Additive Strategy Enhancing In Situ Polymerization Uniformity for High-Voltage Sodium Metal Batteries.

In situ polymerization to prepare quasi-solid electrolyte has attracted wide attentions for its advantage in achieving intimate electrode-electrolyte contact and the high process compatibility with current liquid batteries; however, gases can be generated during polymerization process and remained in the final electrolyte, severely impairing the electrolyte uniformity and electrochemical performance. In this work, an in situ polymerized poly(vinylene carbonate)-based quasi-solid electrolyte for high-voltage sodium metal batteries (SMBs) is demonstrated, which contains a novel multifunctional additive N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA). MSTFA as high-efficient plasticizer diminishes residual gases in electrolyte after polymerization; the softer and homogeneous electrolyte enables much faster ionic conduction. The HF/H2 O scavenge effect of MSTFA mitigates the corrosion of free acid to cathode and interfacial passivating layers, enhancing the cycle stability under high voltage. As a result, the 4.4 V Na||Na3 V2 (PO4 )2 F3 cell employing the optimized electrolyte possesses an initial discharge capacity of 112.0 mAh g-1 and a capacity retention of 91.3% after 100 cycles at 0.5C, obviously better than those of its counterparts without MSTFA addition. This work gives a pioneering study on the gas residue phenomenon in in situ polymerized electrolytes, and introduces a novel multifunctional silane additive that effectively enhances electrochemical performance in high-voltage SMBs, showing practical application significance.

Heavily Tungsten-Doped Sodium Thioantimonate Solid-State Electrolytes with Exceptionally Low Activation Energy for Ionic Diffusion.

A strategy for modifying the structure of solid-state electrolytes (SSEs) to reduce the cation diffusion activation energy is presented. Two heavily W-doped sodium thioantimonate SSEs, Na2.895 W0.3 Sb0.7 S4 and Na2.7 W0.3 Sb0.7 S4 are designed, both exhibiting exceptionally low activation energy and enhanced room temperature (RT) ionic conductivity; 0.09 eV, 24.2 mS/cm and 0.12 eV, 14.5 mS/cm. At -15 °C the Na2.895 W0.3 Sb0.7 S4 displays a total ionic conductivity of 5.5 mS/cm. The 30 % W content goes far beyond the 10-12 % reported in the prior studies, and results in novel pseudo-cubic or orthorhombic structures. Calculations reveal that these properties result from a combination of multiple diffusion mechanisms, including vacancy defects, strongly correlated modes and excessive Na-ions. An all-solid-state battery (ASSB) using Na2.895 W0.3 Sb0.7 S4 as the primary SSE and a sodium sulfide (Na2 S) cathode achieves a reversible capacity of 400 mAh g-1 .

Sodium halide solid state electrolyte of Na3YBr6 with low activation energy.

Halide solid-state electrolytes (SSEs) are considered promising candidates for practical applications in all-solid-state batteries (ASSBs), due to their outstanding high voltage stability and compatibility with electrode materials. However, Na+ halide SSEs suffer from low ionic conductivity and high activation energy, which limit their applications in sodium all-solid-state batteries. Here, sodium yttrium bromide solid-state electrolytes (Na3YBr6) with a low activation energy of 0.15 eV is prepared via solid state reaction. Structure characterization using X-ray diffraction reveals a monoclinic structure (P21/c) of Na3YBr6. First principle calculations reveal that the low migration activation energy comes from the larger size and vibration of Br- anions, both of which expand the Na+ ion migration channel and reduce its activation energy. The electrochemical window of Na3YBr6 is determined to be 1.43 to 3.35 V vs. Na/Na+, which is slightly narrower than chlorides. This work indicates bromides are a good catholyte candidate for sodium all solid-state batteries, due to their low ion migration activation energy and relatively high oxidation stability.

LaCl3-based sodium halide solid electrolytes with high ionic conductivity for all-solid-state batteries.

To enable high performance of all solid-state batteries, a catholyte should demonstrate high ionic conductivity, good compressibility and oxidative stability. Here, a LaCl3-based Na+ superionic conductor (Na1-xZrxLa1-xCl4) with high ionic conductivity of 2.9 × 10-4 S cm-1 (30 °C), good compressibility and high oxidative potential (3.80 V vs. Na2Sn) is prepared via solid state reaction combining mechanochemical method. X-ray diffraction reveals a hexagonal structure (P63/m) of Na1-xZrxLa1-xCl4, with Na+ ions forming a one-dimensional diffusion channel along the c-axis. First-principle calculations combining with X-ray absorption fine structure characterization etc. reveal that the ionic conductivity of Na1-xZrxLa1-xCl4 is mainly determined by the size of Na+-channels and the Na+/La3+ mixing in the one-dimensional diffusion channels. When applied as a catholyte, the NaCrO2||Na0.7Zr0.3La0.7Cl4||Na3PS4||Na2Sn all-solid-state batteries demonstrate an initial capacity of 114 mA h g-1 and 88% retention after 70 cycles at 0.3 C. In addition, a high capacity of 94 mA h g-1 can be maintained at 1 C current density.

