CN119683642A - A preparation method of lithium (difluorophosphoryloxy) trifluoroborate - Google Patents
A preparation method of lithium (difluorophosphoryloxy) trifluoroborate Download PDFInfo
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- -1 difluorophosphoryloxy Chemical group 0.000 title claims abstract description 143
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 title claims description 71
- PBIMIGNDTBRRPI-UHFFFAOYSA-N trifluoro borate Chemical compound FOB(OF)OF PBIMIGNDTBRRPI-UHFFFAOYSA-N 0.000 title claims description 71
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 17
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 16
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- PDECINHTUQHWJM-UHFFFAOYSA-N lithium;trifluoroborane Chemical compound [Li].FB(F)F PDECINHTUQHWJM-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 229910015900 BF3 Inorganic materials 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 abstract description 36
- 239000000126 substance Substances 0.000 abstract description 18
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 description 53
- 229910003002 lithium salt Inorganic materials 0.000 description 52
- 159000000002 lithium salts Chemical class 0.000 description 52
- 239000000047 product Substances 0.000 description 43
- 239000000243 solution Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 14
- 239000012141 concentrate Substances 0.000 description 14
- 229910052731 fluorine Inorganic materials 0.000 description 14
- 239000011737 fluorine Substances 0.000 description 14
- 230000010354 integration Effects 0.000 description 14
- 238000004364 calculation method Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000002000 Electrolyte additive Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- VEWIGYNQVZOINO-UHFFFAOYSA-N C(OCC)(OC)=O.B(F)(F)F Chemical compound C(OCC)(OC)=O.B(F)(F)F VEWIGYNQVZOINO-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Abstract
The invention discloses a preparation method of (difluorophosphoryloxy) lithium trifluoroborate, which comprises the steps of preparing a reaction solution containing (difluorophosphoryloxy) lithium trifluoroborate by taking lithium hexafluorophosphate and diboron trioxide as raw materials in an organic solvent, wherein the reaction solution does not contain lithium difluorophosphate. The method has the advantages of simple operation, few reaction steps, high reaction conversion rate, no need of taking lithium difluorophosphate as a raw material, difficult generation of insoluble substances in the reaction process, high product purity, good quality and low production cost, and is suitable for industrial application.
Description
Technical Field
The invention relates to synthesis of electrolyte additives, in particular to a novel preparation method of (difluorophosphoryloxy) lithium trifluoroborate.
Background
The electrolyte additive is used as an indispensable component in a lithium ion battery or a sodium ion battery and is mainly responsible for constructing a stable electrode/electrolyte interface film so as to achieve the effects of electronic insulation and being beneficial to lithium ion or sodium ion transmission, and the composition and the structure of the battery interface film are changed under the influence of different functional groups of different additives, so that the performances of the battery such as cycle life, high-temperature storage, low-temperature discharge and the like are finally influenced.
The boron-containing additive can dissolve LiF and other inorganic lithium salts on the surface of the interface film due to the electron-deficient effect of boron atoms, thereby reducing the internal resistance of the battery and improving the low-temperature performance of the battery. The phosphorus-containing additive, such as phosphate and phosphate, has a strong interaction between the P=O functional group and the transition metal element on the surface of the positive electrode, so that a stable positive electrode interface film can be formed on the surface, the storage performance and the cycle performance of the battery are improved, and the phosphorus-containing additive has a certain flame retardant effect in the electrolyte. The phosphorus and boron elements are simultaneously present in one additive, so that the additive has the advantages.
Patent CN102414902a discloses an electrolyte salt containing both boron and phosphorus and a synthesis method thereof, and the electrolyte salt is prepared by reacting lithium difluorophosphate with boron trifluoride diethyl ether complex to obtain a product containing at least lithium trifluoroborate (difluorophosphoryloxy), and the product is used as an electrolyte additive to improve the normal temperature cycle performance of the battery and inhibit the impedance from growing in the cycle process.
However, the preparation of the lithium (difluorophosphoryloxy) trifluoroborate by using the lithium difluorophosphate as the raw material has the following defects that 1) the solubility of the lithium difluorophosphate in most solvents is low, the use amount of the solvents needs to be increased in the reaction process, the turbidity of the prepared lithium (difluorophosphoryloxy) trifluoroborate solution is high, the electrolyte can not reach the industry standard due to the direct use as an additive, and 2) the lithium difluorophosphate has high production cost, complex process, is generally obtained through crystallization, has 5-10% loss and has poor economy.
