Nanoparticle LiFePO4, the basis for an entire class of high power Li-ion batteries, has recently been shown to exist in binary lithiated/delithiated states at intermediate states of charge. The Mn-bearing version, LiMn(y)Fe(1-y)PO4, exhibits even higher rate capability as a lithium battery cathode than LiFePO4 of comparable particle size. To gain insight into the cause(s) of this desirable performance, the electrochemically driven phase transformation during battery charge and discharge of nanoscale LiMn0.4Fe0.6PO4 of three different average particle sizes, 52, 106, and 152 nm, is investigated by operando synchrotron radiation powder X-ray diffraction. In stark contrast to the binary lithiation states of pure LiFePO4 revealed in recent investigations, the formations of metastable solid solutions covering a remarkable wide compositional range, including while in two-phase coexistence, are observed. Detailed analysis correlates this behavior with small elastic misfits between phases compared to either pure LiFePO4 or LiMnPO4. On the basis of time- and state-of-charge dependence of the olivine structure parameters, we propose a coherent transformation mechanism. These findings illustrate a second, completely different phase transformation mode for pure well-ordered nanoscale olivines compared to the well-studied case of LiFePO4.

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Virtually all intercalation compounds exhibit significant changes in unit cell volume as the working ion concentration varies. NaFePO (0 < x < 1, NFP) olivine, of interest as a cathode for sodium-ion batteries, is a model for topotactic, high-strain systems as it exhibits one of the largest discontinuous volume changes (∼17% by volume) during its first-order transition between two otherwise isostructural phases. Using synchrotron radiation powder X-ray diffraction (PXD) and pair distribution function (PDF) analysis, we discover a new strain-accommodation mechanism wherein a third, amorphous phase forms to buffer the large lattice mismatch between primary phases. The amorphous phase has short-range order over ∼1nm domains that is characterized by a and b parameters matching one crystalline end-member phase and a c parameter matching the other, but is not detectable by powder diffraction alone. We suggest that this strain-accommodation mechanism may generally apply to systems with large transformation strains.

In this work we investigated an energy-efficient biotemplated route to synthesize nanostructured FePO4 for sodium-based batteries. Self-assembled M13 viruses and single wall carbon nanotubes (SWCNTs) have been used as a template to grow amorphous FePO4 nanoparticles at room temperature (the active composite is denoted as Bio-FePO4-CNT) to enhance the electronic conductivity of the active material. Preliminary tests demonstrate a discharge capacity as high as 166 mAh/g at C/10 rate, corresponding to composition Na0.9FePO4, which along with higher C-rate tests show this material to have the highest capacity and power performance reported for amorphous FePO4 electrodes to date.

In this paper, we generalize the concept of well-posedness to a system of hemivariational inequalities in Banach space. By introducing several concepts of well-posedness for systems of hemivariational inequalities considered, we establish some metric characterizations of well-posedness and prove some equivalence results of strong (generalized) well-posedness between a system of hemivariational inequalities and its derived system of inclusion problems.