Energy Consumption in Batch-Mode Capacitive Deionization

Maxing Out Water Desalination with MXenes

Review on the science and technology of water desalination by capacitive deionization

Comparison of energy consumption in desalination by capacitive deionization and reverse osmosis

Capacitive deionization (CDI) is a water desalination technology in which salt ions are removed from brackish water by flowing through a spacer channel with porous electrodes on each side. Upon applying a voltage difference between the two electrodes, cations move to and are accumulated in electrostatic double layers inside the negatively charged cathode and the anions are removed by the positively charged anode. One of the key parameters for commercial realization of CDI is the salt adsorption capacity of the electrodes. State-of-the-art electrode materials are based on porous activated carbon particles or carbon aerogels. Here we report the use for CDI of carbide-derived carbon (CDC), a porous material with well-defined and tunable pore sizes in the sub-nanometer range. When comparing electrodes made with CDC with electrodes based on activated carbon, we find a significantly higher salt adsorption capacity in the relevant cell voltage window of 1.2-1.4 V. The measured adsorption capacity for four materials tested negatively correlates with known metrics for pore structure of the carbon powders such as total pore volume and BET-area, but is positively correlated with the volume of pores of sizes <1 nm, suggesting the relevance of these sub-nanometer pores for ion adsorption. The charge efficiency, being the ratio of equilibrium salt adsorption over charge, does not depend much on the type of material, indicating that materials that have been identified for high charge storage capacity can also be highly suitable for CDI. This work shows the potential of materials with well-defined sub-nanometer pore sizes for energy-efficient water desalination.

Energetic performance optimization of a capacitive deionization system operating with transient cycles and brackish water

Capacitive deionisation (CDI) is a promising alternative technology in desalination. It targets to remove the salt ions which are only a small percentage of the feed solution, as compared to most other technologies that aim to shift water which accounts of 90% of the feed solution. As a result, CDI requires less energy to operate and the electrodes are easily regenerated. The basic concept of CDI is electrical potential induced surface adsorption of ions on to electrodes. An electrical field forces charged sodium (Na+) and chloride (Cl-) ions in the brackish water to move towards oppositely charged electrodes, by forming electrical double layers, and remove them from the water. It needs low voltage to operate, and it does not require harsh chemical cleaning process. The most critical component of CDI is the carbon electrode materials, as reported that the electrosorptive capacity strongly depends on the physical properties such as surface area and conductivity of the electrode. This chapter reports the current research efforts and progress in the development of porous carbon electrodes conducted in our research group, the commercial activated carbons (ACs), carbon nanotubes (CNTs) including single walled CNTs (SWCNTs) and double walled CNTs (DWCNTs), ordered mesoporous carbons (OMCs), and more recently, graphene nano-flakes were prepared and used as the electrodes of capacitive deionization device. Their salt removal performances were investigated. Their morphology and specific surface area were characterized. The electrosorption experiment results showed that their electrosorptive capacities are in the order of OMCs >SWCNTs>DWCNTs>ACs, ie. 0.93, 0.81, 0.80, 0.62 mg/g respectively. This is attributed to their differences in pore size distribution, pore pattern arrangement and specific surface area. In addition, the ion sorption onto these mentioned materials follows a Langmuir isotherm, indicating monolayer adsorption. Finally, we have investigated the regeneration property of both CNTs and AC through charge-discharge experiment and found that their regeneration was effective. Chemically modified graphene has been studied in the context of many applications due to its excellent electrical, mechanical and thermal properties. Chemical modification of graphene oxide, which is generated from graphite powder as start material, has been a promising route to achieve mass production of graphene platelets. Hummers and Offeman (1958) developed a powerful oxidation method involving reacting graphite with a mixture of potassium permanganate (KMnO4) and concentrated sulfuric acid (H2SO4) to

Can capacitive deionization outperform reverse osmosis for brackish water desalination?

