244761-29-3

Basic information

• Product Name: Lithium bis(oxalate)borate
• Synonyms: LIBOB;lithium bis(oxalate)borate;LITHIUM BIS(OXALATO)BORATE;CHEMLYTE BO M1;CHEMLYTE BO MX;LITHIUM BIS (OXALATE) BORATE(LiBOB);Borate(1-), bis(ethanedioato(2-)-kappao1,kappao2)-, lithium (1:1), (T-4)-;Borate(1-), bis(ethanedioato(2-)-kappao1,kappao2)-, lithium, (T-4)-
• CAS NO: 244761-29-3
• Molecular Formula: C₄BO₈*Li
• Molecular Weight: 193.79
• Mol File: 244761-29-3.mol
• Article Data: 13

Chemical Properties

• Melting Point: >300°C (lit.)
• Appearance: /
• Vapor Pressure: 0.004Pa at 20℃
• Storage Temp.: Inert atmosphere,Room Temperature
• Water Solubility: 1015g/L at 20℃
• CAS DataBase Reference: Lithium bis(oxalate)borate(CAS DataBase Reference)
• NIST Chemistry Reference: Lithium bis(oxalate)borate(244761-29-3)
• EPA Substance Registry System: Lithium bis(oxalate)borate(244761-29-3)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26
• WGK Germany: 3
• Hazardous Substances Data: 244761-29-3(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 244761-29-3 differently. You can refer to the following data:
1. Lithium bis(oxalate)borate is a new and proprietary conductive salt for the use in high performance batteries like lithium batteries, lithium ion batteries and lithium polymer batteries. The new halide-free product may be used instead of traditional fluorinated compounds like LiPF6, LiBF4, Li-triflate, methanides, imides etc.
2. LiBOB is a novel boron based Li salt electrolyte material for Li ion batteries. It is environmentally friendly with good film forming property and high thermal stability and is compatible with a variety of anodes and metal oxide cathode.

General Description

This product has been enhanced for energy efficiency.

Flammability and Explosibility

Nonflammable

InChI:InChI=1/C4H2BO11.3Li/c6-1(7)3(10)13-15-5(12)16-14-4(11)2(8)9;;;/h(H,6,7)(H,8,9);;;/q-1;3*+1/p-2

Synthetic route

Glyoxal (131543-46-9) + boron fluoridedichloride (14720-30-0) → lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3)

Conditions	Yield
In 1,4-dioxane at 30℃; under 0 Torr; for 3h; Flow reactor;	99.2%

lithium tetrafluoroborate + silicon dimethyl oxalate → lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3)

Conditions	Yield
In acetonitrile at 43 - 57℃; for 11h; Inert atmosphere;	98.8%

lithium difluoromono[1,2-oxalato(2-)-O,O'] borate (409071-16-5) → lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3)

Conditions	Yield
With 1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)propane; 2,3-(4-formylbenzo)-1,4,7,10-tetraoxa-2-cyclododecene; 10-benzyl-1,4,7-trioxa-10-azacyclododecane at 90℃; under 900.09 Torr; for 5h; Inert atmosphere;	93%

bis(trimethylsilyl)ethanedioic acid ester (18294-04-7) → lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3)

Conditions	Yield
With lithium tetramethanolatoborate In acetonitrile at 45 - 50℃;	92%

lithium hydroxide monohydrate (1310-66-3) + tris-(triethylsilyl)-borate (18546-66-2) + oxalic acid (144-62-7) → lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3)

Conditions	Yield
Stage #1: lithium hydroxide monohydrate; oxalic acid In tetrahydrofuran for 2h; Reflux; Stage #2: tris-(triethylsilyl)-borate at 150℃; for 1h;	83.3%

lithium hydroxide monohydrate (1310-66-3) + tris(trimethylsilyl)borate (4325-85-3) + oxalic acid (144-62-7) → lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3)

