The microstructure matters: breaking down the barriers with single crystalline silicon as negative electrode in Li-ion batteries.

Silicon-based microelectronics forms a major foundation of our modern society. Small lithium-ion batteries act as the key enablers of its success and have revolutionised portable electronics used in our all everyday's life. While large-scale LIBs are expected to help establish electric vehicles, on the other end of device size chip-integrated Si-based µ-batteries may revolutionise microelectronics once more. In general, Si is regarded as one of the white hopes since it offers energy densities being ten times higher than conventional anode materials. The use of monocrystalline, wafer-grade Si, however, requires several hurdles to be overcome since it its volume largely expands during lithiation. Here, we will show how 3D patterned Si wafers, prepared by the sophisticated techniques from semiconductor industry, are to be electrochemically activated to overcome these limitations and to leverage their full potential being reflected in stable charge capacities (>1000 mAhg(-1)) and high Coulomb efficiencies (98.8%).

Li ion dynamics along the inner surfaces of layer-structured 2H-LixNbS2.

Layer-structured materials, such as graphite (LiCy) or Lix(Co,Ni,Mn)O2, are important electrode materials in current battery research that still relies on insertion materials. This is due to their excellent ability to reversibly accommodate small alkali ions such as Li(+) and Na(+). Despite of these applications, microscopic information on Li ion self-diffusion in transition metal sulfides are relatively rare. Here, we used (7)Li nuclear magnetic resonance (NMR) spectroscopy to study translational Li ion diffusion in hexagonal (2H) LixNbS2 (x = 0.3, 0.7, and 1) by means of variable-temperature NMR relaxometry. (7)Li spin-lattice relaxation rates and (7)Li NMR spectra were used to determine Li jump rates and activation barriers as a function of Li content. Hereby, NMR spin-lattice relaxation rates recorded with the spin-lock technique offered the possibility to study Li ion dynamics on both the short-range and long-range length scale. Information was extracted from complete diffusion-induced rate peaks that are obtained when the relaxation rate is plotted vs inverse temperature. The peak maximum of the three samples studied shifts toward higher temperatures with increasing Li content x in 2H-LixNbS2. Information on the dimensionality of the diffusion process was experimentally obtained by frequency dependent Rρ measurements carried out at T = 444 K, that is in the high-temperature regime of the rate peaks. A slight, but measurable frequency-dependence within this limit is found for all samples; it is in good agreement with predictions from relaxation models developed to approximate low-dimensional (2D) jump diffusion.

Evidence of low dimensional ion transport in mechanosynthesized nanocrystalline BaMgF4.

Mechanochemical milling provides a versatile method for the preparation of nano-sized, defect rich, polycrystalline materials. If ionic materials are considered, the transport parameters of the mobile ions may greatly differ from those of the microcrystalline counterparts prepared by conventional synthesis routes. Little is known about ionic conduction in nanocrystalline materials having crystal structures that offer spatially confined transport pathways. Here, we focused on mechanosynthesized BaMgF4 that combines both nanocrystallinity and anisotropic F(-) transport. The preparation of nanocrystalline BaMgF4 is presented as a facile and rapid one-pot procedure. The reaction was followed by X-ray diffraction and high-resolution (19)F nuclear magnetic resonance (NMR) spectroscopy. NMR helped prove the formation of X-ray amorphous compounds as well as the transformation of the starting materials into the final product BaMgF4. Most importantly, besides enhanced conduction properties compared to a single crystal, our broadband impedance spectra reveal characteristics pointing to anisotropic (low dimensional) ion transport processes even in the nanocrystalline form of BaMgF4.

Correlated fluorine diffusion and ionic conduction in the nanocrystalline F(-) solid electrolyte Ba(0.6)La(0.4)F(2.4)-(19)F T1(ρ) NMR relaxation vs. conductivity measurements.

