THE IN VENTION will now be described by way of example only, with reference to the following examples.

Example 1: Reaction between LiF and PP\ gas m the presence of a cyclic or polycyclic perfluorocarbon solvent

LiF in solid form is dispersed in liquid perfluorodecalin (C_!OF_1S), and PF? in gaseous form is dissolved in the C_1UF_3g liquid.

The reaction that takes place is in accordance with reaction equation 1:

LiF(s) + PF₅ (g) .................>LiPF₆ (s) (Eq. 1)

The reaction temperature range is -10°C to 100 °C.

The reaction pressure range is 0 kPa to 1000 kPa.

Up to 99% recovery of LiPF₆ is achieved when produced LiPF₍, is dissolved in a solvent for LiPF₆in solid form, which solvent comprises ethylene carbonate, propylene carbonate, dimethyl carbonate, dimethyl ether, or any combination thereof.

Example 2: A reaction between LiF and PF$ gas in the presence of non-cyclic or branched perfluorocarbon solvent

LiF in solid form is dispersed in liquid perfluoroheptane or any non-cyclic perfluorocarbons of range CjF₄, and CfiF_w to C9F20liquid.

The reaction that takes place is in accordance with reaction equation I.

The reaction temperature range is -94 °C to 127 °C.

The reaction pressure range is 0 kPa to 1000 kPa.

Up to 99% recover}' of LiPF₆ is achieved when produced LiPF<, is dissolved in a solvent for LiPF₆in solid form, which solvent comprises ethylene carbonate, propylene carbonate, dimethyl carbonate, dimethyl ether, or any combination thereof.

Exgm^leJ^ A reaction between LiF and PF_S gas in the presence of 'perfluoroaromatic solvent LiF in solid form is dispersed in liquid hexafluorobenzene or a perfluoroaromatic liquid compound in the range C₍,F₍, to CioF_s.

The reaction that takes place is in accordance with reaction equation 1.

The reaction temperature range is 5°C to 100 °C.

The reaction pressure range is 0 kPa to 1000 kPa.

Up to 99% recover}' of LiPF₆ is achieved when produced LiPF₆ is dissolved in a solvent for LiPF₆in solid form, which solvent comprises ethylene carbonate, propylene carbonate, dimethyl carbonate, dimethyl ether, or any combination thereof.

reaction between LiF and PF< gas in the presence of fluoroalkene solvent.

LiF in solid form is dispersed in hquid tetrafluoroethylene solvent (CLFh) or a hquid fluoroalkene compound selected from C₃F₆ or CJF_S.

The reaction that takes place is in accordance with reaction equation 1.

The reaction temperature range is -94°C to 100 °C.

The reaction pressure range is 0 kPa to 1000 kPa.

DISCUSSION

THE METHOD OF THE FIRST ASPECT OF THE INVENTION uses an inert, non-corrosive, non-poisonous liquid medium for the reaction of LiF and PF₅ instead of corrosive HF which is the preferred liquid med ium for this reaction in the art of the in vention.

Thus the inventors have eliminated the need to remove the HF from the product through tiresome purification processes such as vacuum distillation.

Furthermore, HF is known to be corrosive and reactive inside a battery', which makes its avoidance for use as a liquid medium all the more desirable.

Some advantages associated with the liquid media exploited by the method of the invention are the following:

it is inert in relation to PF₅ gas;

it is inert in relation to the product LiPF₆:

it is not poisonous;

it dissolves the PF_S gas, making it readily accessible to the lithium fluoride without mass transfer limitations;

no azeotropic formation of PF₅ gas with the solvent is experienced, which tends to compete with lithium fluoride for PF₅ gas in traditional HF involved processes; and the liquid media are non-corrosive.

Thus, the inventors have provided an attractive, utile and sustainable alternative for the production of LiPFf, which is particularly advantageous over prior art processes, some of which have been discussed herein.

Claims

CLAUSES

I. A method of producing lithium hexafluorophosphate (LiPF _fi ) in solid form, the method including fluorinating lithium fluoride (LiF) in solid form by reacting it with gaseous phosphorous pentafluoride (PFj), the reaction is performed in a liquid medium that comprises a perhalogenated organic compound that is inert to the PF ₅ and is a solvent to the PF ₅ , requiring producing LiPF ₍ , in solid form.

2. The method according to clause 1, reacting the LiF with gaseous PF ₅ includes dispersing the LiF in solid form in the liquid medium; and dissolving gaseous PF? in the liquid medium containing the LiF in solid form.

3. The method according to any of clauses I to 2, the perhalogenated organic compound is a perfluorocarbon.

4. The method according to clauses 3, where the perfluorocarbon is selected from cyclic and non-cyclic perfluoroalkanes, and cyclic and non-cyclic perfluoroalkenes.

5. The method according to any of clauses 1 to 4, the perfluorocarbon is selected from perfluorodecalin, perfluoroheptane, hexafluorobenzene, and tetrafluoroethylene.

6. The method according to any of clauses 1 to 5, which includes dissolving produced LiPF? in solid form in a solvent for LiPF ₍₎ .

7. The method according to clause 6, the solvent for LiPF ₀ is selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, dimethyl ether, and mixtures thereof.

CONCLUSIONS

A method for the production of lithium hexafluorophosphate (LiPF ₆ ) in solid form, wherein the method comprises fluoridation of lithium fluoride (LiF) in solid form by reacting with gaseous phosphorus pentafluoride (PF ₅ ), wherein the reaction is carried out in a liquid medium comprising a perhalogenated organic compound that is inert to the PF ₅ and is a solvent to the PF ₅ , thereby producing FiPF ₆ in solid form.

2. A method as claimed in claim 1, wherein hell reacting the LiF with gaseous PF _5, the distribution of the LiF in solid form in the liquid medium; and dissolving gaseous PF ₅ in the liquid medium containing the LiF in solid form.

Method according to one of claims 1 to 2, characterized in that the perhalogenated organic compound is a perfluorocarbon.

The method of claim 3, wherein the perfluorocarbon is selected from cyclic and nielcyclic perfluoroalkanes, and cyclic and non-cyclic perfluoroalkenes.

The method of any one of claims 1 to 4, wherein the perfluorocarbon is selected from perfluorodecalin, perfluoroheptane, hexafluorobenzene and tetrafluoroethylene.

The method according to any of claims 1 to 5, comprising dissolving produced LiPF ₆ in solid form in a solvent for LiPF ₍₁ .

The method of claim 6, wherein the solvent for LiPF ₍ is selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, dimethyl ether, and mixtures thereof.