Conditions	Yield
Stage #1: lithium hydroxide monohydrate; oxalic acid In N,N-dimethyl-formamide at 100℃; for 1h; Stage #2: tris(trimethylsilyl)borate at 120℃; for 6h; Solvent; Temperature;	83.1%

tris(dimethylvinylsilyl) borate (383189-04-6) + oxalic acid (144-62-7) + lithium carbonate (554-13-2) → lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3)

Conditions	Yield
Stage #1: oxalic acid; lithium carbonate With 1,2-propylene cyclic carbonate at 200℃; for 1h; Stage #2: tris(dimethylvinylsilyl) borate at 250℃; for 2h;	81.9%

lithium hydroxide monohydrate (1310-66-3) + boric acid (11113-50-1) + oxalic acid (144-62-7) → lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3)

Conditions	Yield
Stage #1: lithium hydroxide monohydrate; boric acid; oxalic acid for 1h; Milling; Stage #2: at 240℃; for 6h; Temperature;	79.5%
In water at 80 - 85℃; for 24h; Solvent;	72%

boron trifluoride dimethyl carbonate complex + oxalic acid (144-62-7) + lithium fluoride → lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3)

Conditions	Yield
Stage #1: boron trifluoride dimethyl carbonate complex; lithium fluoride In dimethyl sulfoxide at 90℃; for 7h; Inert atmosphere; Stage #2: oxalic acid With tetrachlorosilane In dimethyl sulfoxide at 20 - 150℃; for 25h; Solvent; Temperature; Reagent/catalyst; Inert atmosphere;	60%

oxalic acid (144-62-7) → lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3)

Conditions	Yield
With lithium hydroxide; boric acid
With lithium hydroxide; boric acid at 179.84℃; for 2h;

boric acid (11113-50-1) + oxalic acid (144-62-7) + lithium hydroxide (1310-65-2) → lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3)

Conditions	Yield
In water evapn. of water from aq. solns. of oxalic acid, boric acid, and LiOH (2:1:1 mol.); refluxed with CH3CN; filtered; dried in vac. oven at 100°C for 2 d;

potassium hexafluorophosphate (17084-13-8) + oxalic acid (144-62-7) → lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3)

Conditions	Yield
Stage #1: potassium hexafluorophosphate; oxalic acid With tetrachlorosilane for 5h; Stage #2: With thionyl chloride at 45 - 70℃; for 2h;	10 g

lithium hydroxide monohydrate (1310-66-3) + boric acid (11113-50-1) + oxalic acid (144-62-7) → lithium oxalate (553-91-3) + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3)

Conditions	Yield
at 110℃; for 6h; Sealed tube;

boric acid (11113-50-1) + oxalic acid (144-62-7) → lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3)

Conditions	Yield
With lithium hydroxide In ethyl acetate; acetonitrile at 50℃; for 5.5h; Solvent; Reagent/catalyst; Temperature;

boron + oxalic acid (144-62-7) + lithium (7439-93-2) → lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3)

Conditions	Yield
at 80℃; for 4h; Milling;	48.72 g

1-butyl-3-methylimidazolium chloride (79917-90-1) + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → 1-butyl-3-methylimidazolium bis[oxalato(2-)]-borate

Conditions	Yield
In neat (no solvent) at 80℃; for 24h; Temperature;	95%
In acetonitrile byproducts: LiCl; onium chloride reacted with excess of Li orthoborate under refluxing for1-3 d; cooled; LiCl filtered off; solvent evapd. at reduced pressure; dried under vac. at 100°C for 1 d; dissolved (CH2Cl2); storage at room temp. overnight; filtered; solvent evapd.; dried under vac. at 90°C (2 d); detn. by NMR (weak Li signal);	76.8%
In acetonitrile Heating;

boron trifluoride dimethyl carbonate complex + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → lithium difluoromono[1,2-oxalato(2-)-O,O'] borate (409071-16-5)

Conditions	Yield
With lithium fluoride; Diethyl carbonate at 70℃; under 900.09 Torr; for 12h; Reagent/catalyst; Temperature;	95%

methoxyethyl dimethyl ethyl ammonium chloride + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → methoxyethyl dimethyl ethyl ammonium bis(oxalato)borate