Therefore, the preparation method of the (difluorophosphoryloxy) lithium trifluoroborate with low turbidity, high quality and low cost is provided, which is favorable for improving the quality of the electrolyte and further improving the performance of the lithium ion battery.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing lithium (difluorophosphoryloxy) trifluoroborate, which is used for reducing the turbidity of a lithium (difluorophosphoryloxy) trifluoroborate product, improving the product quality, and has the advantages of simple operation, fewer reaction steps, high reaction conversion rate and low production cost, and is suitable for industrial application.
The invention aims at realizing the following technical scheme:
a preparation method of (difluorophosphoryloxy) lithium trifluoroborate comprises the steps of preparing and obtaining a reaction solution containing (difluorophosphoryloxy) lithium trifluoroborate by taking lithium hexafluorophosphate and diboron trioxide as raw materials in an organic solvent, wherein the chemical reaction equation is as follows:
the preparation method of the invention is a one-step reaction, and the reaction liquid does not contain lithium difluorophosphate.
The organic solvent is at least one selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl acetate, ethyl acetate, methyl propionate, gamma-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, acetonitrile, benzyl cyanide or propionitrile. Preferably, the organic solvent is at least one selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl acetate, ethyl acetate, methyl propionate.
The mass ratio of the organic solvent to the lithium hexafluorophosphate is (4-15): 1, preferably (5-12): 1. When the mass ratio of the organic solvent to the lithium hexafluorophosphate is lower than 4:1, part of BF 3 generated by the reaction may escape and not participate in the reaction, so that precipitation of lithium difluorophosphate solid is caused, and the purity and quality of the product are affected.
The molar ratio of lithium hexafluorophosphate to diboron trioxide is (1.5-3) 1, preferably (1.5-2) 1. The preparation method of the invention preferably has the advantages that the excessive lithium hexafluorophosphate can promote the forward reaction, and the excessive lithium hexafluorophosphate is not required to be removed, and the addition amount of the lithium hexafluorophosphate serving as a lithium salt is correspondingly reduced when the electrolyte is prepared.
In the preparation process of the (difluorophosphoryloxy) lithium trifluoroborate, the reaction temperature is 0-120 ℃, the reaction time is 0.5-48 h, the preferable reaction temperature is 30-90 ℃, and the reaction time is 0.5-8 h.
In order to improve the reactivity and shorten the reaction time and ensure that no residual unreacted complete diboron trioxide raw material exists in the reaction product, the method also comprises the step of adding chain alkyl alcohol as a catalyst into the reaction system, wherein the chain alkyl alcohol is at least one of methanol, ethanol, isopropanol, butanol or ethylene glycol.
In the reaction process, the chain alkyl alcohol and the diboron trioxide form a boric acid monoester intermediate, the intermediate has high solubility in an organic solvent, and the intermediate reacts with lithium hexafluorophosphate to generate (difluorophosphoryloxy) lithium trifluoroborate, and then the chain alkyl alcohol is released to continuously catalyze the subsequent reaction, so that the reaction activity can be greatly increased, the reaction time can be shortened, and the turbidity of a product can be reduced by adding a small amount of the chain alkyl alcohol. Specifically, the catalyst is used in an amount of 0.1-2%, preferably 0.2-1.5%, more preferably 0.5-1.0% of the molar amount of lithium hexafluorophosphate.
The reaction of the present invention is carried out in a closed vessel or an open vessel provided with a condensing reflux member, because boron trifluoride gas is generated during the reaction, and thus, in order to suppress the problems of an increase in turbidity and a decrease in purity of the product due to the formation of lithium difluorophosphate impurities in the product (particularly when the reaction temperature is high), whether or not the reaction is carried out in the presence of a catalyst.
Since two molecules of lithium (difluorophosphoryloxy) trifluoroborate can generate one molecule of lithium bis (difluorophosphoryloxy) trifluoroborate and LiBF 4, the reaction formula is as follows:
The reaction is a reversible reaction and has relatively low forward reaction activity, so the reaction liquid prepared by the invention mainly contains (difluorophosphoryloxy) lithium trifluoroborate, bis (difluorophosphoryloxy) lithium trifluoroborate and LiBF 4. Specifically, the reaction liquid contains at least 60% by weight of lithium (difluorophosphoryloxy) trifluoroborate, preferably at least 70% by weight of lithium (difluorophosphoryloxy) trifluoroborate, more preferably at least 80% by weight of lithium (difluorophosphoryloxy) trifluoroborate, based on the total mass of the product (excluding the solvent).
