Gelled ionic liquid sodium ion conductors for sodium batteries

Owing to the unique properties of certain Ionic liquids (ILs) as safe and green solvents, as well as the potential of sodium as an alternative to lithium as charge carriers, we investigate gel sodium electrolytes as safe, low cost and high performance materials with sufficient mechanical properties for application in sodium battery technologies. We investigate the effect of formation of two types of gel electrolytes on the properties of IL electrolytes known to support Na/Na⁺ electrochemistry. The ionic conductivity is only slightly decreased by 0.0005 and 0.0002 S cm^-1 in the case of 0.3 and 0.5 M NaNTf2 systems respectively as the physical properties transition from liquid to gel. We observed facile plating and stripping of Na metal around 0 V vs. Na/Na⁺ through the cyclic voltammetry. A wide-temperature range of the gelled IL state, of more than 100 K around room temperature, is achieved in the case of 0.3 and 0.5 M NaNTf2. We conclude that the formation of a gel does not significantly affect the liquid-like ion dynamics in these materials, as further evidenced by DSC and FTIR analysis.

Understanding structure-function relationship in hybrid Co3O4-Fe2O3/C lithium-ion battery electrodes

A range of high-capacity Li-ion anode materials (conversion reactions with lithium) suffer from poor cycling stability and limited high-rate performance. These issues can be addressed through hybridization of multiple nanostructured components in an electrode. Using a Co3O4-Fe2O3/C system as an example, we demonstrate that the cycling stability and rate performance are improved in a hybrid electrode. The hybrid Co3O4-Fe2O3/C electrode exhibits long-term cycling stability (300 cycles) at a moderate current rate with a retained capacity of approximately 700 mAh g(-1). The reversible capacity of the Co3O4-Fe2O3/C electrode is still about 400 mAh g(-1) (above the theoretical capacity of graphite) at a high current rate of ca. 3 A g(-1), whereas Co3O4-Fe2O3, Fe2O3/C, and Co3O4/C electrodes (used as controls) are unable to operate as effectively under identical testing conditions. To understand the structure-function relationship in the hybrid electrode and the reasons for the enhanced cycling stability, we employed a combination of ex situ and in situ techniques. Our results indicate that the improvements in the hybrid electrode originate from the combination of sequential electrochemical activity of the transition metal oxides with an enhanced electronic conductivity provided by percolating carbon chains.

Self-assembled V2O5 interconnected microspheres produced in a fish-water electrolyte medium as a high-performance lithium-ion-battery cathode

Interconnected microspheres of V2O5 composed of ultra-long nanobelts are synthesized in an environmental friendly way by adopting a conventional anodization process combined with annealing. The synthesis process is simple and low-cost because it does not require any additional chemicals or reagents. Commercial fish-water is used as an electrolyte medium to anodize vanadium foil for the first time. Electron microscopy investigation reveals that each belt consists of numerous nanofibers with free space between them. Therefore, this novel nanostructure demonstrates many outstanding features during electrochemical operation. This structure prevents self-aggregation of active materials and fully utilizes the advantage of active materials by maintaining a large effective contact area between active materials, conductive additives, and electrolyte, which is a key challenge for most nanomaterials. The electrodes exhibit promising electrochemical performance with a stable discharge capacity of 227 mAh·g–1 at 1C after 200 cycles. The rate capability of the electrode is outstanding, and the obtained capacity is as high as 278 at 0.5C, 259 at 1C, 240 at 2C, 206 at 5C, and 166 mAh·g–1 at 10C. Overall, this novel structure could be one of the most favorable nanostructures of vanadium oxide-based cathodes for Li-ion batteries. [Figure not available: see fulltext.]

Synthesis of an indium oxide nanoparticle embedded graphene three-dimensional architecture for enhanced lithium-ion storage

Indium oxide nanoparticles were synthesised by using a facile and scalable strategy. The as-prepared nanoparticles (20-40 nm) were in situ and homogeneously distributed in a three-dimensional (3D) graphene architecture subsequently during the fabrication process. The obtained nanocomposite acts as a high capacity anode material for lithium-ion batteries and demonstrates good cycle stability. A drastically enhanced capacity of 750 mA h g^-1 in comparison with that of bare In2O3 nanoparticles can be maintained after 100 cycles, along with an improved high rate performance (210 mA h g^-1 at 1 A g^-1 and 120 mA h g^-1 at 2 A g^-1). The excellent performance is linked with the indium oxide nanoparticles and the unique 3D interconnected porous graphene structure. The highly conductive and porous 3D graphene structure greatly enhances the performance of lithium-ion batteries by protecting the nanoparticles from the electrolyte, stabilizing the nanoparticles during cycles and buffering the volume expansion upon lithium insertion.

