CN100567141C - A kind of preparation method of lithium hexafluoro phosphate - Google Patents
A kind of preparation method of lithium hexafluoro phosphate Download PDFInfo
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- CN100567141C CN100567141C CNB2005101158564A CN200510115856A CN100567141C CN 100567141 C CN100567141 C CN 100567141C CN B2005101158564 A CNB2005101158564 A CN B2005101158564A CN 200510115856 A CN200510115856 A CN 200510115856A CN 100567141 C CN100567141 C CN 100567141C
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- lithium
- hexafluoro phosphate
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- lithium hexafluoro
- fluoride
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 73
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 68
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 67
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 title claims abstract description 64
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 64
- 239000010452 phosphate Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 37
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 31
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 31
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 45
- 239000007789 gas Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000008151 electrolyte solution Substances 0.000 abstract description 10
- 235000021317 phosphate Nutrition 0.000 description 64
- 239000000243 solution Substances 0.000 description 18
- 238000004821 distillation Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 8
- -1 Phosphorates phosphorus Halides Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000001838 alkalimetric titration Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 238000003869 coulometry Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000010421 standard material Substances 0.000 description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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Abstract
A kind of preparation method of lithium hexafluoro phosphate, this method comprise that wherein, described lithium fluoride is made by Quilonum Retard and hydrogen fluoride reaction with lithium fluoride and the reaction of phosphorus source.Because Quilonum Retard is the forms of elemental lithium in a large amount of existence of occurring in nature, thereby raw material is easy to get, low price.And with the lithium hexafluoro phosphate product yield height of the inventive method preparation, purity is good, moisture content is low and Free HF content is low, and the electric conductivity of the electrolytic solution that makes is up to 9.7mS/ centimetre.
Description
Technical field
The invention relates to a kind of preparation method of lithium hexafluoro phosphate, especially about a kind of preparation method who is used as the lithium hexafluoro phosphate of lithium-ion battery electrolytes.
Background technology
Lithium-ion secondary cell mainly is (as LiCoO by the Lithium Oxide 98min anode
2, LiNiO
2, LiMn
2O
4), carbon material negative electrode (as graphite) and electrolytic solution forms.The example that forms the organic solvent of electrolytic solution comprises the mixed solvent etc. of mixed solvent, NSC 11801 (EC) and the diethyl carbonate (DEC) of ethylene carbonate (VC) and methylcarbonate (DMC).Must satisfy following performance as the ionogen of lithium ion battery electrolyte solution, promptly electric conductivity height, chemistry and electrochemical stability are good, but the use temperature wide ranges, security is good, price is low.Lithium hexafluoro phosphate then is the solute commonly used of electrolyte of lithium-ion secondary battery.
When lithium-ion secondary cell was recharged, lithium ion entered and locates attached to the hole of negative electrode; And lithium-ion secondary cell comes back to anode attached to the lithium ion on the negative electrode when being discharged.In this case, lithium ion moves by electrolyte solution.As a result, in order to keep the performance of battery, for example work-ing life, reply electrolytical purity in electrolytic solution is carried out strict restriction.At present, because preparation lithium hexafluoro phosphate (LiPF
6) many, the complex process of production link, equipment requirements very high, so cause production cost high.
The flat 5-279003 of Japanese Unexamined Patent Publication No discloses a kind of method for preparing lithium hexafluoro phosphate, this method comprises phosphorus pentachloride and hydrogen fluoride gas reaction generation phosphorus pentafluoride and hydrogen chloride gas, making the phosphorus pentafluoride of generation and hydrogen chloride gas then is-40 to-80 ℃ cooling tower by tower temperature, enters afterwards in the reactor of the hydrofluoric acid solution that contains lithium fluoride to prepare lithium hexafluoro phosphate again.The shortcoming of this method is that reaction yield is no more than 65%.
CN 1212264C discloses a kind of preparation method of lithium hexafluoro phosphate, and this method comprises that with exsiccant solid lithium fluoride (LiF) and gaseous state phosphorus pentafluoride be raw material, is solvent with the anhydrous hydrogen fluoride, prepares lithium hexafluoro phosphate down at 0-20 ℃.Adopting the yield of the lithium hexafluoro phosphate that this method makes is 80.7%.It is raw material with the gaseous state phosphorus pentafluoride that there is shortcoming in this method, phosphorus pentafluoride easily is decomposed into phosphoric acid and hydrogenchloride in air, thus must under airtight anhydrous condition, carry out, and reaction is a solvent with the anhydrous hydrogen fluoride, all increased the requirement of producing, increased production cost equipment.
