CN106349271A - Catalytic synthesis method of lithium difluoro(oxalato)borate - Google Patents
Catalytic synthesis method of lithium difluoro(oxalato)borate Download PDFInfo
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- CN106349271A CN106349271A CN201610732281.9A CN201610732281A CN106349271A CN 106349271 A CN106349271 A CN 106349271A CN 201610732281 A CN201610732281 A CN 201610732281A CN 106349271 A CN106349271 A CN 106349271A
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- lithium
- oxalic acid
- solution
- catalytic synthesis
- waterless
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 20
- 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 108
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- -1 lithium tetrafluoroborate Chemical compound 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 25
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 25
- 229960002645 boric acid Drugs 0.000 claims description 25
- 235000010338 boric acid Nutrition 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 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 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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
- 229910000831 Steel Inorganic materials 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
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process 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
- 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
- 238000002360 preparation method Methods 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000007039 two-step reaction Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a catalytic synthesis method of lithium difluoro(oxalato)borate. 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) adding a certain amount of dry waterless lithium tetrafluoborate and a catalyst into a certain amount of organic solvent of a stirred reactor, and dissolving to prepare a solution; and (3) slowly adding a certain amount of waterless oxalic acid or waterless oxalic acid solution 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 catalytic synthesis method of lithium difluoro(oxalato)borate has the advantages of simple process route and high product yield, and does not pollute the environment since the exhaust gas generated in the reaction process is absorbed by alkali liquor.
Description
Technical field
The present invention relates to the process for catalytic synthesis of difluorine oxalic acid boracic acid lithium, belong to lithium ion battery material synthetic technology neck
Domain.
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 is it is achieved that the synthesis of liodfb.Wherein raw material libf4 is expensive, and more sensitive to moisture content, operating difficultiess,
The sample purity obtaining 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, the process for catalytic synthesis of difluorine oxalic acid boracic acid lithium is it is characterised in that comprise the following steps: (1) all production reaction vessel
After nitrogen displacement, it is placed in high pure nitrogen protection lower addition material；(2) urge quantitation waterless lithium terafluoroborate is dried with quantitative
Agent is added in the quantitative organic solvent of stirred reactor and dissolves, and is configured to solution；(3) by quantitative anhydrous oxalic acid or no pasture and water
Acid solution is slowly added in lithium tetrafluoroborate solution, fully anti-under 30 DEG C 100 DEG C, negative pressure and tail gas absorption hydraulic control system
Should, obtain difluorine oxalic acid boracic acid lithium solution.
2nd, difluorine oxalic acid boracic acid lithium according to claim 1 process for catalytic synthesis it is characterised in that: step (1)
Described in high pure nitrogen be the nitrogen that purity is more than 99.5%.
3rd, difluorine oxalic acid boracic acid lithium according to claim 1 process for catalytic synthesis it is characterised in that: step (2)
Described in catalyst be 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 waterless lithium terafluoroborate quality.
4th, difluorine oxalic acid boracic acid lithium according to claim 1 process for catalytic synthesis it is characterised in that: step (2)
Described in organic solvent be dimethyl carbonate, or diethyl carbonate, or Ethyl methyl carbonate, or ethyl acetate.
5th, difluorine oxalic acid boracic acid lithium according to claim 1 process for catalytic synthesis it is characterised in that: step (3)
Described in anhydrous oxalic acid solution solvent consistent with the solvent of lithium tetrafluoroborate solution；Anhydrous oxalic acid and waterless lithium terafluoroborate thing
The ratio of the amount of matter is 0.98.1:1 1:1.