Advanced N-doped mesoporous molybdenum disulfide nanosheets and the enhanced lithium-ion storage performance

With the increasing interest in two-dimensional van der Waals materials, molybdenum disulfide (MoS2) has emerged as a promising material for electronic and energy storage devices. It suffers from poor cycling stability and low rate capability when used as an anode in lithium ion batteries. Here, N-doped MoS2 nanosheets with 2-8 atomic layers, increased interlayer distance, mesoporous structure and high surface area synthesised by a simple sol-gel method show an enhanced lithium storage performance, delivering a high reversible capacity (998.0 mA h g-1, 50 mA g-1), high rate performance (610 mA h g-1, 2 A g-1), and excellent cycling stability. The excellent lithium storage performance of the MoS2 nanosheets might be due to the better electrical and ionic conductivity and improved lithium ion diffusion which are related to their structural characteristics and high concentration N doping. The possible mechanism of the improved performance is proposed and discussed.

Solid-state NMR, ionic conductivity, and thermal studies of lithium-doped siloxane-poly(propylene glycol) organic-inorganic nanocomposites

Hybrid organic-inorganic ionic conductors, also called ormolytes (organically modified electrolytes), were obtained by dissolution of LiClO 4 in siloxane-poly(propylene glycol) matrixes. The dynamic features of these nanocomposites were studied and correlated to their electrical properties. Solid-state nuclear magnetic resonance (NMR) spectroscopy was used to probe the effects of the temperature and nanocomposite composition on the dynamic behaviors of both the ionic species ( 7Li) and the polymer chains ( 13C). NMR, dc ionic conductivity, and DSC results demonstrate that the Li + mobility is strongly assisted by the segmental motion of the polymer chain above its glass transition temperature. The ac ionic conductivity in such composites is explained by use of the random free energy barrier (RFEB) model, which is agreement with their disordered and heterogenous structures. These solid ormolytes are transparent and flexible, and they exhibit good ionic conductivity at room temperature (up to 10 -4 S/cm). Consequently, they are very promising candidates for use in several applications such as batteries, sensors, and electrochromic and photoelectro-chemical devices.

Ionenleitfähigkeit in polymeren Matrizes – Synthese, Charakterisierung und Untersuchung dynamischer Prozesse von neuen Lithium- und Protonenleitern

