Browsing by Author "Xie, Jian"

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    Achieving SEI preformed graphite in flow cell to mitigate initial lithium loss
    (Elsevier, 2022) Yu, Yikang; Yang, Zhenzhen; Xie, Jian; Mechanical and Energy Engineering, Purdue School of Engineering and Technology
    The irreversible lithium loss due to the formation of solid electrolyte interphase (SEI) in the initial cycle on the graphite anode greatly reduces the overall cell energy density of lithium ion batteries, that is, the lost Li ions from forming SEI lead to the decrease of Li ions for the intercalation. The method of cathode prelithiation has been widely explored to compensate this lithium loss. However, these cathode additives with high lithium contents inevitably lower the loading of the cathode active materials. Here we report a novel approach to solve this challenge, a facile graphite prelithiation method by preforming SEI layers on the surface of graphite powders (Pre-SEI graphite) utilizing a specially designed flow cell. The Li accommodation in the graphite anode can be controlled by the operating time and current density in the flow cell for the electrochemical SEI formation. As a result, we demonstrate a 10% initial Columbic efficiency increase of the LiFePO4 electrode in a full cell configuration using the Pre-SEI graphite, compared with the pristine graphite anode. The electrochemical preformation of SEI on the graphite powders offers a complete solution to offset initial lithium loss without a sacrifice of active cathode material loading.
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    Atomic Structure Evolution of Pt–Co Binary Catalysts: Single Metal Sites versus Intermetallic Nanocrystals
    (Wiley, 2021-12) Li, Xing; He, Yanghua; Cheng, Shaobo; Li, Boyang; Zeng, Yachao; Xie, Zhenhua; Meng, Qingping; Qingping, Lu; Kisslinger, Kim; Tong, Xiao; Hwang, Sooyeon; Yao, Siyu; Li, Chenzhao; Qiao, Zhi; Shan, Chongxin; Zhu, Yimei; Xie, Jian; Wang, Guofeng; Wu, Gang; Su, Dong; Mechanical and Energy Engineering, School of Engineering and Technology
    Due to their exceptional catalytic properties for the oxygen reduction reaction (ORR) and other crucial electrochemical reactions, PtCo intermetallic nanoparticle (NP) and single atomic (SA) Pt metal site catalysts have received considerable attention. However, their formation mechanisms at the atomic level during high-temperature annealing processes remain elusive. Here, the thermally driven structure evolution of Pt–Co binary catalyst systems is investigated using advanced in situ electron microscopy, including PtCo intermetallic alloys and single Pt/Co metal sites. The pre-doping of CoN4 sites in carbon supports and the initial Pt NP sizes play essential roles in forming either Pt3Co intermetallics or single Pt/Co metal sites. Importantly, the initial Pt NP loadings against the carbon support are critical to whether alloying to L12-ordered Pt3Co NPs or atomizing to SA Pt sites at high temperatures. High Pt NP loadings (e.g., 20%) tend to lead to the formation of highly ordered Pt3Co intermetallic NPs with excellent activity and enhanced stability toward the ORR. In contrast, at a relatively low Pt loading (<6 wt%), the formation of single Pt sites in the form of PtC3N is thermodynamically favorable, in which a synergy between the PtC3N and the CoN4 sites could enhance the catalytic activity for the ORR, but showing insufficient stability.
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    Atomically dispersed iron sites with a nitrogen–carbon coating as highly active and durable oxygen reduction catalysts for fuel cells
    (Springer Nature, 2022) Liu, Shengwen; Li, Chenzhao; Zachman, Michael J.; Zeng, Yachao; Yu, Haoran; Li, Boyang; Wang, Maoyu; Braaten, Jonathan; Liu, Jiawei; Meyer, Harry M., III; Lucero, Marcos; Kropf, A. Jeremy; Alp, Esen E.; Gong, Qing; Shi, Qiurong; Feng, Zhenxing; Xu, Hui; Wang, Guofeng; Myers, Deborah J.; Xie, Jian; Cullen, David A.; Litster, Shawn; Wu, Gang; Mechanical and Energy Engineering, Purdue School of Engineering and Technology
    Nitrogen-coordinated single atom iron sites (FeN4) embedded in carbon (Fe–N–C) are the most active platinum group metal-free oxygen reduction catalysts for proton-exchange membrane fuel cells. However, current Fe–N–C catalysts lack sufficient long-term durability and are not yet viable for practical applications. Here we report a highly durable and active Fe–N–C catalyst synthesized using heat treatment with ammonia chloride followed by high-temperature deposition of a thin layer of nitrogen-doped carbon on the catalyst surface. We propose that catalyst stability is improved by converting defect-rich pyrrolic N-coordinated FeN4 sites into highly stable pyridinic N-coordinated FeN4 sites. The stability enhancement is demonstrated in membrane electrode assemblies using accelerated stress testing and a long-term steady-state test (>300 h at 0.67 V), approaching a typical Pt/C cathode (0.1 mgPt cm−2). The encouraging stability improvement represents a critical step in developing viable Fe–N–C catalysts to overcome the cost barriers of hydrogen fuel cells for numerous applications.
