Lithium Bis(oxalato)borate

• CAS: 244761-29-3
• Catalog Number: ACM244761293-5
• Category: Main Products
• Molecular Weight: 193.79
• Molecular Formula: LiB(C2O4)2
• Description: Lithium bis(oxalato)borate (LiBOB) is a lithium-boron salt for use as an electrolyte material in lithium ion batteries.
• Synonyms: Lithium bis(oxalate)borate, LiBOB, Lithium bis(ethanedioato)borate, LiBOB abg, Lithium bis-(oxalato)borate advanced battery grade, lithium bisoxylate borate
• IUPAC Name: lithium;1,4,6,9-tetraoxa-5-boranuidaspiro[4.4]nonane-2,3,7,8-tetrone
• Canonical SMILES: [Li+].[B-]12(OC(=O)C(=O)O1)OC(=O)C(=O)O2
• InChI: InChI=1S/C4BO8.Li/c6-1-2(7)11-5(10-1)12-3(8)4(9)13-5;/q-1;+1
• InChI Key: NVQAYVUCVASGDK-UHFFFAOYSA-N
• Melting Point: >300 ℃
• Appearance: White powder or crystals
• Complexity: 280
• Covalently-Bonded Unit Count: 2
• EC Number: 456-990-3;607-383-9
• Exact Mass: 193.984626g/mol
• Formal Charge: 0
• Hazard Statements: H315-H319-H335
• H-Bond Acceptor: 9
• H-Bond Donor: 0
• Heavy Atom Count: 14
• MDL Number: MFCD07776904
• Monoisotopic Mass: 193.984626g/mol
• Precautionary Statements: P261-P264-P271-P280-P302+P352-P304+P340-P305+P351+P338-P312-P321-P332+P313-P337+P313-P362-P403+P233-P405-P501
• Rotatable Bond Count: 0
• Signal Word: Warning

Case Study

Lithium Bis(oxalato)borate Enables High-Performance Blend Electrolytes via In Situ LiDFOB Formation

Schedlbauer, T., et al. Electrochimica Acta 107 (2013): 26-32.

Lithium bis(oxalato)borate (LiBOB) was blended with lithium tetrafluoroborate (LiBF4) in ethylene carbonate (EC) : diethyl carbonate (DEC) (3:7 wt.) electrolytes to investigate lithium cycling performance on copper substrates. This approach was motivated by observed ligand exchange phenomena in borate salts.
Mechanism
NMR confirmed spontaneous ligand exchange occurs at room temperature in LiBOB/LiBF4 blends, generating trace lithium difluoro(oxalato)borate (LiDFOB). This in situ LiDFOB formation is critical for optimizing solid electrolyte interphase (SEI) composition and enhancing electrochemical stability.
Key Results
· Coulombic Efficiency: Increased with higher LiBF4 content; nearly matched pure LiDFOB at high current densities.
· SEI Composition (XPS): Progressively resembled LiDFOB-derived SEI as LiBF4 content increased.
· Electrochemical Behavior: Superior lithium cycling vs. single-salt electrolytes (LiBOB or LiBF4 alone). Voltage drop, conductivity measurement and AC impedance measurement all indicate good performance of LiBOB/LiBF4 blends.

Lithium Bis(Oxalato)Borate in Polymer Electrolytes for Li-Ion Batteries

Swiderska-Mocek, Agnieszka, et al. Solid State Ionics 364 (2021): 115628.

