Influence of electrolyte additives on the cathode electrolyte interphase (CEI) formation on LiNi1/3Mn1/3Co1/3O2 in half cells with Li metal counter electrode

Qian, Yunxian; Niehoff, Philip; Börner, Markus; Grützke, Martin; Mönnighoff, Xaver; Behrends, Pascal; Nowak, Sascha; Winter, Martin; Schappacher, Falko M.

doi:10.1016/j.jpowsour.2016.08.023

Cited by 210 publications

(151 citation statements)

References 46 publications

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“…The process of contact loss based on the formation of a CEI was shown previously. 41 The lacking relithiation during aging was confirmed via XRD measurements (see Fig. 3).…”

mentioning

confidence: 74%

Thermal Analysis of LiNi_0.4Co_0.2Mn_0.4O₂/Mesocarbon Microbeads Cells and Electrodes: State-of-Charge and State-of-Health Influences on Reaction Kinetics

Hildebrand

Rheinfeld

Friesen

et al. 2018

J. Electrochem. Soc.

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The thermal stability of lithium ion batteries was studied by means of Accelerating Rate Calorimetry in Heat-Wait-Search operation on both electrode and cell level. Fresh and aged samples were investigated depending on the state-of-charge (SoC) of a 5 Ah pouch cell comprising mesocarbon microbeads and LiNi 0.4 Co 0.2 Mn 0.4 O 2 as the anode and cathode materials. 1 M LiPF 6 in EC:DEC 3:7 (by weight) containing 2 wt% VC and 0.5 wt% LiBOB was chosen as the electrolyte. Measurements on the electrode level revealed a higher self-heating rate (SHR) of the cathode compared to the anode for all SoC and state-of-health (SoH) combinations in the temperature range where a self-sustaining decomposition reaction could be detected. A lower SoC showed a lower SHR of the electrode/electrolyte mixture with no reaction detected on the anode side ≤ 50% cell SoC. Cyclic aging led to a decrease in thermal stability of the cathode at lower SoC values with no significant influence on the anode implying a larger safety threat on the cell level. Avrami-Erofeev and autocatalytic reaction models were used to quantify the influences of SoC and SoH on reaction kinetics. Based on their high energy and power density combined with a long cycle life, high energy efficiency and low costs, lithium ion batteries are currently the state-of-the-art energy source for electric vehicles (EV). 1-3 A long cycle life requires excellent aging behavior, whereas a high energy and power density demands for a high level of safety in order to comply with automotive prerequisites. [4][5][6] Many studies have dealt with the investigation of aging and safety individually as well as their interplay. 4,[7][8][9][10][11][12][13] Yet, these interactions are not fully understood. Accelerating Rate Calorimetry (ARC) has been reported to be a promising method to measure the thermal stability of samples under quasi-adiabatic conditions. This method can be applied from single battery materials [14][15][16][17][18][19][20] up to full cells. 11,13,21 Based on the prevailing quasi-adiabatic conditions, a worst-case scenario can be simulated. With no heat dissipation taking place, the generated heat can be evaluated by measuring the temperature increase of the sample, knowing its total heat capacity. 22 This behavior can be readily transferred to real life scenarios where heat dissipation during cell failure is partially inhibited by the cell surroundings.Predicting a cell's behavior during thermal abuse conditions is a topic of major interest in order to prevent hazardous situations on the battery pack level such as the propagation of thermal runaway after a single cell failure. 23 Due to the complexity of cell thermal runaway dynamics influenced e.g. by material composition 14,15 and morphology, [24][25][26] modeling and simulation can help to identify the dominating processes and interactions within a single cell based on individual material decomposition reactions. [27][28][29] Characteristic kinetic parameters of predominantly empirical decomposition reaction models were...

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“…The process of contact loss based on the formation of a CEI was shown previously. 41 The lacking relithiation during aging was confirmed via XRD measurements (see Fig. 3).…”

mentioning

confidence: 74%

Thermal Analysis of LiNi_0.4Co_0.2Mn_0.4O₂/Mesocarbon Microbeads Cells and Electrodes: State-of-Charge and State-of-Health Influences on Reaction Kinetics

Hildebrand

Rheinfeld

Friesen

et al. 2018

J. Electrochem. Soc.

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“…In the F 1s spectra, three peaks at binding energies (BEs) of 688.7, 686.4 and 685.3 eV, respectively, are detected. These peaks are assigned to polyvinylidene difluoride (PVDF), decomposition products of BF 4 −[32] and LiF, and the content of the LiF of LBW sample is more than LB155. LiF, which has poor conductive property, can influence the electrochemical performance of cell.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Water‐Removing Method and Influences of Trace Water for LiBF₄

et al. 2019

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Recent works show the promise for lithium tetrafluoroborate (LiBF4) as an electrolyte salt for lithium‐ion batteries. In this paper, LiBF4 is synthesized by a novel reaction between the as‐prepared anhydrous Li2SO3 and (C2H5)2O⋅BF3 in an aprotic solvent. The moisture sensitivity and water‐removing method of LiBF4 materials which has been dried under vacuum for 2 h at different temperature, is studied by Fourier transform infrared spectroscopy measurements. Results show that almost all of the adsorbed water would be removed at above 65 °C. With the increase of drying temperature, crystal water will decrease slowly, and almost disappear completely at 170 °C. However, due to the thermal decomposition of LiBF4, LiF and BF2OH impurities are formed as the temperature reaches 165 °C. So, we determine that the proper drying temperature is 155 °C, though the trace water cannot be removed thoroughly. Besides, influences of trace water on the electrochemical performance of Li/MCMB half‐cell with LiBF4 as electrolyte salt has been investigated. Results show that discharge plateaus at about 1.5 V vs. Li/Li+ will be lengthened with the increase of water content. Subsequently, the so‐called solid‐electrolyte interphase (SEI) film will become thicker and more resistant, which leads to poor Li+ ion migration and bad cycling performance.

