Lithium difluoro(oxalate)borate and LiBF4 blend salts electrolyte for LiNi0.5Mn1.5O4 cathode material

Zhou, Hongming; Xiao, Kaiwen; Li, Jian

doi:10.1016/j.jpowsour.2015.10.073

Cited by 67 publications

(85 citation statements)

References 29 publications

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“…5 However, when cycled below 4.4 V, cells with LiBF 4 electrolyte produced less gas, and had higher coulombic efficiency (CE) than cells containing LiPF 6 alone. Curiously, cells containing equal amounts of LiPF 6 and LiBF 4 had higher CE than cells containing either LiPF 6 or LiBF 4 alone. This phenomenon suggests that blends of LiPF 6 and LiBF 4 salts may improve performance of cells, when cycled below 4.4 V.…”

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confidence: 99%

“…Both these salts have different advantages and disadvantages in lithiumion cells. LiPF 6 has high solution conductivity in carbonate solvents, and helps passivate the negative electrode SEI. However, LiPF 6 is known to have poor thermal and hydrolytic stability.…”

mentioning

confidence: 99%

“…10,11 Decomposition of LiPF 6 results in the formation of reactive species, notably HF and PF 5 , which are thought to cause a cascade of undesirable side-reactions inside the cell. [10][11][12] LiBF 4 has often been studied as a substitute for LiPF 6 in lithium-ion cells because of its improved thermal and hydrolytic stability. 3,[12][13][14][15][16][17] LiBF 4 has demonstrated several other important advantages over LiPF 6 : improved performance at sub-zero temperatures, improved passivation of the Al current collector, and improved performance at the positive electrode.…”

mentioning

confidence: 99%

“…[10][11][12] LiBF 4 has often been studied as a substitute for LiPF 6 in lithium-ion cells because of its improved thermal and hydrolytic stability. 3,[12][13][14][15][16][17] LiBF 4 has demonstrated several other important advantages over LiPF 6 : improved performance at sub-zero temperatures, improved passivation of the Al current collector, and improved performance at the positive electrode. 1,[3][4][5][6][7][8][9][12][13][14]17 The disadvantages of LiBF 4 are lower conductivity compared to LiPF 6 and poor performance at the negative electrode.…”

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confidence: 99%

“…The effect of electrolyte additives in cells cycling up to 4.4 V with LiBF 4 electrolyte was explored (previous work showed that electrolyte additives were ineffective at protecting cells with LiBF 4 from gassing and impedance growth at voltages > 4.4 V). 5 The effect of mixing LiPF 6 and LiBF 4 was studied, to search for the optimum ratio of the two salts. Evaluation of cell performance was done using UHPC and long-term cycling experiments.…”

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confidence: 99%

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Synergistic Effect of LiPF₆and LiBF₄as Electrolyte Salts in Lithium-Ion Cells

Ellis

Hill

Gering

et al. 2017

J. Electrochem. Soc.

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Recent work shows promise for LiBF 4 as an electrolyte salt for high voltage lithium-ion batteries. LiBF 4 is more hydrolytically stable than LiPF 6 , and in some cases has proved to be more stable at high voltage. This work shows that 1.0 M electrolytes consisting of equal parts LiBF 4 and LiPF 6 have better performance in certain high voltage (4.35 V) lithium-ion cells than electrolytes with LiPF 6 or LiBF 4 alone. This is shown using long-term cycling and ultra-high precision coulometry on lithium-ion cells, with and without electrolyte additives. Ultra-high precision coulometry showed that electrolyte with 1:1 LiPF 6 :LiBF 4 and no other additives performed as well as electrolyte with LiPF 6 and state-of-the-art additive blends in these cells. The synergism between LiPF 6 and LiBF 4 was explored using XPS, symmetric cells and EIS analysis. These show that LiBF 4 reduces impedance growth at the positive electrode, while LiPF 6 improves passivation at the negative electrode.

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confidence: 99%

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Synergistic Effect of LiPF₆and LiBF₄as Electrolyte Salts in Lithium-Ion Cells

Ellis

Hill

Gering

et al. 2017

J. Electrochem. Soc.

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Extreme Temperature Electrolytes

2022

Liquid Electrolyte Chemistry for Lithium Metal Batteries

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Prescribing Functional Additives for Treating the Poor Performances of High‐Voltage (5 V‐class) LiNi_0.5Mn_1.5O₄/MCMB Li‐Ion Batteries

Pang

Chen

et al. 2017

Advanced Energy Materials

175

147

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In this paper, tris(trimethylsilyl) phosphite (TMSP) and 1,3‐propanediolcyclic sulfate (PCS) are unprecedentedly prescribed as binary functional additives for treating the poor performances of high‐voltage (5 V‐class) LiNi0.5Mn1.5O4/MCMB (graphitic mesocarbon microbeads) Li‐ion batteries at both room temperature and 50 °C. The high‐voltage LiNi0.5Mn1.5O4/MCMB cell with binary functional additives shows a preponderant discharge capacity retention of 79.5% after 500 cycles at 0.5 C rate at room temperature. By increasing the current intensity from 0.2 to 5 C rate, the discharge capacity retention of the high‐voltage cell with binary functional additives is ≈90%, while the counterpart is only ≈55%. By characterizations, it is rationally demonstrated that the binary functional additives decompose and participate in the modification of solid–electrolyte interface layers (both electrodes), which are more conductive, protective, and resistant to electrolyte oxidative/reductive decompositions (accompanying active‐Li+ consuming parasitic reactions) due to synergistic effects. Specifically, the TMSP additive can stabilize LiPF6 salt and scavenge erosive hydrofluoric acid. More encouragingly, at 50 °C, the high‐voltage cell with binary functional additives holds an ultrahigh discharge capacity retention of 79.5% after 200 cycles at 1 C rate. Moreover, a third designed self‐extinguishing flame‐retardant additive of (ethoxy)‐penta‐fluoro‐cyclo‐triphosphazene (PFPN) is introduced for reducing the flammability of the aforementioned binary functional additives containing electrolyte.

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Lithium difluoro(oxalate)borate and LiBF4 blend salts electrolyte for LiNi0.5Mn1.5O4 cathode material

Cited by 67 publications

References 29 publications

Synergistic Effect of LiPF₆and LiBF₄as Electrolyte Salts in Lithium-Ion Cells

Synergistic Effect of LiPF₆and LiBF₄as Electrolyte Salts in Lithium-Ion Cells

Extreme Temperature Electrolytes

Prescribing Functional Additives for Treating the Poor Performances of High‐Voltage (5 V‐class) LiNi_0.5Mn_1.5O₄/MCMB Li‐Ion Batteries

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Lithium difluoro(oxalate)borate and LiBF4 blend salts electrolyte for LiNi0.5Mn1.5O4 cathode material

Cited by 67 publications

References 29 publications

Synergistic Effect of LiPF6and LiBF4as Electrolyte Salts in Lithium-Ion Cells

Synergistic Effect of LiPF6and LiBF4as Electrolyte Salts in Lithium-Ion Cells

Extreme Temperature Electrolytes

Prescribing Functional Additives for Treating the Poor Performances of High‐Voltage (5 V‐class) LiNi0.5Mn1.5O4/MCMB Li‐Ion Batteries

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Synergistic Effect of LiPF₆and LiBF₄as Electrolyte Salts in Lithium-Ion Cells

Synergistic Effect of LiPF₆and LiBF₄as Electrolyte Salts in Lithium-Ion Cells

Prescribing Functional Additives for Treating the Poor Performances of High‐Voltage (5 V‐class) LiNi_0.5Mn_1.5O₄/MCMB Li‐Ion Batteries