Chemical reactions induced by mechanical treatment may give access to new compounds whose properties are governed by chemical metastability, defects introduced and the size effects present. Their interplay may lead to nanocrystalline ceramics with enhanced transport properties being useful to act as solid electrolytes. Here, the introduction of large amounts of La into the cubic structure of BaF2 served as such an example. The ion transport properties in terms of dc-conductivity values of the F(-) anion conductor Ba1-xLaxF2+x (here with x = 0.4) considerably exceed those of pure, nanocrystalline BaF2. So far, there is only little knowledge about activation energies and jump rates of the elementary hopping processes. Here, we took advantage of both impedance spectroscopy and (19)F NMR relaxometry to get to the bottom of ion jump diffusion proceeding on short-range and long-range length scales in Ba0.6La0.4F2.4. While macroscopic transport is governed by an activation energy of 0.55 to 0.59 eV, the elementary steps of hopping seen by NMR are characterised by much smaller activation energies. Fortunately, we were able to deduce an F(-) self-diffusion coefficient by the application of spin-locking NMR relaxometry.

Long-range Li+ dynamics in the lithium argyrodite Li7PSe6 as probed by rotating-frame spin-lattice relaxation NMR.

Lithium-rich argyrodites belong to a relatively new group of fast ion conducting solids. They might serve as powerful electrolytes in all-solid-state lithium-ion batteries being, from a medium-term point of view, the key technology when safe energy storage systems have to be developed. Spin-lattice relaxation (SLR) nuclear magnetic resonance (NMR) measurements carried out in the rotating frame of reference turned out to be the method of choice to study Li dynamics in argyrodites. When plotted as a function of the inverse temperature, the SLR rates log10(R1ρ) reveal an asymmetric diffusion-induced rate peak. The rate peak contains information on the Li jump rate, the activation energy of the hopping process as well as correlation effects. In particular, considering the high-temperature flank of the SLR NMR rate peak recorded in the rotating frame of reference, an activation energy of approximately 0.49 eV is found. This value represents long-range lithium jump diffusion in crystalline Li7PSe6. As an example, at 325 K the Li jump rate determined from SLR NMR is in the order of 1.4 × 10(5) s(-1). The pronounced asymmetry of the rate peak R1ρ(1/T) points to correlated Li motion. It is comparable to that which is typically found for structurally disordered materials showing a broad range of correlation times.

Two-dimensional diffusion in Li0.7NbS2 as directly probed by frequency-dependent 7Li NMR.

Li ion diffusion in layer-structured Li0.7NbS2 has been complementary investigated by nuclear magnetic resonance (NMR) spectroscopy from an atomic scale point of view. In the present case, (7)Li NMR spin-lattice relaxation (SLR) rates R1ρ probed in the rotating frame of reference proved very informative in characterizing the Li self-diffusion process in the van der Waals gap between the NbS2 layers. While temperature-variable SLRρ measurements were used to determine dynamic parameters such as jump rates (τ(-1)) and the activation energy (Ea), frequency-dependent measurements were used to specify the dimensionality of the diffusion process. In particular, the effect of annealing, i.e., the distribution of Li ions between the layers, on overall Li dynamics has been studied. When plotted in an Arrhenius diagram, the R1ρ rates of an annealed sample, which were recorded at a locking frequency of 20 kHz, pass through a diffusion-induced relaxation peak whose maximum shows up at 320 K. Employing an appropriate diffusion model and appropriately accounting for a non-diffusive background relaxation, a Li jump rate τ(-1)(300 K) ≈ 1.3 × 10(5) s(-1) and an activation energy Ea of 0.43(2) eV can be deduced. Most importantly, in the high-T limit of the diffusion-induced rate peak, i.e., when ω1τ << 1 holds, the rates follow a logarithmic frequency dependence. This points to a diffusion process of low dimensionality and is in good agreement with predictions of relaxation models developed for 2D diffusion.

NMR relaxometry as a versatile tool to study Li ion dynamics in potential battery materials.