CN 1124975C discloses a kind of preparation method of lithium hexafluoro phosphate, this method comprises phosphorus pentachloride and anhydrous hydrofluoric acid reaction generation phosphorus pentafluoride and hydrogenchloride, then phosphorus pentafluoride that generates and the lithium fluoride that is dissolved in anhydrous hydrofluoric acid or return in the mother liquor are reacted under agitation condition, and, obtain lithium hexafluoro phosphate-40 to-20 ℃ of following crystallizations.This method exists shortcoming to be: the reaction of phosphorus pentachloride and anhydrous hydrofluoric acid is difficulty, reaction product crystallization under the low temperature under-40 to-20 ℃, and-40 to-20 ℃ low temperature difficulty reach.
CN 1151960C discloses a kind of preparation method of lithium hexafluoro phosphate, and this method comprises F
2Production, PF
5The separating out of synthetic, lithium hexafluoro phosphate, the collection of lithium hexafluoro phosphate of production, lithium hexafluoro phosphate product, wherein lithium hexafluoro phosphate synthetic be by with concentration be the hydrogen fluoride solution of lithium fluoride of 2-10% under the 0.3-0.6 MPa with PF
5Gas reaction makes.The shortcoming that this method exists is F
2Production difficulty, need higher processing condition and harsh equipment.
And aforesaid method all has a common shortcoming: lithium fluoride expensive raw material price and moisture content height as the lithium source, must carry out drying, and it is synthetic that drying process easily enters the follow-up chemical industry of impurity effect; Material transmits and to have some setbacks etc.
For this reason, CN 1108985C discloses a kind of preparation method of lithium hexafluoro phosphate, this method comprises employing phosphorus pentachloride and anhydrous hydrofluoric acid prepared in reaction phosphorus pentafluoride, then with gained phosphorus pentafluoride and lithium chloride prepared in reaction lithium hexafluoro phosphate, and prevent that by in reaction system, feeding high-purity fluorine gas contained humidity in the solid feed and other moisture of introducing between the reaction period from causing the generation of fluorine oxidation Trilithium phosphate by product, thereby guarantee the purity of prepared lithium hexafluoro phosphate, and reaction yield is up to more than 90%.But there is following shortcoming in this method: high-purity fluorine gas is difficult for making, and cost an arm and a leg, and security and stability is poor, has increased the requirement of reaction pair equipment.And there is not natural lithium chloride in occurring in nature, and used lithium chloride is normally made by chemical reaction by Quilonum Retard.
Summary of the invention
The objective of the invention is provides the preparation method of the lithium hexafluoro phosphate that a kind of raw material is easy to get, production cost is low in order to overcome the shortcoming that preparation method's raw material is not easy to obtain, production cost is high of lithium hexafluoro phosphate in the prior art.
The invention provides a kind of preparation method of lithium hexafluoro phosphate, this method comprises that wherein, described lithium fluoride is made by Quilonum Retard and hydrogen fluoride reaction with lithium fluoride and the reaction of phosphorus source.
Because Quilonum Retard is that elemental lithium is in the most ubiquitous form of occurring in nature, especially Zhong Guo Quilonum Retard mining deposits is very abundant, as long as promptly can be used as raw material of the present invention Quilonum Retard extracted purifying from mineral reserve after, and need not to change into lithium fluoride or Quilonum Retard through complicated synthetic preparation feedback, thereby be that the preparation method of feedstock production lithium hexafluoro phosphate compares with lithium fluoride or lithium chloride in preparation method provided by the invention and the prior art, have that raw material is easy to get and cheap advantage.And the yield for preparing lithium hexafluoro phosphate with method provided by the invention is up to 95%, and the specific conductivity of the electrolytic solution made from the gained lithium hexafluoro phosphate is up to 9.7mS/ centimetre (25 ℃).