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    Atomically dispersed single iron sites for promoting Pt and Pt3Co fuel cell catalysts: performance and durability improvements
    (RSC, 2021-09) Qiao, Zhi; Wang, Chenyu; Li, Chenzhao; Zeng, Yachao; Hwang, Sooyeon; Li, Boyang; Karakalos, Stavros; Park, Jaehyung; Kropf, A. Jeremy; Wegener, Evan C.; Gong, Qing; Xu, Hui; Wang, Guofeng; Myers, Deborah J.; Xie, Jian; Spendelow, Jacob S.; Wu, Gang; Mechanical and Energy Engineering, School of Engineering and Technology
    Significantly reducing platinum group metal (PGM) loading while improving catalytic performance and durability is critical to accelerating proton-exchange membrane fuel cells (PEMFCs) for transportation. Here we report an effective strategy to boost PGM catalysts through integrating PGM-free atomically-dispersed single metal active sites in the carbon support toward the cathode oxygen reduction reaction (ORR). We achieved uniform and fine Pt nanoparticle (NP) (∼2 nm) dispersion on an already highly ORR-active FeN4 site-rich carbon (FeN4–C). Furthermore, we developed an effective approach to preparing a well-dispersed and highly ordered L12 Pt3Co intermetallic nanoparticle catalyst on the FeN4–C support. DFT calculations predicted a synergistic interaction between Pt clusters and surrounding FeN4 sites through weakening O2 adsorption by 0.15 eV on Pt sites and reducing activation energy to break O–O bonds, thereby enhancing the intrinsic activity of Pt. Experimentally, we verified the synergistic effect between Pt or Pt3Co NPs and FeN4 sites, leading to significantly enhanced ORR activity and stability. Especially in a membrane electrode assembly (MEA) with a low cathode Pt loading (0.1 mgPt cm−2), the Pt/FeN4–C catalyst achieved a mass activity of 0.451 A mgPt−1 and retained 80% of the initial values after 30 000 voltage cycles (0.60 to 0.95 V), exceeding DOE 2020 targets. Furthermore, the Pt3Co/FeN4 catalyst achieved significantly enhanced performance and durability concerning initial mass activity (0.72 A mgPt−1), power density (824 mW cm−2 at 0.67 V), and stability (23 mV loss at 1.0 A cm−2). The approach to exploring the synergy between PGM and PGM-free Fe–N–C catalysts provides a new direction to design advanced catalysts for hydrogen fuel cells and various electrocatalysis processes.
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    Au nanoparticle assembly on cnts using flash induced solid-state dewetting
    (2015-04-28) Kulkarni, Ameya; Ryu, Jong Eun; Agarwal, Mangilal; Xie, Jian; Cheng, Ruihua
    Carbon Nanotubes (CNTs) are used extensively in various applications where substrate are required to be possessing higher surface area, porosity and electrical and thermal conductivity. Such properties can be enhanced to target a particular gas and biochemical for efficient detection when CNT matrix is functionalized with Nanoparticles (NPs). Conventional functionalization involves harsh oxidation repeated washing, filtration and sonication, which induce defects. The defects lead to hindered mobility of carriers, unwanted doping and also fragmentation of the CNTs in some cases. In this document we demonstrate functionalization of CNT with Au nanoparticles on a macro scale under dry and ambient condition using Xenon ash induced solid-state dewetting. A sputtered thin film was transformed into nanoparticles which were confirmed to be in a state of thermodynamic equilibrium. We worked on 3 nm, 6 nm, 9 nm, 15 nm, 30 nm initial thickness of thin films. Xenon ash parameters of energy, number of pulse, duration of pulse, duration of gap between consecutive pulses were optimized to achieve complete dewetting of Au thin films. 3 nm deposition was in the form of irregular nano-islands which were transformed into stable nanoparticles with a single shot of 10 J/cm2 of 2 ms duration. 6 nm and 9 nm deposition was in form of continues film which was also dewetted into stable nanoparticles with a single pulse but with an increased energy density of 20 J/cm2 and 35 J/cm2 respectively. In case of 15 nm and 30 nm deposition the thin film couldn't be dewetted with a maximum energy density of 50 J/cm2, it was observed that 3 and 4 pulses of 2 ms pulse duration and 2 ms gap duration with an energy density of 50 J/cm2 were required to completely dewet the thicker films. However irregularity was induced in the sizes of the NPs due to Ostwald ripening phenomenon which causes smaller particle within a critical difiusion length to combine and form a larger particle during or after dewetting process. For comparison, the Au thin films were also dewetted by a conventional process involving annealing of samples until the thin film was fully transformed into NPs and the size of NPs seized to grow. Scanning electron microscope (SEM) was used to characterize the samples. Thermodynamic stability of the particles was confirmed with statistical analyses of size distribution after every additional pulse.
