CN106674261B - The method of purification of LiODFB - Google Patents
The method of purification of LiODFB Download PDFInfo
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- CN106674261B CN106674261B CN201611009295.4A CN201611009295A CN106674261B CN 106674261 B CN106674261 B CN 106674261B CN 201611009295 A CN201611009295 A CN 201611009295A CN 106674261 B CN106674261 B CN 106674261B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
Abstract
The method of purification of LiODFB, by the crude product of LiODFB, BF3Class compound, aprotic apolar or the lesser solvent of aprotonic polar are uniformly mixed in mass ratio for 1:1:50~1:31:31；(2) 10 DEG C~80 DEG C at a temperature of stirring 1~10 hour after, then be separated by solid-liquid separation, it is dry after being washed to obtained solid substance, i.e., LiODFB is successfully purified, with C in potassium permanganate oxidation reductometry LiODFB product2O4 2‑, 61.19% can be reached, mannitol method titrates the content of B (III) in LiODFB product, reaches 7.51% (theoretical value is respectively 61.22%, 7.52%), product purity 99.9%, product yield is 99% after purification.
Description
Technical field
The present invention relates to the purification techniques of LiODFB.
Background technique
One of main composition material as lithium ion battery, electrolyte restricts lithium ion battery to a certain extent
Development.Traditional electrolyte matter LiPF6There is a problem of that thermal stability and chemical stability are poor, the research of novel electrolytes lithium salts is compeled
In the eyebrows and eyelashes.LiODFB can be enhanced the stability of battery, reduce impedance, improve cycle life and high rate performance, in wider temperature
Spending has good ionic conductivity in range, it is considered to be most potential substitution LiPF6Electrolyte lithium salt.
The preparation of LiODFB, initially with LiBF4、CH(CF3)2OLi and H2C2O4For raw material, with carbonic ester or acetonitrile (AN) etc.
Polar aprotic solvent is reaction medium, and the purity of products therefrom is lower, wherein LiBF4Content be up to 15% or more.(referring to:
S. Tsujiokam, H. Takase, M. Takahashi. Electrolyte for electrochemical
device.
EP.1195834A2.2002-02-07.).
As an improvement method, S. Tsujiok etc. in European patent with oxalic acid, LiBF4 and aluminium chloride or
Person's silicon tetrachloride reacts in dimethyl carbonate or with oxalic acid, LiBF4, lithium fluoride and boron chloride or trimethoxy-boron
Reaction realizes the synthesis of LiODFB in dimethyl carbonate.Still there is unreacted LiBF4, it is not mentioned how purification
LiODFB.(referring to: S. Tsujioka, H. Takase, M. Takahasi, et al. Process for
Synthesizing ionic metal complex. EP:1308449A2,2003-05-07.).
Preparation method generally used now (referring to: S. S. Zhang. An unique lithium salt for the
improved electrolyte of Li-ion battery. Electrochem. Commun., 2006.8:1423-
It 1428.) is by BF3·O(CH2CH3)2With Li2C2O4It is reacted in DMC, although not prepared using LiBF4 as raw material
LiBF4 easily generated, reaction equation are as follows in journey:
Li2C2O4+BF3O(C2H5)2---C2H5OC2H5+LiF+LiODFB
LiF+BF3O(C2H5)2 ---C2H5OC2H5+LiBF4
It obtains LiODFB by extracting and recrystallization being purified by solvent of dimethyl carbonate with after confined reaction.
And LiBF4It is very close with solubility of the LiODFB in common organic solvents, it is difficult to be carried out effectively by recrystallization method
Separation, to become a great problem for preparing high-purity lithium oxalyldifluoroborate.
Z. A. Zhang separates impurity with the method for dissolution crystallization in patent CN 101265176A, purifies LiODFB.
But this method is complex, need to can be only achieved higher degree by repeatedly purification.
It to sum up analyzes, cooling crystallization and dissolution crystallization are the two methods for purifying LiODFB.But both sides
Method can not all accomplish first separation, must can just be completely separated through repeated multiple times.So LiODFB and LiBF4
Separation also researcher is needed further to probe into.
Summary of the invention
The object of the present invention is to provide a kind of methods of purification of LiODFB.