Description of drawings
Fig. 1 is a lithium hexafluoro phosphate preparation method's provided by the invention process flow sheet.
Embodiment
The preparation method of lithium hexafluoro phosphate provided by the invention comprises that wherein, described lithium fluoride is made by Quilonum Retard and hydrogen fluoride reaction with lithium fluoride and the reaction of phosphorus source.
Described Quilonum Retard can be commercially available, and is preferably technical grade or battery-level lithium carbonate.Also can carry out separation and purification as methods such as washing, recrystallizations to the technical pure Quilonum Retard and obtain purity greater than 99.9% pure Lithium Carbonate by the whole bag of tricks.
If the reactive system at the preparation lithium hexafluoro phosphate contains water, then can produce fluorine oxidation Trilithium phosphate (LiPO
xF
y) byproduct, fluorine oxidation Trilithium phosphate also can portion be decomposed into LiF, and LiF then becomes the impurity in the lithium hexafluoro phosphate.Therefore, moisture content should be low as far as possible in the reactive system of preparation lithium hexafluoro phosphate.In addition, if contain moisture in the finished product, lithium hexafluoro phosphate will resolve to LiF, HF and PF so, and they will be transformed into gaseous state subsequently, increase inner pressure of battery thus.Therefore, hydrogen fluoride of the present invention is preferably anhydrous hydrogen fluoride.Can adopt the whole bag of tricks to remove moisture contained in the hydrogen fluoride, for example can remove by method described in the CN 1108985C.The document is introduced reference in the lump at this.
The present invention has no particular limits the feed molar ratio of Quilonum Retard and anhydrous hydrogen fluoride, can be reinforced by stoichiometric ratio, and also can make wherein a kind of raw material excessive.Consider that the Quilonum Retard ratio is easier to reclaim, and all need usually to reclaim, and hydrofluoric recovery relatively difficulty and entering can pollute environment in the atmosphere, and when HF and organic solvent react, also the corrosion of the housing that can use sealed cell exerts an influence, and the stability of battery is had side effect.Thereby the present invention preferably makes Quilonum Retard excessive, and Quilonum Retard and hydrofluoric mol ratio are preferably 1-8, more preferably 2-6.
The preparation method of described lithium fluoride comprises makes Quilonum Retard and anhydrous hydrogen fluoride under protection of inert gas, reacts 1-10 hour down at 100-200 ℃.Described rare gas element comprise nitrogen, argon gas etc. not with the gas of reaction such as reaction raw materials, water, oxygen.Be preferably drying nitrogen in the specific embodiment of the invention.Because Quilonum Retard still be solid under 100-200 ℃, and hydrogen fluoride next in this temperature be gas, so the reaction between hydrogen fluoride and the Quilonum Retard belongs to gas-solid out-phase and reacts.Therefore preferred above-mentioned being reflected under the agitation condition of the present invention carried out, and more preferably carries out under the hot gas flow circulation that is formed by nitrogen and anhydrous hydrogen fluoride is stirred.Reaction is preferably carried out under reduced pressure, is to carry out under the 0.01-0.09 MPa condition in vacuum tightness more preferably.Vacuum tightness of the present invention is meant the absolute value (absolute pressure is less than barometric point) of the difference of absolute pressure and barometric point, also is gauge pressure.HF, CO that reaction generates
2Available alkali lye absorbs.The bell-jar vacuum apparatus that adopts Zhongshan city, Guangdong Tianyuan vacuum apparatus technology company limited to produce can be realized above-mentioned reaction environment.
Described phosphorus source is generally Phosphorates phosphorus Halides, as PCl
5, PF
5, PBr
5, PI
5In one or more, be preferably PCl
5, PF
5, PBr
5In one or more, the mol ratio in described lithium fluoride and phosphorus source is 0.5-5 (with the molar ratio computing of lithium atom and phosphorus atom).
According to the present invention, the reaction in described lithium fluoride and phosphorus source can be that carry out in anhydrous hydrogen fluoride, dense hydrofluoric acid solution or fluorine gas in lithium fluoride and phosphorus source.For example, can adopt CN 1212264C disclosed method, the drying solid lithium fluoride that with weight ratio is 1 weight part under 0-20 ℃ fully is dissolved in the 1-50 weight part anhydrous hydrogen fluoride, import 0.5-5 weight part gaseous state phosphorus pentafluoride then, continue to stir and finish until reaction, then products therefrom is carried out low temperature recrystallization, crystallization filtration and washing and filtering, final drying promptly gets the final product lithium hexafluoro phosphate.