Multifunctional Electrolyte Additive Stabilizes Electrode-Electrolyte Interface Layers for High-Voltage Lithium Metal Batteries.

A lithium metal anode and high nickel ternary cathode are considered viable candidates for high energy density lithium metal batteries (LMBs). However, unstable electrode-electrolyte interfaces and structure degradation of high nickel ternary cathode materials lead to serious capacity decay, consequently hindering their practical applications in LMBs. Herein, we introduced N,O-bis(trimethylsilyl) trifluoro acetamide (BTA) as a multifunctional additive for removing trace water and hydrofluoric acid (HF) from the electrolyte and inhibiting corrosive HF from disrupting the electrode-electrolyte interface layers. Furthermore, the BTA additive containing multiple functional groups (C-F, Si-O, Si-N, and C═N) promotes the formation of LiF-rich, Si- and N-containing solid electrolyte interfacial films on a lithium metal anode and LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode surfaces, thereby improving the electrode-electrolytes interfacial stability and mitigating the capacity decay caused by structural degradation of the layered cathode. Using the BTA additive had tremendous benefits through modification of both anode and cathode surface layers. This was demonstrated using a Li||NMC811 metal battery with the BTA electrolyte, which exhibits remarkable cycling and rate performances (122.9 mA h g-1 at 10 C) and delivers a discharge capacity of 162 mA h g-1 after 100 cycles at 45 °C. Likewise, this study establishes a cost-effective approach of using a single additive to improve the electrochemical performance of LMBs.

Stable Potassium Metal Anodes with an All-Aluminum Current Collector through Improved Electrolyte Wetting.

This is the first report of successful potassium metal battery anode cycling with an aluminum-based rather than copper-based current collector. Dendrite-free plating/stripping is achieved through improved electrolyte wetting, employing an aluminum-powder-coated aluminum foil "Al@Al," without any modification of the support surface chemistry or electrolyte additives. The reservoir-free Al@Al half-cell is stable at 1000 cycles (1950 h) at 0.5 mA cm-2 , with 98.9% cycling Coulombic efficiency and 0.085 V overpotential. The pre-potassiated cell is stable through a wide current range, including 130 cycles (2600 min) at 3.0 mA cm-2 , with 0.178 V overpotential. Al@Al is fully wetted by a 4 m potassium bis(fluorosulfonyl)imide-dimethoxyethane electrolyte (θCA  = 0°), producing a uniform solid electrolyte interphase (SEI) during the initial galvanostatic formation cycles. On planar aluminum foil with a nearly identical surface oxide, the electrolyte wets poorly (θCA  = 52°). This correlates with coarse irregular SEI clumps at formation, 3D potassium islands with further SEI coarsening during plating/stripping, possibly dead potassium metal on stripped surfaces, and rapid failure. The electrochemical stability of Al@Al versus planar Al is not related to differences in potassiophilicity (nearly identical) as obtained from thermal wetting experiments. Planar Cu foils are also poorly electrolyte-wetted and become dendritic. The key fundamental takeaway is that the incomplete electrolyte wetting of collectors results in early onset of SEI instability and dendrites.

Improving the electrochemical performance of Li4Ti5O12 anode by phosphorus reduction at a relatively low temperature.

A novel and efficient method is demonstrated to improve the electrochemical performance of Li4Ti5O12 and metal-oxide anodes. In contrast to other methods, inexpensive red phosphorus powder is used as a reducing reagent, and the reduction is conducted at a relatively low temperature of 400 °C. This method offers a low cost and effective way for Li4Ti5O12 and metal-oxide anode applications.

Li Distribution Heterogeneity in Solid Electrolyte Li10GeP2S12 upon Electrochemical Cycling Probed by 7Li MRI.

All-solid-state rechargeable batteries embody the promise for high energy density, increased stability, and improved safety. However, their success is impeded by high resistance for mass and charge transfer at electrode-electrolyte interfaces. Li deficiency has been proposed as a major culprit for interfacial resistance, yet experimental evidence is elusive due to the challenges associated with noninvasively probing the Li distribution in solid electrolytes. In this Letter, three-dimensional 7Li magnetic resonance imaging (MRI) is employed to examine Li distribution homogeneity in solid electrolyte Li10GeP2S12 within symmetric Li/Li10GeP2S12/Li batteries. 7Li MRI and the derived histograms reveal Li depletion from the electrode-electrolyte interfaces and increased heterogeneity of Li distribution upon electrochemical cycling. Significant Li loss at interfaces is mitigated via facile modification with a poly(ethylene oxide)/bis(trifluoromethane)sulfonimide Li salt thin film. This study demonstrates a powerful tool for noninvasively monitoring the Li distribution at the interfaces and in the bulk of all-solid-state batteries as well as a convenient strategy for improving interfacial stability.

