CN103253688A - Method for preparing high-purity lithium fluoride and lithium hexafluorophosphate by utilization of organo tin fluoride - Google Patents

Method for preparing high-purity lithium fluoride and lithium hexafluorophosphate by utilization of organo tin fluoride Download PDF

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CN103253688A
CN103253688A CN2013100982180A CN201310098218A CN103253688A CN 103253688 A CN103253688 A CN 103253688A CN 2013100982180 A CN2013100982180 A CN 2013100982180A CN 201310098218 A CN201310098218 A CN 201310098218A CN 103253688 A CN103253688 A CN 103253688A
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lithium
reaction
organic solvent
snf
organotin
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CN103253688B (en
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余佩华
余佩娟
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ZHONGSHAN HUAWEI NEW ENERGY TECHNOLOGY Co Ltd
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ZHONGSHAN HUAWEI NEW ENERGY TECHNOLOGY Co Ltd
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Abstract

The invention discloses a method for preparing high-purity lithium fluoride and lithium hexafluorophosphate by the utilization of organo tin fluoride. As for preparation of lithium fluoride, a fluorine/halogen exchange reaction between lithium halide and organo tin fluoride is carried out to generate lithium fluoride. As for preparation of lithium hexafluorophosphate, a fluorine/halogen exchange reaction between phosphorus pentahalide and organo tin fluoride is firstly carried out to generate phosphorus pentafluoride, and a contact reaction between phosphorus pentafluoride and lithium fluoride is carried out to generate lithium hexafluorophosphate; or, lithium halide and phosphorus pentahalide are firstly dissolved in an organic solvent until a clear intermediate solution, and then the intermediate solution reacts with organo tin fluoride to generate lithium hexafluorophosphate, wherein lithium halide is lithium chloride or lithium bromide. The lithium fluoride prepared in the invention has high purity. Meanwhile, adoption of highly corrosive HF as a fluorinated reagent is avoided so as to avoid the possibility of introducing impurities and guarantee that high-quality LiPF6 can be prepared in the next step.

Description

Utilize the organotin fluorochemical to prepare the method that high purity is fluoridized lithium and lithium hexafluoro phosphate
[technical field]
The present invention relates to a kind of method for preparing lithium fluoride and lithium hexafluoro phosphate, relate in particular to a kind of organotin fluorochemical that utilizes and prepare the method that high purity is fluoridized lithium and lithium hexafluoro phosphate.
[background technology]
In recent years, the fundamental research of lithium ion battery and application and development have become one of focus of new energy field, and each flourishing state of the world all develops its breakthrough point as next new industry and study.Lithium hexafluoro phosphate (LiPF 6) be widely used in commercial lithium ion battery with its good specific conductivity and stable chemical property, be one of critical material of making lithium ion battery.LiPF 6Be the white powder solid, not only very easily moisture absorption is decomposed, and thermostability is relatively poor.LiPF as lithium ion battery electrolyte 6, must reach following technical indicator: purity is greater than 99.5%, and acid content (in HF) is less than 150 * 10 -6, H 2O content is less than 20 * 10 -6, other metallic impurity ion content all should be less than 20 * 10 -6Because the LiPF as the lithium ion battery electrolyte lithium salts 6Satisfy above requirement, its preparation process is difficulty especially, because will make highly purified LiPF like this 6, at first needing highly purified raw material, many raw materials all will obtain through special purification step or special preparation method; Water content of its less important establishment is less than 10 * 10 -6Dry environment, and product also must be through purifying process such as specific dehydration, depicklings, quality product can satisfy above requirement.The solubleness of LiF in water and other organic solvent is very low, is difficult to reach by the method for recrystallization the purity requirement of cell-grade material, PF 5Be a kind of to the highstrung gas of moisture, the aqueous vapor of trace also can make it generate POF 3And HF, and be difficult for preserving.In prior preparation method, all need to adopt a large amount of high-purity anhydrous HF as raw material or solvent, because HF is the severe corrosive highly toxic substance, prepare in large quantities and use high-purity anhydrous HF, technology difficulty is big, equipment requirements and environmental protection cost height, introduce impurity easily, make the PF for preparing 5Purity is low, and then has influence on LiPF 6Purity.Just because of production link is many, complex process, equipment requirements are very high, add more and more tighter environmental requirement, so cause production cost high.
Both at home and abroad to LiPF 6Preparation and purifying carried out a large amount of research, especially in this respect research work of Japan is the most outstanding, LiPF 6Industrialization do best.Gu relate to gas in a large number though have--reaction method, HF solvent method, organic solvent method and ion exchange method prepare LiPF 6Patent documentation, but the HF solvent method is really to have realized LiPF at present 6The production method of industrialization.Japanese Patent JP-OS60-251109 and JP-OS5-279003, Chinese patent CN1124975C and CN101723346B etc. disclose a kind of LiPF 6The preparation method, wherein with PCl 5In liquid HF, react generation PF with HF 5And HCl, with the LiF reaction that is dissolved among the liquid HF, generate LiPF then 6The HF solvent method prepares LiPF 6Have very fast, the product yield advantage of higher of speed of response, but because aforesaid method all adopts liquid HF as solvent, must resolve the use of erosion resistance material.Because PCl 5Violent with the HF reaction, speed of response is difficult to control, blasts easily, and reaction needed is (78～0 ° of C) operation under cold condition, and cost is higher.In addition, because the solubleness of LiF in HF is lower, and the LiPF that generates 6Parcel LiF stops reaction to be proceeded, and unconverted LiF and HF form adducts (with LiHF 2Form) sneak into the finished product, residual HF also is difficult to thoroughly remove from the finished product.
