Green Route for Fabrication of Water-Treatable Thermoelectric Generators

Since future energy harvesting technologies require stable supply and high-efficiency energy conversion, there is an increasing demand for high-performance organic thermoelectric generators (TEGs) based on waterproof thermoelectric materials. The poor stability of n-type organic semiconductors in air and water has proved a roadblock in the development of reliable thermoelectric power generators. We developed a simple green route for preparing n-type carbon nanotubes (CNTs) by doping with cationic surfactants and fabricated films of the doped CNTs using only aqueous media. The thermoelectric properties of the CNT films were investigated in detail. The nanotubes doped using a cationic surfactant (cetyltrimethylammonium chloride (CTAC)) retained an n-doped state for at least 28 days when exposed to water and air, indicating higher stability than that for contemporary CNT-based thermoelectric materials. The wrapping of the surfactant molecules around the CNTs is responsible for blocking oxygen and water from attacking the CNT walls, thus, extending the lifetime of the n-doped state of the CNTs. We also fabricated thermoelectric power conversion modules comprising CTAC-doped (n-type) and sodium dodecylbenzenesulfonate- (SDBS-) doped (p-type) CNTs and tested their stabilities in water. The modules retained 80±2.4% of their initial maximum output power (at a temperature difference of 75°C) after being submerged in water for 30 days, even without any sealing fills to prevent device degradation. The remarkable stability of our CNT-based modules can enable the development of reliable soft electronics for underwater applications.

Crosslinked Polyethyleneimine Gel Polymer Interface to Improve Cycling Stability of RFBs

Redox flow batteries are considered a promising technology for grid energy storage. However, capacity decay caused by crossover of active materials is a universal challenge for many flow battery systems, which are based on various chemistries. In this paper, using the vanadium redox flow battery as an example, we demonstrate a new gel polymer interface (GPI) consisting of crosslinked polyethyleneimine with a large amount of amino and carboxylic acid groups introduced between the positive electrode and the membrane. The GPI functions as a key component to prevent vanadium ions from crossing the membrane, thus supporting stable long-term cycling. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were conducted to investigate the effect of GPI on the electrochemical properties of graphitic carbon electrodes (GCFs) and redox reaction of catholyte. X-ray photoelectron spectroscopy (XPS) and 1H nuclear magnetic resonance (NMR) spectra demonstrated that the crosslinked GPI is chemically stable for 100 cycles without dissolution of polymers and swelling in the strong acidic electrolytes. Results from inductively coupled plasma mass spectrometry (ICP-MS), Fourier-transform infrared (FTIR) spectroscopy, and energy-dispersive X-ray (EDX) spectroscopy proved that the GPI is effective in maintaining the concentration of vanadium species in their respective half-cells, resulting in improved cycling stability because of it prevents active species from crossing the membrane and stabilizes the oxidation states of active species.

Mg-Li Hybrid Batteries: The Combination of Fast Kinetics and Reduced Overpotential

It is imperative for the development of cost-effective and high-performance batteries. Currently, lithium-ion batteries still occupy most of the market. However, limited lithium (Li) resource and energy density retard their further development. The magnesium (Mg) metal has several significant advantages; those make it a viable alternative to Li as anode, including high volume specific capacity and dendrite-free plating during cycling and high abundance. The Mg-Li hybrid batteries can combine the advantages of Li ion and Mg metal to achieve fast electrode kinetics and smooth anode deposition morphology. This review summarizes recent progresses in cathode material design and anode interface modification for Mg-Li hybrid batteries. We aim to illustrate the contribution of Li+ to the electrochemical performance improvement at both cathode and anode sides and to provide inspiration for the future research in this field.

