The mitigation of decomposition reactions of lithium-ion battery electrolyte solutions is of critical importance in controlling device lifetime and performance. However, due to the complexity of the system, exacerbated by the diverse set of electrolyte compositions, electrode materials, and operating parameters, a clear understanding of the key chemical mechanisms remains elusive. In this work, operando pressure measurements, solution NMR, and electrochemical methods were combined to study electrolyte oxidation and reduction at multiple cell voltages. Two-compartment LiCoO 2 /Li cells were cycled with a lithium-ion conducting glass-ceramic separator so that the species formed at each electrode could be identified separately and further reactions of these species at the opposite electrode prevented. One principal finding is that chemical oxidation (with an onset voltage of ~4.7 V vs Li/Li + for LiCoO 2), rather than electrochemical reaction, is the dominant decomposition process at the positive electrode surface in this system. This is ascribed to the well-known release of reactive oxygen at higher states-of-charge, indicating that reactions of the electrolyte at the positive electrode are intrinsically linked to surface reactivity of the active material. Soluble electrolyte decomposition products formed at both electrodes are characterised, and a detailed reaction scheme is constructed to rationalise the formation of the observed species. The insights on electrolyte decomposition through reactions with reactive oxygen species identified through this work have direct impact on understanding and mitigating degradation in high voltage/higher energy density LiCoO 2-based cells, and more generally for cells containing nickel-containing cathode materials (e.g. LiNi x Mn y Co z O 2 ; NMCs), as they lose oxygen at lower operating voltages. File list (3) download file view on ChemRxiv Electrolyte Decomposition Paper_SI.pdf (0.92 MiB) download file view on ChemRxiv Electrolyte Decomposition Paper _final.pdf (1.13 MiB) download file view on ChemRxiv Electrolyte oxidation pathways in lithium-ion batteries.pdf (1.16 MiB)
Large-scale energy storage is becoming increasingly critical to balance the intermittency between renewable energy production and consumption 1. Organic redox flow batteries (RFBs), based on inexpensive and sustainable redox-active materials, are promising storage technologies that are cheaper and have fewer environmental hazards than the more mature vanadium-based batteries (typically < 15 Wh/dm 3 , vs. 20-35 Wh/dm 3 , respectively) 2,3. Unfortunately, they have shorter calendar lifetimes and lower energy-densities and fundamental insight at the molecular level is thus required to improve performance 4,5. Here we report two in situ NMR methods to study flow batteries, which are applied on two separate anthraquinones, 2,6-dihydroxyanthraquinone, DHAQ and 4,4'-((9,10-anthraquinone-2,6diyl)dioxy) dibutyrate, DBEAQ as redox-active electrolytes. In one method we follow the changes of the liquids as they flow out of the electrochemical cell, while in the second, we observe the changes that occur in both the positive and negative electrodes in the full electrochemical cell. Making use of the bulk magnetisation changes, observed via the 1 H NMR shift of the water resonance, and the linebroadening of the 1 H shifts of the quinone resonances as a function of state of charge, we determine the potential differences of the two one-electron couples, identify and quantify the rate of electron transfer between reduced and oxidised species and the extent of electron delocalization of the unpaired spins over the radical anions. The method allows electrolyte decomposition and battery self-discharge to be explored in real time, showing that DHAQ is decomposed electrochemically via a reaction which can be minimized by limiting the voltage used on charging. Applications of the new NMR metrologies to understand a wide range of redox processes in flow and other battery systems are readily foreseen. The two in situ NMR setups Ex situ characterization of RFBs can be challenging due to the high reactivity, sensitivity to sample preparation and short lifetimes of some of the oxidised and/or reduced redox-active molecules and ions within the electrolytes. However, one of the distinct features of RFBs is the decoupling of energy storage and power generation, providing different opportunities for in situ monitoring. To date, methods such as in situ optical spectrophotometry 6 and Electron Paramagnetic Resonance (EPR) 7 have been used to study, for example, crossover of quinones and vanadyl ions, but considerable opportunities remain to improve characterization methods to address limitations inherent to each method and to probe different phenomena. Nuclear Magnetic Resonance (NMR) spectroscopy was used to study benzoquinone and polyoxometalate redox reactions in an in situ
LiI-promoted LiOH formation in Li-O 2 batteries with wet ether electrolytes has been investigated by Raman, nuclear magnetic resonance spectroscopy, operando pressure tests, and molecular dynamics simulations. We find that LiOH formation is a synergistic effect involving both H 2 O and LiI additives, whereas with either alone Li 2 O 2 forms. LiOH is generated via a nominal four-electron oxygen reduction reaction, the hydrogen coming from H 2 O and the oxygen from both O 2 and H 2 O, and with fewer side reactions than typically associated with Li 2 O 2 formation; the presence of fewer parasitic reactions is attributed to the proton donor role of water, which can coordinate to O 2 − and the higher chemical stability of LiOH. Iodide plays a catalytic role in decomposing H 2 O 2 /HO 2 − and thereby promoting LiOH formation, its efficacy being highly dependent on the water concentration. This iodide catalysis becomes retarded at high water contents due to the formation of large water-solvated clusters, and Li 2 O 2 forms again.