Publication US3607020A and US3907977A propose a kind of production LiPF 6Method, wherein LiF and PF 5In inert organic solvents, react PF 5Be soluble in these solvents, reaction can be carried out under higher temperature, yet all requires directly to use PF 5As raw material, but this raw material can not be bought from the market.For this reason, publication CN101353161B proposes a kind of improved method, and this method is utilized PCl 5With HF prepared in reaction PF in inert organic solvents 5Gas, the PF that obtains 5Gas purity height, it and the LiF that is suspended in the inert organic solvents react, and can high-level efficiency prepare the LiPF of high purity (99.95%) (93%) 6It is raw material that this method still adopts HF, and product also has HF residual unavoidably, and the by product that produces is HCl, have stronger corrodibility, still higher to synthesis device and environmental protection requirement, temperature of reaction is that subzero 50 ° of C are to subzero 10 ° of C, operation easier is bigger, and cost is still higher.
The inventor is at patent CN(201310020380.0) in disclose a kind of organotin fluorochemical that utilizes and prepared high-purity phosphorus pentafluoride, directly and the lithium fluoride reaction generate the method for lithium hexafluoro phosphate, reacting does not namely need to use HF, does not need to carry out at low temperatures yet.Yet, more than these methods all to need directly to buy from the market high purity cell-grade LiF be raw material.
[summary of the invention]
The objective of the invention is in order to overcome prior art for preparing LiPF 6Production link many, need cold operation, complex process, equipment and environmental requirement are very high, the shortcoming that the productive rate of product and purity are not high provides a kind of technical simple controllable system, the processing condition organotin fluorochemical that utilizes simple, that reduce equipment corrosion to prepare the method that high purity is fluoridized lithium and lithium hexafluoro phosphate.
Another object of the present invention provides a kind of method of utilizing same materials in the aforesaid method directly to prepare the high purity lithium hexafluoro phosphate.
Method among the present invention is used the cheap raw material that obtains easily, highly purified product is provided, and can carries out under the simplest processing condition, avoids using and form corrosive material as far as possible.
The present invention for achieving the above object, by the following technical solutions:
Organotin fluorochemical R nSnF 4-nBe a kind of fluorination reagent efficiently (H.W.Roesky, Chem.Rev.1997, 973425), they can be under condition as mild as a dove, with nitrogen (N), phosphorus (P), sulphur (S) and transition metal chloride (Cl) and bromide (Br) quantitative F/Cl (Br) permutoid reaction taking place, generates some and adopt ordinary method to be difficult to nitrogen (N), phosphorus (P), sulphur (S) and the transition metal fluorides of preparation; The organotin halogenide R that reaction is remaining nSnX 4-n(X=Cl, Br) reclaim after can with common fluorochemical M'F(M'=H +, Na +, K +, NH 4 +, Et 4N +, Me 4N +Deng) become corresponding organotin fluorochemical R by equation (1) reaction regeneration nSnF 4-n, can be recycled, be a kind of very economical fluorine chemical technology.
R nSnX 4-n+M'F→R nSnF 4-n+M'X（1）。
Utilize the organotin fluorochemical to prepare the method that high purity is fluoridized lithium, it is characterized in that by with lithium halide and organotin fluorochemical R nSnF 4-nCarry out fluorine/halogen exchange reaction and generate lithium fluoride in the presence of organic solvent in dry nitrogen atmosphere, reaction formula is:
LiX+R nSnF 4-n→LiF+R nSnX 4-n（2）；
Wherein said lithium halide is lithium chloride or lithiumbromide;
Wherein said organotin fluorochemical R nSnF 4-nIn R represent methyl, ethyl, propyl group, sec.-propyl, a kind of in normal-butyl, isobutyl-, the tertiary butyl, the straight or branched alkane that contains 1-10 carbon, phenyl, benzyl and other substituted aroma alkyl, n represents 2 or 3;
Wherein said organic solvent is selected from least a in alcohol, ether, acetonitrile, the organic bases;
The mol ratio of wherein said lithium halide and the reaction of organotin fluorochemical is 1:0.5～1.0, and the quality of described lithium halide is 0.1～0.5:1～10 with volume of organic solvent than (w/v).
When the present invention prepares high purity and fluoridizes lithium in the used organic solvent, alcohol is selected from least a in methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol and the isopropylcarbinol; Ether is selected from least a in methyl ether, ether, glycol dimethyl ether, ethylene glycol diethyl ether, Propylene Glycol Dimethyl Ether, diglyme, methyl-phenoxide, phenyl ethyl ether and the tetrahydrofuran (THF); Organic bases is selected from least a in pyridine, Trimethylamine, diethylamide, triethylamine, dipropylamine, tripropylamine and methylethyl amine, methyl-propyl amine, the ethyl propyl amine etc.
The present invention utilizes the organotin fluorochemical to prepare high purity to fluoridize the fluorine of lithium/halogen exchange reaction temperature and control at 20～150 ℃, be preferably 30～82 ℃, dry nitrogen atmosphere be water-content less than the nitrogen gas of 10ppm, reaction pressure is normal pressure, the reaction times is 5～10 hours.