In order to obtain the (difluorophosphoryloxy) lithium trifluoroborate product, the preparation method of the invention further comprises the steps of removing the organic solvent, the catalyst and boron trifluoride gas in the reaction liquid by normal pressure distillation or reduced pressure distillation to obtain the (difluorophosphoryloxy) lithium trifluoroborate product. The lithium (difluorophosphoryloxy) trifluoroborate product is a concentrate (containing an organic solvent) due to the solvation of the lithium (difluorophosphoryloxy) trifluoroborate. Thus, the organic solvent of the present invention is preferably an organic solvent commonly used in electrolytes, so that the lithium (difluorophosphoryloxy) trifluoroborate product (concentrate) can be directly used for the preparation of electrolytes. And when the (difluorophosphoryloxy) lithium trifluoroborate product is used as an additive in electrolyte, a small amount of the lithium bis (difluorophosphoryloxy) trifluoroborate and the lithium tetrafluoroborate contained in the lithium trifluoroborate product have small influence on the performance of the battery and can be ignored.
Compared with the prior art, the invention has the following beneficial effects:
1. The invention provides a new method for preparing and obtaining (difluorophosphoryloxy) lithium trifluoroborate by taking lithium hexafluorophosphate and diboron as raw materials through a one-step method, which has the advantages of simple operation, fewer reaction steps, no need of taking lithium difluorophosphate as raw materials, no increase of turbidity of the product caused by insoluble substances in the reaction process, high purity and good quality of the product, and low production cost, and is very suitable for industrial application.
2. In the invention, a small amount of chain alkyl alcohol is added as a catalyst in the reaction process, so that the reaction activity is further improved, the reaction time is greatly shortened, the unreacted diboron trioxide is ensured not to exist in the product, the turbidity of the product is reduced, and the product yield is improved.
Drawings
FIG. 1 is a 19 F-NMR chart of a lithium salt #1 prepared in example 1 of the present invention;
FIG. 2 is a 31 P-NMR chart of a lithium salt #1 prepared in example 1 of the present invention;
FIG. 3 is a 19 F-NMR chart of a 1# control lithium salt prepared in comparative example 1 of the present invention;
FIG. 4 is a 31 P-NMR chart of a 1# control lithium salt prepared in comparative example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, without limiting the invention to these specific embodiments. It will be appreciated by those skilled in the art that the invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
The structures and contents of the products and the control samples prepared in examples 1-9 and comparative examples 1-4 are confirmed by characterization through 400M nuclear magnetic resonance fluorine spectrum (19 F-NMR) and 400M nuclear magnetic resonance phosphorus spectrum (31 P-NMR), wherein the characterization method comprises the steps of adding a small amount of the products into a nuclear magnetic tube, adding a proper amount of diethyl carbonate for dilution, and ensuring that the height of the solution is not higher than 1/3 of the height of the nuclear magnetic tube. Since the NMR spectra of the same substance are substantially identical and the shift in the position of the peak is extremely small in the same solvent environment, the detailed NMR spectra and results are only described in example 1 and comparative example 1.
Example 1
This example provides the preparation of lithium (difluorophosphoryloxy) trifluoroborate, comprising in particular the following steps:
s1, adding 0.15mol (22.8 g, purity 99%) of lithium hexafluorophosphate and 0.1mol (6.96 g, purity 99%) of diboron trioxide into a reaction bottle in a drying room with a dew point of-40 ℃, adding 0.0015mol (0.05 g) of methanol as a reaction catalyst, adding 200ml of methyl ethyl carbonate as a solvent (the mass ratio of the solvent to LiPF 6 is 8.77), stirring under a closed environment to uniformly mix the systems, and reacting for 2 hours at 50 ℃ to obtain a methyl ethyl carbonate solution containing (difluorophosphoryloxy) lithium trifluoroborate, wherein insoluble substances do not exist, which indicates that the diboron trioxide is completely reacted;
S2, removing most of the solvent and all residual boron trifluoride and methanol in the reaction solution by reduced pressure distillation, controlling the reduced pressure distillation temperature to be 60 ℃ and the time to be 0.5h, and obtaining a product concentrated solution of lithium (difluorophosphoryloxy) trifluoroborate, namely 1# lithium salt.