Also can adopt CN 1151960C disclosed method, lithium fluoride is dissolved in the hydrogen fluoride, and forming concentration is the solution of 2-10 weight %, feeds phosphorus pentafluoride gas then under the 0.3-0.6 MPa, stirred 3 hours down at 25-30 ℃, separating then purifies obtains the final product lithium hexafluoro phosphate.
Can also adopt CN 1124975C disclosed method, in-40 to-20 ℃ of scopes, with 10 kilograms/hour speed anhydrous hydrogen fluoride is joined and to make phosphorus pentafluoride in the phosphorus pentachloride, then the phosphorus pentafluoride that generates is joined in the anhydrous hydrogen fluoride solution of lithium fluoride, at-40 to-20 ℃ of following prepared in reaction lithium hexafluoro phosphates.
According to the present invention, the reaction in described lithium fluoride and phosphorus source can also adopt following method to carry out: in the presence of solvent, with lithium fluoride, hydrogen fluoride with by PCl
5Mix the solution that obtains with acetonitrile and under agitation condition, react, described lithium fluoride, hydrogen fluoride and by PCl
5The mol ratio of mixing the solution that obtains with acetonitrile is (0.2-3): (4-8): 1.Add-on to solvent has no particular limits, and preferably makes lithium fluoride form the solution of 1-3 mol.Described solvent can be an all kinds of SOLVENTS, as long as can effectively dissolve lithium fluoride, PCl
5Mixing the solution that obtains with acetonitrile and get final product, for example can be methylcarbonate, diethyl carbonate, Methyl ethyl carbonate.It is described that to mix the solution that obtains with acetonitrile by phosphorus pentachloride be by weight obtaining for the 0.1-1 mixing by phosphorus pentachloride and acetonitrile.Because the color is too dark for the reaction system that obtains after the reaction, therefore method of the present invention also preferably includes decolouring step that reaction system is decoloured and the drying step that reaction system is further dewatered.The concrete operations step of this method comprises: solvent joined contains in lithium fluoride and the hydrofluoric container, and will be in 30-80 ℃ of scope by PCl
5Mixing the solution that obtains with acetonitrile slowly joins in the container, and under agitation condition, reacted 1-6 hour, then reaction system is filtered, and use the DMC debris, with discoloring agent filtrate is decoloured then, the decolouring back adds siccative and carries out drying, removes with split reduction distillatory mode then and desolvates, and carries out promptly getting the final product lithium hexafluoro phosphate after the drying again.
Wherein, can adopt atomization that solvent is joined in the reaction vessel.Described discoloring agent can be various discoloring agents, and as in aluminum oxide, gac, the high-efficient activated clay one or more, the add-on of discoloring agent can be that per 100 grams treat to add in the de-inking solution 20-30 gram discoloring agent.The concrete operations of decolouring be conventionally known to one of skill in the art, for example, and usually in room temperature or be lower than under the solvent boiling point temperature stirring 2-4 hour.Described siccative can be various siccative, as in silica gel, molecular sieve, graphite, the calcium chloride one or more.The add-on of siccative and exsiccant working method have been conventionally known to one of skill in the art, do not repeat them here.Described split reduction distillatory mode can reduce pressure by gradient increased temperature and gradient and realize.Adopt 3 sections underpressure distillation modes to carry out in the specific embodiment of the invention, every section distillation temperature, distillation pressure are different with content and different with the boiling point of solvent with distillation time.For example, every section distillation temperature can be 55-75 ℃, 45-60 ℃ and 30-45 ℃, and the vacuum tightness of underpressure distillation is 0.05-0.07 MPa, 0.07-0.09 MPa and 0.08-0.10 MPa; Distillation time can be 60-90 minute, 70-100 minute and 90-120 minute.It is more thorough that split reduction can make the acetonitrile in the lithium hexafluoro phosphate remove.The drying that distillation removes after desolvating is generally vacuum-drying, and the exsiccant temperature can be 20-150 ℃, and can be 2-12 hour time of drying.
