M. Stanley Whittingham

Binghamton University, Binghamton, New York, United States

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Publications (248)856.45 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: Much groundbreaking research in the field of lithium batteries occurred in the 1970s. Some of “the first” rechargeable lithium cells for commercial applications were fabricated by the Exxon Enterprises Battery Division in New Jersey. A small collection of 1978-era 25 mAh and 100 mAh button cells were preserved in the personal collections of the original researchers. This presented a unique opportunity to evaluate lithium cells after 35 years of storage. Cells were characterized for capacity, cycling, rate and impedance. Results were compared with original data as recovered from historical documents.
    Journal of Power Sources 04/2015; 280. DOI:10.1016/j.jpowsour.2015.01.056 · 5.21 Impact Factor
  • M Stanley Whittingham
    Chemical Reviews 12/2014; 114(23):11413. DOI:10.1021/cr500639y · 45.66 Impact Factor
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    ABSTRACT: This work attempts to understand the rate capability of layered transition metal oxides LiNiyMnyCo1−2yO2 (0.33 ≤ y ≤ 0.5). The rate capability of LiNiyMnyCo1−2yO2 increase with increasing Co in the compounds and with increasing amount of carbon additives in the electrodes. The lithium diffusion coefficients and electronic conductivities of LixNiyMnyCo1−2yO2 are investigated and compared. The 333 compound has higher diffusivity and electronic conductivity and thus better rate performance than 550. Chemical diffusion coefficients for both delithiation and lithiation of LixNiyMnyCo1−2yO2 investigated by GITT and PITT experiments are calculated to be around 10−10 cm2 s−1, lower than that of LixCoO2. The electronic conductivity of LixNiyMnyCo1−2yO2 is inferior compared to LixCoO2 at same temperature and delithiation stage. However, the LixNiyMnyCo1−2yO2 are able to deliver 55%–80% of theoretical capacity at 5 C with good electronic wiring in the composite electrode that make them very promising candidates for electric propulsion in terms of rate capability.
    Journal of Power Sources 12/2014; 268:106–112. DOI:10.1016/j.jpowsour.2014.05.142 · 5.21 Impact Factor
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    ABSTRACT: Fe-P alloys with high phosphorous content have been targeted as promising anode materials because of their high theoretical capacity. However, the synthesis and cycling performance remain great challenges. Hereby FePy (3 <= y <= 4) nanoparticles are facilely synthesized through a dry mechanochemical method by reacting iron and red phosphorus powders in an inert atmosphere. The morphology and crystal structure of this material are characterized by SEM and XRD, respectively, while the electrochemical performance is evaluated by a number of different techniques. The 1st and 2nd discharge capacity of FePy reaches 1984 mAh g(-1) and 1486 mAh g(-1), respectively, and after 10 cycles at 0.03 mA cm(-2) (20 mA g(-1) 0.03C), the capacity remains 1089 mAh g(-1) with a coulombic efficiency of 97%, much higher than the reported results to date. The cyclability of this material becomes fairly better at a higher current density, but the specific capacity is lower compared to that of the smaller current density. By adding fluoroethylene carbonate (FEC) to the electrolyte, the cycling performance of this material was improved. The EIS analysis has also been performed in order to better understand the capacity fade mechanism of FePy.
    Journal of Power Sources 12/2014; 270:248–256. DOI:10.1016/j.jpowsour.2014.07.095 · 5.21 Impact Factor
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    ABSTRACT: Understanding the reaction mechanism of olivine compounds as electrode materials for lithium lithium-ion batteries have has received much attention recently. The question whether olivine LiFePO4 undergoes two-phase or non-nonequilibrium single-phase reaction during electrochemical processes has taken center stage in the understanding of the faster reaction kinetics observed in this material. Here, the lithiation/delithiation mechanism of Mg Mg-substituted LiFePO4 using high high-resolution X-ray diffraction(XRD), transmission electron microscopy(TEM), and electrochemical measurements is reported. Ex situ partially (de)lithiated olivine- LiMg0.2Fe0.8PO4 show the existence of stable equilibrium intermediate phases as characterized by the presence of more than two phases and broadness of diffraction peaks. Electron energy loss spectroscopy profiles across individual nanoparticles further confirm uniform lithiation with a constant Fe–L3 energy measured across each nanoparticle, suggestive of solid solution behavior in individual particles. In addition, a continuous shift in the diffraction peak position is observed even in the “two-phase” region in the ex situ electrochemical (de)lithiated electrodes.