The product is colorless and transparent, and has turbidity of 5.23NTU by turbidimeter analysis.
Fig. 1 and 2 show 19 F-NMR and 31 P-NMR spectra of 1 # lithium salt, respectively, as can be seen from fig. 1 and 2:
the nuclear magnetic F spectrum of lithium salt # 1 is shown below:
lithium (difluorophosphoryloxy) trifluoroborate delta = -92.41ppm (d, j= 958.5 Hz), delta = -157.57 ppm(s)
Lithium bis (difluorophosphoryloxy) trifluoroborate delta = -92.00ppm (d, J = 963.1 Hz), delta = -151.88 ppm(s)
The nuclear magnetic P-spectrum of lithium salt # 1 is shown below:
Lithium (difluorophosphoryloxy) trifluoroborate delta = -27.91ppm (t, j= 958.3 Hz)
Lithium bis (difluorophosphoryloxy) trifluoroborate delta = -29.26ppm (t, J = 963.1 Hz)
As can be seen from the integral of the peak areas of the nuclear magnetic F spectra, the integral area ratio of (difluorophosphoryloxy) lithium trifluoroborate (marked with symbol "■"), bis (difluorophosphoryloxy) lithium trifluoroborate (marked with symbol "∈"), and lithium tetrafluoroborate (marked with symbol "Δ") was 3.11:1.00:0.84, which was converted to a molar ratio of 1:0.16:0.068, and further converted to a mass ratio of 1:0.24:0.036, whereby the 1# lithium salt was converted to contain 78.7wt% of (difluorophosphoryloxy) lithium trifluoroborate, 18.5wt% of bis (difluorophosphoryloxy) lithium trifluoroborate, and 2.8wt% of lithium tetrafluoroborate, based on 100wt% of the total amount of the fluorine-containing lithium salt. And the area integration conversion is further carried out through the P spectrum, so that the result is uniform, and the calculation reliability is high.
In this example, no peak of lithium difluorophosphate was detected in both the nuclear magnetic F spectrum and the nuclear magnetic P spectrum.
Example 2
The operation of this example was the same as that of example 1 except that the amount of methanol added was adjusted from 0.0015mol to 0.003mol, and a product concentrate of lithium (difluorophosphoryloxy) trifluoroborate was obtained, which was designated as lithium salt # 2.
The product is colorless and transparent, and has turbidity of 5.16NTU by turbidimeter analysis.
The peak area of the nuclear magnetic F spectrum was integrated and calculated to obtain a 2# lithium salt containing 84.9wt% of lithium (difluorophosphoryloxy) trifluoroborate, 13.9wt% of lithium bis (difluorophosphoryloxy) trifluoroborate and 1.2wt% of lithium tetrafluoroborate, based on 100wt% of the total amount of the fluorine-containing lithium salt. And the area integration conversion is further carried out through the P spectrum, so that the result is uniform, and the calculation reliability is high.
In this example, no peak of lithium difluorophosphate was detected in both the nuclear magnetic F spectrum and the nuclear magnetic P spectrum.
Example 3
The operation of this example was the same as in example 1 except that methanol was replaced with ethanol to obtain a product concentrate of lithium (difluorophosphoryloxy) trifluoroborate, designated as 3# lithium salt.
The product is colorless and transparent, and has turbidity of 5.22NTU by turbidimeter analysis.
The peak area of the nuclear magnetic F spectrum was integrated and calculated to obtain a 3# lithium salt containing 80.2wt% of lithium (difluorophosphoryloxy) trifluoroborate, 17.4wt% of lithium bis (difluorophosphoryloxy) trifluoroborate and 2.4wt% of lithium tetrafluoroborate, based on 100wt% of the total amount of the fluorine-containing lithium salt. And the area integration conversion is further carried out through the P spectrum, so that the result is uniform, and the calculation reliability is high.
In this example, no peak of lithium difluorophosphate was detected in both the nuclear magnetic F spectrum and the nuclear magnetic P spectrum.
Example 4
The operation of this example was the same as in example 1 except that methanol was replaced with isopropyl alcohol to obtain a product concentrate of lithium (difluorophosphoryloxy) trifluoroborate, designated as lithium salt # 4.
The product is colorless and transparent, and has turbidity of 5.28NTU by turbidimeter analysis.