Even though two-thirds of our world's surface is covered by water, less than 1% of that water can be directly consumed to satisfy the rapid growth in population, urbanization, and industrialization.[1] Water quality and scarcity have become some of the most important global challenges of our time. Current desalination technologies such as multi-stage flash distillation and reverse osmosis can be costly to implement and operate, requiring significant pretreatment and consistent maintenance procedures.[2] Thus, investigations into alternative desalination options are being explored toward building more sustainable water treatment systems.Capacitive deionization (CDI) is a desalination technology using highly porous carbon electrodes that can reversibly adsorb dissolved ions. By regulating applied voltages to a CDI cell, ionized salts are trapped in the electric double layers (EDLs) at carbon electrodes, thereafter desalinating water in the CDI cell.[3] CDI technology may have potential advantages over current desalination methods in that no heat treatment or high pressure is required, potentially leading to a significant decrease in the operational and energy costs compared to current desalination processes and aiding in the production of clean/fresh water.Since 2011, researchers from the University of Kentucky Center for Applied Energy Research (UK CAER) have contributed to ongoing efforts to advance CDI technology from theoretical studies to applied process research.[3-22] Works primarily include the improvement of desalination capacity, mitigation of performance degradation, and technology commercialization. In this talk, one of the presenters will provide key milestones of the CDI technology developed at UK CAER in honor of Prof. D. Noel Buckley for his 50-year experience in electrochemistry research.Ref:[1] M. Elimelech, W.A. Phillip, The future of seawater desalination: energy, technology, and the environment, Science, 333 (6043) (2011), pp. 712-717[2] J.-J. Yan, S.-F. Shao, J.-H. Wang, J.-P. Liu, Improvement of a multi-stage flash seawater desalination system for cogeneration power plants, Desalination, 217 (1) (2007), pp. 191-202[3] A. Omosebi, X. Gao, J. Rentschler, J. Landon, K.-K. Liu, Continuous operation of membrane capacitive deionization cells assembled with dissimilar potential of zero charge electrode pairs, J. Colloid Interf. Sci., 446 (2015), pp. 345-351[4] J. Landon, X. Gao, A. Omosebi, K. Liu, “Local pH Effects on Carbon Oxidation in Capacitive Deionization Architectures” Environmental Science: Water Research & Technology, 7, 861 – 869 (2021)[5] A. Omosebi, Z. Li, N. Holubowitch, X. Gao, J. Landon, A. Cramer, K. Liu, “Energy recovery in capacitive deionization systems with inverted operation characteristics”, Environmental Science: Water Research & Technology, 6, 321-330 (2020)[6] X. Gao, A. Omosebi, Z. Ma, F. Zhu, J. Landon, M. Ghorbanian, N. Kern, K. Liu, “Capacitive Deionization Using Symmetric Carbon Electrode Pairs”, Enviro. Sci.: Water Res. Tech., 5, 660-671 (2019).[7] J. Landon, X. Gao, A. Omosebi, K. Liu, “Progress and outlook for capacitive deionization technology”, Current Opinion in Chemical Engineering, 25, 1-8 (2019)[8] N. Holubowitch, A. Omosebi, X. Gao, J. Landon, K. Liu, “Membrane-Free Electrochemical Deoxygenation of Aqueous Solutions Using Symmetric Activated Carbon Electrodes in Flow-Through Cells”, Electrochim. Acta., 297, 163-172 (2019).[9] X. Gao, A. Omosebi, J. Landon, K. Liu, “Voltage-Based Stabilization of Microporous Carbon Electrodes for Inverted Capacitive Deionization”, J. Phys. Chem. C, 122, 1158-1168 (2018).[10] A. Omosebi, X. Gao, N. Holubowitch, Z. Li, J. Landon, K. Liu, “Anion Exchange Membrane Capacitive Deionization Cells”, J. Electrochem. Soc., 164, E242-E247 (2017).[11] N. Holubowitch, A. Omosebi, X. Gao, J. Landon, K. Liu, “Quasi-Steady-State Polarization Reveals the Interplay of Capacitive fand Faradaic Process in Capacitive Deionization”, ChemElectroChem, 4, 2404-2413 (2017).[12] X. Gao, A. Omosebi, N. Holubowitch, J. Landon, K. Liu, “Capacitive Deionization Using Alternating Polarization: Effect of Surface Charge on Salt Removal”, Electrochim. Acta, 233, 249-255 (2017).[13] X. Gao, A. Omosebi, N. Holubowitch, A. Liu, K. Ruh, J. Landon, K. Liu, “Polymer-Coated Composite Anodes for Efficient and Stable Capacitive Deionization”, Desalination, 399, 16-20 (2016).[14] X. Gao, S. Porada, A. Omosebi, K. Liu, P. M. Biesheuvel, J. Landon, “Complementary Surface Charge for Enhanced Capacitive Deionization”, Water Res., 92, 275-282 (2016).[15] X. Gao, A. Omosebi, J. Landon, K. Liu, “Enhanced Salt Removal in an Inverted Capacitive Deionization Cell Using Amine Modified Microporous Carbon Electrode”, Environ. Sci. Tech., 49, 10920 (2015).[16] X. Gao, A. Omosebi, J. Landon, K. Liu, “Surface Charge Enhanced Carbon Electrodes for Stable and Efficient Capacitive Deionization Using Inverted Adsorption-Desorption Behavior”, Energy Environ. Sci., 8, 897 (2015)[17] X. Gao, A. Omosebi, J. Landon, K. Liu, “Dependence of the Capacitive Deionization Performance of Potential of Zero Charge Shifting of Carbon Xerogel Electrodes during Long-Term Operation”, J. Electrochem. Soc., 161, E159 (2014).

