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Item Blade-Type Reaction Front in Micrometer-Sized Germanium Particles during Lithiation(ACS, 2020-09) Zhou, Xinwei; Li, Tianyi; Cui, Yi; Meyerson, Melissa L.; Weeks, Jason A.; Mullins, C. Buddie; Jin, Yang; Shin, Hosop; Liu, Yuzi; Zhu, Likun; Mechanical and Energy Engineering, School of Engineering and TechnologyTo investigate the lithium transport mechanism in micrometer-sized germanium (Ge) particles, in situ focused ion beam–scanning electron microscopy was used to monitor the structural evolution of individual Ge particles during lithiation. Our results show that there are two types of reaction fronts during lithiation, representing the differences of reactions on the surface and in bulk. The cross-sectional SEM images and transmission electron microscopy characterizations show that the interface between amorphous LixGe and Ge has a wedge shape because of the higher Li transport rate on the surface of the particle. The blade-type reaction front is formed at the interface of the amorphous LixGe and crystalline Ge and is attributed to the large strain at the interface.Item Characterization of dynamic morphological changes of tin anode electrode during (de)lithiation processes using in operando synchrotron transmission X-ray microscopy(Elsevier, 2019) Li, Tianyi; Zhou, Xinwei; Cui, Yi; Lim, Cheolwoong; Kang, Huixiao; Yan, Bo; Wang, Jiajun; Wang, Jun; Fu, Yongzhu; Zhu, Likun; Mechanical and Energy Engineering, School of Engineering and TechnologyThe morphological evolution of tin particles with different sizes during the first lithiation and delithiation processes has been visualized by an in operando synchrotron transmission X-ray microscope (TXM). The in operando lithium ion battery cell was operated at constant current condition during TXM imaging. Two-dimensional projection images with 40 nm resolution showing morphological evolution were obtained and analyzed. The analysis of relative area change shows that the morphology of tin particles with different sizes changed simultaneously. This phenomenon is mainly due to a negative feedback mechanism among tin particles in the battery electrode at a constant current operating condition. For irregular-shaped tin particles, the contour analysis shows that the regions with higher curvature started volume expansion first, and then the entire particle expanded almost homogeneously. This study provides insights for understanding the dynamic morphological change and the particle-particle interactions in high capacity lithium ion battery electrodes.Item A Class of Organopolysulfides As Liquid Cathode Materials for High-Energy-Density Lithium Batteries(ACS, 2018) Bhargav, Amruth; Bell, Michaela Elaine; Karty, Jonathan; Cui, Yi; Fu, Yongzhu; Mechanical Engineering, School of Engineering and TechnologySulfur-based cathodes are promising to enable high-energy-density lithium–sulfur batteries; however, elemental sulfur as active material faces several challenges, including undesirable volume change (∼80%) when completely reduced and high dependence on liquid electrolyte wherein an electrolyte/sulfur ratio >10 μL mg–1 is required for high material utilization. These limit the attainable energy densities of these batteries. Herein, we introduce a new class of phenyl polysulfides C6H5SxC6H5 (4 ≤ x ≤ 6) as liquid cathode materials synthesized in a facile and scalable route to mitigate these setbacks. These polysulfides possess sufficiently high theoretical specific capacities, specific energies, and energy densities. Spectroscopic techniques verify their chemical composition and computation shows that the volume change when reduced is about 37%. Lithium half-cell testing shows that phenyl hexasulfide (C6H5S6C6H5) can provide a specific capacity of 650 mAh g–1 and capacity retention of 80% through 500 cycles at 1C rate along with superlative performance up to 10C. Furthermore, 1302 Wh kg–1 and 1720 Wh L–1 are achievable at a low electrolyte/active material ratio, i.e., 3 μL mg–1. This work adds new members to the cathode family for Li–S batteries, reduces the gap between the theoretical and practical energy densities of batteries, and provides a new direction for the development of alternative high-capacity cathode materials.Item Comprehensive Proteomics Analysis of Stressed Human Islets Identifies GDF15 as a Target for Type 1 Diabetes Intervention(Elsevier, 2020-02-04) Nakayasu, Ernesto S.; Syed, Farooq; Tersey, Sarah A.; Gritsenko, Marina A.; Mitchell, Hugh D.; Chan, Chi Yuet; Dirice, Ercument; Turatsinze, Jean-Valery; Cui, Yi; Kulkarni, Rohit N.; Eizirik, Decio L.; Qian, Wei-Jun; Webb-Robertson, Bobbie-Jo M.; Evans-Molina, Carmella; Mirmira., Raghavendra G.; Metz, Thomas O.; Pediatrics, School of MedicineType 1 diabetes (T1D) results from the progressive loss of β cells, a process propagated by pro-inflammatory cytokine signaling that disrupts the balance between pro- and anti-apoptotic proteins. To identify proteins involved in this process, we performed comprehensive proteomics of human pancreatic islets treated with interleukin-1β and interferon-γ, leading to the identification of 11,324 proteins, of which 387 were significantly regulated by treatment. We then tested the function of growth/differentiation factor 15 (GDF15), which was repressed by the treatment. We found that GDF15 translation was blocked during inflammation, and it was depleted in islets from individuals with T1D. The addition of