De Jonghe Research Articles

(Invited) A Brief History of Sodium-Ion Battery Research

Interest in sodium-ion batteries (NIBs) has never been greater than it is now. This is in great part due to concerns about the sustainability and cost of energy storage devices based on lithium. Another advantage to sodium-ion systems is their similarity to lithium-ion batteries (LIBs); knowledge gained over the past few decades on the latter has been leveraged to rapidly develop the former. For this reason, sodium-ion batteries are the closest to commercialization of all the “Beyond Lithium-Ion Battery” chemistries. NIBs are particularly attractive for large-scale energy storage, but may also have a place in vehicular applications, particularly if vehicle-to-grid systems are considered.Intercalation of sodium into host structures such as TiS2 was described as early as 1978.[1] A few attempts at making “rocking chair” batteries based on sodium followed a few years later, including one using Na0.7CoO2 as the positive electrode and a sodium-lead alloy as the negative.[2] In 1993, the first NIB using a disordered carbon anode was described.[3] Although performance was poor by today’s standards, it set the stage for further work in the area. However, research on NIBs languished for several decades after this while the battery community largely turned its attention to the newly commercialized Li-ion systems. It was not until the early 2010s that interest picked up again, as LIBs matured and concerns about lithium supply security heightened.This talk will cover the history of sodium-ion battery research, including the speaker’s early contributions to the field, as well as her more recent work on titanate anodes. An overview of the advantages and possible applications of NIBs will be included. [1] M. S. Whittingham, Prog. Solid State Chem. 12 , 41 (1978). [2] L. W. Shacklette, T.R. Jow, and L. Townsend, J. Electrochem. Soc. 135, 2669 (1988). [3] M. M. Doeff, Y. Ma, S.J. Visco and L.C. De Jonghe, J. Electrochem. Soc. 140, L169 (1993).

(Digital Presentation) Water-Soluble Binders That Enhance Electrochemical Sodium-Ion Storage Properties of NaTi2(PO4)3 Nanoparticle Anodes

Sodium ion batteries (SIBs) have been considered as one of the most promising alternative to conventional lithium-ion batteries (LIBs) for next generation energy storage systems.1 , 2 In terms of anodes, commercial graphite only delivers a sodium-ion storage capacity of 31 mAh g−1.3 The polyanionic-type NaTi2(PO4)3 material is an attractive anode because of the crystal structure of a Na-super-ionic conductor (NASICON), high theoretical capacity, safety characterization and ‘zero-stress’ framework upon sodiation/desodiation.4 , 5 The primary role played by the binder is to link different types of small particles together and to ensure the active material adheres to the current collector, which has an important contribution to the electrical and mechanical behaviour of the electrode.6 , 7 Poly(vinylidene fluoride) (PVDF) is a common organic binder using N-methyl-2-pyrrolidone (NMP) as solvents. Sodium carboxymethyl cellulose (CMC) has been considered as an effective and green water-soluble binders. Styrene butadiene rubber (SBR) typically serves as an elastomer in water-soluble CMC binders and further increases binding force, adhesion, heat resistance, and flexibility of an electrode. The role of different binders on the structural/chemical stability of NaTi2(PO4)3 anode in SIBs has rarely been studied.Here, we synthesized NaTi2(PO4)3 nanoparticles using the hydrothermal method and explore the effects and influence of PVDF, CMC and CMC-SBR binders on the sodium-ion storage performance of NaTi2(PO4)3 anodes. Compared to traditional organic PVDF binder, water-soluble binders improved the cycling stability by increasing adhesion, flexibility, and mechanical properties between the active materials, conductive addictive and current collector. Notably, water-soluble binders show an important effect on the sodium storage mechanism of NaTi2(PO4)3 nanoparticles. The addition of SBR in the water-soluble binders further enhances the active materials areal specific capacity because of its better adhesion ability, reducing the overall quantity of binder polymer required for the electrode. This novel exploration of the effective combination of water-soluble CMC and SBR binders for NaTi2(PO4)3 anodes in SIBs not only provides an opportunity to enhance their electrochemical sodium storage properties, but may enables their practical application in high areal energy density sodium ion batteries in the future. References (1) Nayak, P. K.; Yang, L.; Brehm, W.; Adelhelm, P.: From Lithium-Ion to Sodium-Ion Batteries: Advantages, Challenges, and Surprises. Angew. Chem. Int. Ed. 2018, 57, 102-120.(2) Kim, S.-W.; Seo, D.-H.; Ma, X.; Ceder, G.; Kang, K.: Electrode Materials for Rechargeable Sodium-Ion Batteries: Potential Alternatives to Current Lithium-Ion Batteries. Adv. Energy Mater. 2012, 2, 710-721.(3) Doeff, M. M.; Ma, Y.; Visco, S. J.; De Jonghe, L. C.: Electrochemical insertion of sodium into carbon. J. Electrochem. Soc. 1993, 140, L169-L170.(4) Delmas, C.; Cherkaoui, F.; Nadiri, A.; Hagenmuller, P.: A nasicon-type phase as intercalation electrode: NaTi2(PO4)3. Mater. Res. Bull. 1987, 22, 631-639.(5) Chen, S.; Wu, C.; Shen, L.; Zhu, C.; Huang, Y.; Xi, K.; Maier, J.; Yu, Y.: Challenges and Perspectives for NASICON-Type Electrode Materials for Advanced Sodium-Ion Batteries. Adv. Mater. 2017, 29, 1700431.(6) Chen, H.; Ling, M.; Hencz, L.; Ling, H. Y.; Li, G.; Lin, Z.; Liu, G.; Zhang, S.: Exploring Chemical, Mechanical, and Electrical Functionalities of Binders for Advanced Energy-Storage Devices. Chem. Rev. 2018, 118, 8936-8982.(7) Bommier, C.; Ji, X.: Electrolytes, SEI Formation, and Binders: A Review of Nonelectrode Factors for Sodium-Ion Battery Anodes. Small 2018, 14, 1703576. Figure 1 (a) SEM image and (b) HRTEM image of NaTi2(PO4)3 nanoparticles with quasi-cubic architecture and hollow structure. (c) XRD analysis of the synthesized nanoparticles. (d) Specific capacity versus rate data using chronoamperometry (CA) method for NaTi2(PO4)3 nanoparticles anode of different binders. (Inset) Corresponding digital photos for NTP electrodes with different binders. (e) The first cycle in the cyclic voltammetric curve at a scan rate of 0.1 mV s-1 for NaTi2(PO4)3 nanoparticles anode. (f) Galvanostatic discharging and charging cycling stability at 0.2 C (1C = 133 mA g-1) for the NaTi2(PO4)3 nanoparticle anode with different binders. Figure 1