Capacitive deionization (CDI) is an emerging salt treatment technology that functions by concentrating ionized salt into porous electrodes with the aid of an applied electric field. Unlike some de-salting technologies like distillation or reverse osmosis that separate water from salt content with the aid of added heat or pressure, CDI electrostatically targets the salt content instead, and it is particularly attractive for the treatment of mid (brackish water) to low (tap water) concentration salt streams [1]. In addition, CDI offers the possibility of energy recovery in the convenient form of electricity which can be used to directly power subsequent CDI units, or other auxiliary devices. Membrane-assisted capacitive deionization (MCDI) is an improvement to conventional CDI whereby ion-exchange membranes (IEMs) are placed next to the porous carbon electrodes to increase desalination performance by mitigating losses that result from converting electronic to ionic charge at the electrode-electrolyte double layer. During MCDI operation, electrode polarization results in the attraction of counter- ions (opposite in polarity to the charged surface), while co-ions (similar in polarity to the charged surface) are repelled away from the polarized surface [2]. The membranes used for the operation hinder the repulsion of co-ions back into the bulk, leading to an increased flux of counter-ions to balance the co-ions contained in the macropore space resulting in typically higher charge efficiencies over the CDI only system. In a departure from the traditional architecture which utilizes the same electrodes to form both the anode and cathode, MCDI systems can instead be asymmetrically assembled with ion-specific electrodes to increase specific charge excesses, and whereby any such specificity can be quantified via potential of zero charge (PZC) measurements. In order to demonstrate benefits to deionization performance, we will present the electrosorption performance and charging characteristics of MCDI cells configured with pristine and nitric acid-treated Zorflex activated carbon electrodes with PZCs of -0.2 and 0.2 V vs SCE, respectively, based on differential capacitance measurements. Results from the asymmetric configuration will be compared to those from pristine anode-pristine cathode configurations to quantify the extent of variation in performance. Acknowledgements The authors are grateful to the U.S. - China Clean Energy Research Center, U.S. Department of Energy for project funding (No. DE-PI0000017), and thankful for the support of the State of Wyoming Advanced Conversion Technologies Task Force for their support.