Die vorliegende Dissertation befasst sich mit der Synthese, physikochemischen und polymerspezifischen Charakterisierung und insbesondere der impedanzspektroskopischen Untersuchung von sowohl neuartigen, solvensfreien lithiumionen- als auch protonenleitfähigen Polymermaterialien für potentielle Anwendungen in sekundären Lithiumionenbatterien bzw. in Hochtemperatur-Protonenaustauschmembran-Brennstoffzellen (engl.: proton exchange membrane fuel cell, auch: polymer electrolyte membrane fuel cell, PEMFC). Beiden Typen von ionenleitfähigen Membranen liegt das gängige Prinzip der chemischen Anbindung einer für den Ionentransport verantwortlichen Seitengruppe an eine geeignete Polymerhauptkette zugrunde („Entkopplung“; auch Immobilisierung), welcher hinsichtlich Glasübergangstemperatur (Tg), elektrochemischer und thermischer Stabilität (Td) eine dynamisch entkoppelte, aber nicht minder bedeutsame Rolle zukommt. Die Transportaktivierung erfolgt in beiden Fällen thermisch. Im Falle der Protonenleiter liegt die zusätzliche Intention darin, eine Alternative aufzuzeigen, in der die Polymerhauptkette gekoppelt direkt am Protonentransportmechanismus beteiligt ist, d.h., dass der translatorisch diffusive Ionentransport entlang der Hauptkette stattfindet und nicht zwischen benachbarten Seitenketten. Ein Hauptaugenmerk der Untersuchungen liegt sowohl bei den lithiumionen- als auch den protonenleitfähigen Polymermembranen auf temperaturabhängigen dynamischen Prozessen der jeweiligen Ionenspezies in der polymeren Matrix, was die Ionenleitfähigkeit selbst, Relaxationsphänomene, die translatorische Ionendiffusion und im Falle der Protonenleiter etwaige mesomere Grenzstrukturübergänge umfasst. Lithiumionenleiter: Poly(meth)acrylate mit (2-Oxo-1,3-dioxolan)resten (Cyclocarbonat-) in der Seitenkette unterschiedlicher Spacerlänge wurden synthetisiert und charakterisiert. Die Leitfähigkeit s(,T) erreicht bei Poly(2-oxo-[1,3]dioxolan-4-yl)methylacrylat (PDOA): Lithium-bis-trifluormethansulfonimid (LiTFSI) (10:3) ca. 10^-3,5 S cm^-1 bei 150 °C. Weichmachen (Dotieren) mit äquimolaren Mengen an Propylencarbonat (PC) bewirkt in allen Fällen einen enormen Anstieg der Leitfähigkeit. Die höchsten Leitfähigkeiten von Mischungen dieser Polymere mit LiTFSI (und LiBOB) werden nicht beim System mit der niedrigsten Tg gefunden. Auch dient Tg nicht als Referenztemperatur (Tref) nach Williams-Landel-Ferry (WLF), so dass eine WLF-Anpassung der Leitfähigkeitsdaten nur über einen modifizierten WLF-Algorithmus gelingt. Die ermittelten Tref liegen deutlich unterhalb von Tg bei Temperaturen, die charakteristisch für die Seitenkettenrelaxation sind („Einfrieren“). Dies legt nahe, dass der Relaxation der Seitenketten eine entscheidende Rolle im Li^+-Leitfähigkeitsmechanismus zukommt. Die Li^+-Überführungszahlen tLi^+ in diesen Systemen schwanken zwischen 0,13 (40 °C) und 0,55 (160 °C). Protonenleiter: Polymere mit Barbitursäure- bzw. Hypoxanthinresten in der Seitenkette und Polyalkylenbiguanide unterschiedlicher Spacerlänge wurden synthetisiert und charakterisiert. Die Leitfähigkeit s(,T) erreicht bei Poly(2,4,6(1H,3H,5H)-trioxopyrimidin-5-yl)methacrylat (PTPMA) maximal ca. 10^-4,4 S cm^-1 bei 140 °C. Höhere Leitfähigkeiten sind nur durch Mischen mit aprotischen Lösungsmitteln erreichbar. Die höchste Leitfähigkeit wird im Falle der Polyalkylenbiguanide bei Polyethylenbiguanid (PEB) erzielt. Sie erreicht 10^-2,4 S cm^-1 bei 190 °C. Die Aktivierungsenergien EA der Polyalkylenbiguanide liegen (jeweils unterhalb von Tg) zwischen ca. 3 – 6 kJ mol^-1. In allen beobachteten Fällen dient Tg als Tref, so dass eine konventionelle WLF-Behandlung möglich ist und davon auszugehen ist, dass die Leitfähigkeit mit dem freien Volumen Vf korreliert.

Investigation of the lithium ion mobility in cyclic model compounds and their ion conducting properties