exogenous GDF15 inhibited interleukin-1β+interferon-γ-induced apoptosis of human islets. Administration of GDF15 reduced by 53% the incidence of diabetes in NOD mice. Our approach provides a unique resource for the identification of the human islet proteins regulated by cytokines and was effective in discovering a potential target for T1D therapy.Item Design, Optimization and Study on Multiple Electrochemical Systems in Energy Dense Rechargeable Lithium Batteries(2019-08) Cui, Yi; Zhu, Likun; Pan, Liang; Mukherjee, Partha P.; Schubert, Peter J.Lithium-ion batteries (LIBs) are commonly and widely applied in current numerous devices such as smart phones, laptops, electric vehicles and medical devices. The LIBs are considered as a mature technology in todays commercial market bene ted from their uncomplicated lithium intercalation and de-intercalation reactions, stable cycling performance and good working life as energy storage devices and power resources. However, the conventional LIBs with technical limits such as high weight, low lithium utilization and low speci c energy density hit the bottlenecks of further improvements and optimizations for meeting the growing power supply requirements. It is urgent to develop the second generations of rechargeable lithium batteries, which have the bene ts of low cost, high speci c capacity and high energy density with light weight. In this context, lithium-sulfur batteries (LSBs) and lithium-selenium (Li-Se) batteries attract much attention due to the high possibility to meet the requirements of high speci c capacity and high energy density. However, the technical challenges they are facing put some barriers before they can be successfully commercialized. By a brief summary, the challenges to be solved are current low energy density because of requiring large amount of liquid electrolyte, the highly ammability and unsafety of lithium metal, low active material content due to the necessary requirement of carbon and binder, and severe so-called shuttle effect resulting in low Coulombic effciency. Before solving these challenges, Li-S batteries or Li-Se batteries are unlikely to be successfully commercialized in our market. Therefore, numerous research is aimed at solving the challenges and further developing more advanced Li-S and Li-Se battery systems. In the present dissertation, the contributions are mainly focused on sulfur-based and selenium-based materials, which aim to solve the current existing challenges and improve the battery performance, herein obtain a higher potential for application. Four chapters are included in this dissertation, which aim to present the four studied projects. The rst research conducted in this dissertation is developing organo S/Se hybrid materials which require low E/S ratios of liquid electrolyte and show light shuttle effect, therefore indicate promising high energy density and cycling life. Secondly, the tin foil is used as lithium sources instead of metallic lithium anode, then incorporated with sulfur cathode as a full cell. The full cell design provides the potential using a metallic anode other than pure lithium and increase the safety factor of a battery system. In addition, nano-scale selenium/carbon nanotubes composite electrode is synthesized via a chemical reduction method. With the optimization on thickness of the composite electrodes, the Se cathode has an active material content of ~60% and shows stable long cycling life with maximizing the utilization of selenium. The nal research conducted in this dissertation is applying a macro molecule named cyanostar, which has the ability to chemically bind with polysul de species, thereupon to alleviate the shuttle effect in Li-S batteries. With the evidence from chemistry analysis and electrochemical comparison results presented in this dissertation, cyanostar is proven to have the potential for further applications in Li-S batteries.Item Electrochemical behavior of tin foil anode in half cell and full cell with sulfur cathode(Elsevier, 2019-01) Cui, Yi; Li, Tianyi; Zhou, Xinwei; Mosey, Aaron; Guo, Wei; Cheng, Ruihua; Fu, Yongzhu; Zhu, Likun; Mechanical Engineering, School of Engineering and TechnologyTin-based (Sn) metal anode has been considered an attractive candidate for rechargeable lithium batteries due to its high specific capacity, safety and low cost. However, the large volume change of Sn during cycling leads to rapid capacity decay. To address this issue, Sn foil was used as a high capacity anode by controlling the degree of lithium uptake. We studied the electrochemical behavior of Sn foil anode in half cell and full cell with sulfur cathode, including phase transform, morphological change, discharge/charge profiles and cycling performance. Enhanced cycling performance has been achieved by limiting the lithiation capacity of the Sn foil electrode. A full cell consisting of a pre-lithiated Sn foil anode and a sulfur cathode was constructed and tested. The full cell exhibits an initial capacity of 1142 mAh g−1 (based on the sulfur mass in the cathode), followed by stable cycling performance with a capacity retention of 550 mAh g−1 after 100 cycles at C/2 rate. This study reports a potential prospect to utilize Sn and S as a combination in rechargeable lithium batteries.Item In Situ and Operando Investigation of the Dynamic Morphological and Phase Changes of Selenium-doped Germanium Electrode during (De)Lithiation Processes(RSC, 