Conditions	Yield
In acetonitrile Heating;	92%
In acetonitrile byproducts: LiCl; onium chloride reacted with excess of Li orthoborate under refluxing for1-3 d; cooled; LiCl filtered off; solvent evapd. at reduced pressure; dried under vac. at 100°C for 1 d; dissolved (CH2Cl2); store at room temp.overnight; filtered; solvent evapd.; dried in vac. oven at 90°C (2 d); detn. by NMR (weak Li signal);	92%

tetraethylammonium chloride (56-34-8) + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → tetraethylammonium bis(oxalate)borate

Conditions	Yield
In acetonitrile at 20℃;	90.6%

N,N,N’,N’-tetrakis[p-di(butyl)aminophenyl]-p-phenylene (4182-80-3) + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → C62H92N6(2+)*2C4BO8(1-)

Conditions	Yield
Stage #1: N,N,N’,N’-tetrakis[p-di(butyl)aminophenyl]-p-phenylene With silver nitrate In N,N-dimethyl-formamide at 70℃; for 5h; Inert atmosphere; Stage #2: lithium bis[1,2-oxalato(2-)-O,O'] borate at 20℃; Inert atmosphere;	90%

5-azoniaspiro<4.4>nonane bromide (16450-38-7) + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → spiro-(1,1')-bipyrrolidinium bis(oxalato)borate

Conditions	Yield
In acetonitrile at 20℃;	89.1%

methyl n-butylbis(diethylamino)phosphonium n-butyl sulfate (940301-94-0) + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → methyl n-butylbis(diethylamino)phosphonium bis(oxalato)borate

Conditions	Yield
In acetonitrile at 20℃; for 48h;	87%

lithium hexafluorophosphate (21324-40-3) + boron trifluoride diethyl etherate (109-63-7) + lithium fluoride + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → lithium difluoromono[1,2-oxalato(2-)-O,O'] borate (409071-16-5) + lithium tetrafluoroborate

Conditions	Yield
at 70℃; for 9h; Reagent/catalyst; Solvent; Time;	A 86% B 9%

1-ethyl-3-methyl-1H-imidazol-3-ium chloride (65039-09-0) + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → 1-ethyl-3-methylimidazolium bis(oxalato)borate

Conditions	Yield
In neat (no solvent) at 80℃; for 24h; Temperature;	82%
In dichloromethane

N,N-dimethylpyrrolidinium iodide (872-44-6) + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → 1,1-dimethylpyrrolidinium bis(oxalato)borate

Conditions	Yield
In acetonitrile at 20℃;	80.1%

yttrium(III) chloride + N,N-dimethyl-formamide (68-12-2, 33513-42-7) + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → C2O4(2-)*Li(1+)*3C3H7NO*Y(3+)*2Cl(1-)

Conditions	Yield
for 58h; Heating; Inert atmosphere; Schlenk technique; Glovebox;	76%

ethoxymethyl dimethyl ethyl ammonium chloride + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → ethoxymethyl dimethyl ethyl ammonium bis(oxalato)borate

Conditions	Yield
In acetonitrile Heating;	71.2%
In acetonitrile byproducts: LiCl; onium chloride reacted with excess of Li orthoborate under refluxing for1-3 d; cooled; LiCl filtered off; solvent evapd. at reduced pressure; dried under vac. at 100°C for 1 d; dissolved (CH2Cl2); store at room temp.overnight; filtered; solvent evapd.; dried in vac. oven at 90°C (2 d); detn. by NMR (weak Li signal);	71.2%

acetonitrile (75-05-8) + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → 1.8C2H3N*C4BO8(1-)*Li(1+)

Conditions	Yield
In toluene at 0℃; for 1.33333h; Inert atmosphere;	67%

1,2-propylene cyclic carbonate (108-32-7) + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → C4BO8(1-)*0.43C4H6O3*Li(1+)

Conditions	Yield
In toluene	64%

lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → lithium triborate + lithium oxalate (553-91-3)

