Transport Properties and Local Ions Dynamics in LATP-Based Hybrid Solid Electrolytes.

Hybrid solid electrolytes (HSEs), namely mixtures of polymer and inorganic electrolytes, have supposedly improved properties with respect to inorganic and polymer electrolytes. In practice, HSEs often show ionic conductivity below expectations, as the high interface resistance limits the contribution of inorganic electrolyte particles to the charge transport process. In this study, the transport properties of a series of HSEs containing Li(1+ x ) Alx Ti(2- x ) (PO4 )3 (LATP) as Li+ -conducting filler are analyzed. The occurrence of Li+ exchange across the two phases is proved by isotope exchange experiment, coupled with 6 Li/7 Li nuclear magnetic resonance (NMR), and by 2D 6 Li exchange spectroscopy (EXSY), which gives a time constant for Li+ exchange of about 50 ms at 60 °C. Electrochemical impedance spectroscopy (EIS) distinguishes a short-range and a long-range conductivity, the latter decreasing with LATP concentration. LATP particles contribute to the overall conductivity only at high temperatures and at high LATP concentrations. Pulsed field gradient (PFG)-NMR suggests a selective decrease of the anions' diffusivity at high temperatures, translating into a marginal increase of the Li+ transference number. Although the transport properties are only marginally affected, addition of moderate amounts of LATP to polymer electrolytes enhances their mechanical properties, thus improving the plating/stripping performance and processability.

Hexavalent Ions Insertion in Garnet Li7 La3 Zr2 O12 Toward a Low Temperature Densification Reaction.

Nowadays, solid electrolytes are considered the main alternative to conventional liquid electrolytes in lithium batteries. The fabrication of these materials is however limited by the strict synthesis conditions, requiring high temperatures which can negatively impact the final performances. Here, it is shown that a modification of garnet-based Li7 La3 Zr2 O12 (LLZO) and the incorporation of tellurium can accelerate the synthesis process by lowering the formation temperature of cubic LLZO at temperatures below 700 °C. Optimized synthesis at 750 °C showed a decrease in particle size and cell parameter for samples with higher amounts of Te and the evaluation of electrochemical performances reported for LLZO Te0.25 a value of ionic conductivity of 5,15×10-5  S cm-1 after hot-pressing at 700 °C, two orders of magnitude higher than commercial Al-LLZO undergoing the same working conditions, and the highest value at this densification temperature. Partial segregation of Te-rich phases occurs for high-temperature densification. Our study shows the advantages of Te insertion on the sintering process of LLZO garnet and demonstrates the achievement of highly conductive LLZO with a low-temperature treatment.

Unveiling the Cation Exchange Reaction between the NASICON Li1.5Al0.5Ge1.5(PO4)3 Solid Electrolyte and the pyr13TFSI Ionic Liquid.

Recently, the formation of the ceramic-ionic liquid composite has attracted huge interest in the scientific community. In this work, we investigated the chemical reactions occurring between NASICON LAGP ceramic electrolyte and ionic liquid pyr13TFSI. This study allowed us to identify the cation exchange reaction pyr13-Li occurring on the LAGP surface, forming a LiTFSI salt that was detected by the nuclear magnetic resonance analysis. In addition, using 6Li foils, we succeeded in demonstrating that both LAGP and LiTFSI:pyr13TFSI participate in the diffusion of Li ions by the formation of an ionic bridge between two species.

Direct observation of lithium metal dendrites with ceramic solid electrolyte.

Dendrite formation, which could cause a battery short circuit, occurs in batteries that contain lithium metal anodes. In order to suppress dendrite growth, the use of electrolytes with a high shear modulus is suggested as an ionic conductive separator in batteries. One promising candidate for this application is Li7La3Zr2O12 (LLZO) because it has excellent mechanical properties and chemical stability. In this work, in situ scanning electron microscopy (SEM) technique was employed to monitor the interface behavior between lithium metal and LLZO electrolyte during cycling with pressure. Using the obtained SEM images, videos were created that show the inhomogeneous dissolution and deposition of lithium, which induce dendrite growth. The energy dispersive spectroscopy analyses of dendrites indicate the presence of Li, C, and O elements. Moreover, the cross-section mapping comparison of the LLZO shows the inhomogeneous distribution of La, Zr, and C after cycling that was caused by lithium loss near the Li electrode and possible side reactions. This work demonstrates the morphological and chemical evolution that occurs during cycling in a symmetrical Li-Li cell that contains LLZO. Although the superior mechanical properties of LLZO make it an excellent electrolyte candidate for batteries, the further improvement of the electrochemical stabilization of the garnet-lithium metal interface is suggested.

Behavior of Solid Electrolyte in Li-Polymer Battery with NMC Cathode via in-Situ Scanning Electron Microscopy.

We present the first results of in situ scanning electron microscopy (SEM) of an all-solid Li battery with a nickel-manganese-cobalt-oxide (NMC-622) cathode at 50 °C and an operating voltage of 2.7-4.3 V. Experiments were conducted under a constant current at several C rates (nC rate: cycling in 1/n h): C/12, C/6, and C/3. The microstructure evolution during cycling was monitored by continuous secondary electron imaging. We found that the chemical degradation of the solid polymer electrolyte (SPE) was the main mechanism for battery failure. This degradation was observed in the form of a gradual thinning of the SPE as a function of cycling time, resulting in gas generation from the cell. We also present various dynamic electrochemical and mechanical phenomena, as observed by SEM images, and compare the performance of this battery with that of an all-solid Li battery with a LiFePO4 cathode.

Facile Protection of Lithium Metal for All-Solid-State Batteries.

