CN101265176B - A kind of purification method of lithium oxalate difluoroborate - Google Patents
A kind of purification method of lithium oxalate difluoroborate Download PDFInfo
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- CN101265176B CN101265176B CN2008100305682A CN200810030568A CN101265176B CN 101265176 B CN101265176 B CN 101265176B CN 2008100305682 A CN2008100305682 A CN 2008100305682A CN 200810030568 A CN200810030568 A CN 200810030568A CN 101265176 B CN101265176 B CN 101265176B
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- lithium oxalate
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- difluoroborate
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- 238000000746 purification Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 21
- RBKMZOVCGJIRNQ-UHFFFAOYSA-N B([O-])(F)F.C(C(=O)O)(=O)O.[Li+] Chemical compound B([O-])(F)F.C(C(=O)O)(=O)O.[Li+] RBKMZOVCGJIRNQ-UHFFFAOYSA-N 0.000 title claims 15
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- 238000002425 crystallisation Methods 0.000 claims description 18
- 230000008025 crystallization Effects 0.000 claims description 18
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims 1
- 239000012043 crude product Substances 0.000 claims 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 48
- 235000006408 oxalic acid Nutrition 0.000 abstract description 16
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000243 solution Substances 0.000 abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000005481 NMR spectroscopy Methods 0.000 abstract description 3
- 239000004411 aluminium Substances 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 abstract description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract 1
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000002667 nucleating agent Substances 0.000 abstract 1
- 239000012047 saturated solution Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 229910013188 LiBOB Inorganic materials 0.000 description 8
- 229910003002 lithium salt Inorganic materials 0.000 description 7
- 159000000002 lithium salts Chemical class 0.000 description 7
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 7
- 229910013870 LiPF 6 Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910013063 LiBF 4 Inorganic materials 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical class [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005443 coulometric titration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- -1 difluoro lithium tetraborate Chemical compound 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a purification method of oxalic acid difluoro lithium borate. The purification method is that the oxalic acid difluoro lithium borate (LiODFB) needing to be purified is dissolved in solvent with high solubility first, then the solution is mixed with nucleation agent, the mixed solution is performed through solid-liquid separation, crystallized solid matters are put in a vacuum drying oven for drying, so that purified LiODFB products are obtained. Confirmed by a nuclear magnetic resonance spectroscopy of <13>C, <11>B and <19>F, the products which are obtained by the purification method are the LiODFB, the moisture content in the products after one time purification is 0.0020 percent, and the mass percentages of metallic ions that are natrium, kalium, aluminium, ferrum, calcium and zinc are 0.0115 percent, 0.0032 percent, 0.0010 percent, 0.00045 percent, 0.0002, and 0.0001 percent respectively. The purification method has the advantages of simple technology, easy operation, mild conditions, low cost, high yield rate, and is suitable for industrialized production.
Description
Technical field
The present invention relates to the crystal chemistry field, particularly a kind of impurity elimination method of purification of the oxalic acid difluoro lithium tetraborate that can in the electrolytic solution of electrochemical appliances such as lithium ion battery, use, this invention also relates to the employed purification solvent of this method.
Background technology
In recent years, because the pressure of environmental pollution and energy shortage forces various countries to strive to find the energy of new green, environmental protection, Sustainable development.The green high-capacity environment-protecting lithium ion battery that occurs the nineties in 20th century because its energy density height, have extended cycle life, the operating voltage advantages of higher, make it become one of electrical source of power that attracts most attention.
