Lithium Superoxide Hydrolysis and Relevance to Li–O₂ Batteries

Wang, Hsien-Hau,Lee, Yun Jung,Assary, Rajeev S.,Zhang, Chengji,Luo, Xiangyi,Redfern, Paul C.,Lu, Jun,Lee, Young Joo,Kim, Do Hyung,Kang, Tae-Geun,Indacochea, Ernesto,Lau, Kah Chun,Amine, Khalil,Curtiss American Chemical Society 2017 The Journal of Physical Chemistry Part C Vol.121 No.18

<P>Fundamental understanding;of reactions, of lithium peroxides and superoxides is this for :the development of Li-O-2 batteries. In context, an investigation is reported of the hydrolysis of lithium superoxide, which has recently been synthesized in a Li-O-2 battery. Surprisingly, the hydrolysis of solid LiO2 is significantly different from that of NaO2 and KO2. Unlike KO2 and NaO2, the hydrolysis of LiO2 does not produce H2O2. Similarly, the reactivity of Li2O2 toward water differs from LiO2 in that Li2O2 results in H2O2 as a product. The difference in the LiO2 reactivity with water due to the more exothermic nature of the formation of LiOH and O-2 compared with the corresponding reactions, of NaO2 and KO2. We also show that a titration method used in this study, based on reaction of the discharge product with a Ti(IV)OSO4 solution; provides a useful diagnostic technique to provide information Oh the composition of a,discharge product in a Li-O-2 battery.</P>

Cross-border R&D alliance networks: an empirical study of the umbilical cord blood banking industry in emerging markets

Hsien-Tang Tsai,Shi-Zheng Huang,Chun-Hsien Wang 기술경영경제학회 2015 ASIAN JOURNAL OF TECHNOLOGY INNOVATION Vol.23 No.3

The concept of the cross-border collaboration network has been recognised as a useful way toobtain external R&D knowledge resources in the biotechnology industry. Drawing on socialcapital theory, this study explores how two types of network position (centrality andstructural holes) and cross-border collaborative ties affect the cross-border R&Dcollaborative alliance of the biotechnology firms and how these effects are contingent onexploratory collaboration with their collaboration partners. Analysis of the data collectedfrom 174 cross-border collaboration partners in the emerging biotechnology sector indicatesthat the two types of network position differ in the extent to which they contribute to thecross-border R&D collaborative alliance. By investigating the contingent role of exploratorycollaboration, we find that exploratory collaboration weakens the impact of networkcentrality on the cross-border R&D collaborative alliance but strengthens the effect ofstructural holes on the establishment of cross-border R&D collaborative alliance. Resultsconfirm that biotechnology firms’ cross-border R&D knowledge resources need to extendbeyond their industry and regional boundaries. More specifically, this study contributes tothe debate on whether network centrality and structural holes are complementary and thusenrich contextual cross-border alliance literature

Evaluation of Ride Comfort for Active Suspension System Based on Selftuning Fuzzy Sliding Mode Control

Chun-Yu Hsiao,Yu-Hsien Wang 제어·로봇·시스템학회 2022 International Journal of Control, Automation, and Vol.20 No.4

This paper describes the application of a self-tuning fuzzy sliding mode controller (STFSMC) to design the control signal of an electro-hydraulic actuator under standard road excitation based on ISO 8608. The proposed damper was designed to achieve effective vibration isolation with an actuator force. The proposed damper was incorporated into a quarter-car system through experiments for the subsequent dynamic analysis of the suspension system. A single-input single-output (SISO) fuzzy inference was strategically used to regulate the slope of a sliding surface. In addition, the fuzzy control methodology was applied to achieve self-tuning online output of the scale factor of the fuzzy sliding mode controller. The comfortable riding time and ride comfort level were also evaluated based on ISO 2631-1. Experimental results revealed that the proposed controller demonstrated evident improvements in vehicle vibration suppression and the ride quality in comparison with passive and fuzzy logic controller control systems.