Conditions	Yield
In neat (no solvent) byproducts: CO, CO2; heated at a heating rate of 1°C/min under N2 atm. to 490°Cin alumina crucible; monitored by X-ray diffraction and IR spectroscopy;

graphite + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → C(x)B[OC(O)C(O)O]2

Conditions	Yield
In nitromethane Electrochem. Process; electrochem. react. of satd. LiB(OOCCOO)2 soln. in nitromethane at ambient temp. under He/Ar using two-compartment cell with glass-frit separator, working electrode: dried cyclohecane slurry of graphite and inert polymer binder onto Pt mesh;

graphite + hydrogen fluoride (7664-39-3) + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → C41B[OC(O)C(O)O]2F4

Conditions	Yield
With fluorine In neat (no solvent) C and Li(O2CCO2)2 loaded into sepd. Teflon tubes, anhydrous HF (AHF) added, fluorine gas added for mins to an overpressure of 1200 Torr,. F2 removed, AHF poured in2. react. tube; rinsing 3 times by recondensing AHF, solube byproducts dissolved, solid dried under vac. for hs, elem. anal.;
With fluorine In water graphite and LiB(O2CCO2)2 loaded into sepd. Teflon tubes, anhydrous HF (AHF) condensed onto the salt, soln. poured onto graphite, F2 added for mins, P=1000-1200 Torr, AHF soln. poured into 2. react. tube, product rinsed 3 times by recondensing AHF; solid dried under vac. hs; elem. anal.;

graphite + hydrogen fluoride (7664-39-3) + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → C120B[OC(O)C(O)O]2F3.1

Conditions	Yield
With fluorine In neat (no solvent) C and Li(O2CCO2)2 loaded into sepd. Teflon tubes, anhydrous HF (AHF) added, fluorine gas added for mins to an overpressure of 1200 Torr,. F2 removed, AHF poured in2. react. tube; rinsing 3 times by recondensing AHF, solube byproducts dissolved, solid dried under vac. for hs, elem. anal.;
With fluorine In water graphite and LiB(O2CCO2)2 loaded into sepd. Teflon tubes, anhydrous HF (AHF) condensed onto the salt, soln. poured onto graphite, F2 added for mins, P=1000-1200 Torr, AHF soln. poured into 2. react. tube, product rinsed 3 times by recondensing AHF; solid dried under vac. hs, elem. anal.;

graphite + hydrogen fluoride (7664-39-3) + lithium bis[1,2-oxalato(2-)-O,O'] borate (244761-29-3) → C110B[OC(O)C(O)O]2F2.9

Conditions	Yield
With fluorine In neat (no solvent) C and Li(O2CCO2)2 loaded into sepd. Teflon tubes, anhydrous HF (AHF) added, fluorine gas added for mins to an overpressure of 1200 Torr,. F2 removed, AHF poured in2. react. tube; rinsing 3 times by recondensing AHF, solube byproducts dissolved, solid dried under vac. for hs, elem. anal.;
With fluorine In water graphite and LiB(O2CCO2)2 loaded into sepd. Teflon tubes, anhydrous HF (AHF) condensed onto the salt, soln. poured onto graphite, F2 added for mins, P=1000-1200 Torr, AHF soln. poured into 2. react. tube, product rinsed 3 times by recondensing AHF; solid dried under vac. hs, elem. anal.;

Upstream product

• 11113-50-1 boric acid 
• 144-62-7 oxalic acid 
• 7439-93-2 lithium 
• 7789-24-4 lithium fluoride 
• 409071-16-5 lithium difluoromono[1,2-oxalato^(2-)-O,O'] borate 
• 131543-46-9 Glyoxal 
• 14720-30-0 boron fluoridedichloride 
• 383189-04-6 tris(dimethylvinylsilyl) borate 
• 554-13-2 lithium carbonate 
• 1310-66-3 lithium hydroxide monohydrate 
• 4325-85-3 tris(trimethylsilyl)borate 
• 18546-66-2 tris-(triethylsilyl)-borate 
• 17084-13-8 potassium hexafluorophosphate 
• 1310-65-2 lithium hydroxide 