Ionogen as lithium ion battery is the important component part of battery, is bearing transmission ionic effect between the positive and negative electrode in the inside of battery, and it has significant effects to the characteristics such as capacity, operating temperature range, cycle performance and safety performance of battery.Lithium salts commonly used in the present business-like lithium ion battery is LiPF
6And LiBF
4LiPF
6Very responsive to moisture, hydrolysis generates corrosive gases HF, and the rising of temperature all can promote the carrying out of above-mentioned reaction, so, LiPF
6High-temperature behavior relatively poor relatively, the generation of gas also makes lithium ion battery exist potential safety hazard.In addition, based on LiPF
6The low-temperature conductivity of electrolytic solution lower.And LiPF
6Usually and NSC 11801 (EC) share and be made into electrolytic solution and could form effective SEI film at negative pole, but the fusing point of EC higher (37 ℃), this has limited the low temperature use properties of battery.LiBF
4Have lower charge-transfer resistance as lithium salts, make battery have the LiPF of ratio
6More superior low-temperature performance.But its oxidizing potential is relatively low, with LiPF
6Similar, to heat and moisture instability, unfavorable to battery cycle life.In addition, LiBF
4Film forming properties bad, thereby cause battery high-multiplying power discharge capacity and first charge-discharge efficiency to reduce.Cause that in recent years di-oxalate lithium borate (LiBOB) that people pay attention to is though have more advantage: not halogen-containing in the molecular structure, do not corrode the aluminium collector, have high conductance and electrochemical window, can in PC, stablize graphite cathode, the positive electrode material of manganese and iron system almost not had dissolving corrode etc.But LiBOB (particularly linear carbonate class) in the solvent of part low-k dissolves hardly, and the deficiency of concentration influences the specific energy of battery.In addition, in use LiBOB electrolytic solution can decompose generation gas, will cause the increase of cell internal pressure, brings unsafe factor.There are some researches show that also LiBOB is too high at the SEI membrane impedance that negative pole forms, can influence the low-temperature performance and the loading capacity of battery.Therefore, the chemical property of system under high temperature, low temperature of the used lithium salts of current electrolysis liquid is unsatisfactory, presses for that to make improvements or seek performance more excellent, the substitute materials that cost is lower.
At present, the most noticeable a kind of novel lithium salts oxalic acid difluoro lithium tetraborate (LiODFB) combines two kinds of Lithium Salt LiBOB and LiBF with it
4Both advantages become the type material that substitutes existing electrolyte lithium salt.This lithium salts molecular structure comprises half LiBOB and half LiBF
4Molecule.Because LiODFB has LiBF
4Part-structure, so low-temperature performance increases, simultaneously, have the part-structure of LiBOB again, also have excellent high, and so responsive to impurity and moisture unlike LiBOB, therefore have the use temperature scope of broad.The solubleness of LiODFB in the linear carbonate solvent is bigger, and therefore higher specific conductivity is just arranged, and can form stable SEI film on the graphite cathode surface with PC, provides favourable prerequisite for solving battery low temperature use problem.LiODFB has good thermostability to the positive electrode material of manganese base and iron-based.LiODFB can also improve the anti-abuse of lithium ion battery.
Lithium ion battery is very strict to electrolytical index request, and usually direct synthetic product can not directly be used as the electrolytic solution of lithium ion battery owing to having higher impurity and moisture content.Therefore must be through purification step to reduce foreign matter content.
S.Tsujioka etc. react in methylcarbonate with oxalic acid, LiBF4 and aluminum chloride or silicon tetrachloride among the EP1308449A2 in European patent or react in methylcarbonate with oxalic acid, LiBF4, lithium fluoride and boron trichloride or trimethoxy-boron and realized that LiODFB's is synthetic.But the not mentioned LiODFB that how to purify.
S.S.Zhang etc. adopt other method to synthesize LiODFB in Electrochemistry Communications 8 (2006) 1423-1428, and adopt methylcarbonate to make solvent to extract the recrystallization LiODFB that purified.Because methylcarbonate solubleness is bigger in this method of purification, very difficult crystallization is separated out and is caused productive rate very low.
Summary of the invention
The purpose of this invention is to provide a kind of method of purification that meets the needed ionogen oxalic acid of lithium ion battery difluoro lithium tetraborate.
The present invention adopts the principle of dilution crystallization, the LiODFB that will purify is dissolved in and makes highly concentrated solution (comprising saturated solution) in the high solvent of solvability earlier, then this solution is mixed with the crystallization agent, cause the mixed solvent supersaturation owing to the solubleness of LiODFB in the crystallization agent is low, separate out LiODFB, low levels compositions such as impurity are stayed in the solution owing to can not reach supersaturation in mixed solvent, will promptly get the LiODFB product of purifying by solid-liquid separation.
Purifying technique step of the present invention is as follows: the oxalic acid difluoro lithium tetraborate that 1) will purify is dissolved in the solvent; 2) then this solution is mixed with the crystallization agent, through solid-liquid separation, the solid matter that obtains; 3) promptly obtain the oxalic acid difluoro lithium tetraborate of purifying through vacuum-drying.
Obtain after the solid-liquid separation solid matter repeating step 1), 2) repeatedly purify.
The solubleness of oxalic acid difluoro lithium tetraborate in solvent is not less than 15 grams.
The solvent temperature of oxalic acid difluoro lithium tetraborate is the boiling point of room temperature to solvent.
