CN117897389A - Preparation method of lithium dioxalate borate and preparation method of lithium ion battery electrolyte - Google Patents
Preparation method of lithium dioxalate borate and preparation method of lithium ion battery electrolyte Download PDFInfo
- Publication number
- CN117897389A CN117897389A CN202180100855.XA CN202180100855A CN117897389A CN 117897389 A CN117897389 A CN 117897389A CN 202180100855 A CN202180100855 A CN 202180100855A CN 117897389 A CN117897389 A CN 117897389A
- Authority
- CN
- China
- Prior art keywords
- lithium
- mixture
- oxalic acid
- product
- dioxalate borate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 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 title claims abstract description 50
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 25
- 239000003792 electrolyte Substances 0.000 title claims description 27
- 238000002360 preparation method Methods 0.000 title abstract description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 28
- -1 oxalic acid compound Chemical class 0.000 claims abstract description 27
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 9
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 9
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 claims description 3
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- KCMQZDMHQCHCDB-UHFFFAOYSA-M C(C(=O)O)(=O)[O-].C(C(=O)O)(=O)O.B(O)(O)O.[Li+] Chemical compound C(C(=O)O)(=O)[O-].C(C(=O)O)(=O)O.B(O)(O)O.[Li+] KCMQZDMHQCHCDB-UHFFFAOYSA-M 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000002000 Electrolyte additive Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 31
- 238000003756 stirring Methods 0.000 description 16
- 239000007787 solid Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 229910001430 chromium ion Inorganic materials 0.000 description 4
- 230000007717 exclusion Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- 235000011837 pasties Nutrition 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910001182 Mo alloy Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000010571 fourier transform-infrared absorption spectrum Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- OGSYQYXYGXIQFH-UHFFFAOYSA-N chromium molybdenum nickel Chemical compound [Cr].[Ni].[Mo] OGSYQYXYGXIQFH-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000010963 304 stainless steel Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910013184 LiBO Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- XJNCHICLWKVTQA-UHFFFAOYSA-N [Mo].[W].[Cr].[Ni] Chemical compound [Mo].[W].[Cr].[Ni] XJNCHICLWKVTQA-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- FJPKZVUTEXZNPN-UHFFFAOYSA-N chromium copper molybdenum nickel Chemical compound [Ni][Cu][Cr][Mo] FJPKZVUTEXZNPN-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000003809 water extraction 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/02—Lithium compounds
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
Abstract
The invention belongs to the field of synthesis of lithium ion battery electrolyte additives, and particularly relates to a preparation method of lithium dioxalate borate, which comprises the following steps: (1) Providing a mixture comprising an oxalic acid compound, an alkaline lithium salt, and a boron-containing compound; (2) Reacting the mixture at a temperature of 50-200 ℃ to form a product comprising lithium dioxalate borate; in step (2), moisture is removed from the reacted mixture. The method can ensure that no side reaction exists basically, and improves the yield; the caking and wrapping phenomena of the product are reduced or eliminated, and the purity of the product is improved; and can greatly reduce the residual metal ions in the product.
Description
The invention belongs to the field of synthesis of additives of lithium ion battery electrolytes, and particularly relates to a preparation method of lithium dioxalate borate and a preparation method of lithium ion battery electrolytes.
The lithium ion battery has the advantages of high energy density, high output voltage, long cycle life, no memory effect, small environmental pollution and the like, is the secondary battery with the most attractive and development potential, gradually expands and is applied to the market of the vehicle-mounted power lithium ion battery along with the improvement and perfection of various material technologies of the lithium battery, and has extremely broad market prospect. The main components of the lithium ion battery electrolyte are electrolyte and electrolyte, wherein the performance of the electrolyte plays a key role on the electrolyte and the lithium ion battery.