NMR spin relaxometry is known to be a powerful tool for the investigation of Li(+) dynamics in (non-paramagnetic) crystalline and amorphous solids. As long as significant structural changes are absent in a relatively wide temperature range, with NMR spin-lattice (as well as spin-spin) relaxation measurements information on Li self-diffusion parameters such as jump rates and activation energies are accessible. Diffusion-induced NMR relaxation rates are governed by a motional correlation function describing the ion dynamics present. Besides the mean correlation rate of the dynamic process, the motional correlation function (i) reflects deviations from random motion (so-called correlation effects) and (ii) gives insights into the dimensionality of the hopping process. In favorable cases, i.e., when temperature- and frequency-dependent NMR relaxation rates are available over a large dynamic range, NMR spin relaxometry is able to provide a comprehensive picture of the relevant Li dynamic processes. In the present contribution, we exemplarily present two recent variable-temperature (7)Li NMR spin-lattice relaxation studies focussing on Li(+) dynamics in crystalline ion conductors which are of relevance for battery applications, viz. Li(7) La(3)Zr(2)O(12) and Li(12)Si(7).

Spin-alignment echo NMR: probing Li+ hopping motion in the solid electrolyte Li7La3Zr2O12 with garnet-type tetragonal structure.

(7)Li spin-alignment echo (SAE) nuclear magnetic resonance (NMR) spectroscopy has been used to measure single-spin hopping correlation functions of polycrystalline Li(7)La(3)Zr(2)O(12). Damping of the echo amplitude S(2)(t(m),t(p)), recorded at variable mixing time t(m) but fixed preparation time t(p), turns out to be solely controlled by slow Li jump processes taking place in the garnet-like structure. The decay rates τ(SAE)(-1) directly obtained by parametrizing the curves S(2)(t(m),t(p)) with stretched exponential functions show Arrhenius behaviour pointing to an activation energy of approximately 0.5 eV. This value, probed by employing an atomic-scale NMR method, is in very good agreement with that deduced from impedance spectroscopy used to measure macroscopic Li transport parameters. Most likely, the two methods are sensitive to the same hopping correlation function although Li dynamics are probed in a quite different manner.

Ultra-slow Li ion dynamics in Li(2)C(2)--on the similarities of results from (7)Li spin-alignment echo NMR and impedance spectroscopy.

Li diffusion and transport parameters of binary lithium carbide Li(2)C(2) were complementarily investigated by (7)Li (nuclear magnetic resonance) NMR and impedance spectroscopy. Long-range Li diffusion parameters were measured by using mixing-time-dependent and temperature-variable stimulated echo NMR spectroscopy. The method is sensitive to ultra-slow Li hopping processes which were probed from an atomic-scale point of view. Two-time phase correlation functions S(2) obtained can be parameterized by stretched exponentials only. The corresponding echo decay rates τ(-1), which were recorded at a resonance frequency of e.g. 155.5 MHz, show Arrhenius behaviour revealing an activation energy of 0.80(2) eV. This value is in very good agreement with that deduced from dc conductivity measurements (0.79(2) eV) probing Li transport processes on a macroscopic length scale. The comparison of impedance data with the measured NMR echo decay functions showed that both methods reflect diffusion processes being characterized by very similar motional correlation functions.

High anion conductivity in a ternary non-equilibrium phase of BaF(2) and CaF(2) with mixed cations.

A highly conductive ternary fluoride with mixed cations is prepared by joint high-energy ball milling of cubic BaF(2) and CaF(2) in the ratio 0.4 : 0.6. The sample produced at room temperature consists of a nanocrystalline, defect-rich mixed (Ba,Ca)F(2) phase with retained cubic symmetry as well as of single-phase CaF(2) particles. The anion conductivity of the mixed phase, which decomposes at higher temperature (770 K) into BaF(2) and CaF(2), exceeds that of single-phase nanocrystalline BaF(2) by two and that of CaF(2) by four orders of magnitude. In turn, these conductivities are each greater by about two orders than those of the respective microcrystalline counterparts. Structural features of the samples are characterized by X-ray diffraction, TEM and (19)F MAS NMR spectroscopy. Static (19)F NMR spectra confirm the unexpectedly high anion conductivity probed by impedance spectroscopy.