Human embryo research, stem cell-derived embryo models and invitro gametogenesis: Considerations leading to the revised ISSCR guidelines.

SummaryThe ISSCR Guidelines for Stem Cell Research and Clinical Translation were last revised in 2016. Since then, rapid progress has been made in research areas related to in vitro culture of human embryos, creation of stem cell-based embryo models, and in vitro gametogenesis. Therefore, a working group of international experts was convened to review the oversight process and provide an update to the guidelines. This report captures the discussion and summarizes the major recommendations made by this working group, with a specific emphasis on updating the categories of review and engagement with the specialized scientific and ethical oversight process.

The Relationship between Funding Shock and Reallocation of Loan Asset in Korean Banks

본 연구는 자금조달 충격이 은행 대출포트폴리오 구성변경에 영향을 미친다는 선행연구에 주목했다. 특히, De Jonghe, Dewachter, Mulier, Ongena, Schepens(2020)는 음(-)의 자금조달 충격발생시 은행은 저위험 차주에 대한 대출을 늘린다는 주장을 제기한 바 있다. 이로써, 본 연구는 국내은행들의 자금조달 충격이 중소기업대출 및 주택담보대출, 그리고 시설자금대출 및 운전자금 대출로 각각 구성된 포트폴리오 조정을 유발하는지 여부를 실증분석했다. 주요 연구결과는 다음과 같다. 첫째, 중소기업대출과 주택담보대출로 구성된 대출포트폴리오는 음(-)의 자금조달 충격에 대해 낮은 위험차주의 대출을 늘리는 조정을 보였다. 즉, 원화예수금을 통한 자금조달에 있어 음(-)의 충격은 상대적으로 중소기업대출 비율 축소를 초래했다. 둘째, 시설자금대출과 운전자금대출로 구성된 포트폴리오도 음(-)의 자금조달 충격에 대해 위험노출도가 낮은 운전자금대출 비중증가를 가져왔다. 셋째, 자산규모가 큰 은행이 원화예수금을 통한 자금조달시 양(+)의 충격에 직면할 경우 주택담보대출 대비 중소기업대출 비중이 늘어났다. 결론적으로 국내 은행들은 자금조달 위기상황시 위험관리차원에서 대출자산을 재구성하는 경향을 보였다.This study paid attention to the previous research reporting the results that funding shock affects allocation of loan portfolio in bank. Especially, De Jonghe, Dewachter, Mulier, Ongena, Schepens (2020) argued that bank tends to increase the loan to borrowers with low risk when negative funding shock is occurred. Accordingly, current study analyzed empirically whether funding shock results in adjustment of portfolio with small and medium sized enterprise (SME) loan and housing loan or with loans for facility funds and for working funds in Korean banks. Main results are as follows. First, loan portfolio with SME loan and housing loan is affected by negative funding shock, and is adjusted into increasing the loan to borrower with low risk. Negative funding shock through Korean won deposit (KRWD) leads to shrinking the weight of SME loan within the portfolio. Second, negative funding shock makes loan for working funds with low risk exposure increased within the portfolio with loans for facility funds and for working funds. Third, the bank with large asset size tends to increase the weight of SME loan within the portfolio with SME loan and housing loan when funding shock through KRWD is positive. As a result, Korean banks tend to reallocate loan asset in terms of risk management when funding crisis is broken out.