Utilize the lithium fluoride of method for preparing to prepare the method for high purity lithium hexafluoro phosphate, it is characterized in that may further comprise the steps:
3a, with phosphorus pentahalides and organotin fluorochemical R nSnF 4-nIn the presence of organic solvent, in dry nitrogen atmosphere, carry out fluorine/halogen exchange reaction and generate phosphorus pentafluoride;
3b, phosphorus pentafluoride is suspended in lithium fluoride in the organic solvent in dry nitrogen atmosphere neutralization reacts to lithium fluoride and react completely, displace remaining phosphorus pentafluoride then, obtain lithium hexafluoro phosphate solution;
3c, with lithium hexafluoro phosphate solution for vacuum concentration to 2/3～1/6 that obtains,-30～0 ℃ of following freezing and crystallizing, remove by filter mother liquor under the uniform temp and get crystal, gained crystal drying under 0～50 ℃ of following vacuum is removed the organic solvent of coordination, obtain high purity lithium hexafluorophosphate;
Wherein the reaction formula of step a is:
PX 5+R nSnF 4-n→PF 5+R nSnX 4-n（3）；
Wherein the reaction formula of step b is: PF 5+ LiF → LiPF 6(4);
Wherein said phosphorus pentahalides turns to phosphorus pentachloride or phosphorus pentabromide;
Wherein said organotin fluorochemical R nSnF 4-nIn R represent methyl, ethyl, propyl group, sec.-propyl, a kind of in normal-butyl, isobutyl-, the tertiary butyl, the straight or branched alkane that contains 1-10 carbon, phenyl, benzyl and other substituted aroma alkyl, n represents 2 or 3;
Wherein said organic solvent is selected from least a in alkane, aromatic hydrocarbons, ether, acetonitrile, carbonic ether and the ethyl acetate;
Wherein said phosphorus pentahalides and organotin fluorochemical R nSnF 4-nMol ratio be 1:2.5～5.2, the quality of described phosphorus pentahalides is 0.1～0.5:1 with volume of organic solvent than (w/v);
The mol ratio of wherein said phosphorus pentafluoride and lithium fluoride reaction is 1～5:1, and the quality of the lithium fluoride among the described step 3b is 0.05～0.2:1 with volume of organic solvent than (w/v).
Prepare among the present invention phosphorus pentafluoride with and identical with used organic solvent in the method for lithium fluoride prepared in reaction lithium hexafluoro phosphate, alkane wherein and aromatic hydrocarbons are selected from least a in sherwood oil, normal hexane, hexanaphthene, normal heptane, isoheptane, the benzene,toluene,xylene; Ether is selected from least a in methyl ether, ether, glycol dimethyl ether, ethylene glycol diethyl ether, Propylene Glycol Dimethyl Ether, diglyme, methyl-phenoxide, phenyl ethyl ether and the tetrahydrofuran (THF); Organic bases is selected from least a in pyridine, Trimethylamine, diethylamide, triethylamine, dipropylamine, tripropylamine and methylethyl amine, methyl-propyl amine, the ethyl propyl amine etc.; Carbonic ether is selected from least a in methylcarbonate, diethyl carbonate, Methyl ethyl carbonate and the NSC 11801.
Utilize the lithium fluoride for preparing to prepare the method for high purity lithium hexafluoro phosphate among the present invention, it is characterized in that the temperature of reaction among described step 3a and the step 3b all controls at 20～100 ℃, be preferably 30～82 ℃, dry nitrogen atmosphere among described step 3a and the step 3b is that water-content is less than the nitrogen gas of 10ppm, reaction pressure is 0.1～1.0Mpa, be preferably 0.1～0.5Mpa, the reaction times is 5～10 hours.
Utilize the organotin fluorochemical to prepare the method for high purity lithium hexafluorophosphate, it is characterized in that may further comprise the steps:
5a, in reactor I, earlier lithium halide and phosphorus pentahalides are dissolved in the organic solvent up to forming limpid intermediate LiPX 6Solution;
5b, with organotin fluorochemical R nSnF 4-nBe suspended in the organic solvent in the reactor II, stir down the lithium halide among the reactor I and phosphorus pentahalides are reacted the LiPX that generates 6Solution imports among the reactor II and reacts under dry nitrogen atmosphere to forming limpid transparent solution, under vacuum condition, with the organotin halogenide R of organic solvent and generation nSnX 4-nDrain, remaining solid with normal hexane or petroleum ether after, solid organic solvent recrystallization, subcooling obtains containing the crystal of organic solvent, remove by filter mother liquor after, crystal is removed organic solvent through vacuum-drying, namely obtains highly purified lithium hexafluoro phosphate;
Wherein step 5a reaction formula is respectively:
LiX+PX 5→LiPX 6（5a）；
Wherein the reaction formula of step 5b is:
LiPX 6+R nSnF 4-n→LiPF 6+R nSnX 4-n（5b）；
Lithium halide wherein is lithium chloride or lithiumbromide, and phosphorus pentahalides turns to phosphorus pentachloride or phosphorus pentabromide;
Wherein the used organic solvent of step 5a and 5b is identical, all is selected from least a in ether, acetonitrile, organic bases, carbonic ether and the ethyl acetate.
Wherein the mol ratio of each reactant is LiX:PX 5: R nSnF 4-n=1:1:3～6.
Among the present invention reaction (5a) and (5b) in the mol ratio of each reactant be preferably LiX:PX 5: R nSnF 4-n=1:1:3～6; Further preferred molar ratio is LiX:PX 5: R nSnF 4-n=1:1:3(is n=2 wherein) or LiX:PX 5: R nSnF 4-n=1:1:6(is n=3 wherein).
Dry nitrogen atmosphere among the present invention when organotin fluorochemical and lithium halide and phosphorus pentahalides one pot reaction be water-content less than the nitrogen gas of 10ppm, temperature of reaction is elected 20～100 ° of C as, reaction pressure is 0.1～1.0MPa, the reaction times is 5～10 hours.
The inventor is at patent of invention CN(201310020380.0) described in LiF, PX 5And R nSnF 4-nIn the one pot reaction that carries out, PX 5Be not easy with organic solvent in the extremely low LiF of solubleness reaction, but elder generation and R nSnF 4-nReaction, generation PF in place in solution 5After, reaction generates LiPF with LiF immediately 6At LiX of the present invention, PX 5And R nSnF 4-nCarry out in (5a) and the one pot reaction (5b), LiX has certain solubleness in organic solvent, is easy to and PX 5Reaction earlier generates the better LiPX of solubleness 6(X=Cl, Br)) intermediate, LiPX then 6Again and R nSnF 4-nReaction generates LiPF 6, the reaction times is shortened, more be conducive to suitability for industrialized production.
