CN101643481A - Synthesis technique for obtaining difluoro oxalate lithium borate and di-oxalate lithium borate - Google Patents
Synthesis technique for obtaining difluoro oxalate lithium borate and di-oxalate lithium borate Download PDFInfo
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Abstract
The invention discloses a synthesis technique for simultaneously obtaining difluoro oxalate lithium borate and di-oxalate lithium borate with outstanding performances, comprising the following steps:1. reacting fluorinated compound, boracic compound, lithium-containing compound and oxalate-containing compound in a reaction medium at 100 DEG C with reaction pressure of 0.1-1MPa, wherein the mol ratio of lithium, fluorine, boron and oxalate ions is 5-9:5-9:-2-3:3-4, and generating a reaction solution containing difluoro oxalate lithium borate and di-oxalate lithium borate; 2. carrying out initial separation on the difluoro oxalate lithium borate and di-oxalate lithium borate in the reaction solution, then carrying out further extraction separation by using organic solvent capable of extracting difluoro oxalate lithium borate or di-oxalate lithium borate; and 3. respectively carrying out recrystallization and vacuum drying to obtain the difluoro oxalate lithium borate and di-oxalate lithium borate of battery level. The invention is suitable for industrially producing two types of lithium salts with excellent performance used for lithium ion batteries.
Description
Technical field
The present invention relates to the preparing technical field of the used electrolytic salt of lithium ion battery, be specifically related to obtain simultaneously the synthesis technique of difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate.
Background technology
Ionogen is one of research emphasis of this technical field as the lithium ion battery chief component always.The LiPF of present commercial large-scale application
6The thermostability deficiency is easy to resolve into LiF and PF
5, the latter is easy to hydrolysis and forms HF and PF
3O.These two kinds of hydrolysates all have high reaction activity and high for anodal and negative pole, and they inevitably are present in LiPF
6The performance of middle counter electrode produces injurious effects.LiAsF
6Have and do not advocated that than high toxicity mass-producing uses owing to containing arsenic.LiClO
4Belong to strong oxidizer, explosive, safe differential.LiBF
4Relatively poor with the negative pole consistency, its thermostability is relatively poor and for moisture-sensitive, BF
4 -Negatively charged ion then is easy to have a strong impact in the negative terminal surface reduction formation of passive film.LiN (SO
2CF
3)
2And LiC (SO
2CF
3)
3Salt can produce corrosion to positive electrode current aluminium collector commonly used, and manufacturing cost is higher, is difficult to mass-producing and uses.Therefore, the development of new lithium salts replaces being used at present the LiPF of commercial Li-ion batteries
6Be very necessary and urgent.The novel lithium salts of research mainly concentrates on lithium-borate complexes and Trilithium phosphate title complex at present, and is wherein the most noticeable with di-oxalate lithium borate (LiBOB) and difluorine oxalic acid boracic acid lithium (LiODFB) again.
The LiBOB thermal stability that is applied to lithium ion battery is good, and its structural formula is as follows:
The LiBOB decomposition temperature is up to 302 ℃, and can form stable SEl film at negative pole, make the anti-over-charging performance of lithium ion battery and rate charge-discharge performance be improved significantly, excellent high is arranged and can in propylene carbonate (PC) solvent separately, use and can not make the carbon negative pole produce obscission.
The structural formula of LiODFB is as follows:
Its unique chemical structure makes its advantage that combines di-oxalate lithium borate and LiBF4, makes it have high temperature performance preferably simultaneously.
In the technology of at present synthetic LiBOB and LiODFB, the investigator concentrates on the synthetic of one matter substantially and purifies, and lessly considers that it is comprehensive, and finishes both synthetic and purify in a kind of reaction.The synthetic method of LiBOB is mainly three kinds, is respectively that water is synthetic, nonaqueous phase synthetic, solid phase synthesis.Water synthesizes with lithium hydroxide, oxalic acid, boric acid are synthetic in water and obtains LiBOB, and this method relates to high temperature and oxalic acid aqueous solution is high to equipment requirements; Nonaqueous phase is synthetic with LiB (OCH
3)
3With (CH
3)
3SiOOCCOOSi (CH
3)
3Synthetic, but the expensive industrial production that is not suitable for of this method cost of material; Solid phase method is synthetic to be at high temperature to generate after grinding evenly with lithium hydroxide, oxalic acid, boric acid, and this method is synthetic equally to the equipment requirements height with the water method.
Difluorine oxalic acid boracic acid lithium (LiODFB) is carried out later and is studied few.Following method in being the file of EP1308449A2, european patent number is disclosed: react in methylcarbonate or react in methylcarbonate with oxalic acid, LiBF4, lithium fluoride and boron trichloride or trimethoxy-boron with oxalic acid, LiBF4 and aluminum chloride or silicon tetrachloride and realized that LiODFB's is synthetic, but there is HCl to produce in this method reaction, and reaction is violent, and the equipment requirements height is unfavorable for suitability for industrialized production.
