Ordering in Crystalline Short-Chain Polymer Electrolytes

Polymer electrolytes are the most obvious candidates for safe "all-solid" Li-ion batteries and other electrochemical devices. However, they still have relatively poor ionic conductivities, which limits their wider adoption in commercial applications. It has earlier been the conventional wisdom that only amorphous phases of polymer electrolytes show usefully high ionic conduction, while crystalline forms are insulators. However, this has been challenged in the last decade by the discovery of highly organized, low-dimensional ion-conducting materials. Specifically, the crystalline phases of LiXF6.PEO6 exhibit higher ionic conductivities than their amorphous counterparts, with the Li-ion conduction taking place along the PEO channels. Polymer chain-length and chain-end registry has emerged as potentially significant in determining ionic conduction in these materials. Molecular Dynamics simulations have therefore been made of short-chain, monodisperse (Mw~1000), methoxy end-capped LiPF6.PEO6 to examine relationships between ion conduction and mode of chain-ordering. Studies of smectic and nematic arrangements of PEO chains have revealed that ion-transport mechanisms within the smectic planes formed by cooperative chain-end registry appear to be more suppressed by ion-pairing than in-channel conduction. Disorder phenomena in the chain-end regions emerge as a critical factor in promoting Li-ion migration across chain-gaps, as does the structural continuity of the PEO channels. Simulations incorporating ~1% aliovalent SiF62- dopants further suggest an increase in Li-ion conduction when the extra Li-ions reside within the PEO channels, with the anion influencing charge-carrier concentration through enhanced ion-pair formation. XRD techniques alone are shown to be inadequate in ascertaining the significance of the various short-chain models proposed; atomistic modelling is clearly a helpful complement in distinguishing more or less favourable situations for ion conduction. Though providing valuable insights, it must be concluded that this work has hardly brought us significantly closer to breakthroughs in polymer electrolyte design; the critical factors which will make this possible remain as yet obscure

Ordering in Crystalline Short-Chain Polymer Electrolytes

Polymer electrolytes are the most obvious candidates for safe "all-solid" Li-ion batteries and other electrochemical devices. However, they still have relatively poor ionic conductivities, which limits their wider adoption in commercial applications. It has earlier been the conventional wisdom that only amorphous phases of polymer electrolytes show usefully high ionic conduction, while crystalline forms are insulators. However, this has been challenged in the last decade by the discovery of highly organized, low-dimensional ion-conducting materials. Specifically, the crystalline phases of LiXF6.PEO6 exhibit higher ionic conductivities than their amorphous counterparts, with the Li-ion conduction taking place along the PEO channels. Polymer chain-length and chain-end registry has emerged as potentially significant in determining ionic conduction in these materials. Molecular Dynamics simulations have therefore been made of short-chain, monodisperse (Mw~1000), methoxy end-capped LiPF6.PEO6 to examine relationships between ion conduction and mode of chain-ordering. Studies of smectic and nematic arrangements of PEO chains have revealed that ion-transport mechanisms within the smectic planes formed by cooperative chain-end registry appear to be more suppressed by ion-pairing than in-channel conduction. Disorder phenomena in the chain-end regions emerge as a critical factor in promoting Li-ion migration across chain-gaps, as does the structural continuity of the PEO channels. Simulations incorporating ~1% aliovalent SiF62- dopants further suggest an increase in Li-ion conduction when the extra Li-ions reside within the PEO channels, with the anion influencing charge-carrier concentration through enhanced ion-pair formation. XRD techniques alone are shown to be inadequate in ascertaining the significance of the various short-chain models proposed; atomistic modelling is clearly a helpful complement in distinguishing more or less favourable situations for ion conduction. Though providing valuable insights, it must be concluded that this work has hardly brought us significantly closer to breakthroughs in polymer electrolyte design; the critical factors which will make this possible remain as yet obscure

