CN106349270A - Catalytic synthesis method of lithium difluoro(oxalato)borate - Google Patents
Catalytic synthesis method of lithium difluoro(oxalato)borate Download PDFInfo
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- CN106349270A CN106349270A CN201610732280.4A CN201610732280A CN106349270A CN 106349270 A CN106349270 A CN 106349270A CN 201610732280 A CN201610732280 A CN 201610732280A CN 106349270 A CN106349270 A CN 106349270A
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- oxalic acid
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 24
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title abstract 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 129
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 54
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- -1 lithium tetrafluoroborate Chemical compound 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 18
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims abstract description 18
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000010521 absorption reaction Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000006227 byproduct Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 31
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 31
- 229960002645 boric acid Drugs 0.000 claims description 31
- 235000010338 boric acid Nutrition 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 7
- XGINAUQXFXVBND-UHFFFAOYSA-N 1,2,6,7,8,8a-hexahydropyrrolo[1,2-a]pyrimidine Chemical compound N1CC=CN2CCCC21 XGINAUQXFXVBND-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 2
- 230000001681 protective effect Effects 0.000 abstract 2
- 230000000694 effects Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 8
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 3
- 229960001826 dimethylphthalate Drugs 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-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
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003385 sodium Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling 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
- 239000012528 membrane Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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 Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/14—Production of inert gas mixtures; Use of inert gases in general
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/10—Inorganic absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
Abstract
The invention relates to a catalytic synthesis method of lithium difluoro(oxalato)borate, belonging to the technical field of new energy material preparation. The method comprises the following steps: (1) after all production reaction vessels are replaced with high-purity nitrogen, adding materials in a high-purity nitrogen protective atmosphere; (2) in a closed dry reactor, adding a certain amount of dry waterless tetrafluoborate and a certain amount of waterless lithium chloride into an organic solvent of a stirred reactor, and dissolving to prepare a solution; (3) adding a certain amount of catalyst into the stirred reactor, and sufficiently reacting at specified temperature by heating and stirring; (4) after the reaction finishes, filtering, separating out the solid byproduct, thereby obtaining a lithium tetrafluoroborate organic solution; (5) in the high-purity nitrogen protective atmosphere, adding a certain amount of waterless oxalic acid into the lithium tetrafluoroborate solution, and sufficiently reacting under the control of specified temperature, specified pressure and a tail gas absorption solution, thereby obtaining the lithium difluoro(oxalato)borate solution. The lithium difluoro(oxalato)borate has the advantages of simple catalytic synthesis method, favorable catalyst effect and high conversion rate; the intermediate lithium tetrafluoroborate does not need to be separated from the solvent, thereby simplifying the technical process; and thus, the method has favorable application prospects in the field of new energy materials.
Description
Technical field
The present invention relates to difluorine oxalic acid boracic acid lithium process for catalytic synthesis, belong to lithium ion battery material synthesis technical field.
Background technology
Lithium-ion battery electrolytes are the important component parts of lithium battery, are the key core components of electrolyte, electrolyte
Must have the advantages that conductivity is high, chemistry and electrochemical stability are good, wide temperature range, safety can be used good.
At present, conventional electrolyte mainly has lithium hexafluoro phosphate (lipf6), di-oxalate lithium borate (libob), Tetrafluoroboric acid
Lithium (libf4), wherein lipf6, with its good combination property, is applied widely.Because lipf6 is very sensitive to moisture, system
Standby complex process, in addition, lipf6 itself heat decomposition temperature relatively low (200 DEG C), easily decomposes in organic solvent (80 DEG C of left sides
Right)；Easily react with manganese anode material, the electrolyte with the presence of pc organic solvent common embedding has occurred, and has been difficult to
Stable sei film is formed on negative pole, these all can affect the chemical property of battery.Libf4 has excellent cryogenic property, but
It is that high-temperature behavior is very poor, applicable temperature range is narrow, and its filming performance is poor, thus leading to high-multiplying power discharge capacity and filling first
Discharging efficiency reduces.Libob is almost insoluble in the solvent of part low-k, and the sei membrane resistance being formed is very big, low temperature
Performance is bad, and libob electrolyte can produce gas in use, there is potential safety hazard, and application is restricted.Cause
This, a kind of in the urgent need to seeking preparation process is simple, easy to operate, the new type lithium ion battery electrolysis of excellent combination property
Matter.