The present invention compared with prior art has following advantage:
LiF of the present invention is generated by cheap raw material Li Cl or lithiumbromide and organotin fluorochemical sluggish, and the purity height than directly the LiF of purchase is more tiny on the market, is conducive to and PF 5Reaction; In addition, it is fluorination reagent that the present invention avoids adopting the HF of severe corrosive, and is to use the organotin fluorochemical R that is easy to purify nSnF 4-nBe fluorination reagent, the reaction conditions gentleness does not have by product HCl to occur, and technological process is simple, and is low to equipment and environmental protection requirement, not only avoided introducing the possibility of impurity, LiF and PF that preparation is generated 5Based on very high purity guarantees that next step can prepare high-quality LiPF 6
On the other hand, when according to reaction formula (5a) and (5b) one pot reaction prepares lithium hexafluoro phosphate, generate the better LiPX of solubleness in the organic solvent earlier 6Intermediate makes reaction generate LiPF 6Time shorten, more be conducive to suitability for industrialized production.
[embodiment]
According to the present invention, wherein a kind of method comprises LiX and PX 5(X=Cl is Br) with organotin fluorochemical R nSnF 4-n(R=Me, Et, Pr, i-Pr, n-Bu, i-Bu, t-Bu etc. contain the straight or branched alkane of 1-10 carbon, phenyl Ph, benzyl Bn and other substituted aroma alkyl; N=2,3) carry out halogen exchange reaction (2) and (3) preparation LiF and PF 5, wherein, lithium halide and organotin fluorochemical R nSnF 4-nMol ratio be 1:0.5～1.1, PX 5With organotin fluorochemical R nSnF 4-nMol ratio be 1:2.5～5.2, above-mentioned two kinds of permutoid reactions are all carried out in the presence of organic solvent, the mass ratio of lithium halide and organic solvent is 0.1～0.5:1～10, PX 5With the mass ratio of organic solvent be 0.1～0.5:1.
Organic solvent among the present invention all passes through suitable drying before use except water treatment, and reaction is all carried out in dry atmosphere, and this drying atmosphere be the nitrogen gas of drying, and water-content wherein is less than 10ppm, the PF in preventing from reacting 5Moisture absorption hydrolysis, and can access highly purified PF 5Gas, thus further prepare highly purified lithium hexafluoro phosphate.
Lithium halide and organotin fluorochemical R nSnF 4-nReaction can further be filtered purification after producing lithium fluoride, isolates highly purified LiF solid and is used as next step reaction raw materials; Also can directly use this suspension to carry out next step reaction without separation.
LiF and PF among the present invention 5Mol ratio be not particularly limited, preferred mol ratio 1:1～5 have no particular limits the add-on of organic solvent, under the optimum condition, LiF quality and its volume of organic solvent of suspending are 0.05～0.2:1 than (w/v).
The concrete preparation method of LiF comprises among the present invention: under the normal temperature condition, under dry nitrogen atmosphere, with LiX and organotin fluorochemical R nSnF 4-nAdd in the organic solvent that is suspended in drying in the reactor, heat up and stirred 5～10 hours, until R nSnF 4-nCompletely dissolve, during temperature of reaction be 20～150 ° of C, be preferably 30～82 ° of C.The LiF that produces is nanoscale solids, is suspended in the organic solvent, removes mother liquor after filtration, isolates highly purified LiF solid and is used as next step reaction raw materials; Also can directly use this suspension to carry out next step reaction without separation.
PF among the present invention 5Concrete preparation method comprise: with PCl 5Be dissolved in the dry organic solvent, under nitrogen protection, with organotin fluorochemical R nSnF 4-nAdding suspends in the reactor stirred 5～10 hours, until R nSnF 4-nDisappear, during temperature of reaction be 20～100 ° of C, be preferably 40～82 ° of C.
The LiF and the PF that prepare with elder generation among the present invention 5Preparation LiPF 6Method specifically comprise: under normal temperature condition, solid LiF is suspended in the dry organic solvent, under protection of nitrogen gas, with PF 5Gas importing and LiF contact reacts 5～10 hours, the mol ratio of reaction is 1～5:1, the preferred 0.1～0.5MPa of reaction pressure.
Under the preferable case, above-mentioned preparation LiF and PF 5Two reactions (2) and (3) can in two reactors, carry out respectively, and two reactions can be carried out simultaneously.For example, preparation LiF and PF 5Reaction in reactor I and reactor II, carry out respectively, earlier in reactor I, carry out the preparation of LiF solid, then can be at any time with the PF that generates among the reactor II 5Gas imports to and reacts (4) generation LiPF among the reactor I 6Solution, through concentrating, freezing and crystallizing filters, and vacuum can obtain final product LiPF after removing organic solvent 6
The detailed process of above-mentioned vacuum concentration drying is: temperature is controlled at 20 ° of C, under the vacuum tightness of 15mmHg, with lithium hexafluoro phosphate solution concentration to 2/3～1/6 that obtains, at-30～0 ℃ of following freezing and crystallizing, remove by filter mother liquor under the uniform temp and get crystal, gained crystal drying under 0～50 ℃ of following vacuum is removed the organic solvent of coordination, obtain high purity lithium hexafluorophosphate.
The present invention reacts (2) and (3) owing to directly do not use HF as raw material and reaction solvent, the LiF of generation and PF 5Gas can not brought HF gas in the reactor into, makes final product LiPF 6It is residual not need to remove HF, and purity is higher.