A nanolayer of reactive propyl acrylate silane groups was deposited on a lithium surface by using a simple dipping method. The polymerization of cross-linkable silane groups with a layer of ally-ether-ramified polyethylene oxide was induced by UV light. SEM analysis revealed a good dispersion of silane groups grafted on the lithium surface and a layer of polymer of about 4 µm was obtained after casting and reticulation. The electrochemical performance for the unmodified and modified lithium electrodes were compared in symmetrical Li/LLZO/Li cells. Stable plating/stripping and low interfacial resistance were obtained when the modified lithium was utilized, indicating that the combination of silane and polymer deposition is promising to increase Li-metal/garnet contact.

High Capacity and High Efficiency Maple Tree-Biomass-Derived Hard Carbon as an Anode Material for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are in the spotlight because of their potential use in large-scale energy storage devices due to the abundance and low cost of sodium-based materials. There are many SIB cathode materials under investigation but only a few candidate materials such as carbon, oxides and alloys were proposed as anodes. Among these anode materials, hard carbon shows promising performances with low operating potential and relatively high specific capacity. Unfortunately, its low initial coulombic efficiency and high cost limit its commercial applications. In this study, low-cost maple tree-biomass-derived hard carbon is tested as the anode for sodium-ion batteries. The capacity of hard carbon prepared at 1400 °C (HC-1400) reaches 337 mAh/g at 0.1 C. The initial coulombic efficiency is up to 88.03% in Sodium trifluoromethanesulfonimide (NaTFSI)/Ethylene carbonate (EC): Diethyl carbonate (DEC) electrolyte. The capacity was maintained at 92.3% after 100 cycles at 0.5 C rates. The in situ X-ray diffraction (XRD) analysis showed that no peak shift occurred during charge/discharge, supporting a finding of no sodium ion intercalates in the nano-graphite layer. Its low cost, high capacity and high coulombic efficiency indicate that hard carbon is a promising anode material for sodium-ion batteries.

High-Capacity and Long-Cycle Life Aqueous Rechargeable Lithium-Ion Battery with the FePO4 Anode.

Aqueous lithium-ion batteries are emerging as strong candidates for a great variety of energy storage applications because of their low cost, high-rate capability, and high safety. Exciting progress has been made in the search for anode materials with high capacity, low toxicity, and high conductivity; yet, most of the anode materials, because of their low equilibrium voltages, facilitate hydrogen evolution. Here, we show the application of olivine FePO4 and amorphous FePO4·2H2O as anode materials for aqueous lithium-ion batteries. Their capacities reached 163 and 82 mA h/g at a current rate of 0.2 C, respectively. The full cell with an amorphous FePO4·2H2O anode maintained 92% capacity after 500 cycles at a current rate of 0.2 C. The acidic aqueous electrolyte in the full cells prevented cathodic oxygen evolution, while the higher equilibrium voltage of FePO4 avoided hydrogen evolution as well, making them highly stable. A combination of in situ X-ray diffraction analyses and computational studies revealed that olivine FePO4 still has the biphase reaction in the aqueous electrolyte and that the intercalation pathways in FePO4·2H2O form a 2-D mesh. The low cost, high safety, and outstanding electrochemical performance make the full cells with olivine or amorphous hydrated FePO4 anodes commercially viable configurations for aqueous lithium-ion batteries.

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries.

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron-hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries.

Accelerated Removal of Fe-Antisite Defects while Nanosizing Hydrothermal LiFePO4 with Ca(2).

Based on neutron powder diffraction (NPD) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), we show that calcium ions help eliminate the Fe-antisite defects by controlling the nucleation and evolution of the LiFePO4 particles during their hydrothermal synthesis. This Ca-regulated formation of LiFePO4 particles has an overwhelming impact on the removal of their iron antisite defects during the subsequent carbon-coating step since (i) almost all the Fe-antisite defects aggregate at the surface of the LiFePO4 crystal when the crystals are small enough and (ii) the concomitant increase of the surface area, which further exposes the Fe-antisite defects. Our results not only justify a low-cost, efficient and reliable hydrothermal synthesis method for LiFePO4 but also provide a promising alternative viewpoint on the mechanism controlling the nanosizing of LiFePO4, which leads to improved electrochemical performances.

Rate-dependent phase transitions in Li2FeSiO4 cathode nanocrystals.

Nanostructured lithium metal orthosilicate materials hold a lot of promise as next generation cathodes but their full potential realization is hampered by complex crystal and electrochemical behavior. In this work Li2FeSiO4 crystals are synthesized using organic-assisted precipitation method. By varying the annealing temperature different structures are obtained, namely the monoclinic phase at 400°C, the orthorhombic phase at 900°C, and a mixed phase at 700°C. The three Li2FeSiO4 crystal phases exhibit totally different charge/discharge profiles upon delithiation/lithiation. Thus the 400°C monoclinic nanocrystals exhibit initially one Li extraction via typical solid solution reaction, while the 900°C orthorhombic crystals are characterized by unacceptably high cell polarization. In the meantime the mixed phase Li2FeSiO4 crystals reveal a mixed cycling profile. We have found that the monoclinic nanocrystals undergo phase transition to orthorhombic structure resulting in significant progressive deterioration of the material's Li storage capability. By contrast, we discovered when the monoclinic nanocrystals are cycled initially at higher rate (C/20) and subsequently subjected to low rate (C/50) cycling the material's intercalation performance is stabilized. The discovered rate-dependent electrochemically-induced phase transition and stabilization of lithium metal silicate structure provides a novel and potentially rewarding avenue towards the development of high capacity Li-ion cathodes.