According to the present invention, can adopt " one kettle way " is the feedstock production lithium hexafluoro phosphate with the Quilonum Retard.Described one kettle way is meant that the lithium fluoride that is made by Quilonum Retard and hydrogen fluoride reaction need not to separate the subsequent reactions that purification is directly used in the preparation lithium hexafluoro phosphate, also promptly after making lithium fluoride, Quilonum Retard and hydrogen fluoride reaction be prepared the subsequent reactions of lithium hexafluoro phosphate in directly with adding reaction systems such as phosphorus source, solvents, so not only can save the operating time, operation simplifies the operation, loss and the pollution that can also avoid lithium fluoride in the separation and purification engineering, to cause, thereby have industrial prospect widely." one kettle way " preparation lithium hexafluoro phosphate technical process as shown in Figure 1, at first with Li
2CO
3With anhydrous HF in reaction 1-10 hour under condition of heating and stirring under the protection of inert gas, the reaction back that finishes adds solvent and makes lithium fluoride solution, then 30-80 ℃ will make in advance down by PCl
5Mixing the solution obtain with acetonitrile joins to react in the above-mentioned reaction vessel that contains lithium fluoride solution and HF and makes the lithium hexafluoro phosphate product.Products therefrom promptly gets the target product lithium hexafluoro phosphate through after decolouring, dewatering, separate.In the above-mentioned one kettle way, raw material HF can once add enough required HF of lithium hexafluoro phosphate that Quilonum Retard transformed fully or be converted into more than 90% when the reaction beginning, also can be reinforced by the required HF amount of preparation lithium fluoride earlier, in lithium fluoride prepares the reaction of lithium hexafluoro phosphate, carry out secondary then again and add the HF material, preferred first kind of mode in the specific embodiment of the invention, only carry out once reinforced to HF, for this reason, preferably in one kettle way of the present invention the reinforced mol ratio of raw material Quilonum Retard, anhydrous hydrogen fluoride and phosphorus pentachloride be (0.2-3): (4-8): 1.
In order to reduce the impurity that brings by reaction vessel, the various containers of making by the material of hydrofluoric acid resistant or hydrogen fluoride corrosion of all preferred use of each reaction described in the present invention, for example, can be the container of being made by materials such as Monel metal, nickel-base alloy, cadmium base alloys, also can be the container that the reaction chamber liner is coated with polyethylene, polystyrene, polyvinyl chloride, polysulfones, polypropylene, polyacrylic ester or tetrafluoroethylene.
The following examples will the invention will be further described.
Embodiment 1
Present embodiment is used to illustrate the preparation method of lithium hexafluoro phosphate provided by the invention.
With 111 gram Li
2CO
3, 40 gram anhydrous HF grams join in 1000 milliliters the bell-jar vacuum apparatus that scribbles PTFE (productions of Zhongshan city, Guangdong Tianyuan vacuum apparatus technology company limited) feeding N
2The air in the container is fallen in displacement, and the temperature of reaction system is controlled at 100 ℃, and vacuum degree control stirred 8 hours under the hot gas flow circulation in 0.07 MPa.Adopt atomization in container, to feed 1000 milliliters of DMC then, continue stirring and with water coolant system is cooled to 45 ℃ after 2 hours, will contain 102 gram PCl then
5150 milliliters of acetonitrile solutions slowly be added drop-wise in the reaction vessel, dripped off at 40 minutes, continue down to stir 2 hours at 45 ℃.