The present invention also provides a kind of usefulness above-mentioned preparation LiPF 6Raw material in the method carries out one pot reaction and prepares LiPF 6Method, this method comprises earlier with solid LiX and PX 5Be dissolved in the organic solvent, under protection of nitrogen gas, add organotin fluorochemical R again nSnF 4-nBe suspended in the organic solvent, carry out one pot reaction according to equation (5a) with (5b), after solution becomes is limpid, remove organic solvent and organotin halogenide R nSnX 4-n, obtain highly purified LiPF through the organic solvent recrystallization 6
Reaction (5a) and (5b) utilize lithium halide and phosphorus pentahalides and organotin fluorochemical R nSnF 4-nThe mol ratio of each reactant is LiX:PX in the method for prepared in reaction lithium hexafluoro phosphate 5: R nSnF 4-n=1:1:3～12 are preferably 1:1:3 (n=2) or 1:1:6(n=3).
Because PF 5Still has corrodibility, moisture absorption hydrolysis also can produce HF, thus the container that each reaction among the present invention all preferably uses various corrosion-resistant materials to make, for example, can be by Monel metal, nickel-base alloy, the container that materials such as cadmium base alloy are made also can be that the reaction chamber liner is coated with polyethylene, polystyrene, polyvinyl chloride, polypropylene, the container of polyacrylic ester or tetrafluoroethylene.
The present invention will be further described in detail below in conjunction with specific embodiment, but the present invention is not limited in present embodiment.
One, by reaction equation of the present invention (2) preparation LiF
Embodiment 1:
In closed reaction kettle, under nitrogen protection, under the normal temperature 42.4g (1mol) LiCl is dissolved in the 500mL anhydrous methanol, add 182.9g (1mol) Me then 3The SnF solid suspension stirs Me down in solution 3The SnF solid fades away, and generates superfine LiF solid suspension simultaneously in solution, react after 10 hours, and solid collected by filtration, and with an amount of methanol wash solid, obtain the 25.4gLiF solid after the vacuum concentration drying, purity is 99.95%.
Embodiment 2:
In closed reaction kettle, under nitrogen protection, under the normal temperature 86.84g (1mol) LiBr is dissolved in the 800mL anhydrous methanol, add 182.9g (1mol) Me then 3The SnF solid suspension is warming up to 80 ℃ and stirs Me down in solution 3The SnF solid fades away, and generates superfine LiF solid suspension simultaneously in solution, reacts after 10 hours, is cooled to room temperature, solid collected by filtration, and with an amount of washing with alcohol solid, obtain the 25.6gLiF solid after the vacuum concentration drying, purity be what 99.95%.
Embodiment 3:
In closed reaction kettle, under nitrogen protection, under the normal temperature 42.4g (1mol) LiCl is dissolved in the 500mL dehydrated alcohol, add 93.45g (0.5mol) Me then 2SnF 2Solid suspension is warming up to 150 ℃ and stirs Me down in solution 2SnF 2Solid fades away, and generates superfine LiF solid suspension simultaneously in solution, reacts after 10 hours, is cooled to room temperature, solid collected by filtration, and with an amount of methanol wash solid, obtain the 25.2gLiF solid after the vacuum concentration drying, purity be what 99.95%.
Two, by reaction equation of the present invention (3) and (4) preparation PF 5And LiPF 6
Embodiment 4:
(1) in closed reaction kettle I, under nitrogen protection, with 10.4g (0.05mol) PCl 5Be dissolved in the 150mL toluene, under agitation add 46.7g (0.255mol) Me then 3SnF is suspended in the solvent, and reacting balance carries out, the Me of suspension 3SnF fades away, and temperature of reaction can be raised to 100 ° of C, PF by room temperature 5The formation speed of gas is accelerated with the rising of temperature, and the best can be controlled in 80 ° of C, the PF of generation 5Gas can directly import among the reactor II under nitrogen protection;
(2) in closed reaction kettle II, under nitrogen protection, under the normal temperature 1.27g prepared among the embodiment 1 (0.049mol) LiF is suspended in the 120mL acetonitrile, then under whipped state, the PF that reactor I is produced 5Import lentamente, generate LiPF through 100 ° of following 5 hours reactions of C 6Solution after reaction is finished, feeds high-purity nitrogen and replaces, and does not have PF in container 5Gas obtains containing LiPF 6Solution, after reactor is cooled to room temperature that temperature control is at 20 ° of C, to 20mL, freezing under-15 ° of C with solution concentration under the vacuum tightness of 15mmHg, obtain solvent-laden LiPF 6Crystal filters the back crystal and was warming up to 50 ° of C dry 2 hours under 15mmHg vacuum tightness, makes LiPF 6Pure product 6.8g, productive rate are 93.0%, detected result purity 99.95%.
Embodiment 5:
(1) in closed reaction kettle I, under nitrogen protection, with 20.8g (0.1mol) PCl 5Be dissolved in the 150mL acetonitrile, under agitation add 93.3g (0.51mol) Me then 3SnF is suspended in the solvent, and reacting balance carries out, the Me of suspension 3SnF fades away, and temperature of reaction can be raised to 80 ° of C, PF by room temperature 5The formation speed of gas is accelerated with the rising of temperature, and the best can be controlled in 60-82 ° of C, the PF of generation 5Gas can directly import among the reactor II under nitrogen protection;
(2) in closed reaction kettle II, under nitrogen protection, under the normal temperature 2.5g prepared among the embodiment 2 (0.095mol) LiF is suspended in the 150mL acetonitrile, then under whipped state, the PF that reactor I is produced 5Import lentamente, generate LiPF through 82 ℃ of following reactions of 6 hours 6Solution after reaction is finished, feeds high-purity nitrogen and replaces, and does not have PF in container 5Gas obtains containing LiPF 6Solution, after reactor is cooled to room temperature that temperature control is at 20 ° of C, to 20mL, freezing under-15 ° of C with solution concentration under the vacuum tightness of 15mmHg, obtain solvent-laden LiPF 6Crystal filters the back crystal and was warming up to 50 ° of C dry 2 hours under 15mmHg vacuum tightness, makes LiPF 6Pure product 13.5g, productive rate are 91.4%, detected result purity 99.95%.