A Low-Crossover and Fast-Kinetics Thiolate Negolyte for Aqueous Redox Flow Batteries

Aqueous redox flow batteries (ARFBs) are a promising technology for large-scale energy storage. Developing high-capacity and long-cycle negolyte materials is one of major challenges for practical ARFBs. Inorganic polysulfide is promising for ARFBs owing to its low cost and high solubility. However, it suffers from severe crossover resulting in low coulombic efficiency and limited lifespan. Organosulfides are more resistant to crossover than polysulfides owing to their bulky structures, but they suffer from slow reaction kinetics. Herein, we report a thiolate negolyte prepared by an exchange reaction between a polysulfide and an organosulfide, preserving low crossover rate of the organosulfide and high reaction kinetics of the polysulfide. The thiolate denoted as 2-hydroxyethyl disulfide+potassium polysulfide (HEDS+K2S2) shows reduced crossover rate than K2S2, faster reaction kinetics than HEDS, and longer lifespan than both HEDS and K2S2. The 1.5 M HEDS+1.5 M K2S2 static cell demonstrated 96 Ah L-1negolyte over 100 and 200 cycles with a high coulombic efficiency of 99.2% and 99.6% at 15 and 25 mA cm-2, respectively. The 0.5 M HEDS+0.5 M K2S2 flow cell delivered a stable and high capacity of 30.7 Ah L-1negolyte over 400 cycles (691 h) at 20 mA cm-2. This study presents an effective strategy to enable low-crossover and fast-kinetics sulfur-based negolytes for advanced ARFBs.

Reviewing the Safe Shipping of Lithium-Ion and Sodium-Ion Cells: A Materials Chemistry Perspective

High energy density lithium-ion (Li-ion) batteries are commonly used nowadays. Three decades’ worth of intense research has led to a good understanding on several aspects of such batteries. But, the issue of their safe storage and transportation is still not widely understood from a materials chemistry perspective. Current international regulations require Li-ion cells to be shipped at 30% SOC (State of Charge) or lower. In this article, the reasons behind this requirement for shipping Li-ion batteries are firstly reviewed and then compared with those of the analogous and recently commercialized sodium-ion (Na-ion) batteries. For such alkali-ion batteries, the safest state from their active materials viewpoint is at 0 V or zero energy, and this should be their ideal state for storage/shipping. However, a “fully discharged” Li-ion cell used most commonly, composed of graphite-based anode on copper current collector, is not actually at 0 V at its rated 0% SOC, contrary to what one might expect—the detailed mechanism behind the reason for this, namely, copper dissolution, and how it negatively affects cycling performance and cell safety, will be summarized herein. It will be shown that Na-ion cells, capable of using a lighter and cheaper aluminum current collector on the anode, can actually be safely discharged to 0 V (true 0% SOC) and beyond, even to reverse polarity (negative voltages). It is anticipated that this article spurs further research on the 0 V capability of Na-ion systems, with some suggestions for future studies provided.

Electrochemical Mechanism of Al Metal–Organic Battery Based on Phenanthrenequinone

Al metal-organic batteries are a perspective high-energy battery technology based on abundant materials. However, the practical energy density of Al metal-organic batteries is strongly dependent on its electrochemical mechanism. Energy density is mostly governed by the nature of the aluminium complex ion and utilization of redox activity of the organic group. Although organic cathodes have been used before, detailed study of the electrochemical mechanism is typically not the primary focus. In the present work, electrochemical mechanism of Al metal-phenanthrenequinone battery is investigated with a range of different analytical techniques. Firstly, its capacity retention is optimized through the preparation of insoluble cross-coupled polymer, which exemplifies extremely low capacity fade and long-term cycling stability. Ex situ and operando ATR-IR confirm that reduction of phenanthrenequinone group proceeds through the two-electron reduction of carbonyl groups, which was previously believed to exchange only one-electron, severely limiting cathode capacity. Nature of aluminium complex ion interacting with organic cathode is determined through multiprong approach using SEM-EDS, XPS, and solid-state NMR, which all point to the dominant contribution of AlCl2+ cation. Upon full capacity utilization, Al metal-polyphenanthrenequinone battery utilizing AlCl2+ offers an energy density of more than 200 Wh/kg making it a viable solution for stationary electrical energy storage.