Efficient energy storage and conversion is playing a key role in overcoming the present and future challenges in energy supply. Batteries provide portable, electrochemical storage of green energy sources and potentially allow for a reduction of the dependence on fossil fuels, which is of great importance with respect to the issue of global warming. In view of both, energy density and energy drain, rechargeable lithium ion batteries outperform other present accumulator systems. However, despite great efforts over the last decades, the ideal electrolyte in terms of key characteristics such as capacity, cycle life, and most important reliable safety, has not yet been identified. rnrnSteps ahead in lithium ion battery technology require a fundamental understanding of lithium ion transport, salt association, and ion solvation within the electrolyte. Indeed, well-defined model compounds allow for systematic studies of molecular ion transport. Thus, in the present work, based on the concept of ‘immobilizing’ ion solvents, three main series with a cyclotriphosphazene (CTP), hexaphenylbenzene (HBP), and tetramethylcyclotetrasiloxane (TMS) scaffold were prepared. Lithium ion solvents, among others ethylene carbonate (EC), which has proven to fulfill together with pro-pylene carbonate safety and market concerns in commercial lithium ion batteries, were attached to the different cores via alkyl spacers of variable length.rnrnAll model compounds were fully characterized, pure and thermally stable up to at least 235 °C, covering the requested broad range of glass transition temperatures from -78.1 °C up to +6.2 °C. While the CTP models tend to rearrange at elevated temperatures over time, which questions the general stability of alkoxide related (poly)phosphazenes, both, the HPB and CTP based models show no evidence of core stacking. In particular the CTP derivatives represent good solvents for various lithium salts, exhibiting no significant differences in the ionic conductivity σ_dc and thus indicating comparable salt dissociation and rather independent motion of cations and ions.rnrnIn general, temperature-dependent bulk ionic conductivities investigated via impedance spectroscopy follow a William-Landel-Ferry (WLF) type behavior. Modifications of the alkyl spacer length were shown to influence ionic conductivities only in combination to changes in glass transition temperatures. Though the glass transition temperatures of the blends are low, their conductivities are only in the range of typical polymer electrolytes. The highest σ_dc obtained at ambient temperatures was 6.0 x 10-6 S•cm-1, strongly suggesting a rather tight coordination of the lithium ions to the solvating 2-oxo-1,3-dioxolane moieties, supported by the increased σ_dc values for the oligo(ethylene oxide) based analogues.rnrnFurther insights into the mechanism of lithium ion dynamics were derived from 7Li and 13C Solid- State NMR investigations. While localized ion motion was probed by i.e. 7Li spin-lattice relaxation measurements with apparent activation energies E_a of 20 to 40 kJ/mol, long-range macroscopic transport was monitored by Pulsed-Field Gradient (PFG) NMR, providing an E_a of 61 kJ/mol. The latter is in good agreement with the values determined from bulk conductivity data, indicating the major contribution of ion transport was only detected by PFG NMR. However, the μm-diffusion is rather slow, emphasizing the strong lithium coordination to the carbonyl oxygens, which hampers sufficient ion conductivities and suggests exploring ‘softer’ solvating moieties in future electrolytes.rn

A Comparison of the Impacts of Lithium Extraction and Lithium Recycling Processes

Lithium is used in the cathode and electrolyte of rechargeable batteries in many portable electronics and electric vehicles, and is thus seen as a critical component of modern technology (Gruber et al., 2011). Electric vehicles are promoted as a way to reduce carbon emissions associated with the transportation sector, which accounts for 14.3% of anthropogenic greenhouse gas emissions (OECD International Transport Forum, 2010). However, the sustainability of lithium procurement will influence the overall environmental impact of this proposed “green” solution. It is estimated that 66% of the world’s lithium resource is contained in natural brines, 24% in pegmatites, and 8% in sedimentary rocks such as hectorite clays (Gruber et al., 2011). It has been shown that “[r]ecycling of lithium from Li-ion batteries may be a critical factor in balancing the supply of lithium with future demand” (Gruber et al., 2011). In an attempt to quantify energy and materials consumption associated with production of a unit of useful lithium compounds, industry reports and peer-reviewed scientific literature concerning lithium mining and lithium recycling were reviewed and compared. Other aspects of sustainability, such as waste or by-products produced in the production of a unit of useful lithium, were also explored. Thus, this paper will serve to further the evaluation of the comparative environmental consequences associated with lithium production via extraction versus recycling. Efficiencies must be made in both processes to maximize productivity while minimizing ecological harm.

Low-cost batteries will not disrupt (all) energy utilities. CEPS Commentary, 5 October 2015

With the launch last April of an affordable lithium-ion home battery – the Powerwall – Tesla’s CEO Elon Musk is betting that batteries are going to become a mass market. This may very well become reality, but this commentary argues that one should not jump to the conclusion that this is the end of energy utilities. Similar to solar panels, batteries have high upfront costs. The massive deployment of solar was driven by dedicated policy support, in many cases without any kind of cost or volume control. There is no such thing for batteries. In the absence of financing programmes, the author finds that high upfront costs provide an unfavourable starting point for a disruptive development. But he notes that the fact that self-consumption of stored solar energy will soon pay for consumers represents a paradigm shift in the power industry, which should be seen as an opportunity, at least for first-movers.

