5 results on '"Peterson, Vanessa K."'
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2. The Origin of Capacity Fade in the Li2MnO3·LiMO22 (M = Li, Ni, Co, Mn) Microsphere Positive Electrode: An Operando Neutron Diffraction and Transmission X-ray Microscopy Study.
- Author
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Chih-Jung Chen, Wei Kong Pang, Tatsuhiro Mori, Peterson, Vanessa K., Sharma, Neerai, Po-Han Lee, She-huang Wu, Chun-Chieh Wang, Yen-Fang Song, and Ru-Shi Liu
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MICROSPHERES , *NEUTRON diffraction , *X-ray microscopy , *X-ray powder diffraction , *ELECTROCHEMICAL analysis - Abstract
The mechanism of capacity fade of the Li2MnO3·LiMO2 (M = Li, Ni, Co, Mn) composite positive electrode within a full cell was investigated using a combination of operando neutron powder diffraction and transmission X-ray microscopy methods, enabling the phase, crystallographic, and morphological evolution of the material during electrochemical cycling to be understood. The electrode was shown to initially consist of 73(1) wt % R3m LiMO2 with the remaining 27(1) wt % C2/m Li2MnO3 likely existing as an intergrowth. Cracking in the Li2MnO3·LiMO2 electrode particle under operando microscopy observation was revealed to be initiated by the solid-solution reaction of the LiMO2 phase on charge to 4.55 V vs Li+/Li and intensified during further charge to 4.7 V vs Li+/Li during the concurrent two-phase reaction of the LiMO2 phase, involving the largest lattice change of any phase, and oxygen evolution from the Li2MnO3 phase. Notably, significant healing of the generated cracks in the Li2MnO3·LiMO2 electrode particle occurred during subsequent lithiation on discharge, with this rehealing being principally associated with the solid-solution reaction of the LiMO2 phase. This work reveals that while it is the reduction of lattice size of electrode phases during charge that results in cracking of the Li2MnO3·LiMO2 electrode particle, with the extent of cracking correlated to the magnitude of the size change, crack healing is possible in the reverse solid-solution reaction occurring during discharge. Importantly, it is the phase separation during the two-phase reaction of the LiMO2 phase that prevents the complete healing of the electrode particle, leading to pulverization over extended cycling. This work points to the minimization of behavior leading to phase separation, such as two-phase and oxygen evolution, as a key strategy in preventing capacity fade of the electrode. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
3. Direct Evidence of Concurrent Solid-Solution and Two-Phase Reactions and the Nonequilibrium Structural Evolution of LiFePO4.
- Author
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Sharma, Neeraj, Xianwei Guo, Guodong Du, Zaiping Guo, Jiazhou Wang, Zhaoxiang Wang, and Peterson, Vanessa K.
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REACTION mechanisms (Chemistry) , *LITHIUM compounds , *CATHODES , *SOLID solutions , *LITHIATION , *LITHIUM-ion batteries , *NONEQUILIBRIUM thermodynamics - Abstract
Lithium-ion batteries power many portable devices and in the future are likely to play a significant role in sustainable-energy systems for transportation and the electrical grid. LiFePO4 is a candidate cathode material for second-generation lithium-ion batteries, bringing a high rate capability to this technology. LiFePO4 functions as a cathode where delithiation occurs via either a solid-solution or a two-phase mechanism, the pathway taken being influenced by sample preparation and electrochemical conditions. The details of the delithiation pathway and the relationship between the two-phase and solid-solution reactions remain controversial. Here we report, using real-time in situ neutron powder diffraction, the simultaneous occurrence of solid-solution and two-phase reactions after deep discharge in nonequilibrium conditions. This work is an example of the experimental investigation of nonequilibrium states in a commercially available LiFePO4 cathode and reveals the concurrent occurrence of and transition between the solid-solution and two-phase reactions. [ABSTRACT FROM AUTHOR]
- Published
- 2012
- Full Text
- View/download PDF
4. Selective Binding of O2 over N2 in a Redox--Active Metal--Organic Framework with Open Iron(II) Coordination Sites.
- Author
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Bloch, Eric D., Murray, Leslie J., Queen, Wendy L., Chavan, Sachin, Maximoff, Sergey N., Bigi, Julian P., Krishna, Rajamani, Peterson, Vanessa K., Grandjean, Fernande, Long, Gary J., Smit, Berend, Bordiga, Silvia, Brown, Craig M., and Long, Jeffrey R.