Lithium hexafluorophosphate is widely used as the most mature electrolyte salt in current commercialization in lithium ion battery electrolyte materials. However, lithium hexafluorophosphate has the defects of easy hydrolysis, poor thermal stability and the like, and is easy to generate hydrofluoric acid through decomposition reaction, so that electrode materials of lithium ion batteries are corroded, and the battery performance is attenuated.
Lithium dioxalate borate (LiBOB) is used as a novel electrolyte lithium salt, has good chemical property and stability, and the thermal decomposition temperature can reach 300 ℃. The lithium dioxalate borate can form a stable SEI film on the surface of the electrode material, prevents solvation reaction of the electrode material, has higher conductivity and wider electrochemical window, can improve the stability and safety of the lithium ion battery, and prolongs the service life of the lithium ion battery.
At present, the preparation method of the lithium dioxalate borate mainly comprises a solid phase method and a liquid phase method, wherein oxalic acid, boric acid and lithium hydroxide or lithium carbonate are adopted as reaction raw materials, and the lithium dioxalate borate is generated in the presence or absence of water. However, lithium dioxalate borate absorbs water easily, forming lithium dioxalate borate hydrate. Meanwhile, under the action of water, partial hydrolysis reaction occurs. The hydrolysis reaction is as follows:
LiB(C 2 O 4 ) 2 +2H 2 O→LiBO 2 +2H 2 C 2 O 4
LiB(C 2 O 4 ) 2 +3H 2 O→LiOOCCOOH+H 3 BO 3 +H 2 C 2 O 4
wherein, the existence of water, the residual raw materials of reaction and the intermediate reaction product all show the proton acid type with stronger acid characteristic, and simultaneously, when the water is gradually removed in the high-temperature drying link of the product, the product is easy to agglomerate and wrap. In addition, when the common metal material is strongly stirred to overcome the caking phenomenon of the product during high-temperature water removal, the existence of strong protonic acid causes the residual exceeding standard of the product, such as iron, nickel, chromium and other ions, caused by material corrosion, and the residual exceeding standard is removed by the complex subsequent solvent extraction process repeated extraction or recrystallization.
At present, a novel preparation method of lithium dioxalate borate is needed, and the method can greatly avoid side reactions such as hydrolysis and the like in the prior art and improve the yield; the low purity of the product caused by caking and wrapping of the product can be avoided. In addition, the method can also greatly reduce the residual metal ions in the product.
Disclosure of Invention
The above and other deficiencies of the prior art are addressed by exemplary embodiments of the present invention.
In one aspect, the present invention provides a method of preparing lithium dioxalate borate, the method comprising:
(1) Providing a mixture comprising an oxalic acid compound, an alkaline lithium salt, and a boron-containing compound;
(2) Reacting the mixture at a temperature of 50-200 ℃ to form a product comprising lithium dioxalate borate;
in step (2), moisture is removed from the reacted mixture.
In an embodiment of the invention, the lithium dioxalate borate containing product is dehydrated at a temperature of from 150 to 250 ℃ to provide an anhydrous lithium dioxalate borate containing product.
In an embodiment of the present invention, the molar ratio of oxalic acid compound, alkaline lithium salt and boron-containing compound is C 2 O 4 2- ∶Li∶B＝(2-2.2)∶(1-1.1)∶1。
In an embodiment of the invention, in step (2), the reaction removes moisture from the reaction mixture under stirring.
In an embodiment of the invention, the method is performed in a glass, glass lined or nickel based alloy container.
In an embodiment of the present invention, the oxalic acid compound comprises anhydrous oxalic acid, oxalic acid hydrate, or a mixture thereof.
In an embodiment of the present invention, the alkaline lithium salt comprises lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, lithium bicarbonate, lithium acetate, or a mixture of two or more thereof.
In an embodiment of the present invention, the boron-containing compound comprises boric acid, metaboric acid, or mixtures thereof.
In an embodiment of the invention, the nickel-based alloy is selected from the group consisting of alloys of nickel with one or more of iron, zinc, copper, chromium, molybdenum and tungsten.