Evaluation of the salt removal efficiency of capacitive deionisation: Kinetics, isotherms and thermodynamics

Brackish water resources may be an attractive option for human consumption, agriculture, and industry if efficient water purification can be implemented. In the past few decades, research and development of various desalination technologies have been carried out, among which distillation, reverse osmosis, and electrodialysis are the most commonly known and widespread.1 Capacitive deionization (CDI) is an alternative, emerging, and energy-efficient technology for water desalination, which employs an electrochemical flow cell configured with polarized porous carbon electrodes to remove ionized salts in a stream with low molar concentration. Briefly, by regulating an external voltage to a CDI cell, ionized salts are electrostatically captured (or released) in the pores of the carbon electrodes, resulting in the stream being deionized (or the electrodes being regenerated).2-4 Recent studies have found that the salt adsorption capacity (SAC) could be substantially improved by using surface modified carbon electrodes resulting from nitric acid and ethylenediamine treatments.5 Combined with the modified Donnan model including a term of chemical surface charge, this improved SAC was accounted for by enhancement of the chemical charges immobilized in the carbon micropores, validating both enhanced CDI (e-CDI) and extended-voltage CDI (eV-CDI) effects in the CDI literature (Fig. 1).6In summary, it is considered that, for the carbon electrodes used in a CDI cell, an increase in the chemical surface charges makes the pores more readily available for salt adsorption under proper applied voltages. In addition to the surface modified carbon electrodes, immobilized chemical charges can be found in ion-exchange materials. For instance, a well-known cation-exchange polymer, Nafion, contains the negative chemical charges, -SO3 -, while an anion-exchange polymer typically holds positive chemical charges, e.g., NR4 + and NR3 +. As a consequence, together with the knowledge gained above, ion-exchange polymers coating were used in our current studies to explore new composite carbon electrodes for CDI cycling tests. As shown in an initial test (Fig. 2), the addition of ion-exchange polymers results in the SAC not only being increased but also being stabilized with operational time when NaCl solution was used. In this presentation, the preparation and characterizations of composite carbon electrodes will be detailed including comparisons to conventional CDI and membrane capacitive deionization cells. Furthermore, these composite electrodes will be configured into a CDI cell to investigate both e-CDI and eV-CDI effects in various salt solutions such as CaCl2, Na2SO4, and NH4NO3. In addition, the relevant charge efficiency and cycling longevity will be reported and discussed. Figure 1. Demonstration of both enhanced CDI (e-CDI) and extended voltage CDI (eV-CDI) effects using the modified Donnan model with the addition of chemical surface charge. The parameters used in the model can be found in ref. (5 and 6). Figure 2. Improved salt adsorption capacity and operational stability using cation- and anion-exchange polymers added to the carbon cathode and anode, respectively, in a CDI cell. The CDI cell was operated using 1 V charging and at 0 V discharging in ~31 L of ~7 mM deaerated NaCl solution.

Desalination technologies are expected to play an important role in producing clean water in the future, resulting a surge in the research and development of energy efficient and cost effective technologies for desalination of seawater and brackish water. Membrane-based desalination technologies such as reverse osmosis (RO) are the most commercially used desalination methods for seawater and treatment of agricultural water, but are highly energy intensive and the future development of desalination is dependent on finding more energy efficient technologies. Capacitive deionization (CDI) is an emerging technology for water desalination, and is based on the phenomenon of ion electrosorption. Simple CDI is an energy efficient technology and its applications for desalination of low molar concentration streams, like brackish water, is demonstrated. However, to expand the applications, research is focused on improving the efficiency and salt removal capacity of CDI systems. To this end, the important requirements are finding electrode materials with higher capacities and CDI systems with higher efficiencies. Also, the large-scale application of CDI for personal and industrial applications is dependent on designing CDI systems with potential to be implemented at different capacities and length scales. In this work, we have studied the CDI for removal of salt and nutrients from agricultural water. Various high surface area electrode materials were considered and the efficiency of CDI for removal is measured via downstream analyses on batch experiments and reported, allowing development of preliminary parameters for optimizing CDI systems for high-strength agricultural wastewaters.