The peak area of the nuclear magnetic F spectrum was integrated and calculated to obtain a 4# lithium salt containing 80.7wt% of lithium (difluorophosphoryloxy) trifluoroborate, 17.1wt% of lithium bis (difluorophosphoryloxy) trifluoroborate and 2.2wt% of lithium tetrafluoroborate, based on 100wt% of the total amount of the fluorine-containing lithium salt. And the area integration conversion is further carried out through the P spectrum, so that the result is uniform, and the calculation reliability is high.
In this example, no peak of lithium difluorophosphate was detected in both the nuclear magnetic F spectrum and the nuclear magnetic P spectrum.
Example 5
The operation of this example was the same as that of example 1 except that the amount of lithium hexafluorophosphate added was adjusted from 0.15mol to 0.20mol, to obtain a product concentrate of lithium (difluorophosphoryloxy) trifluoroborate, designated as lithium salt # 5.
The product is colorless and transparent, and has turbidity of 5.20NTU by turbidimeter analysis.
The peak area of the nuclear magnetic F spectrum was integrated and calculated to obtain a 5# lithium salt, which contained 22.4wt% of unreacted lithium hexafluorophosphate, 61.0wt% of lithium (difluorophosphoryloxy) trifluoroborate, 14.4wt% of lithium bis (difluorophosphoryloxy) trifluoroborate, and 2.20wt% of lithium tetrafluoroborate, based on 100wt% of the total amount of the fluorine-containing lithium salt. And the area integration conversion is further carried out through the P spectrum, so that the result is uniform, and the calculation reliability is high.
In this example, no peak of lithium difluorophosphate was detected in both the nuclear magnetic F spectrum and the nuclear magnetic P spectrum.
Example 6
The operation of this example was the same as in example 1 except that methanol was not added in the reaction, the reaction time was prolonged from 2 hours to 12 hours, and a methyl ethyl carbonate solution containing lithium (difluorophosphoryloxy) trifluoroborate was obtained in step S1, which contained an insoluble substance, and was subjected to turbidity test of 52.3NTU, and after filtration, 1.25g of the insoluble substance was obtained, which was unreacted diboron trioxide, and the filtrate was subjected to step S2 to obtain a product concentrate of lithium (difluorophosphoryloxy) trifluoroborate, designated as lithium salt # 6.
The peak area of the nuclear magnetic F spectrum was integrated and calculated to obtain a 6# lithium salt, wherein the 6# lithium salt contains 15.9wt% of unreacted raw material lithium hexafluorophosphate, 68.0wt% of (difluorophosphoryloxy) lithium trifluoroborate, 14.2wt% of bis (difluorophosphoryloxy) lithium trifluoroborate and 1.90wt% of lithium tetrafluoroborate, calculated based on 100wt% of the total amount of the fluorine-containing lithium salt. And the area integration conversion is further carried out through the P spectrum, so that the result is uniform, and the calculation reliability is high.
In this example, no peak of lithium difluorophosphate was detected in both the nuclear magnetic F spectrum and the nuclear magnetic P spectrum.
Example 7
The operation of this example was the same as in example 6 except that the reaction time was prolonged from 12 hours to 24 hours, and a solution of lithium (difluorophosphoryloxy) trifluoroborate in methylethyl carbonate was obtained in step S1, which contained an insoluble substance, and was found to be 39.5NTU in turbidity test, 0.84g of the insoluble substance was obtained after filtration, which was unreacted diboron trioxide, and a concentrated solution of lithium (difluorophosphoryloxy) trifluoroborate was obtained in step S2 from the filtrate, which was designated as lithium salt # 7.
The peak area of the nuclear magnetic F spectrum was integrated and calculated to obtain a lithium salt 7, wherein the lithium salt 7 contains 10.4wt% of unreacted raw material lithium hexafluorophosphate, 72.3wt% of (difluorophosphoryloxy) lithium trifluoroborate, 15.3wt% of bis (difluorophosphoryloxy) lithium trifluoroborate and 2.00wt% of lithium tetrafluoroborate, based on 100wt% of the total amount of the fluorine-containing lithium salt. And the area integration conversion is further carried out through the P spectrum, so that the result is uniform, and the calculation reliability is high.
In this example, no peak of lithium difluorophosphate was detected in both the nuclear magnetic F spectrum and the nuclear magnetic P spectrum.