Penetration Processes of Soft Solid Materials by Needle-Free Micro-Injections

( Muh Rong Wang ),( Chun Hsien Chiu ),( Chien Chih Huang ),( Li Jay Cheng ),( Yang Sheng Huang ),( Min Chen ) 한국액체미립화학회 2010 한국액체미립화학회 학술강연회 논문집 Vol.2010 No.-

Penetration characteristics of the single pulse micro-jets into the soft solid materials of gelatin gels and porcine colons are investigated in this paper. The images of penetration processes were taken by IDT high-speed digital camera at the sampling rate of 2500 frames per second. The evolution of the penetration process, penetration depth, volume of infection and penetration rate is investigated. Gelatin gel is a good model material for the observation of the penetration processes because of the translucent property. In vitro penetrations of porcine colons were also tested for the prior study of endoscopic needle-free injection. The penetration test was performed under the single-pulsed mode at injection time of 0.1, 0.25 and 0.5 seconds. The injection pressure was in the range of 50 to 125 bar. The diameter of the injectors, do, is 250 and 300 m. According to the high-speed photos of the gel penetration, the injection processes can be described as four steps: 1. Initial compression period: the elastic compression of the soft solid material at the penetration site and the neighborhood. 2. Material failure period: the jet penetrates inside the gelatin gel including the initial surface crack and growth of the injected volume. 3. Elastic rebounding period: It takes place when the injection is stopped. The injected water starts to be squeezed out of the gelatin gel under the compression of the gelatin gel during the elastic relaxation processes until the final penetration depth and width. 4. Final stable period: the penetration depth and width inside the gelatin gel are fixed afterward. Furthermore, the injection tests on the porcine colon show the penetration into submucosal layer is possible under the injection pressure less than 60 bar with the orifice of 300 m and injection time of 0.1 sec. The injection power is 16 W under this condition. However, higher injection power is needed for the punch through injection of porcine colon. The failure stress of the porcine colon is 1.077 0.333 MPa by the deep penetration test.

Evidence for lithium superoxide-like species in the discharge product of a Li–O₂ battery

Yang, Junbing,Zhai, Dengyun,Wang, Hsien-Hau,Lau, Kah Chun,Schlueter, John A.,Du, Peng,Myers, Deborah J.,Sun, Yang-Kook,Curtiss, Larry A.,Amine, Khalil The Royal Society of Chemistry 2013 Physical chemistry chemical physics Vol.15 No.11

<P>We report on the use of a petroleum coke-based activated carbon (AC) with very high surface area for a Li–O<SUB>2</SUB> battery cathode without the use of any additional metal catalysts. Electrochemical measurement in a tetra(ethylene) glycol dimethyl ether–lithium triflate (TEGDME–LiCF<SUB>3</SUB>SO<SUB>3</SUB>) electrolyte results in two voltage plateaus during charging at 3.2–3.5 and 4.2–4.3 V <I>versus</I> Li<SUP>+</SUP>/Li. Herein we present evidence from Raman and magnetic measurements that the lower plateau corresponds to a form of lithium peroxide with superoxide-like properties characterized by a low temperature magnetic phase transition and a high O–O stretching frequency (1125 cm<SUP>−1</SUP>). The magnetic phase transition and the high O–O stretching frequency disappear when charged to above 3.7 V. Theoretical calculations indicate that a surface superoxide structure on lithium peroxide clusters and some lithium peroxide surfaces have an unpaired electron and a high O–O stretching frequency that help explain the observations. These results provide evidence that the form of the lithium peroxide discharge product is important to obtaining a low charge overpotential, and thus improving the round-trip efficiency between discharge and charge.</P> <P>Graphic Abstract</P><P>We report on the use of a petroleum coke-based activated carbon in a Li–O<SUB>2</SUB> battery that gives two voltage plateaus during charging and evidence for a superoxide-like species. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c3cp00069a'> </P>

<i>In Situ</i> Formed Ir₃Li Nanoparticles as Active Cathode Material in Li-Oxygen Batteries

Halder, Avik,Ngo, Anh T.,Luo, Xiangyi,Wang, Hsien-Hau,Wen, J. G.,Abbasi, Pedram,Asadi, Mohammad,Zhang, Chengji,Miller, Dean,Zhang, Dongzhou,Lu, Jun,Redfern, Paul C.,Lau, Kah Chun,Amine, Rachid,Assary, American Chemical Society [etc.] 2019 The Journal of physical chemistry A Vol. No.