Abstract 5879: Spatially-segmented single-cell transcriptomics by diffusional accessibility to a small-molecule dye

Abstract High-throughput single-cell RNA-seq (scRNA-seq) is used to describe complex tissues by characterizing transcriptional states of individual cells. Defining a cell's position, both in regard to tissue margins and its social context, is essential for understanding the intrinsic and extrinsic variables that effect the transcriptional identity of individual cells. Conventional high-throughput scRNA-seq assays, however, decouple cells from their original locations within tissues. In situ hybridization readouts of gene expression and in situ sequencing preserve spatial information in tissues, but currently have a lower total read threshold than NextGen sequencing – imposing a restriction on either cell throughput or transcriptional breadth. Combining the above methods or using regional barcodes to define 2D positions have spatially-reconstructed tissue regions but are seldom employed in unspecialized laboratories. We describe SEgmentation by Exogenous Perfusion (SEEP), a rapid, integrated, method for providing 3D spatial-segmentation to scRNA-seq data. Tissues are divided into layers based on accessibility of a fluorescent dye allowing sorted cells to be characterized by transcriptomic and regional identity. We use SEEP to explore how the transcriptional states of cells in high-grade serous ovarian cancer vary with respect to intratumoral position. We describe an integrated method for correlating 3D radial-spatial cell positions with scRNA-seq data. By employing a basic stain-and-sort method using an off-the-shelf live-dead stain, we are able to correlate transcriptional profiles with radial-spatial positions in both radially symmetric tissues (e.g., spheroids, organoids, spherical tumor masses) and linear tissue samples (e.g., punch biopsies). SEEP uses an imaging-based calibration step to inform the parameters of a FACS and sequencing based measurement step. Across spheroid, organoid, and PDX models of high-grade serous ovarian cancer, we find common positional transcriptomic profiles, ranging from single-gene proclivities to multi-gene-set enrichments across tissue layers. Citation Format: David B. Morse, Michele Ceribelli, Joachim De Jonghe, Aleksandra Michalowski, Christoph Muus, Maria Vias, Samantha Boyle, David A. Weitz, James Brenton, Jason D. Buenrostro, Craig Thomas, Tuomas P. Knowles. Spatially-segmented single-cell transcriptomics by diffusional accessibility to a small-molecule dye [abstract]. In: Proceedings of the Annual Meeting of the American Association for Cancer Research 2020; 2020 Apr 27-28 and Jun 22-24. Philadelphia (PA): AACR; Cancer Res 2020;80(16 Suppl):Abstract nr 5879.

Determination of the Transport Properties of Liquid Electrolytes Using a Multi-Electrode Cell

Reliable electrochemical models are necessary for performing numerical battery-related studies. These models must be comprehended with a number of input parameters.Many literature papers deal with the determination of electrolyte transport properties [1- 4] but only a minority of them proposes an exhaustive characterization (namely the determination of the transference number, the conductivity, the diffusion coefficient and the thermodynamic factor, for the simplest case of a binary electrolyte). Furthermore, when comparison can be made[5], it is often the case that data gathered from different sources for a same electrolyte are not in good quantitative agreement with each other [1,6].The most commonly used experimental methods for a complete determination of the set of properties are: The Hittorf method [2,3] (for transference number), the restricted diffusion method [7] (for diffusion coefficient), the electrochemical impedance spectroscopy (for conductivity) and the concentration cell (for the activity coefficient).Back in 2016 [6], Farkhondeh and coworkers proposed to alleviate the tedious multi-experimental protocol by introducing a novel multi-electrode cell design, in which the potential between inner Li reference electrodes is measured during and after a current pulse applied between two outer Li working electrodes. The measured potential is free of any electrode polarization and can be fitted with a mathematical model of the electrolyte so that conductivity, salt diffusion coefficient, and lithium transference number are simultaneously determined in single experiment.Our current work builds on the prior art by Farkhondeh and coworkers. It deals with the use of a “multi-electrode electrochemical cell”. Different routes are being explored and will be discussed in the presentation, namely: Using more reference electrodes for the method to gain accuracy, and possibly to evaluate the composition dependence of parameters in a limited number of experiments (fig.1).Bypassing metallic-lithium-related problems by finding alternatives to be used as active electrodes. Theoretical and practical aspects will be discussed and LiPF6 dissolved in 1:1 weight proportions EC:DEC will be investigated as a benchmark electrolyte and compared with already-published data [1].Our work aims at (i) showing how the parameters evaluation process could be simplified, and (ii) reduce drastically the number of experiments needed for fully characterizing a liquid electrolyte. This is an essential step towards the elaboration of an electrolyte-property database, supplying valuable information for modeling, as well as formulation-engineering, purposes. Fig. 1 : Representation of voltage measured between reference electrodes (blue red and orange crosses), during a current-pulse (black dashed line) of 1.9 A/m² and following relaxation. These experimental data were used to fit the electrolyte transport parameters using a mathematical model (in purple, green and cyan). Determined parameters are the following : . D = 2.85×10-10 m²/s , t+ 0 = 0.217 and κ eff = 0.602 S/m. The gradient-colored strip at the bottom highlights the parts of the signal where the different transport parameters have the largest sensivity. The multi-reference cell is represented in inset: (dark-grey: Li metal reference electrodes, dark grey: polyethylene spacers).References :[1] H. Lundgren, M. Behm, and G. Lindbergh, “Electrochemical Characterization and Temperature Dependency of Mass-Transport Properties of LiPF6 in EC:DEC,” J. Electrochem. Soc., vol. 162, no. 3, pp. A413–A420, 2014.[2] L. O. Valo̸en and J. N. Reimers, “Transport Properties of LiPF[sub 6]-Based Li-Ion Battery Electrolytes,” J. Electrochem. Soc., vol. 152, no. 5, p. A882, 2005.[3] T. Hou and C. W. Monroe, “Composition-Dependent Thermodynamic and Mass-Transport Characterisation of Lithium Hexafluorophosphate in Propylene Carbonate,” Manuscr. Submitt. Publ., p. 135085, 2019.[4] Yanping Ma, Marc Doyle, Thomas F Fuller, Marca M. Doeff, Lutgard C. De Jonghe, and John Newman. The measurement of a complete set of transport properties of a concentrated solid polymer electrolyte solution. Journal of The Electrochemical Society, 142(6):1859–1868, 1995[5] A. Ehrl, J. Landesfeind, W. A. Wall, and H. A. Gasteiger, “Determination of Transport Parameters in Liquid Binary Electrolytes: Part II. Transference Number,” J. Electrochem. Soc., vol. 164, no. 12, pp. A2716–A2731, 2017.[6] FARKHONDEH, Mohammad, PRITZKER, Mark, FOWLER, Michael, et al. Transport property measurement of binary electrolytes using a four-electrode electrochemical cell. Electrochemistry Communications, 2016, vol. 67, p. 11-15.. [7] Herbert S. Harned and Douglas M. French. A conductance method for the determination of the diffusion coefficients of electrolytes. Annals of the New York Academy of Sciences, 46(1):267–284, 1945 Figure 1