Example 8
The operation of this example was the same as in example 6 except that the reaction time was prolonged from 12 hours to 36 hours, and a solution of methyl ethyl carbonate containing lithium (difluorophosphoryloxy) trifluoroborate, which contained an insoluble substance, was obtained in the step S1, and the solution was subjected to turbidity test to 38.9NTU, and 0.77g of the insoluble substance was obtained after filtration, which was unreacted diboron trioxide, and the filtrate was subjected to the step S2 to obtain a product concentrate of lithium (difluorophosphoryloxy) trifluoroborate, designated as 8# lithium salt.
As a result of integrating the peak areas of the nuclear magnetic F spectra, it was found that the 8# lithium salt contained 9.50wt% of unreacted lithium hexafluorophosphate as a raw material, and 73.0wt% of lithium (difluorophosphoryloxy) trifluoroborate, 15.5wt% of lithium bis (difluorophosphoryloxy) trifluoroborate and 2.00wt% of lithium tetrafluoroborate, based on 100wt% of the total amount of the fluorine-containing lithium salt, as a result of the conversion. And the area integration conversion is further carried out through the P spectrum, so that the result is uniform, and the calculation reliability is high.
In this example, no peak of lithium difluorophosphate was detected in both the nuclear magnetic F spectrum and the nuclear magnetic P spectrum.
Example 9
The operation of this example was the same as in example 6 except that the reaction solvent was changed from ethyl methyl carbonate to diethyl carbonate, the reaction temperature was increased from 50℃to 80℃and S1 was conducted to obtain a solution of ethyl methyl carbonate containing lithium (difluorophosphoryloxy) trifluoroborate containing an insoluble substance, turbidity test was conducted to 48.6NTU, 1.04g of the insoluble substance was obtained after filtration, as unreacted diboron trioxide, and the filtrate was subjected to S2 to obtain a concentrated solution of lithium (difluorophosphoryloxy) trifluoroborate, designated as lithium salt No. 9.
The peak area of the nuclear magnetic F spectrum was integrated and calculated to obtain a 9# lithium salt, wherein the 9# lithium salt contains 13.0wt% of unreacted raw material lithium hexafluorophosphate, 70.1wt% of (difluorophosphoryloxy) lithium trifluoroborate, 14.9wt% of bis (difluorophosphoryloxy) lithium trifluoroborate and 2.00wt% of lithium tetrafluoroborate in terms of 100wt% of the total amount of the fluorine-containing lithium salt. And the area integration conversion is further carried out through the P spectrum, so that the result is uniform, and the calculation reliability is high.
In this example, no peak of lithium difluorophosphate was detected in both the nuclear magnetic F spectrum and the nuclear magnetic P spectrum.
Comparative example 1
The procedure of this comparative example was the same as in example 1 except that the amount of the reaction solvent added was reduced from 200ml to 80ml, and in the step S1, a methyl ethyl carbonate solution containing lithium (difluorophosphoryloxy) trifluoroborate was obtained, which contained an insoluble substance, and in the turbidity test, 73.9NTU was obtained, and 3.03g of the insoluble substance was obtained after filtration, as a by-product of lithium difluorophosphate, and in the step S2, a product concentrate of lithium (difluorophosphoryloxy) trifluoroborate was obtained as a 1# control lithium salt.
The peaks (marked with the symbol "") of lithium difluorophosphate are detected in both the nuclear magnetic F spectrum and the nuclear magnetic P spectrum. As a result of integrating the peak areas of the nuclear magnetic F spectra, the 1# control lithium salt was converted to 73.9wt% of lithium (difluorophosphoryloxy) trifluoroborate, 10.9wt% of lithium bis (difluorophosphoryloxy) trifluoroborate, 3.6wt% of lithium tetrafluoroborate and 11.6wt% of lithium difluorophosphate, based on 100wt% of the total amount of the fluorine-containing lithium salt. And the area integration conversion is further carried out through the P spectrum, so that the result is uniform, and the calculation reliability is high.
Comparative example 2
The operation of this comparative example was the same as in example 1 except that the reaction vessel was replaced with an open vessel from a closed vessel, and a methyl ethyl carbonate solution containing lithium (difluorophosphoryloxy) trifluoroborate, which contained an insoluble substance, was measured as 66.8NTU by turbidity, 2.21g of the insoluble substance was obtained after filtration, and a product concentrate of lithium (difluorophosphoryloxy) trifluoroborate was obtained after the filtrate was subjected to step S2, which was designated as a # 2 control lithium salt.