<P>Lithium-oxygen (Li-O<SUB>2</SUB>) batteries are a promising class of rechargeable Li batteries with a potentially very high achievable energy density. One of the major challenges for Li-O<SUB>2</SUB> batteries is the high charge overpotential, which results in a low energy efficiency. In this work size-selected subnanometer Ir clusters are used to investigate cathode materials that can help control lithium superoxide formation during discharge, which has good electronic conductivity needed for low charge potentials. It is found that Ir particles can lead to lithium superoxide formation as the discharge product with Ir particle sizes of ∼1.5 nm giving the lowest charge potentials. During discharge these 1.5 nm Ir nanoparticles surprisingly evolve to larger ones while incorporating Li to form core-shell structures with Ir<SUB>3</SUB>Li shells, which probably act as templates for growth of lithium superoxide during discharge. Various characterization techniques including DEMS, Raman, titration, and HRTEM are used to characterize the LiO<SUB>2</SUB> discharge product and the evolution of the Ir nanoparticles. Density functional calculations are used to provide insight into the mechanism for formation of the core-shell Ir<SUB>3</SUB>Li particles. The <I>in situ</I> formed Ir<SUB>3</SUB>Li core-shell nanoparticles discovered here provide a new direction for active cathode materials that can reduce charge overpotentials in Li-O<SUB>2</SUB> batteries.</P> [FIG OMISSION]</BR>

ALDH2 Gene: Its Effects on the Neuropsychological Functions in Patients with Opioid Use Disorder Undergoing Methadone Maintenance Treatment

Po-Wei Lee,Tzu-Yun Wang,Yun-Hsuan Chang,Sheng-Yu Lee,Shiou-Lan Chen,Ze-Cheng Wang,Po See Chen,Chun-Hsien Chu,San-Yuan Huang,Nian-Sheng Tzeng,I Hui Lee,Kao Chin Chen,Yen Kuang Yang,Jau-Shyong Hong,Ru-B 대한정신약물학회 2020 CLINICAL PSYCHOPHARMACOLOGY AND NEUROSCIENCE Vol.18 No.1

Objective: Patients with opioid use disorder (OUD) have impaired attention, inhibition control, and memory function. The aldehyde dehydrogenase 2 (ALDH2 ) gene has been associated with OUD and ALDH2 gene polymorphisms may affect aldehyde metabolism and cognitive function in other substance use disorder. Therefore, we aimed to investigate whether ALDH2 genotypes have significant effects on neuropsychological functions in OUD patients undergoing methadone maintenance therapy (MMT). Methods: OUD patients undergoing MMT were investigated and followed-up for 12 weeks. ALDH2 gene polymorphisms were genotyped. Connors’ Continuous Performance Test (CPT) and the Wechsler Memory Scale-Revised (WMS-R) were administered at baseline and after 12 weeks of MMT. Multivariate linear regressions and generalized estimating equations (GEEs) were used to examine the correlation between the ALDH2 genotypes and performance on the CPTs and WMS-R. Results: We enrolled 86 patients at baseline; 61 patients completed the end-of-study assessments. The GEE analysis showed that, after the 12 weeks of MMT, OUD patients with the ALDH2 *1/*2+*2/*2 (ALDH2 inactive) genotypes had significantly higher commission error T-scores (p = 0.03), significantly lower hit reaction time T-scores (p = 0.04), and significantly lower WMS-R visual memory index scores (p = 0.03) than did patients with the ALDH2 1 */*1 (ALDH2 active) genotype. Conclusion: OUD patients with the ALDH2 inactive genotypes performed worse in cognitive domains of attention, impulse control, and memory than did those with the ALDH2 active genotype. We conclude that the ALDH2 gene is important in OUD and is associated with neuropsychological performance after MMT.

Magnetism in lithium-oxygen discharge product.

Lu, Jun,Jung, Hun-Ji,Lau, Kah Chun,Zhang, Zhengcheng,Schlueter, John A,Du, Peng,Assary, Rajeev S,Greeley, Jeffrey,Ferguson, Glen A,Wang, Hsien-Hau,Hassoun, Jusef,Iddir, Hakim,Zhou, Jigang,Zuin, Lucia Wiley-VCH 2013 ChemSusChem Vol.6 No.7

<P>Nonaqueous lithium-oxygen batteries have a much superior theoretical gravimetric energy density compared to conventional lithium-ion batteries, and thus could render long-range electric vehicles a reality. A molecular-level understanding of the reversible formation of lithium peroxide in these batteries, the properties of major/minor discharge products, and the stability of the nonaqueous electrolytes is required to achieve successful lithium-oxygen batteries. We demonstrate that the major discharge product formed in the lithium-oxygen cell, lithium peroxide, exhibits a magnetic moment. These results are based on dc-magnetization measurements and a lithium-oxygen cell containing an ether-based electrolyte. The results are unexpected because bulk lithium peroxide has a significant band gap. Density functional calculations predict that superoxide-type surface oxygen groups with unpaired electrons exist on stoichiometric lithium peroxide crystalline surfaces and on nanoparticle surfaces; these computational results are consistent with the magnetic measurement of the discharged lithium peroxide product as well as EPR measurements on commercial lithium peroxide. The presence of superoxide-type surface oxygen groups with spin can play a role in the reversible formation and decomposition of lithium peroxide as well as the reversible formation and decomposition of electrolyte molecules.</P>