The present invention is the method for purification of LiODFB, be the steps include:
(1) by the crude product of LiODFB, BF3Class compound and aprotic apolar or the lesser solvent of polarity are in mass ratio
It is uniformly mixed for 1:1:50~1:31:31；
(2) by mixture obtained by step (1), 10 DEG C~80 DEG C at a temperature of stirring 1~10 hour after carry out solid-liquid point
From respectively obtaining solid A and liquor B；
(3) the resulting solid A aprotic apolar of step (2) or the lesser solvent of polarity are washed, after washing
Solution return step one reuse, the solid after washing can be obtained after drying purity be 99.9% LiODFB；
(4) by step (2) resulting liquor B 10 DEG C~100 DEG C at a temperature of be evaporated under reduced pressure, solvent recovery return step
(1) it reuses.
Relative to conventional method, the method for purification for the LiODFB (LiODFB) that this patent is invented mainly has
Following advantages and innovative point: (1) in purification process, impurity be preferably dissolved in preferred organic solvent, and mesh lithium salts
LiODFB is then fairly insoluble, effectively reduces the content of impurity in LiODFB product, effectively reduces purifying difficulty.(2) entire
Purification process carries out in water-free organic solvent, reduces the difficulty in drying process to moisture removal.(3) purifying products
Process only needs to can be realized by dissolution, filtering, distillation, washing, drying steps, and the more traditional recrystallizing technology of method is simply easy
Row, and the use for the more severe operating conditions such as avoid low temperature.
The present invention has the advantages that impurity separation is thoroughly, product purity is high, high income；Process flow is short, production cost
It is low, it is suitble to industrialized production.
Detailed description of the invention
Fig. 1 is LiODFB19F nuclear magnetic spectrogram.
Specific embodiment
The present invention is the method for purification of LiODFB, be the steps include:
(1) by the crude product of LiODFB, BF3Class compound and aprotic apolar or the lesser solvent of polarity are in mass ratio
It is uniformly mixed for 1:1:50~1:31:31；
(2) by mixture obtained by step (1), 10 DEG C~80 DEG C at a temperature of stirring 1~10 hour after carry out solid-liquid point
From respectively obtaining solid A and liquor B；
(3) the resulting solid A aprotic apolar of step (2) or the lesser solvent of polarity are washed, after washing
Solution return step one reuse, the solid after washing can be obtained after drying purity be 99.9% LiODFB；
(4) by step (2) resulting liquor B 10 DEG C~100 DEG C at a temperature of be evaporated under reduced pressure, solvent recovery return step
(1) it reuses.
The lesser solvent of aprotic apolar or polarity, specially ether perhaps ethyl acetate or just oneself
Alkane perhaps carbon tetrachloride perhaps dioxolanes perhaps benzene perhaps gamma-butyrolacton perhaps toluene perhaps in dimethylbenzene or
Any one either several mixture.
BF used3Class compound is BF3Gas, or dissolved with BF3Ether perhaps acetonitrile or tetrahydrofuran are molten
Liquid or BF3·O(C2H5)2Or BF3N(C2H3)2Or BF3·OC4H11It is either one such or several
Mixture.
In step (3), each dosage of cleaning solvent is 1~5 times of washed solid volume when separation of solid and liquid, and washing times are
1 time~3 times.
Embodiment 1:
(1) the crude product 10g of the LiODFB through 120 DEG C of dry 4h is added in the dry reactor equipped with blender, so
The mixed solution (three's mass ratio is 1:2:49) that 710mL boron trifluoride ether and anhydrous ether are added afterwards stirs evenly, 50 DEG C
Under be heated to reflux and stir 2h, to guarantee that material is sufficiently mixed.Solidliquid mixture after stirring and evenly mixing is filtered separation, so
Separating obtained solid is attached to the BF of the surface of solids with 100mL washed with ether afterwards3, then by solid at 120 DEG C vacuum
Dry 12h, obtains the product of the high-purity LiODFB of 9.81g, and product yield is 98.1% after purification.