Difluorine oxalic acid boracic acid lithium (liodfb) is a kind of new type lithium ion battery electrolyte, it combine libf4 and
The construction featuress of libob, have the advantages that the two simultaneously.Liodfb has higher heat stability (240 DEG C about), existing
The high-temperature behavior of libob, has the cryogenic property of libf4 again, and the temperature range of use is very wide.The filming performance of liodfb is very simultaneously
Good, can participate in being formed stable sei film in the electrolyte with the presence of pc, there is good cycle performance.Meanwhile, liodfb
The electrode compatibility very well, particularly with manganese anode material.
At present, there is the report of the more synthetically prepared research with regard to liodfb both at home and abroad.European patent
With oxalic acid, LiBF4 as raw material in ep1308449a2, with aluminum chloride or Silicon chloride. as catalyst, in dimethyl carbonate
Middle reaction, it is achieved that the synthesis of liodfb, reacts, operating difficultiess more sensitive to moisture content, and the sample purity of acquisition is low.
S.s.zhang etc. adopts boron trifluoride diethyl etherate and lithium oxalate to synthesize liodfb crude product for raw material direct reaction, then
Make solvent with dimethyl carbonate, sample purified by extraction and recrystallization, this synthetic method response time is long, complex operation,
Low yield, the liodfb sample purity of acquisition is low, complex technical process.
The method obtaining LiBF4 and difluorine oxalic acid boracic acid lithium disclosed in Chinese patent cn102702243b, the party
Method needs two kinds of catalyst, and complex process, step are many, product yield is relatively low.
Content of the invention
It is an object of the invention to overcome prior art deficiency and provide a kind of process is simple reasonable, easy to operate, produce
The high difluorine oxalic acid boracic acid lithium process for catalytic synthesis of rate.
Difluorine oxalic acid boracic acid lithium process for catalytic synthesis of the present invention is achieved through the following technical solutions:
1st, difluorine oxalic acid boracic acid lithium process for catalytic synthesis is it is characterised in that comprise the following steps: (1) all production reaction vessel
After high pure nitrogen displacement, it is placed in high pure nitrogen protection lower addition material；(2) in close drying reactor, fixed by being dried
Measure anhydrous tetrafluoroborate and quantitative anhydrous Lithium chloride is added in the organic solvent of stirred reactor and dissolves, prepare solution；(2)
Add weighed catalyst in stirred reactor, carry out heated and stirred 0.5 12 hours at 30 DEG C 100 DEG C, fully react；
(3) filter after the completion of reacting, separate solid by-product, obtain the organic solution of LiBF4；(4) under high pure nitrogen protection
Quantitative anhydrous oxalic acid is added in lithium tetrafluoroborate solution, under 30 DEG C 100 DEG C, authorized pressure and tail gas absorption hydraulic control system
React 0.5 12 hours, obtain difluorine oxalic acid boracic acid lithium solution.
2nd, difluorine oxalic acid boracic acid lithium process for catalytic synthesis according to claim 1 it is characterised in that: in step (1)
Described high pure nitrogen is the nitrogen that purity is more than 99.5%.
3rd, difluorine oxalic acid boracic acid lithium process for catalytic synthesis according to claim 1 it is characterised in that: in step (2)
Described tetrafluoroborate is sodium tetrafluoroborate, or ammonium tetrafluoroborate, or potassium tetrafluoroborate, or the former two kinds, three kinds
Mixture；The ratio of the amount of anhydrous tetrafluoroborate and quantitative anhydrous Lithium chloride material is between 1.1:1 1:1.
