17 research outputs found
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High Rate Lithium Ion Battery with Niobium Tungsten Oxide Anode
Highly stable lithium-ion battery cycling of niobium tungsten oxide (Nb16W5O55, NWO) is demonstrated in full cells with cathode materials LiNi0.6Mn0.2Co0.2O2 (NMC-622) and LiFePO4 (LFP). The cells show high rate performance and long-term stability under 5 C and 10 C cycling rates with a conventional carbonate electrolyte without any additives. The degradation of the cell performance is mainly attributed to the increased charge transfer resistance at the NMC side, consistent with the ex situ XRD and XPS analysis demonstrating the structural stability of NWO during cycling together with minimal electrolyte decomposition. Finally, we demonstrate the temperature-dependent performance of this full cell at 10, 25 and 60 °C and confirm, using operando XRD, that the structural change of the NWO material during lithiation/de-lithiation at 60 °C is very similar to its behaviour at 25 °C, reversible and with a low volume change. With the merits of high rate performance and long cycle life, the combination of NWO and a commercial cathode represents a promising, safe battery for fast charge/discharge applications
Selective NMR observation of the SEIâmetal interface by dynamic nuclear polarisation from lithium metal
Funder: Oppenheimer Foundation, Cambridge. Blavatnik Cambridge Fellowships.Abstract: While lithium metal represents the ultimate high-energy-density battery anode material, its use is limited by dendrite formation and associated safety risks, motivating studies of the solidâelectrolyte interphase layer that forms on the lithium, which is key in controlling lithium metal deposition. Dynamic nuclear polarisation enhanced NMR can provide important structural information; however, typical exogenous dynamic nuclear polarisation experiments, in which organic radicals are added to the sample, require cryogenic sample cooling and are not selective for the interface between the metal and the solidâelectrolyte interphase. Here we instead exploit the conduction electrons of lithium metal to achieve an order of magnitude hyperpolarisation at room temperature. We enhance the 7Li, 1H and 19F NMR spectra of solidâelectrolyte interphase species selectively, revealing their chemical nature and spatial distribution. These experiments pave the way for more ambitious room temperature in situ dynamic nuclear polarisation studies of batteries and the selective enhancement of metalâsolid interfaces in a wider range of systems
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NMR Studies of Interfacial Reactions in Lithium-Ion Batteries
The development of rechargeable batteries with higher energy densities and longer lifetimes represents a major challenge in enabling the shift from fossil fuel-powered to electric vehicles. Preventing the parasitic reactions between the electrodes (positive and negative) and the electrolyte solution, is essential for enabling longer lasting lithium-ion batteries. In this work, solution- and solid-state nuclear magnetic resonance (NMR) methodologies are developed for studying the electrode-electrolyte reactions.
The decomposition reactions of the electrolyte solution at positive electrodes, layered transition metal oxides (LiMO2, M = Ni, Mn, Co or Al, e.g. LiCoO2, LCO; LiNixMnyCo1-x-yO2, NMC), are investigated by a combination of solution NMR spectroscopy and operando gas measurements. The soluble products formed at LCO electrodes are identified, and reaction mechanisms are proposed to rationalise the formation of the observed species. The proposed mechanisms are confirmed by isotopic labelling and by comparing the decomposition products formed at the positive electrode to those formed in a controlled setup simulating specific battery conditions. This methodology is then extended to NMC electrodes with various compositions (i.e., different ratios of Ni, Mn and Co), which revealed that the mechanisms for electrolyte decomposition were the same for all compositions, but the onset voltage for the Ni-rich materials was lower.
At the negative electrode, the reduction and deposition of the electrolyte solution at the metal surface results in the formation of a passivating layer, the solid electrolyte interphase (SEI). The interface between a lithium metal electrode and the SEI is studied by dynamic nuclear polarisation (DNP) enhanced solid-state NMR. The signals from SEI components are selectively enhanced in 1H, 7Li and 19F NMR spectra via an Overhauser DNP mechanism, and the proximity of the SEI species to the metal can be inferred from the relative DNP enhancements of the signals. The effect of temperature, magnetic field strength, microwave power and sample dilution on the enhancement are also explored, to understand what the limitations are when using this mechanism to study the lithium metal-SEI interface
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Electrolyte Oxidation Pathways in Lithium-Ion Batteries.
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 LiCoO2/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 âŒ4.7 V vs Li/Li+ for LiCoO2), 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 characterized, and a detailed reaction scheme is constructed to rationalize the formation of the observed species. The insights on electrolyte decomposition through reactions with reactive oxygen species identified through this work have a direct impact on understanding and mitigating degradation in high-voltage/higher-energy-density LiCoO2-based cells, and more generally for cells containing nickel-containing cathode materials (e.g., LiNi
x
Mn
y
Co
z
O2; NMCs), as they lose oxygen at lower operating voltages.US Department of Energy, the Faraday Institution and the European Research Counci
Two electrolyte decomposition pathways at nickel-rich cathode surfaces in lithium-ion batteries.
Preventing the decomposition reactions of electrolyte solutions is essential for extending the lifetime of lithium-ion batteries. However, the exact mechanism(s) for electrolyte decomposition at the positive electrode, and particularly the soluble decomposition products that form and initiate further reactions at the negative electrode, are still largely unknown. In this work, a combination of operando gas measurements and solution NMR was used to study decomposition reactions of the electrolyte solution at NMC (LiNi x Mn y Co1-x-y O2) and LCO (LiCoO2) electrodes. A partially delithiated LFP (Li x FePO4) counter electrode was used to selectively identify the products formed through processes at the positive electrodes. Based on the detected soluble and gaseous products, two distinct routes with different onset potentials are proposed for the decomposition of the electrolyte solution at NMC electrodes. At low potentials (80% SOC), 1O2 released from the transition metal oxide chemically oxidises the electrolyte solvent (EC) to form CO2, CO and H2O. The formation of water via this mechanism was confirmed by reacting 17O-labelled 1O2 with EC and characterising the reaction products via 1H and 17O NMR spectroscopy. The water that is produced initiates secondary reactions, leading to the formation of the various products identified by NMR spectroscopy. Noticeably fewer decomposition products were detected in NMC/graphite cells compared to NMC/Li x FePO4 cells, which is ascribed to the consumption of water (from the reaction of 1O2 and EC) at the graphite electrode, preventing secondary decomposition reactions. The insights on electrolyte decomposition mechanisms at the positive electrode, and the consumption of decomposition products at the negative electrode contribute to understanding the origin of capacity loss in NMC/graphite cells, and are hoped to support the development of strategies to mitigate the degradation of NMC-based cells
Electrolyte Oxidation Pathways in Lithium-Ion Batteries
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
LiCoO2/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 LiCoO2), 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 LiCoO2-based
cells, and more generally for cells containing nickel-containing
cathode materials (e.g. LiNixMnyCozO2;
NMCs), as they lose oxygen at lower operating voltages.</p
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Research data Supporting "Preventing degradation in a flavin mononucleotide-based redox flow battery â an NMR and EPR study"
Zip folders contain data to the publication "Preventing degradation in a flavin mononucleotide-based redox flow battery â an NMR and EPR study" (Nature Communication 2023).
It contains the zip file âCode.zipâ, which is the code the electrochemistry and in-situ EPR and NMR have been processed. The software to run the code is MATLAB.
âElectrochemistry â ph 14.zipâ and âElectrochemistry â pH 11.zipâ contain the electrochemical data acquired for figure 1 and 5. The files were collected with the Biologic Software EC-Lab.
âNMR-EPR-Echem - fresh sample - pH 14.zipâ and âNMR-EPR-Echem - aged sample - pH 14.zipâ contain the data for figure 2 in the aforementioned publication. It provides the raw NMR (from Bruker Topspin) and EPR data (.csv and .xml), clearly labelled. To analyse the NMR data, the software Topspin by Bruker is needed. Additionally, the electrochemistry is provided for each experiment.
âex situ NMR - 31P - fresh, old, hydrolysed.zipâ and âNMR-EPR-Echem - hydrolysed sample - pH 14.zipâ is used to make figure 3. All data is in clearly labelled folders. Here, Topspin is needed to analyse and display the data, or the code provided above. The code provided will help to plot the data.
The data Figure 4 consists of the folder âNMR - hydrolysed sample plus addition of fresh FMN - pH 14.zipâ. Here, the code or topspin can be used to analyse the data
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Identifying and preventing degradation in flavin mononucleotide-based redox flow batteries via NMR and EPR spectroscopy.
While aqueous organic redox flow batteries (RFBs) represent potential solutions to large-scale grid storage, their electrolytes suffer from short lifetimes due to rapid degradation. We show how an understanding of these degradation processes can be used to dramatically improve performance, as illustrated here via a detailed study of the redox-active biomolecule, flavin mononucleotide (FMN), a molecule readily derived from vitamin B2. Via in-situ nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) we identify FMN hydrolysis products and show that these give rise to the additional plateau seen during charging of an FMN-cyanoferrate battery. The redox reactions of the hydrolysis product are not reversible, but we demonstrate that capacity is still retained even after substantial hydrolysis, albeit with reduced voltaic efficiency, FMN acting as a redox mediator. Critically, we demonstrate that degradation is mitigated and battery efficiency is substantially improved by lowering the pH to 11. Furthermore, the addition of cheap electrolyte salts to tune the pH results in a dramatic increase in solubility (above 1âM), this systematic improvement of the flavin-based system bringing RFBs one step closer to commercial viability.D.H. acknowledges support from the Sheldrick Scholarship in Chemistry, Jesus College Cambridge, and the EPSRC iCASE PhD Fees Only Studentship. C.P.G. acknowledges support from the European Research Council (ERC) 835073 BATNMR. D.H., R.J., E.W.Z., N.L.F. and C.P.G. acknowledge support from Shell; R.J. and N.L.F. acknowledge support from the EPSRC and Shell via I-Case studentships EP/R511870/1 and EP/V519662/1, respectively. E.W.Z. and C.P.G. acknowledge support from Centre of Advanced Materials for Integrated Energy Systems (CAM-IES), via EPSRC grant number EP/P007767/1. We thank D.S. Wright, A.C. Forse, M. De Volder, and E.J. Latchem from University of Cambridge and P.A.A. Klusener from Shell for many fruitful discussions
Electrolyte Oxidation Pathways in Lithium-Ion Batteries.
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 LiCoO2/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 âŒ4.7 V vs Li/Li+ for LiCoO2), 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 characterized, and a detailed reaction scheme is constructed to rationalize the formation of the observed species. The insights on electrolyte decomposition through reactions with reactive oxygen species identified through this work have a direct impact on understanding and mitigating degradation in high-voltage/higher-energy-density LiCoO2-based cells, and more generally for cells containing nickel-containing cathode materials (e.g., LiNixMnyCozO2; NMCs), as they lose oxygen at lower operating voltages.US Department of Energy, the Faraday Institution and the European Research Counci
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Supporting data for "Selective NMR Observation of the SEIâMetal Interface by Dynamic Nuclear Polarisation from Lithium Metal"
1H, 7Li and 19F FIDs, Fourier transformed spectra, and metadata for the conventional and lithium metal DNP enhanced NMR of lithium metal microstructures and their SEI. The .zip file contains a folder system in the TopSpin format that has been organised by sample, as described in Supplementary Table 7 of the publication