    Advanced Energy Materials 12/2014; 5(7). DOI:10.1002/aenm.201401204 · 14.39 Impact Factor
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    ABSTRACT: In order to address lithium dendrite formation and low cycling efficiency issues, Pulse Plating (PP) and Reverse Pulse Plating (RPP) have been systematically investigated for lithium electrodeposition with a modified button cell device. Compared with Direct Current (DC) electrodeposition, PP waveforms with short and widely spaced pulses improve lithium deposition morphology and cycling efficiency under diffusion-controlled conditions. While RPP waveforms with high current density anodic pulses further improve lithium cycling efficiency, no obvious improvement in morphology was seen under the conditions tested. This study suggests that PP and RPP could be powerful tools for utilizing lithium metal anodes in high energy density rechargeable battery systems, especially when high instant power is required.
    Journal of Power Sources 11/2014; 272. DOI:10.1016/j.jpowsour.2014.09.026 · 5.21 Impact Factor
  • M Stanley Whittingham
    Chemical Reviews 10/2014; 46(8). DOI:10.1021/cr5003003 · 45.66 Impact Factor
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    ABSTRACT: Lithium cobalt germanate (Li2CoGeO4) has been synthesized for the first time by a hydrothermal method at 150 °C. Elemental composition, morphology, and crystal structure of this compound were characterized by various analytical techniques including SEM, TEM, ICP, and XRD analyses. Structure refinement and DFT calculation suggests the resulting Li2CoGeO4 from hydrothermal synthesis has a crystal structure isostructural with Li2ZnGeO4, significantly different from previous reports. Electrochemical studies confirmed Li2CoGeO4 as an active catalyst for oxygen evolution reaction (OER). In alkaline electrolyte (0.1 M NaOH), rotating disk electrodes made with Li2CoGeO4 as catalyst have a Tafel slope of c.a. 67 mV/dec and an overpotential of 330 mV at 50 μA/cm2cat, about 90 mV less than electrodes containing another known OER catalyst, Co3O4. Further characterization with cyclic voltammetry, high resolution transmission electron microscopy, X-ray photoelectron spectroscopy and elemental analyses revealed the oxidation of cobalt from 2+ to 3+ during the reaction, along with significant surface amorphization and loss of Li and Ge from the catalyst.
    09/2014; 2(43). DOI:10.1039/C4TA03325F
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    ABSTRACT: VOPO4 is an example of a Li-ion battery cathode that can achieve over 300 Ah/kg when two Li-ions are intercalated. A two phase beta-VOPO4/epsilon-VOPO4 composite was found to improve the cycling capacity of epsilon-VOPO4 from tetragonal H2VOPO4, particularly as the rate is increased. In the potential range of 2.0-4.5 V, this composite showed an initial electrochemical capacity of 208 mAh/g at 0.08 mA/cm(2), 190 mAh/g at 0.16 mA/cm(2), and 160 mAh/g at 0.41 mA/cm(2).