The peaks of lithium difluorophosphate were detected in both the nuclear magnetic F spectrum and the nuclear magnetic P spectrum of the comparative example. The peak area of the nuclear magnetic F spectrum was integrated and calculated to obtain a 2# control lithium salt containing 70.2wt% of lithium (difluorophosphoryloxy) trifluoroborate, 12.1wt% of lithium bis (difluorophosphoryloxy) trifluoroborate, 4.8wt% of lithium tetrafluoroborate and 12.9wt% of lithium difluorophosphate, based on 100wt% of the total amount of the fluorine-containing lithium salt. And the area integration conversion is further carried out through the P spectrum, so that the result is uniform, and the calculation reliability is high.
Comparative example 3
The comparative example adopts methyl ethyl carbonate complex of lithium difluorophosphate and boron trifluoride as raw materials to prepare methyl ethyl carbonate solution containing lithium difluorophosphoryloxy) trifluoroborate, and the product concentrate of the lithium difluorophosphoryloxy) trifluoroborate is obtained after reduced pressure distillation, and the method specifically comprises the following steps:
S1, adding 0.15mol of lithium difluorophosphate (purity 99%), 0.15mol of boron trifluoride methyl ethyl carbonate complex (purity 99%) and 200ml of methyl ethyl carbonate serving as a solvent into a reaction bottle in a drying room with a dew point of-40 ℃, stirring under a closed environment to uniformly mix the systems, reacting for 12 hours at 50 ℃ to obtain methyl ethyl carbonate solution containing (difluorophosphoryloxy) lithium trifluoroborate, wherein the solution contains a small amount of insoluble matters which are possibly undissolved lithium difluorophosphate, analyzing by a turbidimeter, and obtaining clear and transparent reaction liquid after filtration, wherein the turbidity is 12.55 NTU;
S2, removing most of the solvent in the reaction solution by reduced pressure distillation, controlling the reduced pressure distillation temperature to be 60 ℃ and the time to be 0.5h, and obtaining a product concentrate of the lithium (difluorophosphoryloxy) trifluoroborate, which is marked as 3# control lithium salt.
The peak area of the nuclear magnetic F spectrum was integrated and calculated to obtain a 3# control lithium salt containing 61.4wt% of lithium (difluorophosphoryloxy) trifluoroborate, 34.3wt% of lithium bis (difluorophosphoryloxy) trifluoroborate and 4.3wt% of lithium tetrafluoroborate, based on 100wt% of the total amount of the fluorine-containing lithium salt. And the area integration conversion is further carried out through the P spectrum, so that the result is uniform, and the calculation reliability is high.
Comparative example 4
The operation of this comparative example was the same as that of comparative example 1 except that after the step S2, poor solvent 1, 2-dichloroethane was added to the product concentrate of lithium (difluorophosphoryloxy) trifluoroborate at a volume ratio of 1:1, the temperature was kept at-20 ℃ for 24 hours, crystals were precipitated, solid products and filtrate were obtained after filtration, and the obtained filtrate was continuously distilled under reduced pressure to obtain a new product concentrate of lithium (difluorophosphoryloxy) trifluoroborate, designated as a 4# control lithium salt.
Nuclear magnetic F spectrum test is carried out on the precipitated crystal, and the result shows that the crystal is lithium tetrafluoroborate instead of lithium difluorophosphate. From the integration of the nuclear magnetic F spectrum peak area of the 4# control lithium salt, it was found that the 4# control lithium salt contained 38.2wt% of lithium (difluorophosphoryloxy) trifluoroborate and 61.8wt% of lithium bis (difluorophosphoryloxy) trifluoroborate, based on 100wt% of the total amount of the fluorine-containing lithium salt. And the area integration conversion is further carried out through the P spectrum, so that the result is uniform, and the calculation reliability is high.
As can be seen from comparing the reaction results of examples 1-5 and examples 6-9, when chain alkyl alcohol is added as a catalyst in the reaction, the reaction can be promoted to completely react the raw materials to improve the reaction yield, and the residue of diboron trioxide can be avoided to reduce the turbidity of the reaction solution, so that the filtration step is omitted to achieve the effect of simplifying the process, the reaction activity is increased, and the reaction time is greatly shortened. And the catalyst can be removed in the subsequent distillation process without affecting the product quality.