A lithium–oxygen battery based on lithium superoxide

Lu, Jun,Jung Lee, Yun,Luo, Xiangyi,Chun Lau, Kah,Asadi, Mohammad,Wang, Hsien-Hau,Brombosz, Scott,Wen, Jianguo,Zhai, Dengyun,Chen, Zonghai,Miller, Dean J.,Sub Jeong, Yo,Park, Jin-Bum,Zak Fang, Zhigang Nature Publishing Group, a division of Macmillan P 2016 Nature Vol.529 No.7586

<P>Batteries based on sodium superoxide and on potassium superoxide have recently been reported(1-3). However, there have been no reports of a battery based on lithium superoxide (LiO2), despite much research(4-8) into the lithium-oxygen (Li-O-2) battery because of its potential high energy density. Several studies(9-16) of Li-O-2 batteries have found evidence of LiO2 being formed as one component of the discharge product along with lithium peroxide (Li2O2). In addition, theoretical calculations have indicated that some forms of LiO2 may have a long lifetime(17). These studies also suggest that it might be possible to form LiO2 alone for use in a battery. However, solid LiO2 has been difficult to synthesize in pure form(18) because it is thermodynamically unstable with respect to disproportionation, giving Li2O2 (refs 19, 20). Here we show that crystalline LiO2 can be stabilized in a Li-O-2 battery by using a suitable graphene-based cathode. Various characterization techniques reveal no evidence for the presence of Li2O2. A novel templating growth mechanism involving the use of iridium nanoparticles on the cathode surface may be responsible for the growth of crystalline LiO2. Our results demonstrate that the LiO2 formed in the Li-O-2 battery is stable enough for the battery to be repeatedly charged and discharged with a very low charge potential (about 3.2 volts). We anticipate that this discovery will lead to methods of synthesizing and stabilizing LiO2, which could open the way to high-energy-density batteries based on LiO2 as well as to other possible uses of this compound, such as oxygen storage.</P>

The feasibility of detecting endometrial and ovarian cancer using DNA methylation biomarkers in cervical scrapings

Cheng-Chang Chang,Hui-Chen Wang,Yu-Ping Liao,Yu-Chih Chen,Yu-Chun Weng,Mu-Hsien Yu,Hung-Cheng Lai 대한부인종양학회 2018 Journal of Gynecologic Oncology Vol.29 No.1

Objective: We hypothesized that DNA methylation of development-related genes may occur in endometrial cancer (EC)/ovarian cancer (OC) and may be detected in cervical scrapings. Methods: We tested methylation status by quantitative methylation-specific polymerase chain reaction for 14 genes in DNA pools of endometrial and OC tissues. Tissues of EC/normal endometrium, OC/normal ovary, were verified in training set using cervical scrapings of 10 EC/10 OC patients and 10 controls, and further validated in the testing set using independent cervical scrapings in 30 EC/30 OC patients and 30 controls. We generated cutoff values of methylation index (M-index) from cervical scrapings to distinguish between cancer patients and control. Sensitivity/specificity of DNA methylation biomarkers in detecting EC and OC was calculated. Results: Of 14 genes, 4 (PTGDR, HS3ST2, POU4F3, MAGI2) showed hypermethylation in EC and OC tissues, and were verified in training set. POU4F3 and MAGI2 exhibited hypermethylation in training set were validated in independent cases. The mean M-index of POU4F3 is 78.28 in EC and 20.36 in OC, which are higher than that in controls (6.59; p<0.001 and p=0.100, respectively), and that of MAGI2 is 246.0 in EC and 12.2 in OC, which is significantly higher that than in controls (2.85; p<0.001 and p=0.480, respectively). Sensitivity and specificity of POU4F3/MAGI2 were 83%–90% and 69%–75% for detection of EC, and 61% and 62%–69% for the detection of OC. Conclusion: The findings demonstrate the potential of EC/OC detection through testing for DNA methylation in cervical scrapings.