Summary of the invention
The technical problem to be solved in the present invention is: a kind of synthesis technique that obtains excellent performance difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate simultaneously will be provided.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of synthesis technique that obtains difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate, comprise the steps: (one) with the compound of fluorine-containing compound, boracic, the compound that contains the compound of lithium and contain oxalate 0～100 ℃, reaction pressure be 0.1～1Mpa, and reaction medium in react, wherein the mol ratio of elemental lithium, fluorine element, boron and oxalate denominationby is 5～9: 5～9: 2～3: 3～4; Generation contains the reaction solution of difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate; (2) difluorine oxalic acid boracic acid lithium in the reaction solution and di-oxalate lithium borate are carried out initial gross separation, carry out further extracting and separating with the organic solvent that can extract difluorine oxalic acid boracic acid lithium or di-oxalate lithium borate then; (3) carry out difluorine oxalic acid boracic acid lithium and the di-oxalate lithium borate that recrystallization and vacuum-drying obtain cell-grade respectively.
Above-mentioned fluorine-containing compound is any one in lithium fluoride, fluoroboric acid, boron trifluoride, boron trifluoride diethyl etherate, boron trifluoride methylcarbonate or the boron trifluoride complex; The compound of above-mentioned boracic is any one in boric acid, borax, fluoroboric acid, boron trifluoride diethyl etherate, boron trifluoride methylcarbonate or the boron trifluoride complex; The above-mentioned compound that contains lithium is any one in lithium hydroxide, lithium bicarbonate, oxalic acid hydrogen lithium, Quilonum Retard or the lithium oxalate; The above-mentioned compound that contains oxalate is any one in oxalic acid hydrogen lithium, lithium oxalate or the oxalic acid; Above-mentioned reaction medium is the mixture of a kind of in acetone, diethyl carbonate, ether, glycol dimethyl ether, methylcarbonate, Methyl ethyl carbonate, ethyl acetate, dioxolane, the acetonitrile or at least two kinds.
The used organic solvent of above-mentioned extracting and separating is acetone, methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, acetonitrile, dioxolane or ethyl acetate.
The solvent of above-mentioned recrystallization is acetone, methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, acetonitrile or ethyl acetate, and recrystallization temperature is-30 ℃～100 ℃.
Temperature during above-mentioned vacuum-drying is 60 ℃～250 ℃, and vacuum tightness is-0.1～0.1Mpa, and be 0～48 hour time of drying.
The invention has the beneficial effects as follows: obtain difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate in the same technology, it is all the electrolytic solution lithium salts of superior performance.Technology of the present invention is simple, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of the difluorine oxalic acid boracic acid lithium that obtains of synthesis technique of the present invention;
Fig. 2 is the X-ray diffraction spectrogram of standard difluorine oxalic acid boracic acid lithium;
The X-ray diffraction spectrogram of the di-oxalate lithium borate that Fig. 3 obtains for synthesis technique of the present invention;
Fig. 4 is the X-ray diffraction spectrogram of standard di-oxalate lithium borate.
Embodiment
The invention will be further described below by specific embodiment; But the present invention should not only limit to these embodiment.
Embodiment one
Adopting boron trifluoride ether solution and lithium oxalate is feedstock production difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate.
Step 1, in being housed, the dry reaction container of magnetic stir bar, thermometer adds the lithium oxalate of 101.9g through 150 ℃ of dry 10h, add 500g methylcarbonate and stirring, slowly drip the 94.5g boron trifluoride ether solution, the heated and stirred reaction while dripping, added in 2 hours, temperature of reaction transfers to 80 ℃ of reactions 24 hours, and reaction generates the difluorine oxalic acid boracic acid lithium that is dissolved in methylcarbonate and the di-oxalate lithium borate and the lithium fluoride that are insoluble to methylcarbonate, is cooled to room temperature subsequently.
Step 2, will react the back mixture and remove by filter lithium fluoride and the di-oxalate lithium borate that the intact lithium oxalate of unreacted and reaction back generate at normal temperatures, with the di-oxalate lithium borate in the back solid of acetonitrile extraction filtration, and carry out concentrating under reduced pressure, usefulness acetonitrile crystallisation by cooling, recrystallization.Concentrating under reduced pressure filtrate is used methylcarbonate crystallisation by cooling, recrystallization simultaneously.