With C in potassium permanganate oxidation reductometry LiODFB product2O4 2-, 61.19% can be reached, the titration of mannitol method
The content of B (III) in LiODFB product reaches 7.51% (theoretical value is respectively 61.22%, 7.52%), and product purity is
99.9%。
Embodiment 2:
(1) the crude product 10g of the LiODFB through 120 DEG C of dry 4h is added in the dry reactor equipped with blender, so
After sequentially add boron trifluoride acetonitrile and anhydrous ether (three is 1:11:47 in mass ratio), be heated to reflux and stir at 50 DEG C
4h, to guarantee that material is sufficiently mixed.Solidliquid mixture after reaction is filtered separation, then uses separating obtained solid
200mL acetonitrile rinses 3 times, is dried in vacuo 12h at 120 DEG C, obtains the product of the high-purity LiODFB of 9.82g.Product after purification
Yield is 98.2%.
With C in potassium permanganate oxidation reductometry LiODFB product2O4 2-, 61.17% can be reached, the titration of mannitol method
The content of B (III) in LiODFB product reaches 7.51% (theoretical value is respectively 61.22%, 7.52%), and product purity reaches
99.9%.
Embodiment 3:
(1) the LiODFB crude product 10g through 120 DEG C of dry 4h is added in the dry reactor equipped with blender, then
The mixed solution (three's mass ratio is 1:13:57) that boron trifluoride ether and ethyl acetate is added stirs evenly, and heats at 55 DEG C
It flows back and stirs 6h, to guarantee that material is sufficiently mixed.Solidliquid mixture after stirring and evenly mixing is filtered separation, then will be divided
The BF of the surface of solids is attached to 150mL washed with ether from resulting solid3, then solid is dried in vacuo at 120 DEG C
15h obtains the product of the high-purity LiODFB of 9.81g, and the yield of product is 98.1% after purification.
With C in potassium permanganate oxidation reductometry LiODFB product2O4 2-, 61.19% can be reached, the titration of mannitol method
The content of B (III) in LiODFB product reaches 7.51% (theoretical value is respectively 61.22%, 7.52%), and product purity is
99.9%。
Such as Fig. 1, product 19 prepared by the present inventionFNMR spectrum confirm be LiODFB product.It is dripped with mannitol
B (III) content in method measurement product is determined, with C in titration of potassium permanganate product2O4 2-Content, as a result, it has been found that the two is divided equally
Not close to the theoretical value of the product.
Claims (2)
1. the method for purification of LiODFB, which is characterized in that the steps include:
(1) by the crude product of LiODFB, BF3Class compound and aprotic apolar or the lesser solvent of polarity are with mass ratio for 1:
1:50 or 1:31:31 is uniformly mixed；
BF used3Class compound is BF3Gas, or dissolved with BF3Ether perhaps acetonitrile or tetrahydrofuran solution, or
Person is BF3·O(C2H5)2Either one such or several mixture；
The lesser solvent of aprotic apolar or polarity is ether or ethyl acetate；
(2) by mixture obtained by step (1), 10 DEG C~80 DEG C at a temperature of stirring 1~10 hour after be separated by solid-liquid separation, point
Solid (A) and filtrate (B) are not obtained；
(3) step (2) resulting solid (A) aprotic apolar or the lesser solvent of polarity are washed, after washing
Solution return step one is reused, and the LiODFB that purity is 99.9% can be obtained in the solid after washing after drying；
(4) by step (2) resulting filtrate (B) 10 DEG C~100 DEG C at a temperature of be evaporated under reduced pressure, solvent recovery return step
(1) it reuses.
2. the method for purification of LiODFB according to claim 1, it is characterised in that: in step (3), solid-liquid point
From when each dosage of cleaning solvent be 1~5 times of washed solid volume, washing times are 1 time~3 times.
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| CN110343125B (en) * | 2019-03-13 | 2020-07-21 | 杉杉新材料（衢州）有限公司 | Method for preparing high-purity proportional mixed lithium salt at low cost and application of mixed lithium salt in lithium ion battery |
| CN111825704A (en) * | 2019-04-17 | 2020-10-27 | 江苏长园华盛新能源材料有限公司 | Method for purifying lithium difluoro (oxalato) borate |
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Non-Patent Citations (1)
| Title |
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| "新型电解质盐草酸二氟硼酸锂的制备与性能研究";刘芙蓉;《中国优秀硕士学位论文全文数据库 工程科技II辑》;20130215(第2期);正文第24页 |
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