Individual and combined presenilin 1 and 2 knockouts reveal that both have highly overlapping functions in HEK293T cells

Presenilins 1 and 2 (PS1 and 2) are the catalytic subunits of γ-secretase, a multiprotein protease that cleaves amyloid protein precursor and other type I transmembrane proteins. Previous studies with mouse models or cells have indicated differences in PS1 and PS2 functions. We have recently reported that clinical γ-secretase inhibitors (GSIs), initially developed to manage Alzheimer's disease and now being considered for other therapeutic interventions, are both pharmacologically and functionally distinct. Here, using CRISPR/Cas9-based gene editing, we established human HEK 293T cell lines in which endogenous PS1, PS2, or both have been knocked out. Using these knockout lines to examine differences in PS1- and PS2-mediated cleavage events, we confirmed that PS2 generates more intracellular β-amyloid than does PS1. Moreover, we observed subtle differences in PS1- and PS2-mediated cleavages of select substrates. In exploring the question of whether differences in activity among clinical GSIs could be attributed to differential inhibition of PS1 or PS2, we noted that select GSIs inhibit PS1 and PS2 activities on specific substrates with slightly different potencies. We also found that endoproteolysis of select PS1 FAD-linked variants in human cells is more efficient than what has been previously reported for mouse cell lines. Overall, these results obtained with HEK293T cells suggest that selective PS1 or PS2 inhibition by a given GSI does not explain the previously observed differences in functional and pharmacological properties among various GSIs.

De muscipulis et caveis. The cage and the mousetrap as pictorical and literary motifs in neo-latin emblem books

Topics and metaphors within the system of classical rhetoric served as store-houses at times, to express ideas from the most general to the most particular, passing through an infinite number of the most varied concepts and realities. The authors sought to evoke a world of conceptual associations in the mind, so as to arrive at the most profound feelings of the reader. The same may be said of emblematic literature, a genre with a moral and didacticvocation. It fully exploits the polyvalent and at times antagonistic symbolism of image and word, to offer its potential readers a flood of reflections with which to orient their political and religious thought. In this work, we shall analyse the graphic and literary motifs of the mousetrap and the cage and their symbolic interpretation through the emblems of the Dutch physician, philologist, historian, and poet Adriaen de Jonghe or Hadrianus Junius (1511-1575).

Open-Source High-Throughput Phenomics of Bacterial Promoter-Reporter Strains.

Open-source electronics are becoming more prevalent in biological sciences, enabling novel and unique means of data acquisition. Here, we present 3D-printed, open-source tools to acquire fluorescence phenotypes with high temporal resolution. Printed fluorescence imaging boxes (PFIboxes) cost approximately 200US dollars to assemble, can be placed in incubators or hypoxic chambers, and accurately read high-density colony arrays of microorganisms. We demonstrate the utility of PFIboxes using a timecourse gene expression approach, examining globalEscherichia coli promoter activity using a fluorescent reporter library across a diverse panel of 15 antibiotics, each at several concentrations. Many secondary and indirect effects were observed when E.coli was challenged with various drugs, including increased gene expression in carbon metabolism processes. Further, kinetic data acquisition enabled non-destructive time course gene expression, clustering of which revealed patterns of co-expression. In all, PFIboxes provide an open solution to gene expression, for about 2US dollars per treatment condition, including technical replicates.

