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Electrochemical ion separation is a promising technology to recover valuable ionic species from water. Pseudocapacitive materials, especially 2D materials, are up-and-coming electrodes for electrochemical ion separation. For implementation, it is essential to understand the interplay of the intrinsic preference of a specific ion (by charge/size), kinetic ion preference (by mobility), and crystal structure changes. Ti3C2Tz MXene is chosen here to investigate its selective behavior toward alkali and alkaline earth cations. Utilizing an online inductively coupled plasma system, it is found that Ti3C2Tz shows a time-dependent selectivity feature. In the early stage of charging (up to about 50 min), K+ is preferred, while ultimately Ca2+ and Mg2+ uptake dominate; this unique phenomenon is related to dehydration energy barriers and the ion exchange effect between divalent and monovalent cations. Given the wide variety of MXenes, this work opens the door to a new avenue where selective ion-separation with MXene can be further engineered and optimized.
Seawater batteries are unique energy storage systems for sustainable renewable energy storage by directly utilizing seawater as a source for converting electrical energy and chemical energy. This technology is a sustainable and cost-effective alternative to lithium-ion batteries, benefitting from seawater-abundant sodium as the charge-transfer ions. Research has significantly improved and revised the performance of this type of battery over the last few years. However, fundamental limitations of the technology remain to be overcome in future studies to make this method even more viable. Disadvantages include degradation of the anode materials or limited membrane stability in aqueous saltwater resulting in low electrochemical performance and low Coulombic efficiency. The use of seawater batteries exceeds the application for energy storage. The electrochemical immobilization of ions intrinsic to the operation of seawater batteries is also an effective mechanism for direct seawater desalination. The high charge/discharge efficiency and energy recovery make seawater batteries an attractive water remediation technology. Here, the seawater battery components and the parameters used to evaluate their energy storage and water desalination performances are reviewed. Approaches to overcoming stability issues and low voltage efficiency are also introduced. Finally, an overview of potential applications, particularly in desalination technology, is provided.
Faradaic electrode materials have significantly improved the performance of membrane capacitive deionization, which offers an opportunity to produce freshwater from seawater or brackish water in an energy-efficient way. However, Faradaic materials hold the drawbacks of slow desalination rate due to the intrinsic low ion diffusion kinetics and inferior stability arising from the volume expansion during ion intercalation, impeding the engineering application of capacitive deionization. Herein, a pseudocapacitive material with hollow architecture was prepared via template-etching method, namely, cuboid cobalt hydroxide, with fast desalination rate (3.3 mg (NaCl)·g-1 (h-Co(OH)2)·min-1 at 100 mA·g-1) and outstanding stability (90% capacity retention after 100 cycles). The hollow structure enables swift ion transport inside the material and keeps the electrode intact by alleviating the stress induced from volume expansion during the ion capture process, which is corroborated well by in situ electrochemical dilatometry and finite element simulation. Additionally, benefiting from the elimination of unreacted bulk material and vertical cobalt hydroxide nanosheets on the exterior surface, the synthesized material provides a high desalination capacity ( mg (NaCl)·g-1 (h-Co(OH)2) at 30 mA·g-1). This work provides a new strategy, constructing microscale hollow faradic configuration, to further boost the desalination performance of Faradaic materials.
Advanced hydrogen technologies contribute essentially to the decarbonization of our industrialized world. Large-scale hydrogen production would benefit from using the abundantly available water reservoir of our planet’s oceans. Current seawater-desalination technologies suffer from high energy consumption, high cost, or low performance. Here, we report technology for water desalination at seawater molarity, based on a polymer ion-exchange membrane fuel cell. By continuously supplying hydrogen and oxygen to the cell, a 160-mM concentration decrease from an initial value of 600 mM is accomplished within 40 h for a 55-mL reservoir. This device’s desalination rate in 600 mM NaCl and substitute ocean water are 18 g/m2/h and 16 g/m2/h, respectively. In addition, by removing 1 g of NaCl, 67 mWh of electric energy is generated. This proof-of-concept work shows the high application potential for sustainable fuel-cell desalination (FCD) using hydrogen as an energy carrier.