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“…此外, 其最高占据轨道(HOMO)能级和最低未被占据轨道(LUMO)能级都低于 EC, 因而其氧化稳定性提高, 而还原稳定性降低, 因此在低电位下, 容易在石墨负极、硅负极被还原, 具有良好的成膜性 [8,25] . [21] , 但部分观点认为过多的 LiF 会增加阻抗 [26] . …”

Section: Fecunclassified

Review of Electrolyte Additives for Ternary Cathode Lithium-ion Battery

Deng¹,

Sun²,

Wan³

et al. 2018

Acta Chim. Sinica

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, M＝Mn, NMC; M＝Al, NCA)} are one of the most promising cathode materials of lithium-ion batteries (LIBs). However, in the traditional electrolyte system, they will undergo dramatic structural changes and interface side reactions at high potential and high temperature, which will bring great challenges to their practical application, especially for their cycle life and safety. Developing appropriate electrolyte additive is one of the most economical and effective methods to improve the electrochemical performance of LIBs. Based on the intrinsic structure of material, electrolyte additives used for NMC and NCA ternary cathode and their reaction mechanism in the past 5 years are reviewed in this paper, which include vinylene carbonate (VC), fluoro-compounds, new lithium salts, P-based, B-based, S-based, nitrile, others and combinative additives. Among them, VC becomes a kind of universal additive, which can improve the efficiency and cycle life at low voltage and normal temperature. Fluoro-compounds have been developed from mono substituted such as Fluorinated ethylene carbonate (FEC) to multi-fluorine substituted, which can improve the stability of electrode/electrolyte interface under high voltage. New lithium salt additives are mainly used to improve the film forming performance under high voltage and high temperature, such as Lithium bis(fluorosulfonyl)imide (LiFSI), Lithium difluorophosphate (LiDFP). P-contained additives [such as Tris(trimethylsilyl)phosphite (TMSPi)] are mainly to improve the stability of anode-electrolyte interface, and it has obvious synergistic effect when they combined with additives such as VC. B-contained additives are mainly used to improve the dissociation degree and stability of lithium salt, such as Tris(trimethylsilyl)borate (TMSB). S-contained additives are mainly used to improve the ionic conductivity and stability of anode SEI film, such as Prop-1-ene-1,3-sultone (PES). Nitriles are benefited from the strong electron withdrawing effect of -CN, which can improve the stability of the electrode/electrolyte interface at high voltage. Other types of additives are some heterocyclic compounds having film forming ability and various silanes which can eliminate HF and H 2 O. Combinative additives are developed from VC based composite to PES and PBF (pyridine boron trifluoride) system, which can endure even harsher conditions.

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Influence of electrolyte additives on the cathode electrolyte interphase (CEI) formation on LiNi1/3Mn1/3Co1/3O2 in half cells with Li metal counter electrode

Cited by 210 publications

References 46 publications

Thermal Analysis of LiNi_0.4Co_0.2Mn_0.4O₂/Mesocarbon Microbeads Cells and Electrodes: State-of-Charge and State-of-Health Influences on Reaction Kinetics

Thermal Analysis of LiNi_0.4Co_0.2Mn_0.4O₂/Mesocarbon Microbeads Cells and Electrodes: State-of-Charge and State-of-Health Influences on Reaction Kinetics

Synthesis, Water‐Removing Method and Influences of Trace Water for LiBF₄

Review of Electrolyte Additives for Ternary Cathode Lithium-ion Battery

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Influence of electrolyte additives on the cathode electrolyte interphase (CEI) formation on LiNi1/3Mn1/3Co1/3O2 in half cells with Li metal counter electrode

Cited by 210 publications

References 46 publications

Thermal Analysis of LiNi0.4Co0.2Mn0.4O2/Mesocarbon Microbeads Cells and Electrodes: State-of-Charge and State-of-Health Influences on Reaction Kinetics

Thermal Analysis of LiNi0.4Co0.2Mn0.4O2/Mesocarbon Microbeads Cells and Electrodes: State-of-Charge and State-of-Health Influences on Reaction Kinetics

Synthesis, Water‐Removing Method and Influences of Trace Water for LiBF4

Review of Electrolyte Additives for Ternary Cathode Lithium-ion Battery

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Product

Resources

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Thermal Analysis of LiNi_0.4Co_0.2Mn_0.4O₂/Mesocarbon Microbeads Cells and Electrodes: State-of-Charge and State-of-Health Influences on Reaction Kinetics

Thermal Analysis of LiNi_0.4Co_0.2Mn_0.4O₂/Mesocarbon Microbeads Cells and Electrodes: State-of-Charge and State-of-Health Influences on Reaction Kinetics

Synthesis, Water‐Removing Method and Influences of Trace Water for LiBF₄