    Electrochemistry Communications 09/2014; 46:67–70. DOI:10.1016/j.elecom.2014.06.009 · 4.29 Impact Factor
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    ABSTRACT: We have revealed the critical role of carbon coating in the stability and thermal behaviour of olivine MnPO4 obtained by chemical delithiation of LiMnPO4. (Li)MnPO4 samples with various particle sizes and carbon contents were studied. Carbon-free LiMnPO4 obtained by solid state synthesis in O2 becomes amorphous upon delithiation. Small amounts of carbon (0.3 wt%) help to stabilize the olivine structure, so that completely delithiated crystalline olivine MnPO4 can be obtained. Larger amount of carbon (2 wt%) prevents full delithiation. Heating in air, O2, or N2 results in structural disorder (<300 °C), formation of an intermediate sarcopside Mn3(PO4)2 phase (350–450 °C), and complete decomposition to Mn2P2O7 on extended heating at 400 °C. Carbon coating protects MnPO4 from reacting with environmental water, which is detrimental to its structural stability.
    07/2014; 2(32). DOI:10.1039/C4TA00434E
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    ABSTRACT: We have successfully prepared nanoribbons of blue potassium molybdenum bronze (K0.3MoO3) from hydrogen molybdenum bronze (H0.3MoO3) by using crystallite splitting induced by solid-phase transformation and subsequent selective growth under hydrothermal conditions. The obtained nanoribbons were single crystals with a size of ca. 100 mu m x 100 nm x 10 nm, well-elongated to the crystal b axis that corresponds to the conduction direction as a quasi-one-dimensional metal. A simple. deaeration procedure necessary for preparing a single phase of blue potassium bronze is also given.
    Chemistry Letters 12/2013; 42(12):1514-1516. DOI:10.1246/cl.130792 · 1.30 Impact Factor
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    ABSTRACT: The layered compound δ-(MoO2)2P2O7 is synthesized by heating MoO2HPO4·H2O (560 °C, 6 min).
    ChemInform 11/2013; 44(46). DOI:10.1002/chin.201346012
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    ABSTRACT: High-voltage cathode material LiNi0.5Mn1.5O4 has been prepared with a novel organic coprecipitation route. The as-prepared sample was compared with samples produced through traditional solid state method and hydroxide coprecipitation method. The morphology was observed by SEM and the spinel structures were characterized by XRD and FTIR. Besides the ordered/disordered distribution of Ni/Mn on octahedral sites, the confusion between Li and transition metal is pointed out to be another important factor responsible for the corresponding performance, which is worthy further investigation. Galvanostatic cycles, CV and EIS are employed to characterize the electrochemical properties. The organic coprecipitation route produced sample shows superior rate capability and stable structure during cycling.
    ACS Applied Materials & Interfaces 09/2013; 5(20). DOI:10.1021/am4029526 · 5.90 Impact Factor
  • Source
    P. Y. Zavalij, F. Zhang, M. S. Whittingham
  • Source
    Jingdong Guo, P. Zavalij, M. S. Whittingham
  • Source
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    ABSTRACT: Aluminum–silicon alloys are an important class of commercial casting materials having wide applications in automotive and aerospace industries. Etching the Al–Si eutectic leads to selective dissolution of Al, resulting in novel morphology – macroporous Si spheres with a three-dimensional nano network. Up to 5% Al is dissolved in Si, leading to an expansion of the crystal lattice. The resulting porous Si is electrochemically active with lithium and thus can be used as a high capacity anode for lithium-ion batteries. The etching of Al–Si provides a simple and low-cost method of producing nano-structured Si materials.
    MRS Communications 09/2013; 3(03). DOI:10.1557/mrc.2013.20 · 1.55 Impact Factor
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    ABSTRACT: The layered structure of molybdenum (oxy)pyrophosphate (δ-(MoO2)2P2O7) was synthesized by heating MoO2HPO4·H2O precursor at 560 °C. The synthesis temperature was selected using in situ high-temperature X-ray diffraction (XRD) depicting phase transformations of the precursor from room temperature up to 800 °C. Electrochemical evaluation reveals that up to four Li ions per formula unit can be intercalated into δ-(MoO2)2P2O7 upon discharge to 2 V. Three voltage plateaus are observed at 3.2, 2.6, and 2.1 V, lower than the theoretical predictions. The first plateau corresponds to the intercalation of 1.2 Li forming δ-Li1.2(MoO2)2P2O7, the same structure formed upon chemical lithiation with LiI. In-situ XRD indicates two-phase reaction upon the first lithium insertion and expansion of the lithiated phase unit cell in the a direction. Intercalation of the second lithium results in a different lithiated structure, which is also reversible, giving the capacity of about 110 mAh/g between 2.3 and 4 V. More lithium-ion intercalation leads to loss of crystallinity and structural reversibility. The Mo reduction upon lithiation is consistent with the amount of Li intercalated as confirmed by the X-ray absorption fine structure.