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DIMETHYLFORMAMIDE , *ADSORPTION (Chemistry) , *FERRIC chloride , *MOSSBAUER effect , *INFRARED spectra , *CHARGE transfer , *NEUTRON diffraction , *ATMOSPHERIC temperature - Abstract
The air-free reaction between FeCl2 and H4dobdc (dobdc4- = 2,5-dioxido-1,4-benzenedicarboxylate) in a mixture of N,N-dimethylformamide (DMF) and methanol affords Fe2(dobdc)·4DMF, a metal-organic framework adopting the MOF-74 (or CPO-27) structure type. The desolvated form of this material displays a Brunauer-Emmett-Teller (BET) surface area of 1360 m²/g and features a hexagonal array of one-dimensional channels lined with coordinatively unsaturated FeII centers. Gas adsorption isotherms at 298 K indicate that Fe2(dobdc) binds O2 preferentially over N2, with an irreversible capacity of 9.3 wt %, corresponding to the adsorption of one O2 molecule per two iron centers. Remarkably, at 211 K, O2 uptake is fully reversible and the capacity increases to 18.2 wt %, corresponding to the adsorption of one O2 molecule per iron center. Mossbauer and infrared spectra are consistent with partial charge transfer from iron(II) to O2 at low temperature and complete charge transfer to form iron(III) and O22- at room temperature. The results of Rietveld analyses of powder neutron diffraction data (4 K) confirm this interpretation, revealing O2 bound to iron in a symmetric side-on mode with dO-O = 1.25(1) Å at low temperature and in a slipped side-on mode with dO-O = 1.6(1) Å when oxidized at room temperature. Application of ideal adsorbed solution theory in simulating breakthrough curves shows Fe2(dobdc) to be a promising material for the separation of O2 from air at temperatures well above those currently employed in industrial settings. [ABSTRACT FROM AUTHOR]
- Published
- 2011
- Full Text
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5. Dynamic Solubility Limits in Nanosized Olivine LiFePO4.
- Author
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Wagemaker, Marnix, Singh, Deepak P., Borghols, Wouter J. H., Lafont, Ugo, Haverkate, Lucas, Peterson, Vanessa K., and Mulder, Fokko M.
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NANOCRYSTALS , *SOLUTION (Chemistry) , *OLIVINE , *SOLUBILITY , *PHASE transitions - Abstract
Because of its stability, nanosized olivine LiFePO4 opens the door toward high-power Li-ion battery technology for large-scale applications as required for plug-in hybrid vehicles. Here, we reveal that the thermodynamics of first-order phase transitions in nanoinsertion materials is distinctly different from bulk materials as demonstrated by the decreasing miscibility gap that appears to be strongly dependent on the overall composition in LiFePO4. In contrast to our common thermodynamic knowledge, that dictates solubility limits to be independent of the overall composition, combined neutron and X-ray diffraction reveals strongly varying solubility limits below particle sizes of 35 nm. A rationale is found based on modeling of the diffuse interface. Size confinement of the lithium concentration gradient, which exists at the phase boundary, competes with the in bulk energetically favorable compositions. Consequently, temperature and size diagrams of nanomaterials require complete reconsideration, being strongly dependent on the overall composition. This is vital knowledge for the future nanoarchitecturing of superior energy storage devices as the performance will heavily depend on the disclosed nanoionic properties. [ABSTRACT FROM AUTHOR]
- Published
- 2011
- Full Text
- View/download PDF
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