Capacitive deionization (CDI) is a class of electrochemical desalination technologies which desalinate via ion storage in electric double-layers. CDI has received renewed attention in recent years due to the ability to couple energy storage with salt separation. During galvanostatic operation, a current is applied between porous carbon electrodes until a limiting voltage is reach. The cell is then discharged by applying a reverse current, generating brine and recovering stored charge. However, CDI desalination and energy efficiency can be limited by parasitic side reactions, and selective adsorption of counter-ions (anions at the positive electrode, and cations at the negative electrode). Several material additions and electrode configurations have been proposed to overcome these limitations, with the most prominent being the addition of ion exchange membranes (IEMs) promote counter ion flux out of the desalination chamber and incorporation of carbon slurry electrodes to increase system adsorption capacity. Likewise, functionalization of carbon electrodes has been studied to improve counter-ion adsorption within EDL micropores. While the incorporation of functionalized carbon, IEMs in membrane capacitive deionization (MCDI), and the use of slurry electrodes in flow capacitive deionization (FCDI) have successfully reduced energy consumption or increased ion adsorption capacity in CDI systems, these modifications are often evaluated under limited conditions on the basis of specific performance enhancements. Additional clarity is necessary to evaluate the associated performance and cost tradeoffs across the design space. In this study, an equivalent circuit (M)CDI model, with porous electrode sub-models, was used to measure the sensitivity of CDI performance to material selection, design, and operating choices. In order to investigate the performance of FCDI, pulse-flowed electrodes of high capacity and electronic resistances were incorporated into the existing model. Similarly, fixed charge in the anodic and cathodic micropores was studied to investigate functionalized carbon. Constrained system parameters were randomly selected via latin hypercube sampling (LHS) across multiple electrode geometries and influent salt concentrations. The resultant model outputs were then correlated with input values to quantify parameter sensitivity. Our sensitivity analysis shows that operating current density, electrode specific capacitance, and contact resistance were the parameters which most significantly dictated (M)CDI performance. These parameters where then used to construct an operational space for CDI, MCDI, and FCDI. The results of our operational space were then used to develop a simplified, operational model for both capacitive and faradic materials in CDI. Using this model we conducted a techno-economic analysis (TEA) of proposed improvement to CDI. From the TEA we are able more directly set operating parameters under which CDI might favorably compete with the primary technology for desalination, reverse osmosis (RO). We are able to evaluate materials lifetimes and costs necessary to economically operate CDI. Lastly, goals for operating parameters highlighted in the sensitivity analysis (specific capacitance, voltage limits, charge efficiency, and cell resistance) were set. These benchmarks will provide target for the continued development of CDI towards and economic and viable alternative to RO for brackish water desalination.

Performance optimization of integrated electrochemical capacitive deionization and reverse electrodialysis model through a series pass desorption process

Capacitive deionization (CDI) is an emerging desalination technology which utilizes porous electrodes to remove ions in water by electrosorption. Similar to electric capacitors, energy is stored and released during charging and discharging cycles, respectively. In this study, a nanoporous activated carbon coupled flow-through CDI device was used to evaluate energy consumption and recovery under various operational conditions by charging and discharging the cell at a constant current, respectively. Results indicated that the charging/discharging current, salt concentration and water flow rate were major factors impacting electrosorption and energy consumption, by changing the structure of the electrical double layer (EDL) and how ion transport occurs between the interface and bulk solution. A porosity-based EDL theory was applied to explain the experimental observations. Between 30 and 45% of the energy consumed during charging could be recovered depending on operational conditions, although thermodynamically more than 98% of the total energy should be recoverable. Results indicated that overpotential and faradaic reactions induced irreversible energy are the major reasons for gaps in observed energy losses. Energy consumption for reducing the salinity of brackish water from 32.7 to 5.5 mM by our device could be as low as 0.85 kWh/m3 under most optimized conditions (dependent on materials used and cell configuration). The energy consumption can be dramatically reduced by employing more electron-conductive and Faradaic-resistant electrode materials.