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    Beyond Lithium Ion: Lithium Metal Batteries with High Specific Energy and Long Cycle Life
    (Office of the Vice Chancellor for Research, 2014-04-11) Xie, Jian
    The lithium ion battery industry has been rapidly growing and now dominating in many power source sectors such as automotive industries, portable devices, and aerospace applications. Lithium ion batteries currently being implemented in electric vehicle (EV) and hybrid electric vehicle (HEV) are not efficient enough to outperform gas combustion vehicles on the road today, which is limited by the theoretical specific energy of cathode (intercalation oxides) and anode (graphite) materials for lithium ion batteries. The next phase in the advancement of the lithium battery technology relies very much on replacing the intercalation electrodes which has limited theoretical specific capacity. Metallic lithium is a good candidate for the anode, since it has a very high theoretical specific capacity which is more than 10 times than graphite. However, the formation of dendrites affects the charge efficiency of this type of electrode, which can be very dangerous, even fatal at time. In our approach, functionalized carbon black (FCB) coating was implemented onto the separator to eliminate the hazard of dendrite formation. Furthermore, the lithium metal batteries with our technology offered much higher specific energy and power, and improved cycle life.
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    Building Better Li Metal Anodes in Liquid Electrolyte: Challenges and Progress
    (ACS, 2021-01) Yu, Yikang; Liu, Yadong; Xie, Jian; Mechanical and Energy Engineering, School of Engineering and Technology
    Li metal has been widely recognized as a promising anode candidate for high-energy-density batteries. However, the inherent limitations of Li metal, that is, the low Coulombic efficiency and dendrite issues, make it still far from practical applications. In short, the low Coulombic efficiency shortens the cycle life of Li metal batteries, while the dendrite issue raises safety concerns. Thanks to the great efforts of the research community, prolific fundamental understanding as well as approaches for mitigating Li metal anode safety have been extensively explored. In this Review, Li electrochemical deposition behaviors have been systematically summarized, and recent progress in electrode design and electrolyte system optimization is reviewed. Finally, we discuss the future directions, opportunities, and challenges of Li metal anodes.
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    Coupled Dynamic Analysis of Flow in the Inlet Section of a Wave Rotor Constant Volume Combustor
    (2011-12) Smith, Keith Cameron; Nalim, M. Razi; Zhu, Likun; Xie, Jian
    A wave rotor constant volume combustor (WRCVC) was designed and built as a collaborative work of Rolls Royce LibertyWorks, Indiana University-Purdue University at Indianapolis (IUPUI), and Purdue University, and ran experimental tests at Purdue's Zucrow Laboratories in 2009. Instrumentation of the WRCVC rig inlet flow included temperature and pressure transducers upstream of the venturi and at the fuel delivery plane. Other instrumentation included exhaust pressures and temperatures. In addition, ion sensors, dynamic pressure sensors, and accelerometers were used to instrument the rotating hardware. The rig hardware included inlet guide vanes directly in front of the rotating hardware, which together with concern for damage potential, prevented use of any pressure transducers at the entrance to the rotor. For this reason, a complete understanding of the conditions at the WRCVC inlet is unavailable, requiring simulations of the WRCVC to estimate the inlet pressure at a specific operating condition based on airflow. The operation of a WRCVC rig test is a sequence of events over a short time span. These events include introduction of the main air flow followed by time-sequenced delivery of fuel, lighting of the ignition source, and the combustion sequence. The fast changing conditions in the rig inlet hardware make necessary a time-dependent computation of the rig inlet section in order to simulate the overall rig operation. The chosen method for computing inlet section temperature and pressure was a time-dependent lumped volume model of the inlet section hardware, using a finite difference modified Euler predictor-corrector method for computing the continuity and energy equations. This is coupled with perfect gas prediction of venturi air and fuel flow rates, pressure drag losses at the fuel nozzles, pressure losses by mass addition of the fuel or nitrogen purge, friction losses at the inlet guide vanes, and a correlation of the non-dimensional flow characteristics of the WRCVC. The flow characteristics of the WRCVC are computed by varying the non-dimensional inlet stagnation pressure and the WRCVC's operational conditions, assuming constant rotational speed and inlet stagnation temperature. This thesis documents the creation of a computer simulation of the entire WRCVC rig, to understand the pressure losses in the inlet system and the dynamic coupling of the inlet section and the WRCVC, so that an accurate prediction of the WRCVC rotor inlet conditions can be computed. This includes the computational development of the WRCVC upstream rig dynamic model, the background behind supporting computations, and results for one test sequence. The computations provide a clear explanation of why the pressures at the rotor inlet differ so much from the upstream measured values. The pressure losses correlate very well with the computer predictions and the dynamic response tracks well with the estimation of measured airflow. A simple Fortran language computer program listing is included, which students can use to simulate charging or discharging of a container.