In another aspect, the present invention also provides a method for preparing an electrolyte of a lithium ion battery, the method comprising:
(a) Directly dissolving a substantially anhydrous lithium dioxalate borate-containing product in an electrolyte solvent without purification; and
(b) And filtering to obtain the lithium ion battery electrolyte.
The invention has the beneficial effects that: the method for preparing the lithium dioxalate borate can ensure that no side reaction exists basically, and improves the yield. In addition, the method can also reduce or eliminate caking and wrapping phenomena of the product, and improve the purity of the product. In addition, the method can also greatly reduce the residual metal ions in the product. In addition, the product containing lithium dioxalate borate prepared by the method for preparing lithium dioxalate borate is dissolved in an electrolyte solvent under the condition of no purification, and is directly used as lithium ion electrolyte after being filtered.
The invention may be better understood by describing exemplary embodiments thereof in conjunction with the accompanying drawings. In the drawings of which there are shown,
FIG. 1 shows a solid core magnet of lithium dioxalate borate prepared in accordance with an embodiment of the present invention 11 B spectrum.
FIG. 2 shows a Fourier transform infrared absorption spectrum (FTIR) of lithium dioxaborate prepared in an embodiment of the present invention.
The present invention will be described more fully hereinafter with reference to exemplary embodiments thereof. These exemplary embodiments are described so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Indeed, this invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; and, these embodiments are provided so that this disclosure will satisfy applicable legal requirements.
In the present invention, the lithium dioxalate borate has the following structure:
in the present invention, the oxalic acid compound comprises the following structure:
in the present invention, the method for preparing lithium dioxalate borate comprises: a mixture comprising an oxalic acid compound, an alkaline lithium salt, and a boron-containing compound is provided. In some embodiments, the oxalic acid compound, the alkaline lithium salt, and the boron-containing compound are mixed, blended, and stirred simultaneously to provide the mixture. The mixing, blending and stirring may be performed by batch mixing, continuous mixing, mechanical mixing, gravity mixing, etc. The equipment used for the above mixing, blending and agitation may be well known to those of ordinary skill in the art, including but not limited to: coulter mixer, ribbon mixer, gravity-free mixer, V-shaped mixer, double helix conical mixer, high-low speed liquid mixer, planetary power mixer, etc.
In the present invention, the mixture comprising oxalic acid compound, alkaline lithium salt and boron-containing compound may be reacted at a temperature of 50-200 ℃, 70-200 ℃, 90-200 ℃, 110-200 ℃, 130-200 ℃, 160-200 ℃, 50-160 ℃, 70-160 ℃, 90-160 ℃, 110-160 ℃, 130-160 ℃, 50-130 ℃, 70-130 ℃, 90-130 ℃, 110-130 ℃, 50-110 ℃, 70-110 ℃, 90-110 ℃, 50-90 ℃, 70-90 ℃ or 50-70 ℃. In a specific embodiment, the mixture comprising oxalic acid compound, alkaline lithium salt and boron-containing compound may be reacted at a temperature of 105-125 ℃.
In some embodiments of the invention, the reaction may be carried out with stirring. Typically, the stirring speed may be 100-600 revolutions per minute (rpm), 100-500 revolutions per minute, 100-400 revolutions per minute, 100-200 revolutions per minute, 200-600 revolutions per minute (rpm), 200-500 revolutions per minute, 200-400 revolutions per minute, 400-600 revolutions per minute (rpm), 400-500 revolutions per minute, or 500-600 revolutions per minute (rpm).
In some embodiments of the invention, the reaction may be carried out for a period of time ranging from 6 to 48 hours, from 6 to 36 hours, from 6 to 24 hours, from 6 to 12 hours, from 12 to 48 hours, from 12 to 36 hours, from 12 to 24 hours, from 24 to 48 hours, from 24 to 36 hours, or from 36 to 48 hours.