A Computational Comparison of Ether and Ester Electrolyte Stability on a Ca Metal Anode

Ca-ion batteries (CIBs) have the potential to provide inexpensive energy storage, but their realization is impeded by the lack of suitable electrolytes. Motivated by recent experimental progress, we perform ab initio molecular dynamics simulations to investigate early decomposition reactions at the anode-electrolyte interface. By examining different combinations of solvent—tetrahydrofuran (THF) or ethylene carbonate (EC)—and salt—Ca(BH4)2, Ca(BF4)2, Ca(BCl4)2, and Ca(ClO4)2—we identify a variety of behavioral trends between electrolyte solutions. Next, we perform a separate trajectory with pure THF and gradually increased negative charge; despite an addition of -32e, no THF decomposition is detected. Charge analysis reveals that in a reductive environment, THF distributes excess charge evenly across its hydrocarbon backbone, while EC concentrates charge on its ester oxygens and carbonyl carbon, resulting in decomposition. Graphs of charge vs. time for both solvents reveal that EC decomposition products can be reduced by up to five electrons, while those of THF are limited to a single electron. Ultimately, we find Ca(BH4)2 and THF to be the most stable solution investigated herein, corroborating experimental evidence of its suitability as a CIB electrolyte.

Sodium-Ion Battery Anode Construction with SnPx Crystal Domain in Amorphous Phosphorus Matrix

The high-capacity phosphorus- (P-) based anode materials for sodium-ion batteries (NIBs) often face poor performance retentions owing to the low conductivity and large volume expansion. It is thus essential to buffer these problems by appropriately alloying with other elements such as tin (Sn) and constructing well-designed microstructures. Herein, a series of P-/Sn-based composites have been synthesized by the facile and low-cost one-step ball milling. Pair distribution function (PDF) has been employed as a hardcore quantitative technique to elucidate their structures combined with other techniques, suggesting the formation and ratios of Sn4P3 and Sn crystalline domains embedded inside an amorphous P/carbon matrix. The composite with the largest amount of Sn4P3 in the P/C matrix can deliver the most balanced electrochemical performance, with a capacity of 422.3 mA-h g−1 for 300 cycles at a current density of 1000 mA g−1. The reaction mechanism has been elucidated by 23Na and 31P solid-state nuclear magnetic resonance (NMR) investigations. The study sheds light on the rational design and concrete identification of P-/Sn-based amorphous-dominant composite materials for NIBs.

Ion Coordination and Transport in Magnesium Polymer Electrolytes Based on Polyester-co-Polycarbonate

Magnesium-ion-conducting solid polymer electrolytes have been studied for rechargeable Mg metal batteries, one of the beyond-Li-ion systems. In this paper, magnesium polymer electrolytes with magnesium bis(trifluoromethane)sulfonimide (Mg(TFSI)2) salt in poly(ε-caprolactone-co-trimethylene carbonate) (PCL-PTMC) were investigated and compared with the poly(ethylene oxide) (PEO) analogs. Both thermal properties and vibrational spectroscopy indicated that the total ion conduction in the PEO electrolytes was dominated by the anion conduction due to strong polymer coordination with fully dissociated Mg2+. On the other hand, in PCL-PTMC electrolytes, there is relatively weaker polymer–cation coordination and increased anion–cation coordination. Sporadic Mg- and F-rich particles were observed on the Cu electrodes after polarization tests in Cu|Mg cells with PCL-PTMC electrolyte, suggesting that Mg was conducted in the ion complex form (MgxTFSIy) to the copper working electrode to be reduced which resulted in anion decomposition. However, the Mg metal deposition/stripping was not favorable with either Mg(TFSI)2 in PCL-PTMC or Mg(TFSI)2 in PEO, which inhibited quantitative analysis of magnesium conduction. A remaining challenge is thus to accurately assess transport numbers in these systems.