4th, difluorine oxalic acid boracic acid lithium process for catalytic synthesis according to claim 1 it is characterised in that: in step (3)
Described catalyst is 1,8- diazabicyclo [5.4.0] 11 carbon -7- alkene, or 1,5- diazabicyclo [4,3,0] nonene -5,
Or the mixture of the two；Catalyst charge is the 0.01%-20% of anhydrous oxalic acid lithium quality.
5th, difluorine oxalic acid boracic acid lithium process for catalytic synthesis according to claim 1 it is characterised in that: in step (2)
Described organic solvent is dimethyl carbonate, or diethyl carbonate, or Ethyl methyl carbonate, or ethyl acetate.
6th, difluorine oxalic acid boracic acid lithium process for catalytic synthesis according to claim 1 it is characterised in that: in step (4)
The ratio of the amount of anhydrous oxalic acid and anhydrous Lithium chloride material is 0.99:1 1:1.
7th, difluorine oxalic acid boracic acid lithium process for catalytic synthesis according to claim 1 it is characterised in that: in step (4)
Authorized pressure is absolute pressure 30kpa-90kpa.
8th, difluorine oxalic acid boracic acid lithium process for catalytic synthesis according to claim 1 it is characterised in that: in step (4)
Described tail gas absorption liquid is dilute calcium hydroxide emulsion, or diluted sodium hydroxide solution.
Difluorine oxalic acid boracic acid lithium process for catalytic synthesis beneficial effect of the present invention is:
1st, after all production reaction vessels adopt high pure nitrogen displacement, on the one hand system can be reduced with the air in metathesis reactor
The oxygen of system and water content；Another aspect nitrogen can suppress the volatilization of organic solvent.
2nd, catalyst is 1,8- diazabicyclo [5.4.0] 11 carbon -7- alkene, or 1,5- diazabicyclo [4,3,0]
Nonene -5, or the mixture of the two.1,8- diazabicyclo [5.4.0] 11 carbon -7- alkene and 1,5- diazabicyclo [4,3,
0] nonene -5 is effective catalyst, may apply to, in two step reactions, substantially increase response speed and production efficiency.
3rd, mixed solution and anhydrous oxalic acid react under negative pressure, have both ensured fully to react, and so that reaction end gas is discharged safely again.
4th, tail gas absorption liquid is dilute calcium hydroxide emulsion, or diluted sodium hydroxide solution, it is to avoid the tail that course of reaction produces
Gas pollutes.
Present invention process is simple, easy to operate, two step synthetic reactions is completed in a reactor, the response time is short,
Equipment investment is few, and yield is high to be suitable for industrialization production, and application prospect is very wide.
Specific embodiment
Following examples are intended to explanation invention rather than limitation of the invention further.
Embodiment 1
1st, first by all production reaction vessels adopt high pure nitrogen replace, after be passed through high pure nitrogen, high pure nitrogen protection under
Add material；
2nd, by dried 42.39 kilograms of anhydrous Lithium chlorides and 110 kilograms of anhydrous sodium tetrafluoroborates, add equipped with 300 kilograms of carbon
In 1000 liters of rustless steel stirred reactors of dimethyl phthalate, it is stirred dissolving；
3 then again toward in described high-purity reactor add the carbon -7- alkene conduct of 0.7 kilogram of 1,8- diazabicyclo [5.4.0] 11
Catalyst；Heat while stirring, controlling reaction temperature is 60 DEG C, fully reaction 6 hours；
4th, pass through the insoluble side product chlorinated sodium of Filter Press, obtain the dimethyl carbonate filtrate containing LiBF4；
5th, under high pure nitrogen guard mode, add 9 kilograms of anhydrous oxalic acid to lithium tetrafluoroborate solution, controlling reaction temperature is 70
DEG C, pressure be absolute pressure 60kpa, reaction makes LiBF4 and oxalic acid fully react generation difluorine oxalic acid boracic acid lithium for 6 hours,
Reacting substance all difluorine oxalic acid boracic acid lithiums solution.
6th, tail gas absorption liquid is concentration 10% calcium hydroxide emulsion, negative-pressure cyclic absorbing reaction tail gas, it is to avoid course of reaction is produced
Raw tail gas pollution.