In some embodiments of the invention, the reaction may be carried out under an air-tight or inert atmosphere (e.g., nitrogen, etc.).
In the present invention, the reaction requires removal of water from the reaction mixture under conditions of water extraction, that is, water removal. In some embodiments of the invention, the reaction may be carried out under normal pressure and under negative pressure. The reaction under negative pressure facilitates rapid removal of moisture from the reaction system. In an embodiment of the invention, the reaction may remove moisture from the reaction mixture under agitation.
In some embodiments of the invention, the moisture is removed from the reaction system at a rate of 100 to 150 grams of water per minute per 400 grams of oxalic acid compound, 100 to 125 grams of water per minute per 400 grams of oxalic acid compound, or 125 to 150 grams of water per minute per 400 grams of oxalic acid compound. In some embodiments of the invention, the proportion of water removed to the total amount of water in the reaction system is 90-98 wt.%, 90-95 wt.%, 90-93 wt.%, or 93-95 wt.%. Typically, the remaining moisture may be removed in a subsequent dewatering operation.
In the present invention, the oxalic acid-containing compound, the alkaline lithium salt and the boron-containing compound may be mixed and reacted in stoichiometric proportions. In some embodiments, the molar ratio of oxalic acid compound, alkaline lithium salt, and boron-containing compound is C 2 O 4 2- Li to B= (2-2.2) to (1-1.1) to 1, (2-2.1) to (1-1.1) to 1 or (2-2.2) to (1-1.05) to 1. In a specific embodiment, the molar ratio of oxalic acid compound, alkaline lithium salt and boron-containing compound may be C 2 O 4 2- ∶Li∶B＝2.05∶1∶1。
In an embodiment of the present invention, the oxalic acid compound includes anhydrous oxalic acid (C 2 H 2 O 4 ) Oxalic acid hydrate (e.g. oxalic acid dihydrate C 2 H 2 O 4 ·2H 2 O) or mixtures thereof. Typically, the oxalic acid compound has a purity requirement of 95% or more, 96% or more, 97% or more, 98% or more, or 99% or more.
In an embodiment of the present invention, the alkaline lithium salt includes lithium hydroxide (LiOH), lithium hydroxide monohydrate (LiOH H 2 O), lithium carbonate (Li) 2 CO 3 ) Lithium bicarbonate (LiHCO) 3 ) Lithium acetate or a mixture of two or more thereof. Typically, the purity requirement of the alkaline lithium salt is 95% or more, 96% or more, 97% or more, 98% or more, or 99% or more. For lithium hydroxide monohydrate, the content of lithium hydroxide is 56% or more.
In an embodiment of the present invention, the boron-containing compound comprises boric acid (H 3 BO 3 ) Metaboric acid (HBO) 2 ) Or a mixture thereof. Typically, the purity requirement of the boron-containing compound is 95% or more, 96% or more, 97% or more, 98% or more, or 99% or more.
In one embodiment of the present invention, the reaction of a mixture comprising lithium hydroxide, anhydrous oxalic acid and boric acid to prepare lithium dioxalate borate is shown below:
LiOH+2H 2 C 2 O 4 +H 3 BO 3 →LiB(C 2 O 4 ) 2 +4H 2 O。
in the present invention, the lithium dioxalate borate-containing product may be dehydrated at a temperature of 150-250 ℃, 180-250 ℃, 200-250 ℃, 230-250 ℃, 150-230 ℃, 180-230 ℃, 200-230 ℃, 150-200 ℃, 180-200 ℃ or 150-180 ℃. In a specific embodiment, the lithium dioxalate borate-containing product may be dehydrated at a temperature of 150 to 200 ℃. By dehydration, the present invention can provide a substantially anhydrous product containing lithium dioxalate borate. In the present invention, the term "substantially" means that the water content in the product is less than 200ppm, 100ppm, or even less than 50 ppm.