Higher education, unbundling, and the end of the university as we know it

Higher education, unbundling, and the end of the university as we know it

First Report of Little cherry virus 1 affecting European Plum (Prunus domestica) in Belgium

Little Cherry Disease (LChD), one of the major viral diseases of cherry worldwide, can be caused by two viruses (Little cherry virus 1 and 2), both Closteroviridae members. LChD has an important impact on both yield and fruit quality in commercial sweet and sour cherry (Prunus avium L. and Prunus cerasus L.) (Ruiz-Garcia et al., 2016). LChV-1 (genus Velarivirus) is known to be graft-transmissible and is spread via infected propagated plant material, but no vector has been identified. For LChV-2 (genus Ampelovirus) at least two species of mealybugs (Hemiptera, Pseudococcidae) are known to transmit the virus, namely the apple mealybug (Phenacoccus aceris Signoret) and grape mealybug (Pseudococcus maritimus Ehrhorn). During two growing seasons (2013-15), intensive surveys were conducted in Belgium to monitor the incidence of LChD in sweet and sour cherries and in ornamental Prunus spp., revealing widespread occurrence of both LChV-1 and 2 (De Jonghe et al. 2016). In the close vicinity of a sweet cherry (Prun...

Ethical Challenges in Geriatric Psychiatry.

Ethical Challenges in Geriatric Psychiatry.

Development of Multilayered Inorganic Protections on Li Electrode to Improve Performance and Safety of Li-S Battery

Over the past 25 years, intense research efforts were focused on lithium-ion batteries due to their advantages such as high energy density, high operating voltage and low self-discharge rate. However, their gravimetric energy density that reaches 250 Wh.kg-1 today is still insufficient to meet some requirements, in particular for electric cars and electrified aircrafts. Among possible alternatives, Li/S system seems to be very promising. Indeed, elemental sulfur is characterized by a high theoretical specific capacity of about 1675 mAh.g-1 of sulfur material [1]. The discharge potential is around 2.1 V (vs. Li+/Li), and the complete Li/S system should allow to reach a gravimetric energy density close to 500 Wh.kg-1. Moreover, elemental sulfur is readily available and non-toxic, advantages that should allow to manufacture cheap and safe high energy batteries requirements for instance. However, despite actual progress, this promising system still suffers from several limitations: low discharge capacity, poor cycle life, low coulombic efficiency, high self-discharge and the compulsory use of the highly reactive lithium metal negative electrode, which may lead to dendrites formation, short-circuits and explosions [2]. Most of research works have been devoted to the positive electrode and the electrolyte and in particular to sulfur/carbon composites [3-6] or to the optimization of ether-based electrolyte compositions [7-9]. Regarding inorganic or organic protective coatings on the lithium metal electrode, numerous efforts were achieved on protective coating of lithium metal electrode either for Li/ion batteries or more recently for Li/air secondary batteries. The proposed solutions are mainly dealing with surfactants, polymers and inorganic materialsto protect the electrode and/or to better control the SEI formation. Hence, the use of polyether surfactants such as PEGDME significantly suppresses the inactivation of deposited lithium. Among inorganic materials, LiPON is commonly used to protect the battery electrodes such as lithium [10]. This material is widely used as electrolyte in all-solid-state thin film batteries [11]. The deposition of LiPON on lithium electrode leads to the formation of a stable electrolyte interface which effectively improves the reaction between lithium and the liquid electrolyte, as impedance measurements indicate that LiPON layer is more ionically conductive than the film formed by electrolyte decomposition. Quite recently, LiPON was associated with LATP in Li/air batteries [12-13]. The use of this glass-ceramic electrolyte allows fast ion conduction but necessitates the use of a LiPON interlayer to protect LATP from metallic lithium, the ceramic being not stable in contact with lithium. Only few studies are related to negative electrode in Li/S batteries [14]. This study aims at developing inorganic layers to protect for lithium metal negative electrode in order to prevent the dendrites formation as well as to improve the system performances (increase of the discharge capacity, reduction of self-discharge and shuttle mechanism). Several ceramic electrolyte materials have been developed and tested to prevent the formation of dendrites as well as the contact of lithium metal electrode with the dissolved active materials. Thorough physico-chemical characterizations were carried out on pristine ceramic materials as well as on ceramic after immersion in the liquid electrolyte to check the chemical stability of the latters (ICP, DRX, SEM, impedance measurements, XPS). Finally, the effect of the multilayered inorganic electrolyte on the electrochemical behavior of Li/S cells will be presented. [[1]] B.L. Ellis, K.T. Lee, L.F. Nazar, Chem. Mater. 22 (2010) 691-714 [2] F. Orsini, A. Du Pasquier, B. Beaudoin, J.M. Tarascon, M. Trentin, N. Langenhuizen, E. De Beer, P. Notten, J. Power Sources 76 (1998) 19-29 [3] X. Ji, L.F. Nazar, J. Mater. Chem. 20 (2010) 9821-9826 [4] H. Schneider, A. Garsuch, A. Panchenko, O. Gronwald, N. Janssen, P. Novak, J. Power Sources 205 (2012) 420-425 [5] G. He, X. Ji, L. Nazar, Energy Environ. Sci. 4 (2011) 2878-2883 [6] R. Elazari, G. Salitra, A. Garsuch, A. Panchenko, D. Aurbach, Adv. Mater. 23 (2011) 5641-5644 [7] WO 00/46870, Y.S. Nimon, S.J. Visco, M.Y. Chu, PolyPlus, (2000) [8] J.Z. Wang, L. Lu, M. Choucair, J.A. Stride, X. Xu, H.K. Liu, J. Power Sources 196 (2011) 7030-7034 [9] US 2008/0193835, Y.V. Mikhaylik, Sion Power, (2008) [[1]0] X. Yu, J.B. Bates, G.E. Jellison, F.X. Hart, J. Electrochem. Soc. 144 (1997) 524 [11] F. Le Cras, B. Pecquenard et al., Adv. Energy Mater., 5 (2015) 1501061 [12] S. Hasegawa, N. Imanishi, T. Zhang, J. Xie, A. Hirano, Y. Takeda, O. Yamamoto, J. Power Sources 189 (2009) 371-377 [13] WO 2011/039449, G. Toussaint, P. Stevens, G. Caillon, P. Viaud, C. Cantau, P. Vinatier, (2011) [14] US 08/0113261, C.L. De Jonghe, S.J. Visco, Y.S. Nimon, A.M. Sukeshini, PolyPlus, (2008)