2020-01) Li, Tianyi; Lim, Cheolwoong; Cui, Yi; Zhou, Xinwei; Kang, Huixiao; Yan, Bo; Meyerson, Melissa L.; Weeks, Jason A.; Liu, Qi; Guo, Fangmin; Kou, Ronghui; Liu, Yuzi; De Andrade, Vincent; De Carlo, Francesco; Ren, Yang; Sun, Cheng-Jun; Mullins, C. Buddie; Chen, Lei; Fu, Yongzhu; Zhu, Likun; Mechanical and Energy Engineering, School of Engineering and TechnologyTo understand the effect of selenium doping on the good cycling performance and rate capability of a Ge0.9Se0.1 electrode, the dynamic morphological and phase changes of the Ge0.9Se0.1 electrode were investigated by synchrotron-based operando transmission X-ray microscopy (TXM) imaging, X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The TXM results show that the Ge0.9Se0.1 particle retains its original shape after a large volume change induced by (de)lithiation and undergoes a more sudden morphological and optical density change than pure Ge. The difference between Ge0.9Se0.1 and Ge is attributed to a super-ionically conductive Li–Se–Ge network formed inside Ge0.9Se0.1 particles, which contributes to fast Li-ion pathways into the particle and nano-structuring of Ge as well as buffering the volume change of Ge. The XRD and XAS results confirm the formation of a Li–Se–Ge network and reveal that the Li–Se–Ge phase forms during the early stages of lithiation and is an inactive phase. The Li–Se–Ge network also can suppress the formation of the crystalline Li15Ge4 phase. These in situ and operando results reveal the effect of the in situ formed, super-ionically conductive, and inactive network on the cycling performance of Li-ion batteries and shed light on the design of high capacity electrode materials.Item In Situ Focused Ion Beam Scanning Electron Microscope Study of Microstructural Evolution of Single Tin Particle Anode for Li-Ion Batteries(ACS, 2019-01) Zhou, Xinwei; Li, Tianyi; Cui, Yi; Fu, Yongzhu; Liu, Yuzi; Zhu, Likun; Mechanical and Energy Engineering, School of Engineering and TechnologyTin (Sn) is a potential anode material for highenergy density Li-ion batteries because of its high capacity, safety, abundance and low cost. However, Sn suffers from large volume change during cycling, leading to fast degradation of the electrode. For the first time, the microstructural evolution of micrometer-sized single Sn particle was monitored by focused-ion beam (FIB) polishing and scanning electron microscopy (SEM) imaging during electrochemical cycling by in situ FIB-SEM. Our results show the formation and evolution of cracks during lithiation, evolution of porous structure during delithiation and volume expansion/contraction during cycling. The electrochemical performance and the microstructural evolution of the Sn microparticle during cycling are directly correlated, which provides insights for understanding Sn-based electrode materials.Item In Situ Focused Ion Beam-Scanning Electron Microscope Study of Crack and Nanopore Formation in Germanium Particle During (De)lithiation(ACS, 2019-04) Zhou, Xinwei; Li, Tianyi; Cui, Yi; Meyerson, Melissa L.; Mullins, C. Buddie; Liu, Yuzi; Zhu, Likun; Mechanical and Energy Engineering, School of Engineering and TechnologyGermanium has emerged as a promising high-capacity anode material for lithium ion batteries. To understand the microstructure evolution of germanium under different cycling rates, we monitored single germanium particle batteries using an in situ focused ion beam-scanning electron microscope. Our results show that both the lithium concentration and delithiation rate have an impact on nanopore formation. This study reveals that germanium electrodes with low and high cycling rates have better microstructure integrity, which leads to better cycling performance. The nanopores tend to aggregate into large porous structures during cycling which leads to particle pulverization and capacity fading of the electrode.Item In Situ Temperature Evolution and Failure Mechanisms of LiNi0.33Mn0.33Co0.33O2 Cell under Over-Discharge Conditions(ECS, 2018-09) Wu, Linmin; Liu, Yadong; Cui, Yi; Zhang, Yi; Zhang, Jing; Mechanical Engineering, School of Engineering and TechnologyIn this work, in situ study of commercial 18650 NMC (LiNi0.33Mn0.33Co0.33O2) cells under over-discharge charge conditions (100%, 110%, and 120%) has been performed. Both voltage and cell skin temperature evolutions were simultaneously monitored in situ during discharge process. The results show that there is a clear correlation between the voltage and temperature. For the NMC cell under 120% over-discharge condition, the cell failed after only 1 cycle. The voltage dropped to negative values at the end of the discharge. The skin temperature at the end of discharge increased dramatically to 73°C, indicating strong exothermal reactions happened inside the cell. For the 110% over-discharged cell, the cell failed after 10 cycles. The voltage at the end of the discharge process became negative after the 1st cycle. The cell skin temperature increased from 23.2°C to 61.7°C. The peak temperature in each cycle kept increasing until failure. These implies the micro short circuits were developed during the charge-discharge process. The failed components were examined by SEM/EDX and XRD. The results show substantial aluminum exists inside the failed separators. The results suggest that during the over-discharge process, the alumina inside the separator was reduced to aluminum. The electrons migrate through aluminum channel, leading to the failure of the cells.