Electrochemical investigation of liquid amalgams of thallium, indium, tin, zinc, cadmium, lead, copper, and lithium.

"Contributions from the Chemical Laboratory of Harvard College."

Assessing charge contribution from thermally treated Ni foam as current collectors for Li-ion batteries

In this report we have investigated the use of Ni foam substrates as anode current collectors for Li-ion batteries. As the majority of reports in the literature focus on hydrothermal formation of materials on Ni foam followed by a high temperature anneal/oxidation step, we probed the fundamental electrochemical responses of as received Ni foam substrates and those subjected to heating at 100°C, 300°C and 450°C. Through cyclic voltammetry and galvanostatic testing, it is shown that the as received and 100°C annealed Ni foam show negligible electrochemical activity. However, Ni foams heated to higher temperature showed substantial electrochemical contributions which may lead to inflated capacities and incorrect interpretations of CV responses for samples subjected to high temperature anneals. XRD, XPS and SEM analyses clearly illustrate that the formation of electrochemically active NiO nanoparticles on the surface of the foam is responsible for this behavior. To further investigate the contribution of the oxidized Ni foam to the overall electrochemical response, we formed Co3O4 nanoflowers directly on Ni foam at 450°C and showed that the resulting electrochemical response was dominated by NiO after the first 10 charge/discharge cycles. This report highlights the importance of assessing current collector activity for active materials grown on transition metal foam current collectors for Li-ion applications.

The structural conversion from α-AgVO3 to β-AgVO3: Ag nanoparticle decorated nanowires with application as cathode materials for Li-ion batteries

The majority of electrode materials in batteries and related electrochemical energy storage devices are fashioned into slurries via the addition of a conductive additive and a binder. However, aggregation of smaller diameter nanoparticles in current generation electrode compositions can result in non-homogeneous active materials. Inconsistent slurry formulation may lead to inconsistent electrical conductivity throughout the material, local variations in electrochemical response, and the overall cell performance. Here we demonstrate the hydrothermal preparation of Ag nanoparticle (NP) decorated α-AgVO3 nanowires (NWs) and their conversion to tunnel structured β-AgVO3 NWs by annealing to form a uniform blend of intercalation materials that are well connected electrically. The synthesis of nanostructures with chemically bound conductive nanoparticles is an elegant means to overcome the intrinsic issues associated with electrode slurry production, as wire-to-wire conductive pathways are formed within the overall electrode active mass of NWs. The conversion from α-AgVO3 to β-AgVO3 is explained in detail through a comprehensive structural characterization. Meticulous EELS analysis of β-AgVO3 NWs offers insight into the true β-AgVO3 structure and how the annealing process facilitates a higher surface coverage of Ag NPs directly from ionic Ag content within the α-AgVO3 NWs. Variations in vanadium oxidation state across the surface of the nanowires indicate that the β-AgVO3 NWs have a core–shell oxidation state structure, and that the vanadium oxidation state under the Ag NP confirms a chemically bound NP from reduction of diffused ionic silver from the α-AgVO3 NWs core material. Electrochemical comparison of α-AgVO3 and β-AgVO3 NWs confirms that β-AgVO3 offers improved electrochemical performance. An ex situ structural characterization of β-AgVO3 NWs after the first galvanostatic discharge and charge offers new insight into the Li+ reaction mechanism for β-AgVO3. Ag+ between the van der Waals layers of the vanadium oxide is reduced during discharge and deposited as metallic Ag, the vacant sites are then occupied by Li+.