In an embodiment of the invention, the method is performed in a glass, glass lined or nickel based alloy container (including stirring devices, etc., e.g., stirring devices may be made of nickel based alloy). This can avoid the introduction of other metal ions during stirring due to the friction of the reaction raw materials, stirring equipment, etc. with the reaction vessel, resulting in subsequent additional purification steps.
In an embodiment of the invention, the nickel-based alloy is selected from the group consisting of alloys of nickel with one or more of iron, zinc, copper, chromium, molybdenum and tungsten. In particular embodiments, the nickel-based alloy materials include, but are not limited to: nickel-copper alloy, nickel-zinc alloy, nickel-chromium alloy, nickel-molybdenum alloy, nickel-chromium-molybdenum-copper alloy, nickel-chromium-molybdenum-tungsten alloy, and the like.
The lithium dioxalate borate prepared by the invention can be used for conveniently preparing lithium ion battery electrolyte. The lithium dioxalate borate prepared by the method can be directly dissolved in an electrolyte solvent under the condition of no need of additional treatment such as purification and the like, and the electrolyte which can be used for a lithium ion battery is directly obtained after filtration.
The product comprising lithium dioxaborate formed by the reaction of the present invention has sufficient purity (e.g., 95% or more, 96% or more, 97% or more, 98% or more, or 99% or more) that can be directly dissolved in a solvent of an electrolyte for a lithium ion battery without additional treatment such as purification. The solvent may be a solvent commonly used in the field of lithium ion battery electrolytes, for example, a mixed solvent of the following three components: dimethyl carbonate, ethylene carbonate and ethylmethyl carbonate in a mass ratio of 1:1:1). Dissolving according to the concentration of 0.8mol/l, and filtering to remove undissolved substances to obtain colorless transparent liquid, namely the lithium ion battery electrolyte.
In other embodiments of the invention, the product containing lithium dioxalate borate obtained by the invention can also be extracted and purified by using a solvent to remove insoluble impurities, thereby obtaining transparent liquid containing lithium dioxalate borate. In a further embodiment, the transparent liquid may remove the solvent to provide a lithium dioxalate borate solid. The solvent molecules wrapped in the solvent can be further removed by decompression and drying, and the solvent-free lithium dioxalate borate product is obtained. The solvent may be selected from one or more of ethyl acetate, methyl acetate, acetonitrile, propylene carbonate, dimethyl carbonate, methylethyl carbonate, acetone, tetrahydrofuran.
In the invention, oxalic acid compound, boron-containing compound and alkaline lithium salt are mechanically mixed in a container made of glass base material or nickel-based alloy, then the temperature is raised to react and water is collected, and high-temperature dehydration is carried out subsequently, so that the anhydrous lithium dioxalate borate product can be prepared. In the product, the contents of water and metal ions are very low, and the product can be directly used as an electrolyte additive to be configured into lithium ion electrolyte, so that the subsequent complicated solvent extraction or recrystallization process and the like are avoided.
Examples
The experimental procedures, which are not specified in the following examples, are generally carried out under conventional conditions or under conditions recommended by the manufacturer. All percentages are by weight unless otherwise indicated.
In the examples, the reaction starting materials are as follows:
oxalic acid dihydrate: purchased from eastern mountain Fengyuan Fine materials Co., ltd or Anhui Dongfeng chemical Co., ltd;
boric acid: purchased from borax group U.S. BORAX.INC); and
lithium hydroxide monohydrate: purchased from Sichuan far lithium industry Co., ltd or Chengdu Sulfan high energy chemical industry Co., ltd.
< determination of product component >
The obtained product is subjected to 11 B solid state nuclear magnetic resonance spectroscopy and fourier transform infrared absorption spectroscopy (FTIR). As shown in fig. 1 and 2, it was confirmed that the present invention prepares lithium dioxalate borate.