Oxalic acid difluoro lithium tetraborate solubleness in the crystallization agent is not more than 5 grams.
After the solid matter that crystallization goes out is filtered, also can be not more than drip washing in the 5 crystallization agent that restrain with oxalic acid difluoro lithium tetraborate in solubleness again.
The mass ratio of consumption and the solid matter that is gone out by the crystallization of drip washing that is used for the crystallization agent of drip washing is 5%～20%.
The concrete purification step of the present invention is:
Earlier the LiODFB that will purify at a certain temperature (normal temperature～solvent boiling point) be dissolved in solubleness greater than 15 the gram solvents in, in this solution, mix (LiODFB solubleness is less than 5 grams) then according to 1: 100 to 10: 1 ratio of solvent and crystallization agent, get solid matter through solid-liquid separation then, according to the consumption of mass ratio 5%～20% solid matter is carried out drip washing less than the crystallization agent of 5 grams with solubleness, be dry in the vacuum chamber of 0.05～0.095Mpa at last in vacuum tightness, drying temperature is a room temperature to 150 ℃, and be 12～48h time of drying.
Need further to purify, can repeatedly repeat above-mentioned technology.
The above-mentioned LiODFB that need to purify can be dissolved in the high solvent of solvability in advance, also can be after building-up reactions finishes, after filtration, the oxalic acid difluoro lithium borate solution of evaporation concentration.The solution of evaporation concentration should guarantee that the content of oxalic acid difluoro lithium tetraborate do not separate out greater than 15%.
Purification solvent of the present invention is preferably: tetrahydrofuran (THF), propylene carbonate, methylcarbonate, diethyl carbonate, butylene, acetonitrile, propionitrile, butyronitrile, acetone, N, the mixture of any one or they in dinethylformamide, tetramethylene sulfone, the dimethyl sulfoxide (DMSO) etc.
Purification crystallization of the present invention agent is preferably: any one in ethyl acetate, normal hexane, benzene,toluene,xylene, gamma-butyrolactone, ether, tetracol phenixin, the dioxolane etc. or their mixture.
Method of purification products obtained therefrom warp of the present invention
13C,
11B and
19The NMR (Nuclear Magnetic Resonance) spectrum of F confirms to be LiODFB.
The moisture content of surveying based on the karl Fischer coulometric titration by the LiODFB product of the present invention after primary purification is 0.0020%.ICP records sodium, potassium, aluminium, iron, the calcium of metal ion, the quality percentage composition of zinc is respectively 0.0115%, 0.0032%, 0.0010%, 0.00045%, 0.0002%, 0.0001%.
The invention has the advantages that: technology is simple, easily operation, mild condition, cost is low, productive rate is high, is fit to suitability for industrialized production.Refined product has good effect in lithium ion battery.
Description of drawings
The product that Fig. 1 obtains for the embodiment of the invention 1
13C,
11B and
19The nmr spectrum chart of F.
The product that Fig. 2 obtains for the embodiment of the invention 1 is mixed with LiODFBPC/EC/DMC (1: 1: the 3) electrolytic solution of 1.2mol/L and is applied to Li/ graphite battery with LiODFB PC/EC/DMC (1: 1: the 3) electrolytic solution of not purifying and carries out charging and discharging curve.The battery charging and discharging stopping potential is 2.000V～0.000V, and charging and discharging currents density is 30mAg
-1, probe temperature is 25 ℃.Ordinate zou is a cell voltage among the figure, the V of unit.1,15,30 charging and discharging curves of representing the 1st time, the 15th time and the 30th time respectively among the figure.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but these embodiment must not be interpreted as limiting the scope of the invention.The present invention can realize by described any mode of summary of the invention.
With the LiODFB product 15g that need are purified, add acetonitrile and be mixed with saturated solution.Add the 200g ether in the Erlenmeyer flask of a 500ml, the acetonitrile saturated solution of LiODFB is slowly added and continuous the stirring, the adularescent crystal is separated out.Add finish after, filter with B, and divide with the 10ml ether and to carry out drip washing three times, (vacuum tightness is 0.05～0.095Mpa) dry 36h, promptly obtains the LiODFB solid 12.9g of purifying to carry out vacuum at 120 ℃ behind the suction filtration.Productive rate is 86%.The product molecular structure of being purified is definite by the NMR test, as shown in Figure 1.LiODFBPC/EC/DMC (1: 1: the 3) electrolytic solution that products obtained therefrom is mixed with 1.2molL is applied to Li/ graphite battery and carries out charge-discharge test.The battery charging and discharging stopping potential is 2.000V～0.000V, and current density is 30mAg
-1, probe temperature is 25 ℃, test result is as shown in Figure 2.Through charge-discharge test as can be seen, have better charge/discharge capacity and excellent capacity hold facility under the Li/ graphite battery normal temperature of the LiODFB after the purification than the electrolytic solution of the LiODFB preparation of not purifying.