Electrochemical processes enable a new generation of energy-efficient desalination technologies. While ion electrosorption via capacitive deionization is only suitable for brackish water with low molar strength, the use of Faradaic materials capable of reversible ion intercalation or conversion reactions allows energy-efficient removal of ions from seawater. However, the limited charge transfer/storage capacity of Faradaic materials indicates an upper limit for their desalination applications. Therefore, a new electrochemical concept must be explored to exceed the current state-of-the-art results and to push the desalination capacity beyond 100–200 mgNaCl/gelectrode. In this proof-of-concept work, we introduce the new concept of using metal–air battery technology for desalination. We do so by presenting performance data for zinc–air desalination (ZAD) in 600 mM NaCl. The ZAD cell provides a desalination capacity of 0.9–1.0 mgNaCl/cm2 (normalized to the membrane area; corresponding to 1300 mgNaCl/gZn) with a charge efficiency of 70% when charging/discharging the cell at 1 mA/cm2. The energy consumption of ZAD is 68–92 kJ/mol.
Abstract The recent advances in chloride-ion capturing electrodes for capacitive deionization (CDI) are limited by the capacity, rate, and stability of desalination. This work introduces Ti3C2Tx/Ag synthesized via a facile oxidation-reduction method and then uses it as an anode for chloride-ion capture in CDI. Silver nanoparticles are formed successfully and uniformly distributed with the layered-structure of Ti3C2Tx. All Ti3C2Tx/Ag samples are hydrophilic, which is beneficial for water desalination. Ti3C2Tx/Ag samples with a low charge transfer resistance exhibit both pseudocapacitive and battery behaviors. Herein, the Ti3C2Tx/Ag electrode with a reaction time of 3 h exhibits excellent desalination performance with a capacity of 135 mg Cl− g−1 at 20 mA g−1 in a 10 × 10−3 m NaCl solution. Furthermore, low energy consumption of 0.42 kWh kg−1 Cl− and a desalination rate of 1.5 mg Cl− g−1 min−1 at 50 mA g−1 is achieved. The Ti3C2Tx/Ag system exhibits fast rate capability, high desalination capacity, low energy consumption, and excellent cyclability, which can be ascribed to the synergistic effect between the battery and pseudocapacitive behaviors of the Ti3C2Tx/Ag hybrid material. This work provides fundamental insight into the coupling of battery and pseudocapacitive behaviors during Cl− capture for electrochemical desalination.
As industrial and agricultural activities expand along with a growing global population, numerous regions are experiencing shortages of water and essential metals. To address these challenges, electrochemical separation methods utilizing electroactive materials and interfaces offer an efficient and straightforward approach to water purification and targeted ion extraction. Although carbon-based materials have been extensively studied and have the advantages of stability and low cost, they suffer from low desalination capacity, particularly for high-salinity water, and low selectivity. This dissertation investigates the potential of Faradaic materials and processes for electrochemical ion/water separation, as well as ion/ion separation, with a focus on alkali and alkaline earth metal ions, which are vital for industrial development but challenging to separate. The study includes synthesizing several Faradaic materials to achieve high ion removal capacity in seawater desalination. This work also develops a strategy to exploit the nuanced differences of ion intercalation kinetics in 2D material to achieve specific ion separation. The study also examines the selectivity and stability of LiFePO4 and presents new ways to optimize its performance. Finally, the study establishes a novel electrochemical process based on redox flow batteries, which promises a more efficient and continuous extraction of lithium ions from seawater.
Heavy metal pollution is a key environmental problem. Selectively extracting heavy metals could accomplish water purification and resource recycling simultaneously. Adsorption is a promising approach with a facile process, adaptability for the broad concentration of feed water, and high selectivity. However, the adsorption method faces challenges in synthesizing high-performance sorbents and regenerating adsorbents effectively. FeOOH is an environmentally friendly sorbent with low-cost production on a large scale. Nevertheless, the selectivity behavior and regeneration of FeOOH are seldom studied. Therefore, we investigated the selectivity of FeOOH in a mixed solution of Co2+, Ni2+, and Pb2+ and proposed to enhance the capacity of FeOOH and regenerate it by using external charges. Without charge, the FeOOH electrode shows a Pb2+ uptake capacity of 20 mg/g. After applying a voltage of −0.2/+0.8 V, the uptake capacity increases to a maximum of 42 mg/g and the desorption ratio is 70%–80%. In 35 cycles, FeOOH shows a superior selectivity towards Pb2+ compared with Co2+ and Ni2+, with a purity of 97% ± 3% in the extracts. The high selectivity is attributed to the lower activation energy for Pb2+ sorption. The capacity retentions at the 5th and the 35th cycles are ca. 80% and ca. 50%, respectively, comparable to the chemical regeneration method. With industrially exhausted granular ferric hydroxide as the electrode material, the system exhibits a Pb2+ uptake capacity of 37.4 mg/g with high selectivity. Our work demonstrates the feasibility of regenerating FeOOH by charge and provides a new approach for recycling and upcycling FeOOH sorbent.