The asymmetric hydrogenation of alpha-ketoesters on cinchona-modified supported platinum particles is a prototype reaction in heterogeneous chiral catalysis. The catalysis literature shows that the reaction is highly metal-specific, that it displays rate-enhancement with respect to the racemic reaction on the nonmodified surface, and that the observed stereoselectivity is a sensitive function of substrate and modifier structure. This set of observations has proven difficult to rationalize within the context of existing models for the mechanism of the Orito reaction. The most widely discussed mechanistic models are based on the formation of chemisorbed 1:1 complexes through H-bonding between the quinuclidine function of the cinchona modifier and the prochiral, keto-carbonyl, function of the substrate. Recent surface science studies, as well as advances in the area of C-H...O hydrogen bonding, suggest that chemisorption-induced polarization may lead to an aromatic-carbonyl H-bonding interaction between the aromatic anchor of the modifier and the coadsorbed substrate. By specifying that the aromatic C-H...O interaction is to the prochiral carbonyl and that it is accompanied by a H-bonding interaction between the ester carbonyl and the quinuclidine function, we show that it is possible to rationalize essentially all of the catalysis literature for the Orito reaction in terms of a single molecular mechanism. The generality of the proposed mechanistic model is demonstrated by addressing data from the literature for a representative range of substrates, modifiers, solvents, and metals. Results of catalytic tests on an asymmetric diketone substrate are presented in support of the model.
The chemical and electrochemical reactions at the positive electrode–electrolyte interface in Li-ion batteries are hugely influential on cycle life and safety. Ni-rich layered transition metal oxides exhibit higher interfacial reactivity than their lower Ni-content analogues, reacting via mechanisms that are poorly understood. Here, we study the pivotal role of the electrolyte solvent, specifically cyclic ethylene carbonate (EC) and linear ethyl methyl carbonate (EMC), in determining the interfacial reactivity at charged LiNi 0.33 Mn 0.33 Co 0.33 O 2 (NMC111) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes by using both single-solvent model electrolytes and the mixed solvents used in commercial cells. While NMC111 exhibits similar parasitic currents with EC-containing and EC-free electrolytes during high voltage holds in NMC/Li 4 Ti 5 O 12 (LTO) cells, this is not the case for NMC811. Online gas analysis reveals that the solvent-dependent reactivity for Ni-rich cathodes is related to the extent of lattice oxygen release and accompanying electrolyte decomposition, which is higher for EC-containing than EC-free electrolytes. Combined findings from electrochemical impedance spectroscopy (EIS), TEM, solution NMR, ICP, and XPS reveal that the electrolyte solvent has a profound impact on the degradation of the Ni-rich cathode and the electrolyte. Higher lattice oxygen release with EC-containing electrolytes is coupled with higher cathode interfacial impedance, a thicker oxygen-deficient rock-salt surface reconstruction layer, more electrolyte solvent and salt breakdown, and higher amounts of transition metal dissolution. These processes are suppressed in the EC-free electrolyte, highlighting the incompatibility between Ni-rich cathodes and conventional electrolyte solvents. Finally, new mechanistic insights into the chemical oxidation pathways of electrolyte solvents and, critically, the knock-on chemical and electrochemical reactions that further degrade the electrolyte and electrodes curtailing battery lifetime are provided.
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