Jianming Fan

K+-Doped Li1.2Mn0.54Co0.13Ni0.13O2: A Novel Cathode Material with an Enhanced Cycling Stability for Lithium-Ion Batteries

Li-rich layered oxides have attracted much attention for their potential application as cathode materials in lithium ion batteries, but still suffer from inferior cycling stability and fast voltage decay during cycling. How to eliminate the detrimental spinel growth is highly challenging in this regard. Herein, in situ K(+)-doped Li1.20Mn0.54Co0.13Ni0.13O2 was successfully prepared using a potassium containing α-MnO2 as the starting material. A systematic investigation demonstrates for the first time, that the in situ potassium doping stabilizes the host layered structure by prohibiting the formation of spinel structure during cycling. This is likely due to the fact that potassium ions in the lithium layer could weaken the formation of trivacancies in lithium layer and Mn migration to form spinel structure, and that the large ionic radius of potassium could possibly aggravate steric hindrance for spinel growth. Consequently, the obtained oxides exhibited a superior cycling stability with 85% of initial capacity (315 mA h g(-1)) even after 110 cycles. The results reported in this work are fundamentally important, which could provide a vital hint for inhibiting the undesired layered-spinel intergrowth with alkali ion doping and might be extended to other classes of layered oxides for excellent cycling performance.

Nickel-Rich Layered Microspheres Cathodes: Lithium/Nickel Disordering and Electrochemical Performance

Nickel-rich layered metal oxide materials are prospective cathode materials for lithium ion batteries due to the relatively higher capacity and lower cost than LiCoO2. Nevertheless, the disordered arrangement of Li(+)/Ni(2+) in local regions of these materials and its impact on electrochemistry performance are not well understood, especially for LiNi(1-x-y)Co(x)Mn(y)O2 (1-x-y > 0.5) cathodes, which challenge ones ability in finding more superior cathode materials for advanced lithium-ion batteries. In this work, Ni-Co-Mn-based spherical precursors were first obtained by a solvothermal method through handily utilizing the redox reaction of nitrate and ethanol. Subsequent sintering of the precursors with given amount of lithium source (Li-excess of 5, 10, and 15 mol %) yields LiNi0.7Co0.15Mn0.15O2 microspheres with different extents of Li(+)/Ni(2+) disordering. With the determination of the amounts of Li(+) ions in transition metal layer and Ni(2+) ions in Li layer using structural refinement, the impact of Li(+)/Ni(2+) ions disordering on the crystal structure, valence state of nickel ions, and electrochemical performance were investigated in detailed. It is clearly demonstrated that with increasing the amount of lithium source, lattice parameters (a and c) and interslab space thickness of unit cell decrease, and more Li(+) ions incorporated into the 3a site of transition metal layer which leads to an increase of Ni(3+) content in LiNi0.7Co0.15Mn0.15O2 as confirmed by X-ray photoelectron spectroscopy and a redox titration. Moreover, the electrochemical performance for as-prepared LiNi0.7Co0.15Mn0.15O2 microspheres exhibited a trend of deterioration due to the changes of crystal structure from Li(+)/Ni(2+) mixing. The preparation method and the impacts of Li(+)/Ni(2+) ions disordering reported herein for the nickel-rich layered LiNi0.7Co0.15Mn0.15O2 microspheres may provide hints for obtaining a broad class of nickel-rich layered metal oxide microspheres with superior electrochemical performance.

Balancing stability and specific energy in Li-rich cathodes for lithium ion batteries: a case study of a novel Li–Mn–Ni–Co oxide

Lithium batteries for UPS, portable electronics and electrical vehicles rely on high-energy cathodes. Li-rich manganese-rich oxide (xLi2MnO3·(1 − x)LiMO2, M = transition metals) is one of the few materials that might meet such a requirement, but it suffers from poor energy retention due to serious voltage and/or capacity fade, which challenges its applications. Here we show that this challenge can be addressed by optimizing the interactions between the components Li2MnO3 and LiMO2 in the Li-rich oxide (i.e. stabilizing the layered structure through Li2MnO3 and controlling Li2MnO3 activation through LiMO2). To realize this synergistic effect, a novel Li2MnO3-stabilized Li1.080Mn0.503Ni0.387Co0.030O2 was designed and prepared using a hierarchical carbonate precursor obtained by a solvo/hydro-thermal method. This layered oxide is demonstrated to have a high working voltage of 3.9 V and large specific energy of 805 W h kg−1 at 29 °C as well as impressive energy retention of 92% over 100 cycles. Even when exposed to 55 °C, energy retention is still as high as 85% at 200 mA g−1. The attractive performance is most likely the consequence of the balanced stability and specific energy in the present material, which is promisingly applicable to other Li-rich oxide systems. This work sheds light on harnessing Li2MnO3 activation and furthermore efficient battery design simply through compositional tuning and temperature regulation.

Smart Solution Chemistry to Sn‐Containing Intermetallic Compounds through a Self‐Disproportionation Process

Developing new methods to synthesize intermetallics is one of the most critical issues for the discovery and application of multifunctional metal materials; however, the synthesis of Sn-containing intermetallics is challenging. In this work, we demonstrated for the first time that a self-disproportionation-induced in situ process produces cavernous Sn-Cu intermetallics (Cu3 Sn and Cu6 Sn5 ). The successful synthesis is realized by introducing inorganic metal salts (SnCl2 ⋅2 H2 O) to NaOH aqueous solution to form an intermediate product of reductant (Na2 SnO2 ) and by employing steam pressures that enhance the reduction ability. Distinct from the traditional in situ reduction, the current reduction process avoided the uncontrolled phase composition and excessive use of organic regents. An insight into the mechanism was revealed for the Sn-Cu case. Moreover, this method could be extended to other Sn-containing materials (Sn-Co, Sn-Ni). All these intermetallics were attempted in the catalytic effect on thermal decompositions of ammonium perchlorate. It is demonstrated that Cu3 Sn showed an outstanding catalytic performance. The superior property might be primarily originated from the intrinsic chemical compositions and cavernous morphology as well. We supposed that this smart solution reduction methodology reported here would provide a new recognition for the reduction reaction, and its modified strategy may be applied to the synthesis of other metals, intermetallics as well as some unknown materials.