Embodiment 6:
(1) in closed reaction kettle I, under nitrogen protection, with 43.1g (0.1mol) PBr 5Be dissolved in the 200mL toluene, under agitation add 93.3g (0.51mol) Me then 3SnF is suspended in the solvent, and reacting balance carries out, the Me of suspension 3SnF fades away, and temperature of reaction can be raised to 100 ° of C, PF by room temperature 5The formation speed of gas is accelerated with the rising of temperature, and the best can be controlled in 80 ° of C, the PF of generation 5Gas can directly import among the reactor II under nitrogen protection;
(2) in closed reaction kettle II, under nitrogen protection, under the normal temperature 2.5g prepared among the embodiment 3 (0.095mol) LiF is suspended in the 150mL acetonitrile, then under whipped state, the PF that reactor I is produced 5Import lentamente, generate LiPF through 80 ℃ of following reactions of 6 hours 6Solution after reaction is finished, feeds high-purity nitrogen and replaces, and does not have PF in container 5Gas obtains containing LiPF 6Solution, after reactor is cooled to room temperature, temperature control at 20 ° of C, under the vacuum tightness of 15mmHg, with solution concentration, until draining solvent, is obtained solvent-laden LiPF 6, continued under 15mmHg vacuum tightness, to be warming up to 50 ° of C then dry 2 hours, make LiPF 6Pure product 13.8g, productive rate are 94.5%, and detected result purity is greater than 99.9%.Embodiment 7:
(1) in closed reaction kettle I, under nitrogen protection, with 20.8g (0.1mol) PCl 5Be dissolved in the 200mL toluene, under agitation add 47.2g (0.26mol) Me then 2SnF 2Be suspended in the solvent, reacting balance carries out, the Me of suspension 2SnF 2Fade away, temperature of reaction can be raised to 100 ° of C, PF by room temperature 5The formation speed of gas is accelerated with the rising of temperature, and the best can be controlled in 80 ° of C, the PF of generation 5Gas can directly import among the reactor II under nitrogen protection;
(2) in closed reaction kettle II, under nitrogen protection, under the normal temperature 2.5g prepared among the embodiment 1 (0.095mol) LiF is suspended in the 150mL acetonitrile, then under whipped state, the PF that reactor I is produced 5Import lentamente, generate LiPF through 40 ℃ of following reactions of 8 hours 6Solution after reaction is finished, feeds high-purity nitrogen and replaces, and does not have PF in container 5Gas obtains LiPF 6Solution, after reactor is cooled to room temperature that temperature control is at 20 ° of C, to 20mL, freezing under-15 ° of C with solution concentration under the vacuum tightness of 15mmHg, obtain solvent-laden LiPF 6Crystal filters the back crystal and was warming up to 50 ° of C dry 2 hours under 15mmHg vacuum tightness, makes LiPF 6Pure product 13.4g, productive rate are 91.5%, detected result purity 99.95%.
Embodiment 8:
(1) in closed reaction kettle I, under nitrogen protection, with 43.1g (0.1mol) PBr 5Be dissolved in the 200mL toluene, under agitation add 47.2g (0.26mol) Me then 2SnF 2Be suspended in the solvent, reacting balance carries out, the Me of suspension 2SnF 2Fade away, temperature of reaction can be raised to 100 ° of C, PF by room temperature 5The formation speed of gas is accelerated with the rising of temperature, and the best can be controlled in 80 ° of C, the PF of generation 5Gas can directly import among the reactor II under nitrogen protection;
(2) in closed reaction kettle II, under nitrogen protection, under the normal temperature 2.5g prepared among the embodiment 1-3 (0.095mol) LiF is suspended in the 150mL acetonitrile, then under whipped state, the PF that reactor I is produced 5Import lentamente, generate LiPF through 80 ℃ of following reactions of 5 hours 6Solution after reaction is finished, feeds high-purity nitrogen and replaces, and does not have PF in container 5Gas obtains LiPF 6Solution after reactor is cooled to room temperature, at 20 ° of C, under the vacuum tightness of 15mmHg, with solution concentration, until draining solvent, obtains solvent-laden LiPF with temperature control 6, continued under 15mmHg vacuum tightness, to be warming up to 50 ° of C then dry 2 hours, make LiPF 6Pure product 13.8g, productive rate are 94.5%, and detected result purity is greater than 99.9%.