< determination of moisture content >
Moisture content was determined by interference-free karl Fei Kulun titration on the basis of N-methylformamide (W.Larsson, J.C.Panitz, A.Cedergren.Talanta,2006, 69:276-280).
< measurement of Metal ion >
The content of the main metal impurity ions is determined by inductively coupled plasma atomic emission spectrometry (e.g., JY/T015-1996 general rule of inductively coupled plasma atomic emission spectrometry). In the invention, the content of metal impurity ions is lower than the industry standard required by the electrolyte of the lithium ion battery.
Example 1
126g (1 mol) of oxalic acid dihydrate, 30.9g (0.5 mol) of boric acid and 21g (0.5 mol) of lithium hydroxide monohydrate were mechanically mixed and then charged into a three-necked glass flask with stirring of a nickel-chromium alloy. Under normal pressure, the mixture was stirred vigorously at a stirring speed of 150 rpm, and the temperature was raised to 110℃to effect a reaction, with 53 g of water being taken during the reaction. The obtained reactant is pasty, and is continuously heated to 150 ℃ for dehydration to form powdery product. The temperature is continuously increased, and the rapid stirring and dehydration are continuously carried out for 2 hours at 160 ℃ until the water is basically free. During dewatering, 26 grams of produced water was collected.
Next, the product was cooled to room temperature under exclusion of air, yielding 95.3g of lithium dioxalate borate solid.
The water content of the lithium dioxalate borate solid was measured to be 76ppm, and the purity of the lithium dioxalate borate was measured to be 99.15%. The yield of lithium dioxalate borate was calculated to be 97.51%.
Further, the lithium dioxaborate solid had an iron ion content of 0.4ppm, a chromium ion content of 0.5ppm and a nickel ion content of 0.6ppm.
Example 2
138g (1.095 mol) of oxalic acid dihydrate, 30.9g (0.5 mol) of boric acid and 22g (0.524 mol) of lithium hydroxide monohydrate are mechanically mixed and then added to a nickel-chromium-molybdenum alloy reaction kettle with stirring of the nickel-chromium-molybdenum alloy. Under normal pressure, the mixture was stirred vigorously at a stirring speed of 150 rpm, and the temperature was raised to 115℃to effect a reaction, and 57 g of water was collected during the reaction. The obtained reactant is pasty, and is continuously heated to 155 ℃ for dehydration to form powdery product. Continuously heating to 180 ℃, continuously and rapidly stirring and dehydrating for 2 hours until the water is basically free. During dewatering, 27 grams of produced water was collected.
Next, the product was cooled to room temperature under exclusion of air, yielding 95.8g of lithium dioxalate borate solid.
The water content of the lithium dioxalate borate solid is 38ppm, and the purity of the lithium dioxalate borate is 98.45 percent. The yield of lithium dioxalate borate was calculated to be 97.34%.
Further, the lithium dioxaborate solid had an iron ion content of 0.5ppm, a chromium ion content of 0.6ppm and a nickel ion content of 0.6ppm.
Comparative example 1
126g (1.0 mol) of oxalic acid dihydrate and 30.9g (0.5 mol) of boric acid are mixed strongly, the temperature is raised to 90-120 ℃ to collect water, 21g (0.5 mol) of aqueous solution of lithium hydroxide monohydrate is dripped into a three-neck flask (a stirring device with a Teflon coating), water is collected to pasty by reaction at 110 ℃, and the temperature is continuously raised to 180-200 ℃ to be in a block shape in the flask until the water is basically absent.
After the reaction, the mixture was cooled to room temperature under the exclusion of air to obtain 91.5g of lithium dioxalate borate solid, wherein the water content was 235ppm, the purity was 65.5%, and the yield was 61.85%. The lithium dioxalate borate solid has an iron ion content of 1.5ppm, a chromium ion content of 1.2ppm and a nickel ion content of 0.3ppm.