Ordering in Crystalline Short-Chain Polymer Electrolytes

Polymer electrolytes are the most obvious candidates for safe "all-solid" Li-ion batteries and other electrochemical devices. However, they still have relatively poor ionic conductivities, which limits their wider adoption in commercial applications. It has earlier been the conventional wisdom that only amorphous phases of polymer electrolytes show usefully high ionic conduction, while crystalline forms are insulators. However, this has been challenged in the last decade by the discovery of highly organized, low-dimensional ion-conducting materials. Specifically, the crystalline phases of LiXF6.PEO6 exhibit higher ionic conductivities than their amorphous counterparts, with the Li-ion conduction taking place along the PEO channels. Polymer chain-length and chain-end registry has emerged as potentially significant in determining ionic conduction in these materials. Molecular Dynamics simulations have therefore been made of short-chain, monodisperse (Mw~1000), methoxy end-capped LiPF6.PEO6 to examine relationships between ion conduction and mode of chain-ordering. Studies of smectic and nematic arrangements of PEO chains have revealed that ion-transport mechanisms within the smectic planes formed by cooperative chain-end registry appear to be more suppressed by ion-pairing than in-channel conduction. Disorder phenomena in the chain-end regions emerge as a critical factor in promoting Li-ion migration across chain-gaps, as does the structural continuity of the PEO channels. Simulations incorporating ~1% aliovalent SiF62- dopants further suggest an increase in Li-ion conduction when the extra Li-ions reside within the PEO channels, with the anion influencing charge-carrier concentration through enhanced ion-pair formation. XRD techniques alone are shown to be inadequate in ascertaining the significance of the various short-chain models proposed; atomistic modelling is clearly a helpful complement in distinguishing more or less favourable situations for ion conduction. Though providing valuable insights, it must be concluded that this work has hardly brought us significantly closer to breakthroughs in polymer electrolyte design; the critical factors which will make this possible remain as yet obscure

Detecting voltage shifts and charge storage anomalies by iron nanoparticles in three-electrode cells based on converted iron oxide and lithium iron phosphate

Noticeable voltage shifts have been observed in the charge/discharge profiles of a three-electrode cell with a lithium metal reference electrode and having a deeply lithiated iron oxide (Fe/Li2O) negative electrode galvanostatically cycled in a limited potential range against a positive LiFePO4 counterpart. The origin of such shifts has been attributed to charge storage anomalies in the Fe/Li2O nanocomposite due to characteristic reduced Fe nanoparticle sizes. These shifts also affected the extreme points of the voltage profiles of the positive electrode, which was also independently monitored. A combined evaluation of voltage profile slippages with possible changes in internal resistance and/or Li+ inventory loss, including an aimed analysis of current interruptions at the end of each lithiation/de-lithiation half-cycle to monitor the internal resistance and diffusion resistance coefficient of the Fe/Li2O electrode, has enabled a clarification of its altered charge storage. An asymmetric behaviour of the Fe/Li2O electrode during Li+ uptake/release has been revealed, highlighting a progressive, diffusion-controlled-type voltage drift at low potentials vs. Li+/Li, and an unusual tendency to slight oxidation with capacitive variations during the reverse electrochemical processes at higher voltages, instead

Manganese Pyrosilicates as Novel Positive Electrode Materials for Na-Ion Batteries

A carbon-coated pyrosilicate, Na2Mn2Si2O7/C, was synthesized and characterized for use as a new positive-electrode material for sodium ion batteries. The material consists of primary 20-80 nm particles embedded in a ≈10 nm-thick conductive carbon matrix. Reversible insertion of Na+ ions is clearly demonstrated with ≈25% of its theoretical capacity (165 mAh/g) accessible at room temperature at a low cycling rate. The material yields an average potential of 3.3 V vs. Na+/Na on charge and 2.2 V on discharge. DFT calculations predict an equilibrium potential for Na2Mn2Si2O7 in the range of 2.8-3.0 V vs. Na+/Na, with a possibility of a complete flip in the connectivity of neighboring Mn-polyhedra – from edge-sharing to disconnected and vice versa. This significant rearrangement in Mn coordination  (≈2 Å) and large volume contraction (>10%) could explain our inability to fully desodiate the material, and illustrates well the need for a new electrode design strategy beyond the conventional “down-sizing/coating” procedure

Fast-charging effects on ageing for energy-optimized automotive LiNi1/3Mn1/3Co1/3O2/graphite prismatic lithium-ion cells

The reactions in energy-optimized 25 Ah prismatic NMC/graphite lithium-ion cell, as a function of fast charging (1C-4C), are more complex than earlier described. There are no clear charging rate dependent trends but rather different mechanisms dominating at the different charging rates. Ageing processes are faster at 3 and 4C charging. Cycling with 3C-charging results in accelerated lithium plating but the 4C-charging results in extensive gas evolution that contribute significantly to the large cell impedance rise. Graphite exfoliation and accelerated lithium inventory loss point to the graphite electrode as the source of the gas evolution. The results are based on careful post-mortem analyses of electrodes using: scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and electrochemical impedance spectroscopy (EIS). SEM results show particle cracking independent of the charging rate used for the cycling. XPS and EIS generally indicate thicker surface film and larger impedance, respectively, towards the edge of the jellyrolls. For the intended application of a battery electric inner-city bus using this type of cell, charging rates of 3C and above are not feasible, considering battery lifetime. However, charging rates of 2C and below are too slow from the point of view of practical charging time