(Invited) Furture and Pressent of Aqueous Lithium-Air Batteries

The rechargeable lithium-air battery is promising for the power source of electrical vehicles, because of its high specific energy density. Now two types of the lithium-air battery have been developed, namely aqueous and non-aqueous. The aqueous system has larger gravimetric energy density of 3505 Wh kg-1 than that of the non-aqueous system of 1917 Wh kg-1. However, the none-aqueous system has severe problems to be solved such as electrolyte decomposition. The gravimetric specific energy density of the aqueous system is comparable to that of internal conversion engines. The severe problem of the electrolyte decomposition would be removed in the aqueous system. The aqueous lithium-air battery consists of a lithium metal anode, a water stable lithium conducting solid electrolyte, an aqueous electrolyte and an air electrode. The concept was proposed by Visco et al. in 20041. The key material for the aqueous system is the water stable solid electrolyte. A few types of the lithium conducting solid electrolytes such as NASICON-type Li1+xAlxTi2-x(PO4)3 (LATP), perovskite-type Li2/3-xLi3xTiO3 (LLTO) and garnet-type Li7La3Zr2O12 (LLZ) are known to be stable in aqueous solutions with LiCl. LLZ is stable in contact with lithium metal, but it has serious problem of a lithium dendrite formation on lithium at a high current density. LATP and LLTO are unstable in contact with lithium metal and an interlayer should be used between lithium and LATP (or LLTO). As the interlayer, polyethylene oxide (PEO) based polymer electrolytes have been successfully used, but the electrical conductivity of the PEO based electrolyte is low at room temperature. The Li/PEO18Li(CF3SO2)2N/LATP/ aqueous 1M LiCl/Pt, air cell was successfully discharge and charge at 60 0C and 0. 5 mA cm-2 for 24 h.2 Imanishi and co-workers3 have proposed a lithium dendrite formation free liquid electrolyte of a solvate ionic liquid of tetraethylene glycol dimethyl ether (TEGDME) and Li(FSO2)2N (LiFSI). A metallic lithium anode could deliver a high area capacity of 12 mAh cm-2 for 40 cycles in TEGDME-2LiFSI with a current density of as high as 6 mA cm-2 at 60 oC. The novel electrolyte as the interlayer between lithium metal and LATP allowed favorable cyclability for the aqueous lithium-oxygen at 0.64 mA cm-2 and 60 0C. To operate the lithium dendrite free electrolyte at room temperature, 1,3-dioxolane (DOL) was added into TEGDME-2LiFSI. TEGDME-2LiFSI-50 vol.% DOL showed a low interface resistance between lithium metal and the electrolyte. No short circuit was observed in the Li/TEGDME-2LiFSI-50 vol% DOL/Li cell at 1.0 mA cm-2 and 25 oC for 40 h polarization. The TEGDME-2FSI-50 vol% DOL electrolyte is quite attractive interlayer between the lithium metal electrode and LATP for the lithium-air battery.References S.J. Visco, E. Nimon, B. Katz, L.C. De Jonghe and M.Y. Chu, 12th International Meeting on Lithium Batteries, Abst. #53, Nara, Japan (2004) T. Zhang, N. Imanishi, S. Hasegawa, A. Hirano, J. Xie, Y. Takeda, O. Yamamoto, and N. Sammes, Electrochem. and Solid State Lett., 12, A132 (2009) H. Wang, S. Sunahiro, M. Matsui, P. Zhang, Y. Takeda, O. Yamamoto, and N. Imanishi, ChemElectroChem, 2, 1144 (2015)