A Comparison of the Impacts of Lithium Extraction and Lithium Recycling Processes

Lithium is used in the cathode and electrolyte of rechargeable batteries in many portable electronics and electric vehicles, and is thus seen as a critical component of modern technology (Gruber et al., 2011). Electric vehicles are promoted as a way to reduce carbon emissions associated with the transportation sector, which accounts for 14.3% of anthropogenic greenhouse gas emissions (OECD International Transport Forum, 2010). However, the sustainability of lithium procurement will influence the overall environmental impact of this proposed “green” solution. It is estimated that 66% of the world’s lithium resource is contained in natural brines, 24% in pegmatites, and 8% in sedimentary rocks such as hectorite clays (Gruber et al., 2011). It has been shown that “[r]ecycling of lithium from Li-ion batteries may be a critical factor in balancing the supply of lithium with future demand” (Gruber et al., 2011). In an attempt to quantify energy and materials consumption associated with production of a unit of useful lithium compounds, industry reports and peer-reviewed scientific literature concerning lithium mining and lithium recycling were reviewed and compared. Other aspects of sustainability, such as waste or by-products produced in the production of a unit of useful lithium, were also explored. Thus, this paper will serve to further the evaluation of the comparative environmental consequences associated with lithium production via extraction versus recycling. Efficiencies must be made in both processes to maximize productivity while minimizing ecological harm.

Electrochemical Investigations into Blended Electrolytes Containing Ionic Liquids and a Glyme Solvent for Li-O­2 batteries

The Li-O2 battery may theoretically possess practical gravimetric energy densities several times greater than the current state-of-the-art Li-ion batteries.1 This magnitude of development is a requisite for true realization of electric vehicles capable of competing with the traditional combustion engine. However, significant challenges must be addressed before practical application may be considered. These include low efficiencies, low rate capabilities and the parasitic decomposition reactions of electrolyte/electrode materials resulting in very poor rechargeability.2-4 Ionic liquids, ILs, typically display several properties, extremely low vapor pressure and high electrochemical and thermal stability, which make them particularly interesting for Li-O2 battery electrolytes. However, the typically sluggish transport properties generally inhibit rate performance and cells suffer similar inefficiencies during cycling.5,6

In addition to the design of new ILs with tailored properties, formulating blended electrolytes using molecular solvents with ILs has been considered to improve their performance.7,8 In this work, we will discuss the physical properties vs. the electrochemical performance of a range of formulated electrolytes based on tetraglyme, a benchmark Li-O2 battery electrolyte solvent, and several ILs. The selected ILs are based on the bis{(trifluoromethyl)sulfonyl}imide anion and alkyl/ether functionalized cyclic alkylammonium cations, which exhibit very good stability and moderate viscosity.9 O2 electrochemistry will be investigated in these media using macro and microdisk voltammetry and O2 solubility/diffusivity is quantified as a function of the electrolyte formulation. Furthermore, galvanostatic cycling of selected electrolytes in Li-O2 cells will be discussed to probe their practical electrochemical performance. Finally, the physical characterization of the blended electrolytes will be reported in parallel to further determine structure (or formulation) vs. property relationships and to, therefore, assess the importance of certain electrolyte properties (viscosity, O2supply capability, donor number) on their performance.

This work was funded by the EPSRC (EP/L505262/1) and Innovate UK for the Practical Lithium-Air Batteries project (project number: 101577).

1. P. G. Bruce, S. A. Freunberger, L. J. Hardwick and J.-M. Tarascon, Nat. Mater., 11, 19 (2012).

2. S. A. Freunberger, Y. Chen, N. E. Drewett, L. J. Hardwick, F. Barde and P. G. Bruce, Angew. Chem., Int. Ed., 50, 8609 (2011).

3. B. D. McCloskey, A. Speidel, R. Scheffler, D. C. Miller, V. Viswanathan, J. S. Hummelshøj, J. K. Nørskov and A. C. Luntz, J. Phys. Chem. Lett., 3, 997 (2012).

4. D. G. Kwabi, T. P. Batcho, C. V. Amanchukwu, N. Ortiz-Vitoriano, P. Hammond, C. V. Thompson and Y. Shao-Horn, J. Phys. Chem. Lett., 5, 2850 (2014).

5. Z. H. Cui, W. G. Fan and X. X. Guo, J. Power Sources, 235, 251 (2013).

6. F. Soavi, S. Monaco and M. Mastragostino, J. Power Sources, 224, 115 (2013).

7. L. Cecchetto, M. Salomon, B. Scrosati and F. Croce, J. Power Sources, 213, 233 (2012).

8. A. Khan and C. Zhao, Electrochem. Commun., 49, 1 (2014).

9. Z. J. Chen, T. Xue and J.-M. Lee, RSC Adv., 2, 10564 (2012).