Above-mentioned system filtered and, use 50 milliliters of DMC at every turn with DMC debris three times.Filtrate is merged the back add 30 gram Al
2O
3, at room temperature stirred 1.5 hours, filter.In filtrate, add 45 gram 5A molecular sieves, at room temperature stirred 1.5 hours, filter.Divide 3 sections underpressure distillation to remove desolvate (three sections temperature is respectively 60 ℃, 50 ℃ and 45 ℃, and the vacuum tightness of underpressure distillation is respectively 0.07 MPa, 0.08 MPa and 0.1 MPa, and distillation time was respectively 70 minutes, 80 minutes and 100 minutes) filtrate.Is 60 ℃ of following vacuum-dryings 2 hours with products therefrom in temperature, obtains 90 gram product lithium hexafluoro phosphates, and in the Quilonum Retard that consumes, the yield of lithium hexafluoro phosphate is 95%.The lithium hexafluoro phosphate of gained is measured through Raman spectrometer (light source is 1064 nm near-infrared LASER Light Source, and light source power is 100 nanowatts), and the spectrogram of sample is respectively at 769 centimetres
-1, 759 centimetres
-1, 746 centimetres
-1, 570 centimetres
-1, 473 centimetres
-1Near go out the peak.With
19FNMR,
31PNMR and
7LiNMR analysis revealed, gained lithium hexafluoro phosphate are almost identical with standard material.Gained lithium hexafluoro phosphate sample is through the assay of glycol dimethyl ether (DME) insolubles, and purity is 99.9%.To record moisture content by the Fischer coulometry be 10ppm, record the free hydrogen fluoride content by alkalimetry is 100ppm.
Embodiment 2
With 74 gram Li
2CO
3, 160.0 gram anhydrous HF grams join in 1000 milliliters the encloses container that scribbles PTFE, feed N
2The air in the container is fallen in displacement, and the temperature of reaction system is controlled at 125 ℃, stirs 3.5 hours under the hot gas flow circulation.Adopt atomization in container, to feed 400 milliliters of DMC then, continue stirring and with water coolant system is cooled to 70 ℃ after 2 hours, will contain 208 gram PCl then
51000 milliliters of acetonitrile solutions slowly be added drop-wise in the reaction vessel, dripped off at 40 minutes, continue down to stir 2 hours at 40 ℃.
Above-mentioned system filtered and, use 50 milliliters of DMC at every turn with DMC debris three times.Filtrate is merged the back add 35 gram gacs, at room temperature stirred 2 hours, filter.In filtrate, add 50 gram 5A molecular sieves, at room temperature stirred 2 hours, filter.Divide 3 sections underpressure distillation to remove desolvate (three sections temperature are respectively 55 ℃, 45 ℃ and 30 ℃, and the vacuum tightness of underpressure distillation is respectively 0.07 MPa, 0.09 MPa and 0.10 MPa, and distillation time was respectively 60 minutes, 70 minutes and 90 minutes) filtrate.Is 40 ℃ of following vacuum-dryings 2 hours with products therefrom in temperature, obtains 130.3 gram product lithium hexafluoro phosphates, and in the Quilonum Retard that consumes, the yield of lithium hexafluoro phosphate is 94%.The lithium hexafluoro phosphate of gained is measured through Raman spectrometer (light source is 1064 nm near-infrared LASER Light Source, and light source power is 100 nanowatts), and the spectrogram of sample is respectively at 769 centimetres
-1, 759 centimetres
-1, 746 centimetres
-1, 570 centimetres
-1, 473 centimetres
-1Near go out the peak.With
19FNMR,
31PNMR and
7LiNMR analysis revealed, gained lithium hexafluoro phosphate are almost identical with standard material.Gained lithium hexafluoro phosphate sample is through the assay of glycol dimethyl ether (DME) insolubles, and purity is 99.9%.To record moisture content by the Fischer coulometry be 8ppm, record the free hydrogen fluoride content by alkalimetry is 95ppm.
Embodiment 3
With 222 gram Li
2CO
3, 80.0 gram anhydrous HF grams join in 1000 milliliters the bell-jar vacuum apparatus that scribbles PTFE (productions of Zhongshan city, Guangdong Tianyuan vacuum apparatus technology company limited) feeding N
2The air in the container is fallen in displacement, and the temperature of reaction system is controlled at 125 ℃, and vacuum degree control stirred 3.5 hours under the hot gas flow circulation in 0.09 MPa.Adopt atomization in container, to feed 400 milliliters of DMC then, continue stirring and with water coolant system is cooled to 40 ℃ after 2 hours, will contain 208 gram PCl then
5500 milliliters of acetonitrile solutions slowly be added drop-wise in the reaction vessel, dripped off at 35 minutes, continue down to stir 2 hours at 40 ℃.