Embodiment 9:
(1) in closed reaction kettle I, under nitrogen protection, with 20.8g (0.1mol) PCl 5Be dissolved in the 150mL acetonitrile, under agitation add 112.5g (0.50mol) Et then 3SnF is suspended in the solvent, and reacting balance carries out, the Et of suspension 3SnF fades away, and temperature of reaction can be raised to 80 ° of C, PF by room temperature 5The formation speed of gas is accelerated with the rising of temperature, and the best can be controlled in 60-80 ° of C, the PF of generation 5Gas can directly import among the reactor II under nitrogen protection;
(2) in closed reaction kettle II, under nitrogen protection, under the normal temperature 2.5g prepared among the embodiment 3 (0.095mol) LiF is suspended in the 100mL acetonitrile, then under whipped state, the PF that reactor I is produced 5Import lentamente, generate LiPF through 60 ℃ of following reactions of 7 hours 6Solution after reaction is finished, feeds high-purity nitrogen and replaces, and does not have PF in container 5Gas obtains LiPF 6Solution after reactor is cooled to room temperature, at 20 ° of C, under the vacuum tightness of 15mmHg, with solution concentration, until draining solvent, obtains solvent-laden LiPF with temperature control 6, continued under 15mmHg vacuum tightness, to be warming up to 50 ° of C then dry 2 hours, make LiPF 6Pure product 13.6g, productive rate are 93.1%, and detected result purity is greater than 99.9%.Three, by reaction equation (5a) and (5b) one pot reaction prepare LiPF 6
Embodiment 10:
(1) in closed reaction kettle I, under nitrogen protection, under the normal temperature with 20.8g (0.1mol) PCl 5And 4.24g (0.1mol) LiCl is dissolved in the 150mL acetonitrile (or tetrahydrofuran (THF)), up to forming limpid LiPCl 6Solution;
(2) in closed reaction kettle II, under nitrogen protection, with 112.0g (0.61mol) Me 3SnF is suspended in the 150mL acetonitrile solvent, then under whipped state, with the LiPCl that generates among the reactor I 6Solution imports lentamente, through 8 hours reaction, forms limpid LiPF under 60 ° of C 6Solution, after reactor is cooled to room temperature, with temperature control at 20 ° of C, under the vacuum tightness of 5-10mmHg, with solution concentration to draining, remaining solid washs 3 times with normal hexane, the solid that obtains after the filtration is with ether (or acetonitrile) recrystallization, and is freezing under-20 ° of C, obtains a large amount of crystal, filter the back crystal and under 15mmHg vacuum tightness, be warming up to 50 ° of C dry 2 hours, make LiPF 6Pure product 13.5g, productive rate are 92.5%, and detected result purity is greater than 99.95%.
Embodiment 11:
(1) in closed reaction kettle I, under nitrogen protection, under the normal temperature 43.1g (0.1mol) PBr5 and 12.3g (0.1mol) LiBr are dissolved in the 150mL acetonitrile (or tetrahydrofuran (THF)), up to forming limpid solution;
(2) in closed reaction kettle II, under nitrogen protection, 112.0g (0.61mol) Me3SnF is suspended in the 150mL acetonitrile solvent, then under whipped state, with the LiPBr of reactor I 6Solution imports lentamente, through 8 hours reaction, forms limpid LiPF under 60 ° of C 6Solution, after reactor is cooled to room temperature, with temperature control at 20 ° of C, under the vacuum tightness of 5-10mmHg, with solution concentration to draining, solid petroleum ether 3 times, the solid that obtains after the filtration is with ether (or acetonitrile) recrystallization, and is freezing under-20 ° of C, obtains a large amount of crystal, filter the back crystal and under 15mmHg vacuum tightness, be warming up to 50 ° of C dry 2 hours, make LiPF 6Pure product 13.7g, productive rate are 93.7%, and detected result purity is greater than 99.95%.
Embodiment 12:
(1) in closed reaction kettle I, under nitrogen protection, under the normal temperature with 20.8g (0.1mol) PCl 5And 4.24g (0.1mol) LiCl is dissolved in the 120mL acetonitrile (or tetrahydrofuran (THF)), up to forming limpid solution;
(2) in closed reaction kettle II, under nitrogen protection, with 56.4g (0.31mol) Me 2SnF 2Be suspended in the 120mL acetonitrile solvent, then under whipped state, with the LiPCl of reactor I 6Solution imports lentamente, through 8 hours reaction, forms limpid LiPF under 60 ° of C 6Solution, after reactor is cooled to room temperature, with temperature control at 20 ° of C, under the vacuum tightness of 5-10mmHg, with solution concentration to draining, solid washs 3 times with normal hexane, the solid that obtains after the filtration is with ether (or acetonitrile) recrystallization, and is freezing under-20 ° of C, obtains a large amount of crystal, filter the back crystal and under 15mmHg vacuum tightness, be warming up to 50 ° of C dry 2 hours, make LiPF 6Pure product 13.4g, productive rate are 91.8%, and detected result purity is greater than 99.9%.
Embodiment 13:
(1) in closed reaction kettle I, under nitrogen protection, under the normal temperature 43.1g (0.1mol) PBr5 and 12.3g (0.1mol) LiBr are dissolved in the 150mL acetonitrile (or tetrahydrofuran (THF)), up to forming limpid solution.
(2) in closed reaction kettle II, under nitrogen protection, 56.4g (0.31mol) Me2SnF2 is suspended in the 120mL acetonitrile solvent; then under whipped state; the LiPBr6 solution of reactor I is imported lentamente, under 60 ° of C, through 8 hours reaction, form limpid LiPF 6Solution, after reactor is cooled to room temperature, with temperature control at 20 ° of C, under the vacuum tightness of 5-10mmHg, with solution concentration to draining, solid petroleum ether 3 times, the solid that obtains after the filtration is with ether (or acetonitrile) recrystallization, and is freezing under-20 ° of C, obtains a large amount of crystal, filter the back crystal and under 15mmHg vacuum tightness, be warming up to 50 ° of C dry 2 hours, make LiPF 6Pure product 13.6g, productive rate are 93.0%, and detected result purity is greater than 99.9%.

Claims (8)

1. utilize the organotin fluorochemical to prepare the method that high purity is fluoridized lithium, it is characterized in that by with lithium halide and organotin fluorochemical R nSnF 4-nCarry out fluorine/halogen exchange reaction and generate lithium fluoride in the presence of organic solvent in dry nitrogen atmosphere, reaction formula is:
LiX+R nSnF 4-n→LiF+R nSnX 4-n；
Wherein said lithium halide is lithium chloride or lithiumbromide;
Wherein said organotin fluorochemical R nSnF 4-nIn R represent methyl, ethyl, propyl group, sec.-propyl, a kind of in normal-butyl, isobutyl-, the tertiary butyl, the straight or branched alkane that contains 1-10 carbon, phenyl, benzyl and other substituted aroma alkyl, n represents 2 or 3;
Wherein said organic solvent is selected from least a in alcohol, ether, acetonitrile, the organic bases;
The mol ratio of wherein said lithium halide and the reaction of organotin fluorochemical is 1:0.5～1.0, and the quality of described lithium halide is 0.1～0.5:1～10 with volume of organic solvent than (w/v).