From ultraslow to fast lithium diffusion in the 2D ion conductor Li0.7TiS2 probed directly by stimulated-echo NMR and nuclear magnetic relaxation.

7Li stimulated-echo NMR and classical relaxation NMR techniques are jointly used for the first time for a comprehensive investigation of Li diffusion in layer-structured Li0.7TiS2. One single 2D Li diffusion process was probed over a dynamic range of almost 10 orders of magnitude. So far, this is the largest dynamic range being measured by 7Li NMR spectroscopy directly, i.e., without the help of a specific theoretical model. The jump rates obey a strict Arrhenius law, determined by an activation energy of 0.41(1) eV and a preexponential factor of 6.3(1)x10(12) s-1, and range between 1x10(-1) s-1 and 7.8x10(8) s-1 (148-510 K). Ultraslow Li jumps in the kHz to sub-Hz range were measured directly by recording 7Li spin-alignment correlation functions. The temperature and, in particular, the frequency dependence of the relaxation rates fully agree with results expected for 2D diffusion.

[Ten-year experience with heart transplantation (1987-1997)]. / Bilan de dix années de transplantation cardiaque (1987-1997).

OBJECTIVES: Analyze ten years experience with heart transplantation at the Dijon University Hospital and determine which parameters control mid and long term outcome. PATIENTS AND METHODS: One hundred thirty six heart transplantations were performed over a 10 year period (1987-1997) in 118 men and 18 women aged 51-87 years. Heart transplantation was indicated on the basis of the following criteria: ejection fraction *20%, pulmonary arteriole resistance < 6 Wood units, peak oxygen uptake < 14 l/kg/min. The Shumway or anatomic technique was used. The triple immunosuppressive protocol combined corticosteroids, azathioprine and cyclosporin. The same team conducted the post-transplantation follow-up with regular programmed consultations in addition to those requested by the general practitioner, the cardiologist or the patient. Follow-up was oriented according to the clinical situation (blood chemistry, cell counts, cyclosporinemia, search for infection, echocardiography, endomyocardial biopsy, coronarography). RESULTS: Five patients (3.6%) died when still on the waiting list. Absolute emergency transplantation was performed for patients (28.1%) including 8 (5.9%) after circulatory assist. Hospital mortality was 11.7% and late mortality was 16.1%. Actuarial survival was 78% at 1 year, 71% at 5 years and 69% at 10 years. Among the survivors, 94% were taking two, three or even four drugs for hypertension. Cyclosporin levels decreased and creatinine levels increased. Episodes of rejection were minimal: 86.57% of the biopsies were * grade 1 and 4.45% * grade 2. Cytomegalovirus infection was documented and treated in 7.55% of the cases. Incidence of graft coronary artery disease was 3.4% at 1 year, 6.5% at 2 years and 7.9% at 3 years. CONCLUSION: Our follow-up structure where the same small team conducts regular examinations together with our approach to heart transplantation appears to be the main factor leading to the quality results obtained in this series.

Potential prognostic value of C-erbB-2 expression in medulloblastomas in very young children.

PURPOSE: The expression of the c-erbB-2 oncogene was studied in childhood medulloblastoma to evaluate its prognostic value, which has been claimed previously. PATIENTS AND METHODS: Tumor material from 45 patients < 15 years old at diagnosis was studied using 3 monoclonal antibodies against the internal and external domains of the c-erbB-2 oncogene product. RESULTS: Six of the 45 (13%) tumor specimens were found to be positive. C-erbB-2 expression was found more often in patients < 3 years old at diagnosis (4 of 15 patients, 27%) than in older patients (2 of 30, 6.6%). During the follow-up period (5.8 +/- 2.8 years) all patients with c-erbB-2 expression died of disease (after 1.2 +/- 0.7 years). Kaplan-Meier estimation revealed a highly significant correlation of c-erbB-2 expression and survival (p = 0.002). A further study of the expression of synaptophysin and the glial fibrillary acidic protein (GFAP) in the 45 tumors revealed a negative correlation of the expression of c-erbB-2 and these proteins. CONCLUSION: C-erbB-2, which may be predominantly expressed by less differentiated tumors, was found to delineate a poorer prognostic subgroup, especially when diagnosed in patients < 3 years old.

