The high-energy-density, Li-rich layered materials, i.e., xLiMO(2)(1-x)Li2MnO3, are promising candidate cathode materials for electric energy storage in plug-in hybrid electric vehicles (PHEVs) and electric vehicles (EVs). The relatively low rate capability is one of the major problems that need to be resolved for these materials. To gain insight into the key factors that limit the rate capability, in situ X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) studies of the cathode material, Li1.2Ni0.15Co0.1Mn0.55O2 0.5Li(Ni0.375Co0.25 Mn-0.375)O(2)0.5Li(2)MnO(3)], are carried out. The partial capacity contributed by different structural components and transition metal elements is elucidated and correlated with local structure changes. The characteristic reaction kinetics for each element are identified using a novel time-resolved XAS technique. Direct experimental evidence is obtained showing that Mn sites have much poorer reaction kinetics both before and after the initial activation of Li2MnO3, compared to Ni and Co. These results indicate that Li2MnO3 may be the key component that limits the rate capability of Li-rich layered materials and provide guidance for designing Li-rich layered materials with the desired balance of energy density and rate capability for different applications.
A solution-processed neutral hole transport layer is developed by in situ formation of MoO3 in aqueous PEDOT:PSS dispersion (MoO3-PEDOT:PSS). This MoO3-PEDOT:PSS composite film takes advantage of both the highly conductive PEDOT:PSS and the ambient conditions stability of MoO3; consequently it possesses a smooth surface and considerably reduced hygroscopicity. The resulting bulk heterojunction polymer solar cells (BHJ PSC) based on poly2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (TQ1):6,6]-phenyl-C71-butyric acid methyl ester (PC70BM) blends using MoO3-PEDOT:PSS composite film as hole transport layer (HTL) show considerable improvement in power conversion efficiency (PCE), from 5.5% to 6.4%, compared with the reference pristine PEDOT:PSS-based device. More importantly, the device with MoO3-PEDOT:PSS HTL shows considerably improved stability, with the PCE remaining at 80% of its original value when stored in ambient air in the dark for 10 days. In comparison, the reference solar cell with PEDOT:PSS layer shows complete failure within 10 days. This MoO3-PEDOT:PSS implies the potential for low-cost roll-to-roll fabrication of high-efficiency polymer solar cells with long-term stability at ambient conditions.
Layered sodium titanium oxide, Na2Ti3O7, is synthesized by a solid-state reaction method as a potential anode for sodium-ion batteries. Through optimization of the electrolyte and binder, the microsized Na2Ti3O7 electrode delivers a reversible capacity of 188 mA h g(-1) in 1 M NaFSI/PC electrolyte at a current rate of 0.1C in a voltage range of 0.0-3.0 V, with sodium alginate as binder. The average Na storage voltage plateau is found at ca. 0.3 V vs. Na+/Na, in good agreement with a first-principles prediction of 0.35 V. The Na storage properties in Na2Ti3O7 are investigated from thermodynamic and kinetic aspects. By reducing particle size, the nanosized Na2Ti3O7 exhibits much higher capacity, but still with unsatisfied cyclic properties. The solid-state interphase layer on Na2Ti3O7 electrode is analyzed. A zero-current overpotential related to thermodynamic factors is observed for both nano- and microsized Na2Ti3O7. The electronic structure, Na+ ion transport and conductivity are investigated by the combination of first-principles calculation and electrochemical characterizations. On the basis of the vacancy-hopping mechanism, a quasi-3D energy favorable trajectory is proposed for Na2Ti3O7. The Na+ ions diffuse between the TiO6 octahedron layers with pretty low activation energy of 0.186 eV.
Li2MnO3 is the parent compound of the well-studied Li-rich Mn-based cathode materials xLi(2)MnO(3)center dot(1-x)LiMO2 for high-energy-density Li-ion batteries. Li2MnO3 has a very high theoretical capacity of 458 mA h g(-1) for extracting 2 Li. However, the delithiation and lithiation behaviors and the corresponding structure evolution mechanism in both Li2MnO3 and Li-rich Mn-based cathode materials are still not very clear. In this research, the atomic structures of Li2MnO3 before and after partial delithiation and relithiation are observed with spherical aberration-corrected scanning transmission electron microscopy (STEM). All atoms in Li2MnO3 can be visualized directly in annular bright-field images. It is confirmed accordingly that the lithium can be extracted from the LiMn2 planes and some manganese atoms can migrate into the Li layer after electrochemical delithiation. In addition, the manganese atoms can move reversibly in the (001) plane when ca. 18.6% lithium is extracted and 12.4% lithium is re-inserted. LiMnO2 domains are also observed in some areas in Li1.63MnO3 at the first cycle. As for the position and occupancy of oxygen, no significant difference is found between Li1.63MnO3 and Li2MnO
A new self-assembly platform for the fast and straightforward synthesis of bicontinuous, mesoporous TiO2 films is presented, based on the triblock terpolymer poly(isoprene-b-styrene-b-ethylene oxide). This new materials route allows the co-assembly of the metal oxide as a fully interconnected minority phase, which results in a highly porous photoanode with strong advantages over the state-of-the-art nanoparticle-based photoanodes employed in solid-state dye-sensitized solar cells. Devices fabricated through this triblock terpolymer route exhibit a high availability of sub-bandgap states distributed in a narrow and low enough energy band, which maximizes photoinduced charge generation from a state-of-the-art organic dye, C220. As a consequence, the co-assembled mesoporous metal oxide system outperformed the conventional nanoparticle-based electrodes fabricated and tested under the same conditions, exhibiting solar power-conversion efficiencies of over 5%.
A simple and scalable method to fabricate graphene-cellulose paper (GCP) membranes is reported; these membranes exhibit great advantages as freestanding and binder-free electrodes for flexible supercapacitors. The GCP electrode consists of a unique three-dimensional interwoven structure of graphene nanosheets and cellulose fibers and has excellent mechanical flexibility, good specific capacitance and power performance, and excellent cyclic stability. The electrical conductivity of the GCP membrane shows high stability with a decrease of only 6% after being bent 1000 times. This flexible GCP electrode has a high capacitance per geometric area of 81 mF cm(-2), which is equivalent to a gravimetric capacitance of 120 F g(-1) of graphene, and retains >99% capacitance over 5000 cycles. Several types of flexible GCP-based polymer supercapacitors with various architectures are assembled to meet the power-energy requirements of typical flexible or printable electronics. Under highly flexible conditions, the supercapacitors show a high capacitance per geometric area of 46 mF cm(-2) for the complete devices. All the results demonstrate that polymer supercapacitors made using GCP membranes are versatile and may be used for flexible and portable micropower devices.