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7439-93-2Relevant academic research and scientific papers
Effect of electrolyte composition on lithium dendrite growth
Crowther, Owen,West, Alan C.
, p. A806-A811 (2008)
Lithium deposition is observed in situ using a microfluidic test cell. The microfluidic device rapidly sets up a steady concentration gradient and minimizes ohmic potential loss, minimizes electrolyte usage, and shows good repeatability. Dendrite growth is observed at different current densities for electrolytes containing lithium hexafluorophosphate or lithium bis(trifluoromethane sulfonyl) imide (LiTFSI) in mixtures of propylene carbonate (PC) and dimethyl carbonate. Dendrites are formed at shorter times in electrolytes containing LiTFSI and high amounts of PC. The time to first observed dendrites increases linearly (for all electrolyte compositions) with a resistance given by the Tafel slope of the lithium reduction polarization curve.
Deposition studies of lithium and bismuth at tungsten microelectrodes in LiCl:KCl eutectic
Carlin,Osteryoung
, p. 1249 - 1255 (1989)
Tungsten microelectrodes (diam = 25 μm) have been used to study the deposition and stripping behavior of Li/Li+ and Bi/Bi3+ in the LiCl:KCl eutectic at 400°C. The Li deposition current can be simulated assuming the growth of a single hemisphere of liquid metal on the microelectrode. High stripping current densities were observed and quantitated using standard electrochemical equipment. An inverted microscope assembly was employed for in situ observation of the Li/Li+ deposition and stripping processes at the microelectrode. A precipitate appears to form in the melt surrounding the electrode during Li deposition.
Electrochemical formation of Sm-Ni alloy films in a molten LiCl-KCl-SmCl3 system
Iida, Takahisa,Nohira, Toshiyuki,Ito, Yasuhiko
, p. 2537 - 2544 (2001)
The electrochemical formation of Sm-Ni alloys was investigated in a molten LiCl-KCl-SmCl3 (0.5 mol%) system at 723 K. The cyclic voltammogram for a Mo electrode showed the reduction wave from Sm(III) to Sm(II) at 1.60 V (vs Li+/Li), but no reduction wave from Sm(II) to Sm metal. For a Ni electrode, small cathodic currents were observed at potentials more negative than 0.10 V, which indicated the formation of Sm-Ni alloy. The formation of an SmNi2 phase was confirmed by XRD analysis of a sample prepared at 0.10 V for 72 h. The thickness of the SmNi2 film was estimated to be approximately 100 nm. A much thicker SmNi2 film (～20 μm) was obtained by cathodic galvanostatic electrolysis at 50 mA cm-2 in a time period as short as 1 h. Since Li metal was codepositing during the electrolysis and the SmNi2 film was rapidly formed, this electrochemical formation method was termed the 'Li codeposition method'. The formed SmNi2 film was changed to other alloy phases by anodic potentiostatic electrolysis. The formation potentials of SmNi5, SmNi3 and SmNi2 were found to be 1.20, 0.65 and 0.29 V, respectively.
Compatibility of Li7La3Zr2 O12 solid electrolyte to all-solid-state battery using Li metal anode
Kotobuki, Masashi,Munakata, Hirokazu,Kanamura, Kiyoshi,Sato, Yosuke,Yoshida, Toshihiro
, p. A1076-A1079 (2010)
Electrochemical properties of Li7La3Zr2 O12 (LLZ) were investigated to reveal its availability as a solid electrolyte for all-solid-state rechargeable batteries with a Li metal anode. After calcination at 1230°C, a well-sintered LLZ pellet with a garnet-like structure was obtained, and its conductivity was 1.8 × 10-4 S cm-1 at room temperature. The cyclic voltammogram of the Li/LLZ/Li cell showed that the dissolution and deposition reactions of lithium occurred reversibly without any reaction with LLZ. This indicates that a Li metal anode can be applied for an LLZ system. A full cell composed of a LiCoO2 /LLZ/Li configuration was also operated successfully at expected voltage estimated from the redox potential of Li metal and LiCoO2. Simultaneously, an irreversible behavior was observed at the first discharge and charge cycle due to an interfacial problem between LiCoO2 and LLZ. The discharge capacity of the full cell was 15 μA h cm-2. These results reveal that LLZ is available for all-solid-state lithium batteries.
Delayed release of Li atoms from laser ablated lithium niobate
Chaos,Dreyfus,Perea,Serna,Gonzalo,Afonso
, p. 649 - 651 (2000)
The present vapor-phase optical (atomic) absorption measurements study the escape dynamics of Li atoms from a LiNbO3 target surface upon laser ablation in vacuum. The objective is to understand the low-Li content of LiNbO3 films prepared by pulsed laser deposition. A primary result is a delayed release of Li atoms, 2-20 μs after the laser pulse; they eject with a velocity of 6 × 105 cms-1, which is consistent with an electronic ejection mechanism. The long emission period means there are almost no intraplume Li collisions in the gas phase and no forward focusing of the delayed released atoms. This appears to explain the low-Li content usually found in films grown in the normal direction.
LITHIUM SODIUM SILICIDE Li3NaSi6 AND THE FORMATION OF ALLO-SILICON.