As is clear from comparison of the embodiment 1 and the comparative examples 1-2, when the reaction solvent is reduced or the reaction container is changed from a closed container to an open container, a large amount of lithium difluorophosphate as a byproduct is generated, on one hand, solid precipitation is generated, the reaction yield is reduced, the filtration process is increased, and on the other hand, lithium difluorophosphate impurities are introduced into the product. The reason is presumed that the reduction of the solvent and the change of the reaction vessel during the reaction process lead to the escape of a large amount of boron trifluoride as an intermediate product, and the lithium trifluoroborate as a target product (difluorophosphoryloxy) cannot be effectively produced in the reaction system, thereby leading to the production of lithium difluorophosphate.
As is clear from comparative examples 1 and 4, concentration of the reaction solution of lithium (difluorophosphoryloxy) trifluoroborate and introduction of a poor solvent for crystallization gave not lithium difluorophosphate but lithium tetrafluoroborate, which indicated that the binding energy of b—o bond in lithium (difluorophosphoryloxy) trifluoroborate was high and the chemical stability of the substance was high, and the decomposition of lithium (difluorophosphoryloxy) trifluoroborate to produce lithium difluorophosphate was impossible by the concentration and crystallization process.
Therefore, compared with the traditional process using lithium difluorophosphate as a raw material, the process for preparing the lithium difluorophosphate by adopting the invention, particularly when chain alkyl alcohol is added as a catalyst, can avoid the crystallization process of the lithium difluorophosphate, improve the utilization rate of the raw material, improve the production efficiency, greatly reduce the cost and be very suitable for industrial application.
Claims (11)
1. A preparation method of (difluorophosphoryloxy) lithium trifluoroborate is characterized by comprising the steps of preparing and obtaining a reaction solution containing (difluorophosphoryloxy) lithium trifluoroborate by taking lithium hexafluorophosphate and diboron trioxide as raw materials in an organic solvent.
2. The method for producing lithium (difluorophosphoryloxy) trifluoroborate according to claim 1, wherein the organic solvent is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, methylethyl carbonate, diethyl carbonate, methyl acetate, ethyl acetate, methyl propionate, gamma-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, acetonitrile, benzyl cyanide and propionitrile.
3. The method for producing lithium trifluoroborate (difluorophosphoryloxy) according to claim 2, wherein the mass ratio of the organic solvent to lithium hexafluorophosphate is (4-15): 1.
4. The method for producing lithium trifluoroborate (difluorophosphoryloxy) according to claim 1, wherein the molar ratio of lithium hexafluorophosphate to diboron trioxide is 1.5 to 3.
5. The method for preparing lithium trifluoroborate (difluorophosphoryloxy) according to claim 1, wherein the reaction temperature is 0-120 ℃ and the reaction time is 0.5-48 h.
6. The method for producing lithium (difluorophosphoryloxy) trifluoroborate according to any one of claims 1-5, wherein the method further comprises adding a chain alkyl alcohol as a catalyst to the reaction system, wherein the chain alkyl alcohol is at least one selected from the group consisting of methanol, ethanol, isopropanol, butanol and ethylene glycol.
7. The method for preparing lithium trifluoroborate (difluorophosphoryloxy) as claimed in claim 6, wherein the catalyst is used in an amount of 0.1-2% of the molar amount of lithium hexafluorophosphate.
8. The method for producing lithium (difluorophosphoryloxy) trifluoroborate according to claim 1 or 6, wherein the reaction is carried out in a closed vessel or an open vessel provided with a condensing reflux means.
9. The method for producing lithium (difluorophosphoryloxy) trifluoroborate according to claim 1 or 6, wherein the reaction solution contains at least 60% by weight of lithium (difluorophosphoryloxy) trifluoroborate.
10. The method for producing lithium (difluorophosphoryloxy) trifluoroborate according to claim 9, wherein the reaction solution further comprises lithium bis (difluorophosphoryloxy) trifluoroborate and lithium tetrafluoroborate.
11. The method for preparing the lithium (difluorophosphoryloxy) trifluoroborate according to claim 10, further comprising removing the organic solvent, the catalyst and the boron trifluoride gas from the reaction liquid by atmospheric distillation or vacuum distillation to obtain a lithium (difluorophosphoryloxy) trifluoroborate product.
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