Comparative example 2
126g (1.0 mol) of oxalic acid dihydrate and 30.9g (0.5 mol) of boric acid are mixed strongly, the temperature is raised to 90-120 ℃ to collect water, 21g (0.5 mol) of aqueous solution of lithium hydroxide monohydrate is dripped into a 304 stainless steel kettle with stirring, the reaction is carried out at 110 ℃ to collect water to pasty, and the temperature is raised to 180-200 ℃ to form blocks in the kettle until the water is basically absent.
After the reaction, the mixture was cooled to room temperature under the exclusion of air to obtain 93.1g of lithium dioxalate borate solid, 187ppm of water, 63.2% of purity and 60.72% of yield. The lithium dioxalate borate solid had an iron ion content of 160ppm, a chromium ion content of 36ppm and a nickel ion content of 18ppm.
It will be appreciated that various changes and modifications may be made by those skilled in the art after reading the above teachings, and such equivalents are intended to fall within the scope of the claims appended hereto.
Claims (10)
- A method of preparing lithium borate di-oxalate, the method comprising:(1) Providing a mixture comprising an oxalic acid compound, an alkaline lithium salt, and a boron-containing compound;(2) Reacting the mixture at a temperature of 50-200 ℃ to form a product comprising lithium dioxalate borate;in step (2), moisture is removed from the reacted mixture.
- The method of claim 1, wherein the lithium dioxalate borate containing product is dehydrated at a temperature of 150-250 ℃ to provide an anhydrous lithium dioxalate borate containing product.
- The method according to claim 1, wherein the molar ratio of oxalic acid compound, alkaline lithium salt and boron-containing compound is C 2 O 4 2- ∶Li∶B＝(2-2.2)∶(1-1.1)∶1。
- The process of claim 1, wherein in step (2), the reaction removes moisture from the reacted mixture with agitation.
- The method according to any of claims 1-4, wherein the method is performed in a glass, glass lined or nickel based alloy container.
- The method of any one of claims 1-4, wherein the oxalic acid compound comprises anhydrous oxalic acid, oxalic acid hydrate, or a mixture thereof.
- The method of any one of claims 1-4, wherein the alkaline lithium salt comprises lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, lithium bicarbonate, lithium acetate, or a mixture of two or more thereof.
- The method of any one of claims 1-4, wherein the boron-containing compound comprises boric acid, metaboric acid, or mixtures thereof.
- The method of claim 5, wherein the nickel-based alloy is selected from the group consisting of alloys of nickel with one or more of iron, zinc, copper, chromium, molybdenum, and tungsten.
- A method of preparing a lithium ion battery electrolyte, the method comprising:(a) Directly dissolving the anhydrous lithium dioxalate borate-containing product prepared by the method of claim 2 in an electrolyte solvent without purification; and(b) And filtering to obtain the lithium ion battery electrolyte.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2021/107565 WO2023000198A1 (en) | 2021-07-21 | 2021-07-21 | Method for preparing lithium bisoxalate borate and method for preparing lithium-ion battery electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117897389A true CN117897389A (en) | 2024-04-16 |
Family
ID=84979693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180100855.XA Pending CN117897389A (en) | 2021-07-21 | 2021-07-21 | Preparation method of lithium dioxalate borate and preparation method of lithium ion battery electrolyte |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN117897389A (en) |
| WO (1) | WO2023000198A1 (en) |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914110B (en) * | 2010-07-21 | 2012-07-11 | 北京科技大学 | Method for synthesizing lithium bis(oxalate)borate by using rheological phase method |