Downstream Products

• 409071-16-5 lithium difluoromono[1,2-oxalato^(2-)-O,O'] borate 
• 553-91-3 lithium oxalate 

Relevant articles and documents

Preparation of LiBOB via rheological phase method and its application to mitigate voltage fade of Li1.16[Mn0.75Ni0.25]0.84O2 cathode

Lithium bis(oxalato)borate (LiBOB) was synthesized via a novel rheological phase reaction method without any recrystallization procedure. The purity of the as-obtained LiBOB has been identified in comparison with the commercial sample and our sample prepared from solid-state reaction method. The results of XRD, ICP, and 11B NMR demonstrate that high pure LiBOB has been synthesized via rheological phase reaction method with significantly simplified synthetic process. Moreover, LiBOB sample has been investigated as electrolyte additive to improve the electrochemical performances of high-energy lithium-rich layered oxide. The cycling performances imply that 0.03 M and 0.05 M LiBOB additive can mitigate discharge voltage fade and enhance the cycle stability of Li1.16[Mn0.75Ni0.25]0.84O2 material. The CV, EIS and XPS data indicate that LiBOB oxidizes at ～4.3 V (vs. Li/Li+) on the cathode surface during the first charge to form a specific SEI layer with larger amount of organic species and fairly less content of LiF, which decreases the interfacial polarization and protects the active material from surface degradation, thereby mitigates the voltage-fade of Li-rich cathode.

Preparation method of lithium bis(oxalato)borate

The invention discloses a preparation method of lithium bis(oxalato)borate. The preparation method mainly comprises: synthesizing a lithium bis(oxalato)borate crude product, concentrating, crystallizing and purifying, and specifically comprises the following steps: weighing and uniformly mixing elemental boron, lithium powder and anhydrous oxalic acid to obtain a raw material mixture; putting theraw material mixture into a ball mill, performing a normal-pressure reaction for 2-6 h, then adding an organic solvent, and performing wet grinding to obtain a solution containing the lithium bis(oxalato)borate crude product; and concentrating, crystallizing and filtering the solution containing the lithium bis(oxalato)borate crude product, and then drying to obtain the lithium bis(oxalato)borate.Production links are few, purification is convenient, the purity of the prepared lithium bis(oxalato)borate product can reach 99.99%, the moisture content is lower than 10 ppm, and the production requirements of lithium ion battery electrolytes are met.

Preparation method of bis(oxalate)borate

The invention relates to the technical field of preparation of lithium battery electrolyte additives, in particular to a preparation method of bis(oxalate)borate. The preparation raw materials of thebis(oxalate)borate at least comprise dialkyl silicon oxalate and MBF4, wherein M is selected from any one of Li, Na, K, Rb and Cs. The bis(oxalate)borate is prepared from at least dialkyl oxalate estersil and MBF4, wherein M is selected from any one of Li, Na, K, Rb and Cs. According to the preparation method of the bis(oxalate)borate, the conversion rate of a target product is higher, the reaction product is single, and almost no by-product is generated; water and oxalic acid are not introduced in the technological process, the reaction and purification process is simple and convenient, and the product quality is easy to control; and almost no three wastes are generated in the implementation process, and a produced recovered solvent and a filtered mother liquor can be repeatedly used after distillation.

Preparation method and purification method of compound comprising at least one cyclic ligand structure

The invention discloses a preparation method and a purification method of a compound comprising at least one cyclic ligand structure. The compound comprising the at least one cyclic ligand structure comprises 1-2 cyclic ligands in different structures, namely a cyclic ligand containing La and/or a cyclic ligand containing Lb, wherein the cyclic ligand containing La comprises one of sulfuryl (-SO2-), sulfinyl (-SO-) and carbonyl. The compound can serve as electrolyte lithium salt of a lithium ion battery independently, and is dissolved in an organic solvent for preparing an electrolyte solutionof the lithium ion battery; or, the compound and the lithium salt are dissolved in the organic solvent to prepare the electrolyte solution of the lithium ion battery; and the electrolyte solution canobviously improve internal resistance of the lithium ion battery and has an effect on cycle performance of the battery.