2. the organotin fluorochemical that utilizes according to claim 1 prepares the method that high purity is fluoridized lithium, it is characterized in that described fluorine/halogen exchange reaction temperature controls at 20～150 ℃, described dry nitrogen atmosphere is that water-content is less than the nitrogen gas of 10ppm, reaction pressure is normal pressure, and the reaction times is 5～10 hours.
3. the lithium fluoride that utilizes the described method of claim 1 to prepare prepares the method for high purity lithium hexafluoro phosphate, it is characterized in that may further comprise the steps:
3a, with phosphorus pentahalides and organotin fluorochemical R nSnF 4-nIn the presence of organic solvent, in dry nitrogen atmosphere, carry out fluorine/halogen exchange reaction and generate phosphorus pentafluoride;
3b, phosphorus pentafluoride is suspended in lithium fluoride in the organic solvent in dry nitrogen atmosphere neutralization reacts to lithium fluoride and react completely, displace remaining phosphorus pentafluoride then, obtain lithium hexafluoro phosphate solution;
3c, with lithium hexafluoro phosphate solution for vacuum concentration to 2/3～1/6 that obtains,-30～0 ℃ of following freezing and crystallizing, remove by filter mother liquor under the uniform temp and get crystal, gained crystal drying under 0～50 ℃ of following vacuum is removed the organic solvent of coordination, obtain high purity lithium hexafluorophosphate;
Wherein the reaction formula of step 3a is: PX 5+ R nSnF 4-n→ PF 5+ R nSnX 4-n
Wherein the reaction formula of step 3b is: PF 5+ LiF → LiPF 6
Wherein said phosphorus pentahalides turns to phosphorus pentachloride or phosphorus pentabromide;
Wherein said organotin fluorochemical R nSnF 4-nIn R represent methyl, ethyl, propyl group, sec.-propyl, a kind of in normal-butyl, isobutyl-, the tertiary butyl, the straight or branched alkane that contains 1-10 carbon, phenyl, benzyl and other substituted aroma alkyl, n represents 2 or 3;
Wherein said organic solvent is selected from least a in alkane, aromatic hydrocarbons, ether, acetonitrile, carbonic ether and the ethyl acetate;
Wherein said phosphorus pentahalides and organotin fluorochemical R nSnF 4-nMol ratio be 1:2.5～5.2, the quality of the phosphorus pentahalides among the described step 3a is 0.1～0.5:1 with volume of organic solvent than (w/v);
The mol ratio of wherein said phosphorus pentafluoride and lithium fluoride reaction is 1～5:1, and the quality of the lithium fluoride among the described step 3b is 0.05～0.2:1 with volume of organic solvent than (w/v).
4. the lithium fluoride of utilization preparation according to claim 3 prepares the method for high purity lithium hexafluoro phosphate, it is characterized in that the temperature of reaction among described step 3a and the step 3b all controls at 20～100 ℃, dry nitrogen atmosphere among described step 3a and the step 3b is that water-content is less than the nitrogen gas of 10ppm, reaction pressure is 0.1～1.0Mpa, and the reaction times is 5～10 hours.
5. utilize the organotin fluorochemical to prepare the method for high purity lithium hexafluorophosphate, it is characterized in that may further comprise the steps:
5a, in reactor I, earlier lithium halide and phosphorus pentahalides are dissolved in the organic solvent up to forming limpid intermediate LiPX 6Solution;
5b, with organotin fluorochemical R nSnF 4-nBe suspended in the organic solvent in the reactor II, stir following intermediate LiPX with the lithium halide among the reactor I and phosphorus pentahalides reaction 6Solution imports among the reactor II, reacts under dry nitrogen atmosphere to forming limpid transparent solution, under the vacuum condition, with the organotin halogenide R of organic solvent and generation nSnX 4-nDrain, remaining solid with normal hexane or petroleum ether after, solid organic solvent recrystallization, subcooling obtains containing the crystal of organic solvent, remove by filter mother liquor after, crystal is removed organic solvent through vacuum-drying, namely obtains highly purified lithium hexafluoro phosphate;
Wherein the reaction formula of step 5a is:
LiX+PX 5→LiPX 6
Wherein the reaction formula of step 5b is:
LiPX 6+R nSnF 4-n→LiPF 6+R nSnX 4-n
Wherein said lithium halide is lithium chloride or lithiumbromide, and described phosphorus pentahalides turns to phosphorus pentachloride or phosphorus pentabromide;
Wherein said organic solvent is selected from least a in ether, acetonitrile, organic bases, carbonic ether and the ethyl acetate.
6. the method for utilizing the organotin fluorochemical to prepare high purity lithium hexafluorophosphate according to claim 5 is characterized in that described each reactant LiX:PX 5: R nSnF 4-nMol ratio be 1:1:3～6.
7. the method for utilizing the organotin fluorochemical to prepare high purity lithium hexafluorophosphate according to claim 6 is characterized in that when n equals 2 LiX:PX 5: R nSnF 4-nMol ratio be 1:1:3, when n equals 3, LiX:PX 5: R nSnF 4-nMol ratio be 1:1:6.
8. the method for utilizing the organotin fluorochemical to prepare lithium hexafluoro phosphate according to claim 5, it is characterized in that the dry nitrogen atmosphere among the described step 5b is that water-content is less than the nitrogen gas of 10ppm, temperature of reaction is elected 20～100oC as, reaction pressure is 0.1～1.0MPa, and the reaction times is 5～10 hours.
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