ABSTRACT
Rechargeable aluminum (Al) metal batteries are enticing for the coming generation of electrochemical energy storage systems due to the earth abundance, high energy density, inherent safety, and recyclability of Al metal. However, few electrolytes can reversibly electrodeposit Al metal, especially at low temperatures. In this study, Al electroplating and stripping were investigated from 25 °C to -40 °C in mixtures of aluminum chloride (AlCl3), 1-ethyl-3-methyl-imidazolium chloride ([EMIm]Cl), and urea. The ternary ionic liquid analogue (ILA) consisting of AlCl3-urea-[EMIm]Cl in a molar ratio of 1.3:0.25:0.75 enabled reversible Al electrodeposition at temperatures as low as -40 °C while exhibiting the highest current density and the lowest overpotential among all of the electrolyte mixtures at 25 °C, including the AlCl3-[EMIm]Cl binary mixture. The ILA electrolyte was further tested in a rechargeable Al-graphite battery system down to -40 °C. The addition of urea to AlCl3-[EMIm]Cl binary mixtures can improve the Al electrodeposition, extend the liquid temperature window, and reduce the cost.
ABSTRACT
Fifty years after its introduction, the lithium-carbon monofluoride (Li-CFx) battery still has the highest cell-level specific energy demonstrated in a practical cell format. However, few studies have analyzed how the main electrochemical discharge product, LiF, evolves during the discharge and cell rest periods. To fill this gap in understanding, we investigated molecular-level and interfacial changes in CFx electrodes upon the discharge and aging of Li-CFx cells, revealing the role of LiF beyond that of a simple discharge product. We reveal that electrochemically formed LiF deposits on the surface of the CFx electrode and subsequently partially disperses into the electrolyte to form a colloidal suspension during cell aging, as determined from galvanostatic electrochemical impedance spectroscopy (EIS), solid-state 19F nuclear magnetic resonance (NMR), dynamic light scattering (DLS), and operando optical light microscopy measurements. Electrochemical LiF formation and LiF dispersion into the electrolyte are distinct competing rate processes that each affect the cell impedance differently. Using knowledge of LiF dispersion and saturation, an in-line EIS method was developed to compute the depth of discharge of CFx cells beyond coulomb counting. Solid-state 19F NMR measurements quantitatively revealed how LiF and CF moieties evolved with discharge. Covalent CF bonds react first, followed by a combination of covalent and ionic CF bonds. Quantitively correlating NMR and electrochemical measurements reveals not only how LiF formation affects cell impedance but also that CF bonds with the most ionic character remain unreacted, which limits realization of the full theoretical specific capacity of the CFx electrode. The results reveal new insights into the electrochemical discharge mechanism of Li-CFx cells and the unique role of LiF in cell discharge and aging, which suggest pretreatment strategies and methods to improve and measure the performance of Li-CFx batteries.
ABSTRACT
Rechargeable zinc (Zn) metal batteries are attractive for use as electrochemical energy storage systems on a global scale because of the low cost, high energy density, inherent safety, and strategic resource security of Zn metal. However, at low temperatures, Zn batteries typically suffer from high electrolyte viscosity and unfavorable ion transport properties. Here, we studied reversible Zn electrodeposition in mixtures of 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide ([EMIm]TFSI) ionic liquid, γ-butyrolactone (GBL) organic solvent, and Zn(TFSI)2 zinc salt. The electrolyte mixtures enabled reversible Zn electrodeposition at temperatures as low as -60 °C. An electrolyte composed of 0.1 M Zn(TFSI)2 in [EMIm]TFSI:GBL with a volume ratio of 1:3 formed a deep eutectic solvent that optimized electrolyte conductivity, viscosity, and the zinc diffusion coefficient. Liquid-state 1H and 13C nuclear magnetic resonance (NMR) spectroscopy and molecular dynamic (MD) simulations indicate increased formation of contact ion pairs and the reduction of ion aggregates are responsible for the optimal composition.
ABSTRACT
Hybrid electric storage systems that combine capacitive and faradaic materials need to be well designed to benefit from the advantages of batteries and supercapacitors. The ultimate capacitive material is graphite (GR), yet high capacitance is usually not achieved due to restacking of its sheets. Therefore, an appealing approach to achieve high power and energy systems is to embed a faradaic 2D material in between the graphite sheets. Here, a simple one-step approach was developed, whereby a faradaic material [layered double hydroxide (LDH)] was electrochemically formed inside electrochemically exfoliated graphite. Specifically, GR was exfoliated under negative potentials by CoII and, in the presence of MnII , formed GR-CoMn-LDH, which exhibited a high areal capacitance and energy density. The high areal capacitance was attributed to the exfoliation of the graphite at very negative potentials to form a 3D foam-like structure driven by hydrogen evolution as well as the deposition of CoMn-LDH due to hydroxide ion generation inside the GR sheets. The ratio between the CoII and MnII in the CoMn-LDH was optimized and analyzed, and the electrochemical performance was studied. Analysis of a cross-section of the GR-CoMn-LDH confirmed the deposition of LDH inside the GR layers. The areal capacitance of the electrode was 186â mF cm-2 at a scan rate of 2â mV s-1 . Finally, an asymmetric supercapacitor was assembled with GR-CoMn-LDH and exfoliated graphite as the positive and negative electrodes, respectively, yielding an energy density of 96.1â µWh cm-3 and a power density of 5â mW cm-3 .