Transmission Electron Microscopy Study of Cr Poisoning of Lscf Cathodes

(La,Sr)(Co,Fe)O3-δ (LSCF) perovskite oxides have been considered to be a promising cathode material for SOFCs operating in the intermediate temperature range due to their significantly higher electrochemical activity for the O2 reduction reaction and higher oxygen ion conductivity than the conventional (La,Sr)MnO3 (LSM) cathode [1,2]. In practice, metallic materials have become a preferential choice for the interconnect due to their excellent physical and chemical properties. However the presence of chromium in all commonly used metallic alloys has been found to cause poisoning of the cathode under operating conditions leading to rapid electrochemical performance degradation of the cathodes including LSCF [3–5]. Development of a Cr tolerant cathode material for increased long-term durability of SOFCs relies on a fundamental understanding of the mechanism of the chromium deposition and poisoning of the cathode materials. Extensive research on the chromium deposition and poisoning processes on SOFC cathodes has been carried out but careful microstructural studies especially on the nanometer to atomic scale are very limited. This is however a subject that can give valuable information on the detailed process of Cr incorporation and evolution in the cathode materials, providing an important insight for the mechanistic understanding of the Cr poisoning. LSCF/CGO/LSCF symmetrical cells were prepared by screen printing the LSCF cathode on Gd doped cerium oxide (CGO) electrolyte pallet, and the effect of Cr poisoning at 900 ˚C in air on the electrochemical behavior of the cell was assessed by impedance spectroscopy. The change in nano/microstructure and chemistry between cells with and without Cr poisoning were studied in parallel by TEM/STEM/EDX/EELS. To facilitate the TEM sample preparation using focus ion beam thinning (FIB), bulk samples containing the porous LSCF layer were firstly embedded in an epoxy resin. Due to the peak overlap between the interested La and Cr and inherently poorer spatial resolution in EDX, EELS was employed with the aim for an improved accuracy in the analysis. Figure 1a shows an example of EDX artefacts where the spectrum from an epoxy area in between LSCF grains exhibit the presence of the LSCF elements. On the other hand, EELS could suffer a higher detection limit compared to EDX due the generally poorer signal to background (S/B) ratio, which is typically worse when the sample thickness increases. Figure 1b shows an example of EELS spectrum, which fails to detect the presence of Co in the thicker area of a LSCF grain (t/λ ~ 0.86). It was found that all the expected elements (apart from Sr) in LSCF can be successfully detected by EELS when t/λ < ~ 0.7, and this criteria was kept during all the later EELS measurements. Our results show that Cr is incorporated in LSCF in more complicated ways than a simple formation of SrCrOx as suggested by previous studies. Cr was found to segregate in Sr rich phases that also contain other elements such as Fe and Co (Figure 2). In addition, Cr was incorporated in the LSCF perovskite structure and repelled sometimes the other B site elements from the lattice. As a result, Cr rich phases take the form of various compositions such as (La,Sr)(Fe,Co,Cr)Ox, (La,Sr)(Fe,Cr)Ox and (La,Sr)CrOx (Figure 3). It is interesting to note that Cr appears to repel more readily Co than Fe. The Cr poisoning also promotes the formation of Co and Co-Fe rich phases that may contribute to the deficiency of Co in the LSCF grains (Figure 4). It can be seen that the area adjacent to the Fe-Co rich particles contains Cr and are deficient in Co with a composition close to that of (La,Sr)(Cr,Fe)Ox. Careful examination of Cr incorporation was also extended to LSCF grain boundaries with both structural and chemical analysis. The high-resolution microscopy results and their implications are discussed in relation to the degraded electrochemical properties of the LSCF cathode and the Cr poisoning mechanisms. [1] S. Jiang, Solid State Ionics 146 (2002) 1. [2] A. Esquirol, N.P. Brandon, J.A. Kilner, M. Mogensen, J. Electrochem. Soc. 151 (2004) A1847. [3] M.C. Tucker, H. Kurokawa, C.P. Jacobson, L.C. De Jonghe, S.J. Visco, J. Power Sources 160 (2006) 130. [4] L. Zhao, J. Drennan, C. Kong, S. Amarasinghe, S.P. Jiang, ECS Trans. 57 (2013) 599. [5] S.P. Jiang, X. Chen, Int. J. Hydrogen Energy 39 (2014) 505. Figure 1

Characterization and Stack Testing of Solid Oxide Fuel Cells with Cathodes Prepared by Infiltration