[Does flumazenil correct disorders of intracardiac conduction induced by accidental intravenous injection of bupivacaine?]. / Le flumazénil corrige-t-il les troubles de la conduction intracardiaque induits par l'injection intraveineuse accidentelle de bupivacaïne?

The authors report the case of a patient who experienced intracardiac conduction disturbances from accidental intravenous injection of bupivacaine, which were reversed by an intravenous injection of flumazenil. Flumazenil could act either in displacing bupivacaine from its binding site, or by an interaction involving the GABAergic system, unless a specific interaction between flumazenil and bupivacaine does exist. In case of experimental confirmation of this feature, flumazenil could be proposed as a new therapeutic tool for bupivacaine-induced cardiotoxicity.

[Validity of cerebral angiography via venous route in the diagnosis of brain death]. / Validité de l'angiographie cérébrale par voie veineuse dans le diagnostic de la mort cérébrale.

The success of transplantations relies on uninjured organs i.e., harvested before circulatory failure. At present, french law concerning cerebral death criteria (circulaire ministérielle n. 3 du 21.01.91) requires the association of clinical patterns and 2 repeated, unreactive and flat electroencephalographic (EEG) tracings. Blood and urinary samples also need to be free from any nervous system depressant drug, the patient has not to be hypothermic. These obligations are not always compatible with patients status or local organization. The consequence might be organ loss or delay in harvesting schedule. A review of the literature points out the trap in realization and analysis of EEG in this kind of intensive care patients. Angiogram, on the opposite, is influenced neither by nervous system depressant drug nor by hypothermia. As it is in some other western countries, it should be proposed as the reference.

[Severe paralysis of the upper limb after axillary brachial plexus block]. / Paralysie grave du membre supérieur après bloc plexique axillaire.

A case is reported of a severe neurological deficit occurring after axillary blockade. The 37-year-old ASA I patient underwent an axillary block for hand surgery using 20 ml of lignocaine 1% with adrenaline and 20 ml of lignocaine 2%. In order to elicit paraesthesia, several attempts were required. Injection of the local anaesthetic was not painful. The tourniquet remained at 250 mmHg for only 35 min. The following day, the patient's arm remained numb. As there was no improvement, epineurotomy was carried out on day 19, to liberate the median nerve which was severely stenosed at the axilla. The patient then started to improve slowly, so that he was able to return to part-time work 6 months later. Prevention of such an accident relies on avoiding intraneural injection and repeated punctures when searching for paraesthesia. When using axillary blockade in day-care surgery, the patient's must be informed upon the possibility of persistent paraesthesia. Should such a rare incident occur, rapid consultation with the anaesthesiologist is essential.

[Early management of severe brain injuries]. / Prise en charge initiale d'un traumatisme cranien grave.

Severe head injury (Glasgow Coma Score less than or equal to 7) is associated with high mortality and morbidity which can be improved by early energetic therapy. Such patients must be picked up by prehospital/EMS service with three aims: controlling ventilation, controlling haemodynamics, avoiding any increased intracranial pressure. After initial neurological assessment, management involves endotracheal intubation, mechanical ventilation following benzodiazepine sedation, early compensation of hypovolemia avoiding any overloading, analgesia for painful injuries; according to the clinical status other pharmacological agents can be used. At admission to emergency unit, intensive care must be continued while X-rays and CT-scan are achieved. Imperative indications of transport to neuro-intensive care unit are discussed for hospitals without a neuro-surgeon.