Von Schnering,Schwarz,Nesper
, p. 297 - 310 (1988)
Metallic grey Li//3NaSi//6 is formed by heating the elements in stoichiometric amounts. The compound is the only stable ternary phase in the Li-Na-Si system, and does not belong to the tetrasilatetrahedrane derivatives. The novel complex layer structure is characterized by two-dimensional infinite polyanions showing polymerized tube-like structural units which are known from Hittorf's violet phosphorus and GeAs//2 respectively. The alkali metal atoms are inserted between the respective polyanionic layers Li//3NaSi//6 is a diamagnetic semiconductor with a molar susceptibility chi //m//o//l of minus 243 multiplied by 10** minus **6 emu mol** minus **1, R(300 K) equals 50 OMEGA and R(2 K) equals 3 multiplied by 10**3 OMEGA . Li//3NaSi//6 reacts with protic solvents as well as with benzophenone (in tetrahydrofuran) topotactically yielding a new metastable silicon modification, namely allo-Si.
Effects of some organic additives on lithium deposition in propylene carbonate
Mogi, Ryo,Inaba, Minoru,Jeong, Soon-Ki,Iriyama, Yasutoshi,Abe, Takeshi,Ogumi, Zempachi
, p. A1578-A1583 (2002)
The effects of some film-forming organic additives, fluoroethylene carbonate (FEC), vinylene carbonate (VC), and ethylene sulfite (ES), on lithium deposition and dissolution were investigated in 1 M LiClO4 dissolved in propylene carbonate (PC) as a base solution. When 5 wt % FEC was added, the cycling efficiency was improved. On the contrary, addition of 5 wt% VC or ES significantly lowered the cycling efficiency. The surface morphology of lithium deposited in each electrolyte solution was observed by in situ atomic force microscopy (AFM). In PC + FEC, the surface was covered with a uniform and closely packed layer of particle-like deposits of about 100-150 nm diam. The surface film seemed to be more solid in PC + VC, and inhomogeneous in PC + ES. From ac impedance measurements, it was revealed that the surface film formed in PC + FEC has a lower resistance than that in the additive-free solution, whereas that formed in PC + VC or PC + ES has a higher resistance. Large volume changes during lithium deposition and dissolution require that the surface film should be elastic (or soft) and be self-repairable when being damaged. In addition, a nonuniform current distribution is liable to cause dendrite formation, which requires that the surface film should be uniform and its resistance should be as low as possible. PC + FEC gave a surface film that satisfies all these requirements, and therefore only FEC was effective as an additive for deposition and dissolution of lithium metal.
Electrochemical deposition of uniform lithium on an Ni substrate in a nonaqueous electrolyte
Kanamura,Shiraishi,Takehara
, p. 108 - 110 (1994)
The electrochemical deposition of lithium on an Ni substrate was conducted in propylene carbonate (PC) containing 1.0 mol dm-3 LiClO4 (LiClO4/PC). The morphology of the lithium deposited on the Ni substrate had the typical dendrite form. The electrodeposition of lithium was then performed in LiClO4/PC containing 5 × 10-3 mol dm-3 HF. The lithium deposited on the Ni substrate in this electrolyte had a hemispherical form, and irregular shapes were not observed. The color of the Ni electrode surface turned to brilliant blue during the electrodeposition of lithium. This indicates that the lithium surface is very smooth and uniform. After five discharge and charge cycles, there were no lithium dendrites on the electrode surface. From these results, it can be concluded that the addition of a small amount of HF to the electrolyte is significantly effective for the suppression to the lithium dendrite formation.
Measurement of concentration profiles during electrodeposition of Li metal from LiP F6 -PC electrolyte solution
Nishikawa,Fukunaka,Sakka,Ogata,Selman
, p. A943-A948 (2007)
During Li metal electrodeposition from a 0.5 M LiP F6 -PC electrolyte solution onto a horizontal Li metal electrode, the refractive index profile corresponding to the concentration profile of Li+ ion near the cathode was measured in situ by holographic interferometry. The Li+ concentration gradient around the rapidly growing dendrite arms is steeper than at the cathode plane, clearly reflecting the local current density convergence at the dendrite tips and arms. As in a LiCl O4 -PC solution, an incubation period was observed between the start of current passage and the onset of the refractive index fringe shift. It increases with decreasing applied current density. The incubation period in LiP F6 -PC is shorter than that in LiCl O4 -PC at current densities greater than 1.0 mA cm-2; however, at 0.5 mA cm-2 in LiP F6 -PC electrolyte solution it is appreciably longer than in LiCl O4 -PC. This complicated behavior is apparently due to the solution chemistry of LiP F6 -PC electrolyte, which produces HF and oxyfluoride impurities that are lacking in the LiCl O4 -PC system. Thus, the different current dependence of the incubation time in these two systems may yield clues for an elucidation of the dynamics of solid electrolyte interphase formation.
Quantum properties of nanoscale metallic Li colloids formed by electron irradiation in LiF
Beuneu,Vajda
, p. 329 - 333 (2003)
We present experimental results on the nucleation of nanoscale metallic lithium colloids, of well-controlled diameter (2-5 nm), in MeV electron-irradiated LiF single crystals. Conduction electron spin resonance experiments show a clear-cut quantum effect in these colloids: the spin susceptibility follows a mixed Curie-Pauli law, characteristic for tiny metallic particles in which the mean level spacing is comparable to kT. The behavior of the spin relaxation times (T1 and T2) is presented and a discussion of quantum size effect in small metallic particles is proposed.