Recently, the use of infiltration as a method for SOFC electrode preparation has gathered significant scientific interest (1-6). The results thus far have been mostly obtained on button cells with electrode active areas on the order of 1 cm2 or less. Here, we report the physical characterization and stack testing of 12 x 12 cm2 planar cells with cathodes prepared by infiltration of a perovskite precursor solution into a stabilized zirconia backbone. As the first step in the development of the new cell design, a stabilized zirconia backbone layer with high surface area and good mechanical compatibility with the rest of the cell was developed. After an optimized sintering procedure was introduced, batches of about 90 cells could reproducibly be manufactured with high yields. The optimized blank cells were infiltrated with a precursor solution of (La0.8Sr0.2)0.95FeO3 and the resulting cells were characterized thoroughly using XRD, van der Pauw in-plane conductivity, BET specific surface area, and electrochemical single-cell measurements. As the in-plane conductivity, the BET surface area as well as the pore-size distribution of the cathode are thought to play a key role in determining the long-term performance and stability of infiltrated cells in a stack, changes in these properties were mapped out as a function of the cathode sintering temperature. Electrochemical testing on both cell and stack level confirmed the enhanced performance of cells with cathodes prepared by infiltration. Results on degradation testing will be reported separately. This work was partly funded by EUDP project J 64012-0225, “SOFC Accelerated”. References S.P. Jiang, Mater. Sci. Eng. A, 418, 199 (2006).J.M. Vohs, R.J. Gorte, Adv. Mater., 21, 943 (2009).A.J. Samson, P. Hjalmarsson, M. Søgaard, J. Hjelm, N. Bonanos, J. Power Sources, 216, 124 (2012).D. Ding, X. Li, S.Y. Lai, K. Gerdes, M. Liu, Energy Environ. Sci., 7, 552 (2014).T.Z. Sholklapper, H. Kurokawa, C.P. Jacobson, S.J. Visco, L.C. De Jonghe, Nano Lett. 7, 2136 (2007).M. Shah, S.A. Barnett, Solid State Ionics, 179, 2059 (2008). Figure 1

Clinical evidence for genetic anticipation in C9orf72 pedigrees

Clinical evidence for genetic anticipation in C9orf72 pedigrees

Clinical characteristics of loss-of function mutations in TBK1 in Belgian FTD and ALS patients

Clinical characteristics of loss-of function mutations in TBK1 in Belgian FTD and ALS patients

SS3.03: Cognitive screening for dementia: crossing four essential borders

SS3.03: Cognitive screening for dementia: crossing four essential borders

Characterization and Electrochemical Behaviour of AV4S8 (A=Ga,Ge) Materials as Negative Electrodes of Sodium-Ion Batteries

Lithium-ion batteries have become essential in recent years. Due to both the difficult access and the cost of the alkaline element, a new field of research concerning sodium-ion batteries has recently emerged. Many compounds have been proposed as positive electrodes for Na-ion batteries. However, since sodium does not intercalate into graphite as much as lithium (1), there is a clear need for high capacity materials for negative electrode materials. Intercalation compounds such as Na2Ti3O7 (2) or NaTi2(PO4)3 (3) or Sb-based compounds (4) come usually with a somehow limited capacity (~ 200-400 mAh.g-1). Here, we present the possible use of a class of chalcogenide materials, AV4S8 (A=Ga,Ge), as a negative electrode in sodium-ion batteries.The reactivity of AV4S8 with Na leads to a remarkable specific capacity of 800 mAh/g for the first discharge at a C/20 rate (1 complete charge in 20 hours), followed by a reversible reaction associated with a 500 mAh/g capacity retained after 30 cycles.Many experiments were performed in order to understand the reaction mechanism of sodium with the AV4S8 materials. Electrochemical, in situ X-ray diffraction (Figure 1) and transmission electron microscopy experiments suggest that a smooth conversion mechanism is occurring and that the capacity fade is largely due to reactions with the electrolyte at low potential.EDX and TEM observations, as well as EELS experiments performed at the vanadium L-edge, indicate that a reduction of the vanadium oxidation state occurs during the discharge process. XAS experiments performed at the Vanadium and Germanium K edges also clearly demonstrate that all the elements are involved during the electrochemical processes.Synthesis, structural characterization and electrochemical behaviour of AV4S8 will be discussed in details in the presentation. Results obtained on the AV4S8 phases are very promising and demonstrate that this new class of materials is a good candidate as a negative electrode for Na-ion batteries.References(1). M. M. Doeff, Y. Ma, S. J. Visco,L. C. De Jonghe, J. Electrochem.Soc. 140, L169 (1993).(2). P. Senguttuvan, G.l. Rousse, V. Seznec, J.-M. Tarascon, M.R. Palacin, Chemistry of Materials, 23, 4109-4111 (2011).(3). S.I. Park, I. Gocheva, S. Okada, J.-i. Yamaki, J. Electrochem. Soc. 158, A1067-A1070 (2011).(4). A. Darwiche, C. Marino, M.T. Sougrati, B. Fraisse, L. Stievano, L. Monconduit, Journal of the American Chemical Society, 134, 20805-20811 (2012).