Product behind step 3, the recrystallization respectively under vacuum-0.08Mpa in 150 ℃ of dryings 48 hours, finally obtain difluorine oxalic acid boracic acid lithium 37.3g, di-oxalate lithium borate 43.4g.
Products obtained therefrom is analyzed difluorine oxalic acid boracic acid lithium purity: 99.55%, moisture content 29ppm, the purity of di-oxalate lithium borate is 99.67%,, moisture content 90ppm.
Embodiment two
Adopting fluoroboric acid, oxalic acid and Quilonum Retard is feedstock production difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate.
Step 1, in the reactor of magnetic stir bar is housed, add in the 300g acetonitrile and slowly add the 295g Quilonum Retard after 136g oxalic acid is stirred to the milkiness lyolysis with the 160g fluoroboric acid, stirring reaction has the gas generation simultaneously while dripping, add to no gas appearance, continue reaction 5 hours, obtain difluorine oxalic acid boracic acid lithium, di-oxalate lithium borate solution and lithium fluoride.
Step 2, reaction back mixture is removed by filter the intact lithium oxalate of unreacted at normal temperatures and reacts the lithium fluoride that the back generates, evaporate to dryness solution to solid repeatedly extracts difluorine oxalic acid boracic acid lithium in the solid with diethyl carbonate on Rotary Evaporators, and carry out concentrating under reduced pressure, use diethyl carbonate crystallisation by cooling, recrystallization.The di-oxalate lithium borate that simultaneously will be not do not extracted by diethyl carbonate with the ethyl acetate extraction dissolving after, again concentrating under reduced pressure, use the ethyl acetate crystallisation by cooling, recrystallization.
Product behind step 3, the recrystallization respectively under vacuum-0.1Mpa in 140 ℃ of dryings 48 hours, finally obtain difluorine oxalic acid boracic acid lithium 49.3g, di-oxalate lithium borate 74.3g.
Products obtained therefrom is analyzed difluorine oxalic acid boracic acid lithium purity: 99.77%, moisture content 40ppm; The purity of di-oxalate lithium borate is 99.5%, moisture content 87ppm.
As Fig. 1, Fig. 2, Fig. 3, shown in Figure 4, the product of synthesis technique gained of the present invention through X-ray diffraction gained collection of illustrative plates with pure sample product collection of illustrative plates relatively proves difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate respectively.
Claims (5)
1, a kind of synthesis technique that obtains difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate, comprise the steps: (one) with the compound of fluorine-containing compound, boracic, the compound that contains the compound of lithium and contain oxalate 0～100 ℃, reaction pressure be 0.1～1Mpa, and reaction medium in react, wherein the mol ratio of elemental lithium, fluorine element, boron and oxalate denominationby is 5～9: 5～9: 2～3: 3～4; Generation contains the reaction solution of difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate; (2) difluorine oxalic acid boracic acid lithium in the reaction solution and di-oxalate lithium borate are carried out initial gross separation, carry out further extracting and separating with the organic solvent that can extract difluorine oxalic acid boracic acid lithium or di-oxalate lithium borate then; (3) carry out difluorine oxalic acid boracic acid lithium and the di-oxalate lithium borate that recrystallization and vacuum-drying obtain cell-grade respectively.
2, synthesis technique according to claim 1 is characterized in that: fluorine-containing compound is any one in lithium fluoride, fluoroboric acid, boron trifluoride, boron trifluoride diethyl etherate, boron trifluoride methylcarbonate or the boron trifluoride complex; The compound of boracic is any one in boric acid, borax, fluoroboric acid, boron trifluoride diethyl etherate, boron trifluoride methylcarbonate or the boron trifluoride complex; The compound that contains lithium is any one in lithium hydroxide, lithium bicarbonate, oxalic acid hydrogen lithium, Quilonum Retard or the lithium oxalate; The compound that contains oxalate is any one in oxalic acid hydrogen lithium, lithium oxalate or the oxalic acid; Reaction medium is the mixture of a kind of in acetone, diethyl carbonate, ether, glycol dimethyl ether, methylcarbonate, Methyl ethyl carbonate, ethyl acetate, dioxolane, the acetonitrile or at least two kinds.
3, synthesis technique according to claim 1 and 2 is characterized in that: the used organic solvent of extracting and separating is acetone, methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, acetonitrile, dioxolane or ethyl acetate.
4, synthesis technique according to claim 1 and 2 is characterized in that: the solvent of recrystallization is acetone, methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, acetonitrile or ethyl acetate, and recrystallization temperature is-30 ℃～100 ℃.
5, synthesis technique according to claim 1 and 2 is characterized in that: the temperature during vacuum-drying is 60 ℃～250 ℃, and vacuum tightness is-0.1～0.1Mpa, and be 0～48 hour time of drying.
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