6th, difluorine oxalic acid boracic acid lithium according to claim 1 process for catalytic synthesis it is characterised in that: step (3)
Described in tail gas absorption liquid be 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 all production reaction vessels are adopted high pure nitrogen to replace, then pass to high pure nitrogen, in high pure nitrogen protection
Lower addition material；
2nd, waterless lithium terafluoroborate 46.9 kilogram will be dried, add 1000 liters of rustless steels equipped with 500 kilograms of dimethyl carbonate to stir
Mix in reactor, be stirred dissolving；
3 then again toward in described stirred reactor add the carbon -7- alkene conduct of 0.9 kilogram of 1,8- diazabicyclo [5.4.0] 11
Catalyst；
4th, under high pure nitrogen guard mode, add 45 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 8 hours,
Reacting substance all difluorine oxalic acid boracic acid lithiums solution.
5th, 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 all production reaction vessels are adopted high pure nitrogen to replace, then pass to high pure nitrogen, in high pure nitrogen protection
Lower addition material；
2nd, waterless lithium terafluoroborate 46.9 kilogram will be dried, add 1000 liters of rustless steels equipped with 500 kilograms of dimethyl carbonate to stir
Mix in reactor, be stirred dissolving；
3 then again toward in described reactor add 0.8 kilogram of catalyst 1,5- diazabicyclo [4,3,0] nonene -5；
4th, under high pure nitrogen guard mode, add 45 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.
5th, 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 (6)
1. the process for catalytic synthesis of difluorine oxalic acid boracic acid lithium is it is characterised in that comprise the following steps: (1) all production reaction vessel
After nitrogen displacement, it is placed in high pure nitrogen protection lower addition material；(2) urge quantitation waterless lithium terafluoroborate is dried with quantitative
Agent is added in the quantitative organic solvent of stirred reactor and dissolves, and is configured to solution；(3) by quantitative anhydrous oxalic acid or no pasture and water
Acid solution is slowly added in lithium tetrafluoroborate solution, fully anti-under 30 DEG C 100 DEG C, negative pressure and tail gas absorption hydraulic control system
Should, obtain difluorine oxalic acid boracic acid lithium solution.
2. difluorine oxalic acid boracic acid lithium according to claim 1 process for catalytic synthesis it is characterised in that: institute in step (1)
State the nitrogen that high pure nitrogen is that purity is more than 99.5%.
3. difluorine oxalic acid boracic acid lithium according to claim 1 process for catalytic synthesis it is characterised in that: institute in step (2)
Stating catalyst is 1,8- diazabicyclo [5.4.0] 11 carbon -7- alkene, or 1,5- diazabicyclo [4,3,0] nonene -5, or
It is the mixture of the two；Catalyst charge is the 0.01%-20% of waterless lithium terafluoroborate quality.
4. difluorine oxalic acid boracic acid lithium according to claim 1 process for catalytic synthesis it is characterised in that: institute in step (2)
Stating organic solvent is dimethyl carbonate, or diethyl carbonate, or Ethyl methyl carbonate, or ethyl acetate.
5. difluorine oxalic acid boracic acid lithium according to claim 1 process for catalytic synthesis it is characterised in that: institute in step (3)
The solvent stating anhydrous oxalic acid solution is consistent with the solvent of lithium tetrafluoroborate solution；Anhydrous oxalic acid and waterless lithium terafluoroborate material
The ratio of amount is 0.98.1:1 1:1.
6. difluorine oxalic acid boracic acid lithium according to claim 1 process for catalytic synthesis it is characterised in that: institute in step (3)
Stating tail gas absorption liquid is dilute calcium hydroxide emulsion, or diluted sodium hydroxide solution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702243A (en) * | 2012-06-12 | 2012-10-03 | 中南大学 | Method for preparation and purifying lithium difluoroborate |
| CN104387411A (en) * | 2014-11-07 | 2015-03-04 | 周阳 | Series one-pot synthesis method of lithium oxalyldifluroborate |
-
2016
- 2016-08-27 CN CN201610732281.9A patent/CN106349271A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702243A (en) * | 2012-06-12 | 2012-10-03 | 中南大学 | Method for preparation and purifying lithium difluoroborate |
| CN104387411A (en) * | 2014-11-07 | 2015-03-04 | 周阳 | Series one-pot synthesis method of lithium oxalyldifluroborate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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