| CN102627661A (en) * | 2011-09-09 | 2012-08-08 | 兰州理工大学 | Preparation method of lithium bis(oxalato)borate |
| KR101358682B1 (en) * | 2013-06-26 | 2014-02-07 | 주식회사 천보정밀 | Synthetic method of lithium bis(oxalato) borate |
| CN105732682B (en) * | 2016-03-24 | 2018-09-14 | 洛阳和梦科技有限公司 | Lithium borate base electrolyte solid phase production method |
| CN107602603A (en) * | 2017-10-13 | 2018-01-19 | 湖北省宏源药业科技股份有限公司 | A kind of preparation method of di-oxalate lithium borate |
| CN109232629A (en) * | 2018-11-28 | 2019-01-18 | 湖南科霸汽车动力电池有限责任公司 | The preparation method of di-oxalate lithium borate |
| CN109734734A (en) * | 2018-12-18 | 2019-05-10 | 朝阳光达化工有限公司 | A kind of preparation method of dioxalic acid lithium borate |
| CN109608485B (en) * | 2018-12-29 | 2020-09-08 | 湖北省宏源药业科技股份有限公司 | Method for continuously preparing lithium bis (oxalato) borate |
| CN111153918A (en) * | 2019-12-16 | 2020-05-15 | 山东石大胜华化工集团股份有限公司 | Preparation method of lithium bis (oxalato) borate |
| CN111943970B (en) * | 2020-09-03 | 2023-07-18 | 江苏华盛锂电材料股份有限公司 | Preparation method of lithium dioxalate borate |
-
2021
- 2021-07-21 CN CN202180100855.XA patent/CN117897389A/en active Pending
- 2021-07-21 WO PCT/CN2021/107565 patent/WO2023000198A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023000198A1 (en) | 2023-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2738861B1 (en) | Method for producing lithium tetrafluoroborate solution | |
| CN100593515C (en) | Method of preparing waterless lithium terafluoroborate | |
| JP6226643B2 (en) | Method for producing lithium difluorophosphate | |
| CN102070661B (en) | Preparation method of high-purity lithium oxalyldifluoroborate | |
| CN108640096B (en) | Preparation method of difluorophosphoric acid and difluorolithium phosphate | |
| CN112707418B (en) | Preparation method of lithium hexafluorophosphate | |
| CN114590785B (en) | Preparation method of lithium bis (fluorosulfonyl) imide and lithium ion battery | |
| CN113948697A (en) | Doped sodium iron phosphate cathode material and preparation method and application thereof | |
| CN102502504A (en) | Method for preparing iodized salt from iodine-contained absorption solution | |
| CN111943970B (en) | Preparation method of lithium dioxalate borate | |
| CN109608485B (en) | Method for continuously preparing lithium bis (oxalato) borate | |
| WO2016072158A1 (en) | Method for purifying electrolyte solution and method for producing electrolyte solution | |
| CN108706565B (en) | Preparation method of lithium difluorophosphate | |
| CN113929711A (en) | Preparation method of lithium difluoroborate | |
| Masuya-Suzuki et al. | Selective crystallization of dysprosium complex from neodymium/dysprosium mixture enabled by cooperation of coordination and crystallization | |
| CN110683564B (en) | Lithium hexafluorophosphate-containing mixture crystal and application thereof | |
| CN117897389A (en) | Preparation method of lithium dioxalate borate and preparation method of lithium ion battery electrolyte | |
| JP6097111B2 (en) | Method for producing lithium fluoride powder and method for producing lithium hexafluorophosphate | |
| CN109796481B (en) | High-purity lithium bis (oxalato) borate prepared by high-temperature aqueous phase method and application thereof | |
| CN111116624A (en) | Preparation method of lithium bis (oxalato) borate | |
| CN109053786B (en) | Preparation method of lithium bis (oxalato) borate | |
| CN111057082A (en) | Preparation method of lithium bis (oxalato) borate | |
| Zhou et al. | Synthesis of lithium difluoro (oxalate) borate (LiODFB), phase diagram and ions coordination of LiODFB in dimethyl carbonate | |
| JP3555720B2 (en) | Addition compound of lithium hexafluorophosphate, method for producing the same, and electrolyte using the same | |
| CN117088390B (en) | Preparation method of hexafluorophosphate, electrolyte and secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication |