40 research outputs found
Dynamic Nuclear Polarization in Battery Materials
The increasing need for portable and large-scale energy storage systems
requires development of new, long lasting and highly efficient battery systems.
Solid state NMR spectroscopy has emerged as an excellent method for
characterizing battery materials. Yet, it is limited when it comes to probing
thin interfacial layers which play a central role in the performance and
lifetime of battery cells. Here we review how Dynamic Nuclear Polarization
(DNP) can lift the sensitivity limitation and enable detection of the
electrode-electrolyte interface, as well as the bulk of some electrode and
electrolyte systems. We describe the current challenges from the point of view
of materials development; considering how the unique electronic, magnetic and
chemical properties differentiate battery materials from other applications of
DNP in materials science. We review the current applications of exogenous and
endogenous DNP from radicals, conduction electrons and paramagnetic metal ions.
Finally, we provide our perspective on the opportunities and directions where
battery materials can benefit from current DNP methodologies as well as project
on future developments that will enable NMR investigation of battery materials
with sensitivity and selectivity under ambient conditions
Monitoring Electron Spin Fluctuations with Paramagnetic Relaxation Enhancement
The magnetic interactions between the spin of an unpaired electron and the
surrounding nuclear spins can be exploited to gain structural information, to
reduce nuclear relaxation times as well as to create nuclear hyperpolarization
via dynamic nuclear polarization (DNP). A central aspect that determines how
these interactions manifest from the point of view of NMR is the timescale of
the fluctuations of the magnetic moment of the electron spins. These
fluctuations, however, are elusive, particularly when electron relaxation times
are short or interactions among electronic spins are strong. Here we map the
fluctuations by analyzing the ratio between longitudinal and transverse nuclear
relaxation times T1 and T2, a quantity which depends uniquely on the rate of
the electron fluctuations and the Larmor frequency of the involved nuclei. This
analysis enables rationalizing the evolution of NMR lineshapes, signal
quenching as well as DNP enhancements as a function of the concentration of the
paramagnetic species and the temperature, demonstrated here for LiMgMnPO4 and
Fe(3+) doped Li4Ti5O12, respectively. For the latter, we observe a linear
dependence of the DNP enhancement and the electron relaxation time within a
temperature range between 100 and 300K
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Solid Electrolyte Interphase Growth and Capacity Loss in Silicon Electrodes.
The solid electrolyte interphase (SEI) of the high capacity anode material Si is monitored over multiple electrochemical cycles by (7)Li, (19)F, and (13)C solid-state nuclear magnetic resonance spectroscopies, with the organics dominating the SEI. Homonuclear correlation experiments are used to identify the organic fragments -OCH2CH2O-, -OCH2CH2-, -OCH2CH3, and -CH2CH3 contained in both oligomeric species and lithium semicarbonates ROCO2Li, RCO2Li. The SEI growth is correlated with increasing electrode tortuosity by using focused ion beam and scanning electron microscopy. A two-stage model for lithiation capacity loss is developed: initially, the lithiation capacity steadily decreases, Li(+) is irreversibly consumed at a steady rate, and pronounced SEI growth is seen. Later, below 50% of the initial lithiation capacity, less Si is (de)lithiated resulting in less volume expansion and contraction; the rate of Li(+) being irreversibly consumed declines, and the Si SEI thickness stabilizes. The decreasing lithiation capacity is primarily attributed to kinetics, the increased electrode tortuousity severely limiting Li(+) ion diffusion through the bulk of the electrode. The resulting changes in the lithiation processes seen in the electrochemical capacity curves are ascribed to non-uniform lithiation, the reaction commencing near the separator/on the surface of the particles.This work was partially supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, under the Batteries for Advanced Transportation Technologies (BATT) Program subcontract #7057154 and the European Commission (EC), through the project EuroLion. G.D. and C.D. acknowledge funding from the ERC under Grants 259619 PHOTO EM and 312483 ESTEEM2. A.L.M. is an awardee of a Schiff Foundation Studentship and a nanoDTC Associate. M.L. is an awardee of the Weizmann Institute of Science - National Postdoctoral Award for Advancing Women in Science and thanks the EU Marie Curie intra-European fellowship for funding.This is the author accepted manuscript. The final version is available from the American Chemical Society via http://dx.doi.org/10.1021/jacs.6b0288
Cycling Li-O2 Batteries via LiOH Formation and Decomposition
The rechargeable aprotic Li-air (O₂) battery is a promising potential technology for next generation energy storage, but its practical realization still faces many challenges. In contrast to the standard Li-O₂ cells, which cycle via the formation of Li₂O₂, we use a reduced graphene oxide electrode, the additive LiI, and the solvent dimethoxyethane to reversibly form/remove crystalline LiOH with particle sizes > 15 μm during discharge/charge. This leads to high specific capacities, excellent energy efficiency (93.2%) with a voltage gap of only 0.2 V, and impressive rechargeability. The cells tolerate high concentrations of water, water being the dominant proton source for the LiOH; together with LiI it has a decisive impact on the chemical nature of the discharge product and battery performance.This work was partially supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, under the Batteries for Advanced Transportation Technologies (BATT) Program subcontract #7057154 (WY, ML, PB), EPSRC (TL), Johnson Matthey (AM) and Marie Curie Actions (PB and ML).This is the author accepted manuscript. The final version is available from AAAS via http://dx.doi.org/10.1126/science.aac773
Surface Sensitive NMR Detection of the SEI Layer on Reduced Graphene Oxide
The solid electrolyte interphase (SEI) is detrimental for rechargeable
batteries performance and lifetime. Understanding its formation requires
analytical techniques that provide molecular level insight. Here dynamic
nuclear polarization (DNP) is utilized for the first time for enhancing the
sensitivity of solid state NMR (ssNMR) spectroscopy to the SEI. The approach is
demonstrated on reduced-graphene oxide (rGO) cycled in Li-ion cells in natural
abundance and 13C-enriched electrolyte solvents. Our results indicate that DNP
enhances the signal of outer SEI layers, enabling detection of natural
abundance 13C spectra from this component of the SEI at reasonable timeframes.
Furthermore, 13C- enriched electrolytes measurements at 100K provide ample
sensitivity without DNP due to the vast amount of SEI filling the rGO pores,
thereby allowing differentiating the inner and outer SEI layers composition.
Developing this approach further will benefit the study of many electrode
materials, equipping ssNMR with the needed sensitivity to efficiently probe the
SEI.The work was supported by a research grant from Dana and Yossie Hollander, the Alon fellowship from Israel council of higher education and partially by the Israel Science Foundation (ISF) in the framework of the INREP project (M.L.). This project has received funding from the European Unions’s Horizon 2020 research and innovation programme under Grant Agreement No. 696656 – GrapheneCore1 (G.K. and C.P.G.). We thank Dr. Wanjing Yu (Central South University, China) for graphene synthesis and related discussions. G.K. thanks Dr. Duhee Yoon (Cambridge Graphene Centre) for Raman measurements and helpful discussions. The research is made possible in part by the historic generosity of the Harold Perlman family. We thank Dr. Frederic Mentink-Vigier for helpful suggestions. DNP experiments at 14.1 T were performed at the DNP MAS NMR Facility at the University of Nottingham, with thanks to the EPSRC for funding of pilot studies (EP/L022524/1)
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Cycling Li-Oâ‚‚ batteries via LiOH formation and decomposition.
The rechargeable aprotic lithium-air (Li-O2) battery is a promising potential technology for next-generation energy storage, but its practical realization still faces many challenges. In contrast to the standard Li-O2 cells, which cycle via the formation of Li2O2, we used a reduced graphene oxide electrode, the additive LiI, and the solvent dimethoxyethane to reversibly form and remove crystalline LiOH with particle sizes larger than 15 micrometers during discharge and charge. This leads to high specific capacities, excellent energy efficiency (93.2%) with a voltage gap of only 0.2 volt, and impressive rechargeability. The cells tolerate high concentrations of water, water being the dominant proton source for the LiOH; together with LiI, it has a decisive impact on the chemical nature of the discharge product and on battery performance.This work was partially supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, under the Batteries for Advanced Transportation Technologies (BATT) Program subcontract #7057154 (WY, ML, PB), EPSRC (TL), Johnson Matthey (AM) and Marie Curie Actions (PB and ML).This is the author accepted manuscript. The final version is available from AAAS via http://dx.doi.org/10.1126/science.aac773
Identifying the Structure of the Intermediate, Li2/3CoPO4, Formed during Electrochemical Cycling of LiCoPO4.
In situ synchrotron diffraction measurements and subsequent Rietveld refinements are used to show that the high energy density cathode material LiCoPO4 (space group Pnma) undergoes two distinct two-phase reactions upon charge and discharge, both occurring via an intermediate Li2/3(Co2+)2/3(Co3+)1/3PO4 phase. Two resonances are observed for Li2/3CoPO4 with intensity ratios of 2:1 and 1:1 in the 31P and 7Li NMR spectra, respectively. An ordering of Co2+/Co3+ oxidation states is proposed within a (a × 3b × c) supercell, and Li+/vacancy ordering is investigated using experimental NMR data in combination with first-principles solid-state DFT calculations. In the lowest energy configuration, both the Co3+ ions and Li vacancies are found to order along the b-axis. Two other low energy Li+/vacancy ordering schemes are found only 5 meV per formula unit higher in energy. All three configurations lie below the LiCoPO4-CoPO4 convex hull and they may be readily interconverted by Li+ hops along the b-direction.This is the final version. It was first published by ACS Publications at http://pubs.acs.org/doi/abs/10.1021/cm502680
Ab initio structure search and in situ 7Li NMR studies of discharge products in the Li-S battery system.
The high theoretical gravimetric capacity of the Li-S battery system makes it an attractive candidate for numerous energy storage applications. In practice, cell performance is plagued by low practical capacity and poor cycling. In an effort to explore the mechanism of the discharge with the goal of better understanding performance, we examine the Li-S phase diagram using computational techniques and complement this with an in situ (7)Li NMR study of the cell during discharge. Both the computational and experimental studies are consistent with the suggestion that the only solid product formed in the cell is Li2S, formed soon after cell discharge is initiated. In situ NMR spectroscopy also allows the direct observation of soluble Li(+)-species during cell discharge; species that are known to be highly detrimental to capacity retention. We suggest that during the first discharge plateau, S is reduced to soluble polysulfide species concurrently with the formation of a solid component (Li2S) which forms near the beginning of the first plateau, in the cell configuration studied here. The NMR data suggest that the second plateau is defined by the reduction of the residual soluble species to solid product (Li2S). A ternary diagram is presented to rationalize the phases observed with NMR during the discharge pathway and provide thermodynamic underpinnings for the shape of the discharge profile as a function of cell composition.Fellowship support to KAS from the ConvEne IGERT Program of the National Science Foundation (DGE 0801627) is gratefully acknowledged. AJM acknowledges the support from the Winton Programme for the Physics of Sus-tainability. PDM and DSW thank the UK-EPSRC for financial support. This research made use of the shared experimental facilities of the Materials Research Laboratory (MRL), sup-ported by the MRSEC Program of the NSF under Award No. DMR 1121053. The MRL is a member of the NSF-funded Mate-rials Research Facilities Network (www.mrfn.org). CPG and ML thank the U.S. DOE Office of Vehicle Technologies (Con-tract No. DE-AC02-05CH11231) and the EU ERC (via an Ad-vanced Fellowship to CPG) for funding.This is the final published version. It first appeared at http://pubs.acs.org/doi/abs/10.1021/ja508982p
Theory and practice: bulk synthesis of C3B and its H2- and Li-storage capacity.
Previous theoretical studies of C3B have suggested that boron-doped graphite is a promising H2- and Li-storage material, with large maximum capacities. These characteristics could lead to exciting applications as a lightweight H2-storage material for automotive engines and as an anode in a new generation of batteries. However, for these applications to be realized a synthetic route to bulk C3B must be developed. Here we show the thermolysis of a single-source precursor (1,3-(BBr2)2C6H4) to produce graphitic C3B, thus allowing the characteristics of this elusive material to be tested for the first time. C3B was found to be compositionally uniform but turbostratically disordered. Contrary to theoretical expectations, the H2- and Li-storage capacities are lower than anticipated, results that can partially be explained by the disordered nature of the material. This work suggests that to model the properties of graphitic materials more realistically, the possibility of disorder must be considered.We thank the ERC (Advance Investigator awards for D.S.W., C.P.G.), the EPSRC (T.C.K., P.D.M., H.G., J.C.), and the Spanish Ministerio de Economia y Competitividad (under grants ENE2011-24-412 and IPT-2011-1553-420000). We thank John Bulmer for Raman spectroscopy and Keith Parmenter for glass blowing. We thank the Schlumberger Gould Research Centre for XPS analysis.This is the author accepted manuscript. The final version is available from Wiley via http://dx.doi.org/10.1002/anie.20141220