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    Design and Fabrication of High Capacity Lithium-Ion Batteries using Electro-Spun Graphene Modified Vanadium Pentoxide Cathodes
    (2019-08) Ahmadian, Amirhossein; Agarwal, Mangilal; Xie, Jian; Dalir, Hamid
    Electrospinning has gained immense interests in recent years due to its potential application in various fields, including energy storage application. The V2O5/GO as a layered crystal structure has been demonstrated to fabricate nanofibers with diameters within a range of ~300nm through electrospinning technique. The porous, hollow, and interconnected nanostructures were produced by electrospinning formed by polymers such as Polyvinylpyrrolidone (PVP) and Polyvinyl alcohol (PVA), separately, as solvent polymers with electrospinning technique. In this study, we investigated the synthesis of a graphene-modified nanostructured V2O5 through modified sol-gel method and electrospinning of V2O5/GO hybrid. Electrochemical characterization was performed by utilizing Arbin Battery cycler, Field Emission Scanning Electron Microscopy (FESEM), X-ray powder diffraction (XRD), Thermogravimetric analysis (TGA), Mercury Porosimetry, and BET surface area measurement. As compared to the other conventional fabrication methods, our optimized sol-gel method, followed by the electrospinning of the cathode material achieved a high initial capacity of 342 mAh/g at a high current density of 0.5C (171 mA/g) and the capacity retention of 80% after 20 cycles. Also, the prepared sol-gel method outperforms the pure V2O5 cathode material, by obtaining the capacity almost two times higher. The results of this study showed that post-synthesis treatment of cathode material plays a prominent role in electrochemical performance of the nanostructured vanadium oxides. By controlling the annealing and drying steps, and time, a small amount of pyrolysis carbon can be retained, which improves the conductivity of the V2O5 nanorods. Also, controlled post-synthesis helped us to prevent aggregation of electro-spun twisted nanostructured fibers which deteriorates the lithium diffusion process during charge/discharge of batteries.
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    Effects of Ink Formulation on Construction of Catalyst Layers for High-Performance Polymer Electrolyte Membrane Fuel Cells
    (ACS, 2021-07) Gong, Qing; Li, Chenzhao; Liu, Yadong; Ilavsky, Jan; Guo, Fei; Cheng, Xuan; Xie, Jian; Mechanical and Energy Engineering, School of Engineering and Technology
    Rational design of catalyst layers in a membrane electrode assembly (MEA) is crucial for achieving high-performance polymer electrolyte membrane fuel cells. Establishing a clear understanding of the property (catalyst ink)-structure (catalyst layer)-performance (MEA) relationship lays the foundation for this rational design. In this work, a synergistic approach was taken to correlate the ink formulation, the microstructure of catalyst layers, and the resulting MEA performance to establish such a property-structure-performance relationship. The solvent composition (n-PA/H2O mixtures) demonstrated a strong influence on the performance of the MEA fabricated with an 830-EW (Aquivion) ionomer, especially polarization losses of cell activation and mass transport. The performance differences were studied in terms of how the solvent composition affects the catalyst/ionomer interface, ionomer network, and pore structure of the resulting catalyst layers. The ionomer aggregates mainly covered the surface of catalyst aggregates acting as oxygen reduction reaction active sites, and the aggregate sizes of the ionomer and catalyst (revealed by ultrasmall angle X-ray scattering and cryo-transmission electron microscopy) were dictated by tuning the solvent composition, which in turn determined the catalyst/ionomer interface (available active sites). In n-PA/H2O mixtures with 50∼90 wt % H2O, the catalyst agglomerates could be effectively broken up into small aggregates, leading to enhanced kinetic activities. The boiling point of the mixed solvents determined the pore structure of ultimate catalyst layers, as evidenced by mercury porosimetry and scanning electron microscopy. For mixed solvents with a higher boiling point, the catalyst-ionomer aggregates in the ink tend to agglomerate during the solvent evaporation process and finally form larger catalyst-ionomer aggregates in the ultimate catalyst layer, resulting in more secondary pores and thus lower mass transport resistance. Both the enlarged catalyst/ionomer interface and appropriate pore structure were achieved with the catalyst layer fabricated from an n-PA/H2O mixture with 90 wt % H2O, leading to the best MEA performance.