    Chemistry of Materials 08/2013; DOI:10.1021/cm401946h · 8.54 Impact Factor
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    ABSTRACT: A series of layered oxides within the NaxNiix/2Mn1-x/2O2 (2/3 ≤ x ≤ 1) system were synthesized by classical solid-state methodologies. A study of their long and short-range structure was undertaken by combining X-ray diffraction and NMR spectroscopy. A transition from P2 to O3 stacking was observed at x > 0.8 when samples were made at 900 °C, which was accompanied by disordering of ions in the transition metal layer. The magnetic properties of the materials were consistent with this picture of ordering, with all samples showing antiferromagnetic character. At x = 2/3, competition between a P2 and a P3 structure, with different degrees of transition metal ordering, was found depending on the synthesis temperature. Na/Li exchange led to structures with octahedral or tetrahedral coordination of the alkali metal, and Li/Ni crystallographic exchange in the resulting O3 phases. The transition from alkali metal prismatic coordination to octahedral/tetrahedral coordination involves [TMO6]∞ layer shearing that induces some structural disorder through the formation of stacking faults.
    Inorganic Chemistry 08/2013; 52(15):8540-50. DOI:10.1021/ic400579w · 4.79 Impact Factor
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    ABSTRACT: Nanostructured epsilon-VOPO4 particles, synthesized by the thermal decomposition of H2VOPO4 have a diameter of 150 nm and a length up to 100 nm. Nanostructuring the material allows access to both the 4 V and 2.5 V redox potentials with an overall capacity approaching 200 mAh/g over 50 cycles. The structure of the epsilon-VOPO4 and its changes were investigated by X-ray diffraction and electron microscopy, and its electrochemical behavior through constant current cycling and cyclic voltammetry.
    Journal of The Electrochemical Society 07/2013; 160(10):A1777-A1780. DOI:10.1149/2.064310jes · 2.86 Impact Factor
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    ABSTRACT: The crystal structure and delithiation mechanism of Li-site substituted LiFePO4 have been revealed by investigation of supervalent V3+ substitution. The combined X-ray and neutron powder diffraction data analysis surprisingly shows that the substituting aliovalent vanadium ions occupy the Fe site while some of the Fe resides at the Li site, probably as sarcopside, which leads to an increase in the unit cell volume. Such substitution reduces the miscibility gap at room temperature and also significantly lowers the solid solution formation temperature in the two-phase region. The effect of the phase diagram modification results in improved kinetics, leading to better rate performance. Such substitution, however, significantly lowers the LiFePO4 capacity at moderate current densities.
    ChemInform 07/2013; 44(37). DOI:10.1002/chin.201337007

Publication Stats

6k Citations
856.45 Total Impact Points

Institutions

  • 1990–2015
    • Binghamton University
      • • Institute for Materials Research
      • • Department of Chemistry
      Binghamton, New York, United States
  • 1997–2014
    • State University of New York
      New York City, New York, United States
  • 2007–2013
    • Stony Brook University
      • Department of Chemistry
      Stony Brook, New York, United States
    • The University of Tennessee Medical Center at Knoxville
      Knoxville, Tennessee, United States
  • 2012
    • SUNY Ulster
      Кингстон, New York, United States
  • 2009
    • Kobe University
      • Department of Chemistry
      Kōbe, Hyōgo, Japan
  • 1999
    • McMaster University
      Hamilton, Ontario, Canada
  • 1998
    • Université de Versailles Saint-Quentin
      Versailles, Île-de-France, France