Operando EPR for Simultaneous Monitoring of Anionic and Cationic Redox Processes in Li-Rich Metal Oxide Cathodes.

Anionic redox chemistry offers a transformative approach for significantly increasing specific energy capacities of cathodes for rechargeable Li-ion batteries. This study employs operando electron paramagnetic resonance (EPR) to simultaneously monitor the evolution of both transition metal and oxygen redox reactions, as well as their intertwined couplings in Li2MnO3, Li1.2Ni0.2Mn0.6O2, and Li1.2Ni0.13Mn0.54Co0.13O2 cathodes. Reversible O2-/O2n- redox takes place above 3.0 V, which is clearly distinguished from transition metal redox in the operando EPR on Li2MnO3 cathodes. O2-/O2n- redox is also observed in Li1.2Ni0.2Mn0.6O2, and Li1.2Ni0.13Mn0.54Co0.13O2 cathodes, albeit its overlapping potential ranges with Ni redox. This study further reveals the stabilization of the reversible O redox by Mn and e- hole delocalization within the Mn-O complex. The interactions within the cation-anion pairs are essential for preventing O2n- from recombination into gaseous O2 and prove to activate Mn for its increasing participation in redox reactions. Operando EPR helps to establish a fundamental understanding of reversible anionic redox chemistry. The gained insights will support the search for structural factors that promote desirable O redox reactions.

Chromium-Modified Li4Ti5O12 with a Synergistic Effect of Bulk Doping, Surface Coating, and Size Reducing.

Bulk doping, surface coating, and size reducing are three strategies for improving the electrochemical properties of Li4Ti5O12 (LTO). In this work, chromium (Cr)-modified LTO with a synergistic effect of bulk doping, surface coating, and size reducing is synthesized by a facile sol-gel method. X-ray diffraction (XRD) and Raman analysis prove that Cr dopes into the LTO bulk lattice, which effectively inhibits the generation of TiO2 impurities. Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) verifies the surface coating of Li2CrO4 on the LTO surface, which decreases impedance of the LTO electrode. More importantly, the size of LTO particles can be significantly reduced from submicroscale to nanoscale as a result of the protection of the Li2CrO4 surface layer and the suppression from Cr atoms on the long-range order in the LTO lattice. As anode material, Li4-xCr3xTi5-2xO12 (x = 0.1) delivers a reversible capacity of 141 mAh g(-1) at 10 °C, and over 155 mAh g(-1) at 1 °C after 1000 cycles. Therefore, the Cr-modified Li4Ti5O12 prepared via a sol-gel method has potential for applications in high-power, long-life lithium-ion batteries.

Ultrathin Li4Ti5O12 Nanosheets as Anode Materials for Lithium and Sodium Storage.

Ultrathin Li4Ti5O12 (LTO) nanosheets with ordered microstructures were prepared via a polyether-assisted hydrothermal process. Pluronic P123, a polyether, can impede the growth of Li2TiO3 in the precursor and also act as a structure-directing agent to facilitate the (Li1.81H0.19)Ti2O5·2H2O precursor to form the LTO nanosheets with the ordered microstructure. Moreover, the addition of P123 can suppress the stacking of LTO nanosheets during calcining of the precursor, and the thickness of the nanosheets can be controlled to be about 4 nm. The microstructure of the as-prepared ultrathin and ordered nanosheets is helpful for Li(+) or Na(+) diffusion and charge transfer through the particles. Therefore, the ultrathin P123-assisted LTO (P-LTO) nanosheets show a rate capability much higher than that of the LTO sample without P123 in a Li battery with over 130 mAh g(-1) of capacity remaining at the 64C rate. For intercalation of larger size Na(+) ions, the P-LTO still exhibits a capacity of 115 mAh g(-1) at a current rate of 10 C and a capacity retention of 96% after 400 cycles.

MoS2 ultrathin nanosheets obtained under a high magnetic field for lithium storage with stable and high capacity.

A new strategy, namely a high magnetic field-induced method, has been designed to enhance lithium storage properties of MoS2 ultrathin nanosheets. The MoS2 ultrathin nanosheets obtained under 8 T exhibit improved cycling stability at high currents, better rate performance and reduced electrochemical impedance, compared to MoS2 ultrathin nanosheets obtained without a high magnetic field.