Embodiment 2
With the LiODFB product 30g that need are purified, add methylcarbonate and be mixed with saturated solution.Add the 400g ether in the Erlenmeyer flask of a 1000ml, the methylcarbonate saturated solution of LiODFB is slowly added and continuous the stirring, the adularescent crystal is separated out.Add finish after, filter with B, and divide with the 20ml ether and to carry out drip washing three times, (vacuum tightness is 0.05～0.095Mpa) dry 48h, promptly obtains the LiODFB solid 24g of purifying to carry out vacuum at 150 ℃ behind the suction filtration.Productive rate is 80%.
Embodiment 3
With the LiODFB product 10g that need are purified, add propylene carbonate and be mixed with saturated solution.Add the 150g tetracol phenixin in the Erlenmeyer flask of a 500ml, the propylene carbonate saturated solution of LiODFB is slowly added and continuous the stirring, the adularescent crystal is separated out.Add finish after, filter with B, and divide with the 10ml tetracol phenixin and to carry out drip washing three times, (vacuum tightness is 0.05～0.095Mpa) dry 16h, promptly obtains the LiODFB solid 8.5g of purifying to carry out vacuum at 100 ℃ behind the suction filtration.Productive rate is 85%.
Embodiment 4
With the LiODFB product 12g that need are purified, add propylene carbonate and be mixed with saturated solution.Add the 180g gamma-butyrolactone in the Erlenmeyer flask of a 500ml, the propylene carbonate saturated solution of LiODFB is slowly added and continuous the stirring, the adularescent crystal is separated out.Add finish after, filter with B, and divide with the 12ml gamma-butyrolactone and to carry out drip washing three times, (vacuum tightness is 0.05～0.095Mpa) dry 20h, promptly obtains the LiODFB solid 10.08g of purifying to carry out vacuum at 120 ℃ behind the suction filtration.Productive rate is 84%.
Embodiment 5
With the LiODFB product 10g that need are purified, the mixing solutions that adds propylene carbonate and tetrahydrofuran (THF) (volume ratio 1: 1) is mixed with saturated solution.Add the 100g gamma-butyrolactone in the Erlenmeyer flask of a 500ml, the saturated solution of LiODFB is slowly added and continuous the stirring, the adularescent crystal is separated out.Add finish after, filter with B, and divide with the 10ml gamma-butyrolactone and to carry out drip washing three times, (vacuum tightness is 0.05～0.095Mpa) dry 16h, promptly obtains the LiODFB solid 7.6g of purifying to carry out vacuum at 130 ℃ behind the suction filtration.Productive rate is 76%.
Claims (8)
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| CN102702243B (en) * | 2012-06-12 | 2014-08-27 | 中南大学 | Method for preparation and purifying lithium difluoroborate |
| CN103382577B (en) * | 2013-07-29 | 2016-04-06 | 中国科学院青海盐湖研究所 | A kind of [(CH 3o) 2cO] 3li 2[C 2bF 2o 4] 2monocrystalline and preparation method thereof and application |
| CN103483368B (en) * | 2013-09-17 | 2016-08-17 | 东莞市凯欣电池材料有限公司 | A kind of preparation method of difluorine oxalic acid boracic acid lithium |
| EP3277694B1 (en) | 2015-03-31 | 2022-10-05 | Bayerische Motoren Werke Aktiengesellschaft | Method of making lithium difluoro (oxalato) borate |
| CN109232625A (en) * | 2018-10-25 | 2019-01-18 | 河南省法恩莱特新能源科技有限公司 | A kind of preparation method of difluorine oxalic acid boracic acid lithium |
| 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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Assignee: JIANGSU JIANGLI SCI & TECH CO., LTD. Assignor: Central South University Contract record no.: 2011430000084 Denomination of invention: Method for purifying LiODFB Granted publication date: 20110126 License type: Exclusive License Open date: 20080917 Record date: 20110620 |
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