Lithium bis(oxalato)borate (LiBOB) or lithium difluoro(oxalato)borate (LiODFB) were evaluated as a key lithium salt in polymer electrolytes for Li-ion polymer batteries in this work. The system combined LiBOB/LiODFB with an ionic liquid (EtMeImNTf2 or MePrPyrNTf2), sulfolane (TMS), and PVdF to form flexible, transparent membranes.
Key Results
· The conductivity of the polymer electrolytes varied between 0.52 and 3.21 mS cm-1, with activation energies of 34.24 and 19.58 kJ mol-1, respectively. The decomposition of the polymer electrolytes does not produce flammable byproducts. The presence of large pores in the membranes facilitates improved lithium ion transport.
· These polymer electrolytes were utilized as electrolytes in Li|LiFePO4 and Li|Li cells, which underwent testing through EIS, cyclic voltammetry, and galvanostatic methods. The electrochemical formation of a solid electrolyte interphase (SEI) helps safeguard the Li|polymer electrolyte system from aging, as indicated by the minimal impedance increase over time.
· Testing revealed that the LiFePO4 cathode using the membrane (comprising 23.9 wt% PVdF, 2.1 wt% LiBOB, 51.8 wt% EtMeImNTf2, and 22.2 wt% TMS) achieved a commendable reversible capacity of 130 mAh g-1 and 106 mAh g-1 at elevated current densities (C/2 and 1C rates). After 50 cycles at a C/10 rate, the discharge specific capacity of LFP|PE 2 reached 164 mAh g-1.

Lithium bis(oxalato)borate as a lithium battery additive

Li, Jianing, et al. Advanced Energy Materials 13.35 (2023): 2301422.

Lithium bis(oxalato)borate (LiBOB) is one of the most commonly used film-forming electrolyte additives in lithium-ion forming batteries (LIBs). It can act as a dense boron-containing polymer solid electrolyte layer (or diabetic interlayer) to isolate the electrode reaction from the electrolyte and prevent hydrofluoric acid. LiBOB can act as a fluoric acid (HF) scavenger to avoid the structural damage of transition metals to dissolve the repair agent caused by hydrofluoric acid (HF). LiBOB can also react with lithium fluorophosphate (LiPF6) to form lithium difluorooxalatoborate (LiDFOB), which can further activate the scavenger of active oxygen activation in the near future. This article lists the application of LiBOB in high-capacity and high-voltage potential materials, and reviews the role of LiBOB in these materials in improving the performance of lithium-ion batteries.
To solve the problem of thermal runaway, researchers have discovered another lithium salt, LiFSI, which has a higher decomposition temperature (>200°C) and better moisture stability. However, the synthesis process of LiFSI is still relatively expensive, and LiFSI easily corrodes the positive electrode current collector aluminum foil at high concentrations and high voltages. The researchers found that adding a small amount of LiBOB as an additive or reducing Cl- impurities during the synthesis process can reduce corrosion. When 0.2 mol/L LiFSI was added to a 1.0 mol/L LiPF6-based electrolyte, it was found that the cycle stability and rate performance of the graphite anode were significantly improved, while the addition of 0.2 mol/L LiBOB can passivate the surface of the aluminum foil and reduce the corrosion of LiFSI. LiBOB can react with aluminum foil to form an AlBO3 passivation layer, and form a highly stable network structure on it as a protective layer, which maximizes the isolation of the electrolyte and reduces the corrosion of the electrolyte to the aluminum foil.

Electrochemical and thermal behavior of lithium bis(oxalato)borate (LiBOB) solutions

Larush-Asraf, L., et al. Journal of power sources 174.2 (2007): 400-407.

Lithium bis(oxalato)borate (LiBOB) has been proposed as an alternative salt to the commonly used electrolyte LiPF. There is evidence that the stability of lithium-ion battery electrodes in this salt solution is enhanced due to the unique surface chemistry developed in LiBOB solutions. The electrochemical and thermal properties of LiBOB solutions in mixtures of alkyl carbonates with inactive metals, graphite, and lithium electrodes were investigated. FTIR spectroscopy, XPS, EQCM, in situ AFM imaging, and DSC were used in conjunction with standard electrochemical techniques. The development of favorable surface chemistry in LiBOB solutions clearly demonstrates that this material provides better passivation for lithium and lithium graphite electrodes.
Solutions of 0.5 and 1 M lithium bis(oxalylformate)borate LiBOB and 1 M LiPF in PC, EC:DMC 1:1, and EC:PC 2:3 were prepared in a VAC glove box under high purity argon atmosphere. The surface films formed on polished high purity Ni foil and polarized in LiBOB solution and placed in a glove box under HO and CO free atmosphere were characterized by Fourier transform infrared (FTIR) spectroscopy and by XPS. Thermal analysis was performed using differential scanning calorimetry (DSC).