Above-mentioned system filtered and, use 50 milliliters of DMC at every turn with DMC debris three times.Filtrate is merged the back add 35 gram Al
2O
3, at room temperature stirred 2 hours, filter.In filtrate, add 50 gram 5A molecular sieves, at room temperature stirred 2 hours, filter.Divide 3 sections underpressure distillation to remove desolvate (three sections temperature is respectively 65 ℃, 50 ℃ and 30 ℃, and the reduced vacuum degree is respectively 0.07 MPa, 0.09 MPa and 0.08 MPa, and distillation time was respectively 90 minutes, 100 minutes and 120 minutes) filtrate.Is 40 ℃ of following vacuum-dryings 2 hours with products therefrom in temperature, obtains 133.1 gram product lithium hexafluoro phosphates, and in the Quilonum Retard that consumes, the yield of lithium hexafluoro phosphate is 96%.The lithium hexafluoro phosphate of gained is measured through Raman spectrometer (light source is 1064 nm near-infrared LASER Light Source, and light source power is 100 nanowatts), and the spectrogram of sample is respectively at 769 centimetres
-1, 759 centimetres
-1, 746 centimetres
-1, 570 centimetres
-1, 473 centimetres
-1Near go out the peak.With
19FNMR,
31PNMR and
7LiNMR analysis revealed, gained lithium hexafluoro phosphate are almost identical with standard material.Gained lithium hexafluoro phosphate sample is through the assay of glycol dimethyl ether (DME) insolubles, and purity is 99.9%.To record moisture content by the Fischer coulometry be 6ppm, record the free hydrogen fluoride content by alkalimetry is 90ppm.
Comparative Examples 1
The method shown in the embodiment prepares lithium hexafluoro phosphate among the employing CN 1108985C.
Conductivity test
The lithium hexafluoro phosphate of the foregoing description 1-3 and Comparative Examples 1 preparation is dissolved in respectively in the DMC solvent, makes the electrolytic solution of 1 mol, measure the electric conductivity (mS/ centimetre) of each electrolytic solution, measurement result is as shown in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | |
| Yield (%) | 95 | 94 | 96 | 88 |
| Purity (%) | 99.9 | 99.9 | 99.9 | 99.8 |
| Moisture content (ppm) | 8 | 6 | 10 | 17 |
| HF content (ppm) | 100 | 90 | 85 | 130 |
| Electric conductivity (mS/ centimetre) | 9.5 | 9.0 | 9.7 | 7.6 |
From last table 1 result as can be seen, the yield for preparing lithium hexafluoro phosphate with method provided by the invention is very high, the purity of products obtained therefrom, moisture content and Free HF content all are better than the product that makes with art methods, and use electrolytic solution electric conductivity that the lithium hexafluoro phosphate by the inventive method preparation makes up to 9.0-9.7mS/ centimetre.
Claims (4)
1; a kind of preparation method of lithium hexafluoro phosphate; this method comprises lithium fluoride and the reaction of phosphorus source; it is characterized in that; described lithium fluoride by Quilonum Retard and anhydrous hydrogen fluoride under protection of inert gas; under agitation condition and in reaction under 100-200 ℃, obtain after 1-10 hour; directly add solvent then and mix the solution that obtains by phosphorus source and acetonitrile; reacted 1-6 hour down at 30-80 ℃; described Quilonum Retard; anhydrous hydrogen fluoride and make Quilonum Retard by the add-on that phosphorus source and acetonitrile mix the solution that obtains: HF: the mol ratio in phosphorus source is (0.2-3): (4-8): 1, and described phosphorus source is PCl
5
2, method according to claim 1, wherein, the described solution that obtains that mixed by phosphorus source and acetonitrile is obtained for 0.1-1 mixes with acetonitrile by weight by the phosphorus source.
3, method according to claim 1, wherein, described solvent is selected from one or more in methylcarbonate, diethyl carbonate, the Methyl ethyl carbonate, and the add-on of solvent makes that the concentration of lithium fluoride is the 1-3 mol.
4, method according to claim 1, wherein, described being reflected under the hot gas flow stirring carried out.
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| 无机精细化学品. 李仲谨，89，化学工业出版社. 2005 |
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