Embodiment 2
1st, first by all production reaction vessels adopt high pure nitrogen replace, after be passed through high pure nitrogen, high pure nitrogen protection under
Add material；
2nd, by dried 42.39 kilograms of anhydrous Lithium chlorides and 111 kilograms of anhydrous sodium tetrafluoroborates, add equipped with 300 kilograms of carbon
In 1000 liters of rustless steel stirred reactors of dimethyl phthalate, it is stirred dissolving；
3 and then add 0.8 kilogram of 1,5- diazabicyclo [4,3,0] nonene -5 again toward in described stirred reactor as catalysis
Agent；Heat while stirring, controlling reaction temperature is 70 DEG C, fully reaction 7 hours；
4th, pass through the insoluble side product chlorinated sodium of Filter Press, obtain the dimethyl carbonate filtrate containing LiBF4；
5th, under high pure nitrogen guard mode, add 9 kilograms of anhydrous oxalic acid to lithium tetrafluoroborate solution, controlling reaction temperature is 75
DEG C, pressure be absolute pressure 55kpa, reaction makes LiBF4 and oxalic acid fully react generation difluorine oxalic acid boracic acid lithium for 7 hours,
Reacting substance all difluorine oxalic acid boracic acid lithiums solution.
6th, tail gas absorption liquid is concentration 10% calcium hydroxide emulsion, negative-pressure cyclic absorbing reaction tail gas, it is to avoid course of reaction is produced
Raw tail gas pollution.
Embodiment 3
1st, first by all production reaction vessels adopt high pure nitrogen replace, after be passed through high pure nitrogen, high pure nitrogen protection under
Add material；
2nd, by dried 42.39 kilograms of anhydrous Lithium chlorides and 105 kilograms of anhydrous ammonium tetrafluoroborates, add equipped with 300 kilograms of carbon
In 1000 liters of rustless steel stirred reactors of dimethyl phthalate, it is stirred dissolving；
3 and then add 0.7 kilogram of 1,5- diazabicyclo [4,3,0] nonene -5 again toward in described stirred reactor as catalysis
Agent；Heat while stirring, controlling reaction temperature is 70 DEG C, fully reaction 7 hours；
4th, pass through the insoluble by-product ammonium chloride of Filter Press, obtain the dimethyl carbonate filtrate containing LiBF4；
5th, under high pure nitrogen guard mode, add 9 kilograms of anhydrous oxalic acid to lithium tetrafluoroborate solution, controlling reaction temperature is 75
DEG C, pressure be absolute pressure 65kpa, reaction makes LiBF4 and oxalic acid fully react generation difluorine oxalic acid boracic acid lithium for 7 hours,
Reacting substance all difluorine oxalic acid boracic acid lithiums solution.
6th, tail gas absorption liquid is concentration 10% calcium hydroxide emulsion, negative-pressure cyclic absorbing reaction tail gas, it is to avoid course of reaction is produced
Raw tail gas pollution.
Claims (8)
1. difluorine oxalic acid boracic acid lithium process for catalytic synthesis is it is characterised in that comprise the following steps: (1) all production reaction vessel
After high pure nitrogen displacement, it is placed in high pure nitrogen protection lower addition material；(2) in close drying reactor, fixed by being dried
Measure anhydrous tetrafluoroborate and quantitative anhydrous Lithium chloride is added in the organic solvent of stirred reactor and dissolves, prepare solution；(2)
Add weighed catalyst in stirred reactor, carry out heated and stirred 0.5 12 hours at 30 DEG C 100 DEG C, fully react；
(3) filter after the completion of reacting, separate solid by-product, obtain the organic solution of LiBF4；(4) under high pure nitrogen protection
Quantitative anhydrous oxalic acid is added in lithium tetrafluoroborate solution, under 30 DEG C 100 DEG C, authorized pressure and tail gas absorption hydraulic control system
React 0.5 12 hours, obtain difluorine oxalic acid boracic acid lithium solution.