Lithium bis(oxalato)borate stabilizes graphite anodes in propylene carbonate

Xu, Kang, et al. Electrochemical and Solid-State Letters 5.11 (2002): A259.

Lithium bis(oxalato)borate (LiBOB) effectively stabilizes graphite anode materials in pure propylene carbonate (PC) while supporting reversible lithium ion intercalation/deintercalation. The ability of LiBOB to protect graphite in PC from exfoliation provides unprecedented flexibility for reformulating lithium-ion electrolytes, where replacement of PC with the high-melting-point solvent component ethylene carbonate is no longer limited by concerns about PC instability on the graphite anode surface.
Lithium bis(oxalato)borate is the only salt that successfully forms a protective film on graphite during the first lithiation process, preventing exfoliation even in pure PC. Lithium ion intercalation occurs at potentials below 0.20 V, and subsequent deintercalation occurs above 0.10 V, which is typical of lithiated graphene structures. In LiBOB/PC, it is 82%, indicating that less than 20% of the electrolyte is irreversibly consumed during the first lithiation process, in a similar manner to state-of-the-art electrolytes.

Reduction mechanism of lithium bis(oxalato)borate

Melin, Tim, Robin Lundstrom, and Erik J. Berg. The Journal of Physical Chemistry Letters 15.9 (2024): 2537-2541.

Electrolyte additives are indispensable for improving the performance of lithium-ion batteries. Lithium bis(oxalato)borate (LiBOB) has been explored for many years as it can improve cathode and anode performance. A modeling study combining attenuated total reflectance infrared spectroscopy (ATR-FTIR), electrochemical quartz crystal microbalance (EQCM) and online electrochemical mass spectrometry (OEMS) was performed to elucidate the reduction of LiBOB and the resulting electrode/electrolyte interface. The reduced BOB- ions also react with themselves and their environment to produce CO2, which in turn affects the interface formed at the negative electrode.
In the voltammogram, the LiBOB electrolyte recorded the highest mpe value of 50 g mol at the peak, indicating the formation of Li2C2O4 with an mpe value of 51 g/mol (assuming two electrons per Li2C2O4 process). An increase in Δm was observed for <1 V, with essentially no current flow other than the adsorption/desorption of Li+ ions. Again, as noted in the ATR-FTIR experiments above, it is unlikely that the lithium oxalate was electrochemically transformed, but rather other chemical reactions likely involved the metastable oxaloformate and the remaining LiBOB salt.

Custom Q&A

What is the PubChem CID for lithium bis(oxalate)borate?

The PubChem CID for lithium bis(oxalate)borate is 23677815.

What is the molecular formula of lithium bis(oxalate)borate?

The molecular formula of lithium bis(oxalate)borate is C4BLiO8.

What is the molecular weight of lithium bis(oxalate)borate?

The molecular weight of lithium bis(oxalate)borate is 193.8 g/mol.

What is the IUPAC Name of lithium bis(oxalate)borate?

The IUPAC Name of lithium bis(oxalate)borate is lithium;1,4,6,9-tetraoxa-5-boranuidaspiro[4.4]nonane-2,3,7,8-tetrone.

What is the InChI of lithium bis(oxalate)borate?

The InChI of lithium bis(oxalate)borate is InChI=1S/C4BO8.Li/c6-1-2(7)11-5(10-1)12-3(8)4(9)13-5;/q-1;+1.

What is the InChIKey of lithium bis(oxalate)borate?

The InChIKey of lithium bis(oxalate)borate is NVQAYVUCVASGDK-UHFFFAOYSA-N.

What is the canonical SMILES of lithium bis(oxalate)borate?

The canonical SMILES of lithium bis(oxalate)borate is [Li+].[B-]12(OC(=O)C(=O)O1)OC(=O)C(=O)O2.

What is the CAS number of lithium bis(oxalate)borate?

The CAS number of lithium bis(oxalate)borate is 244761-29-3.

What is the hydrogen bond donor count of lithium bis(oxalate)borate?

The hydrogen bond donor count of lithium bis(oxalate)borate is 0.

Is lithium bis(oxalate)borate a canonicalized compound?

Yes, lithium bis(oxalate)borate is a canonicalized compound.