2. difluorine oxalic acid boracic acid lithium process for catalytic synthesis according to claim 1 it is characterised in that: described in step (1)
High pure nitrogen is the nitrogen that purity is more than 99.5%.
3. difluorine oxalic acid boracic acid lithium process for catalytic synthesis according to claim 1 it is characterised in that: described in step (2)
Tetrafluoroborate is sodium tetrafluoroborate, or ammonium tetrafluoroborate, or potassium tetrafluoroborate, or the former two kinds, three kinds of mixing
Thing；The ratio of the amount of anhydrous tetrafluoroborate and quantitative anhydrous Lithium chloride material is between 1.1:1 1:1.
4. difluorine oxalic acid boracic acid lithium process for catalytic synthesis according to claim 1 it is characterised in that: described in step (3)
Catalyst is 1,8- diazabicyclo [5.4.0] 11 carbon -7- alkene, or 1,5- diazabicyclo [4,3,0] nonene -5, or
The mixture of the two；Catalyst charge is the 0.01%-20% of anhydrous oxalic acid lithium quality.
5. difluorine oxalic acid boracic acid lithium process for catalytic synthesis according to claim 1 it is characterised in that: described in step (2)
Organic solvent is dimethyl carbonate, or diethyl carbonate, or Ethyl methyl carbonate, or ethyl acetate.
6. difluorine oxalic acid boracic acid lithium process for catalytic synthesis according to claim 1 it is characterised in that: anhydrous in step (4)
The ratio of the amount of oxalic acid and anhydrous Lithium chloride material is 0.99:1 1:1.
7. difluorine oxalic acid boracic acid lithium process for catalytic synthesis according to claim 1 it is characterised in that: regulation in step (4)
Pressure is absolute pressure 30kpa-90kpa.
8. difluorine oxalic acid boracic acid lithium process for catalytic synthesis according to claim 1 it is characterised in that: described in step (4)
Tail gas absorption liquid is dilute calcium hydroxide emulsion, or diluted sodium hydroxide solution.
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| CN108910919A (en) * | 2018-09-05 | 2018-11-30 | 九江天赐高新材料有限公司 | A kind of preparation method of the double oxalic acid lithium phosphates of electron level difluoro |
| 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 |
| CN109678898A (en) * | 2019-02-14 | 2019-04-26 | 东港华邦科技有限公司 | A kind of preparation method of difluorine oxalic acid boracic acid lithium |
| CN111393464A (en) * | 2020-05-09 | 2020-07-10 | 洛阳和梦科技有限公司 | Method for optimizing production of lithium bis (fluorooxalate) borate |
| CN114864888A (en) * | 2022-04-07 | 2022-08-05 | 湖南金硅科技有限公司 | Lithium difluorooxalato borate doped and coated SiO/C composite material and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108910919A (en) * | 2018-09-05 | 2018-11-30 | 九江天赐高新材料有限公司 | A kind of preparation method of the double oxalic acid lithium phosphates of electron level difluoro |
| CN108910919B (en) * | 2018-09-05 | 2020-09-29 | 九江天赐高新材料有限公司 | Preparation method of electronic-grade lithium difluorobis (oxalate) phosphate |
| 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 |
| CN109678898A (en) * | 2019-02-14 | 2019-04-26 | 东港华邦科技有限公司 | A kind of preparation method of difluorine oxalic acid boracic acid lithium |
| CN111393464A (en) * | 2020-05-09 | 2020-07-10 | 洛阳和梦科技有限公司 | Method for optimizing production of lithium bis (fluorooxalate) borate |
| CN114864888A (en) * | 2022-04-07 | 2022-08-05 | 湖南金硅科技有限公司 | Lithium difluorooxalato borate doped and coated SiO/C composite material and preparation method and application thereof |
| CN114864888B (en) * | 2022-04-07 | 2023-08-01 | 湖南金硅科技有限公司 | Lithium difluoro oxalate borate doped coated SiO/C composite material and preparation method and application thereof |
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