The present invention relates to the deionization of saline solutions, and more particularly to capacitive deionization systems and methods.
Potable water is a scarce, critical resource on Earth. The west coast in the USA, as well as countries including India, China, and other African states already experience water scarcity. Times of water scarcity affect nearly four billion people and this problem is expected to compound as population growth continues and living standards improve. Better watershed management can improve water availability, but other advancements are also necessary to provide water resources for the future. Water purification technologies currently include distillation, membrane filtration methods, and electrodialysis. Distillation is widely used but is energy intensive compared to other desalination methods. Membrane filtration, namely reverse osmosis and nanofiltration, also are widely used for full-scale desalination. Materials using physical separation methods suffer from fouling issues as well as complications with chemical and thermal tolerance. These issues lead to difficulties, with membrane maintenance decreasing their overall longevity. Reverse osmosis is further complicated by elevated temperature, pressure, and specific pH operational ranges. Electrodialysis uses stacks of cationic and anionic membranes with applied electric current to channel ions between streams of concentrated and dilute salt solutions. This method is restricted to pre-reverse osmosis treatment of seawater, due to decreased solution conductivity at low salt concentrations. Electrodialysis, while less costly than thermal distillation and reverse osmosis, is still expensive compared to more advanced desalination methods. Thus, researching alternative desalination techniques that are both energy efficient and economically feasible is a topic of growing interest.
One such method is capacitive deionization (CDI). CDI demonstrates promise as a more cost-effective and efficient water purification method, compared to current technology. CDI processes operate at ambient pressures, low temperatures, and small cell voltages, allowing for cheap, scalable systems. CDI also has the ability to be more efficient than the current industry standard, reverse osmosis, at lower salt concentrations. The electrodes used for CDI at industrial scales are predominantly activated carbon, due to its low cost.
CDI operates by sending a potential difference across a set of electrodes submerged in an aqueous solution containing ions. The electrodes are composed of an active material coated onto a current collector with a binding agent. When the potential has been applied to the electrodes, positive and negative ions in the solution migrate to their respective counter-charged electrodes. They then adsorb onto the electrode surface and are held in place via an electrostatic attraction. This adsorption mechanism is reversible, and by reversing or zeroing the applied potential, the intercalated surface ions can be discharged back into the solution, allowing the electrodes to regenerate and be reused. It is possible to use a solar cell or other renewal forms of energy to initiate the CDI process. There are many different models to describe the interfacial interaction between the solution and the electrode surface. The most elementary of these is the electrical double layer (EDL) model. Here, the model assumes that kinetics will not limit the rate, the concentration will not affect charge transfer, and that side faradaic reactions that may occur will be negligible to cell performance. The Gouy-Chapman-Stern double-layer theory takes into account the omissions from the EDL model offering a more robust explanation of the interplay between the electrode structure and salt solution.
CDI has been performed with various carbon-based materials, including: carbon aerogels, carbon nanotubes, ordered mesoporous carbon, carbon nanofibers, metal-organic-framework derived porous carbon, graphene and graphene oxide-derived materials, and carbide and nitride-derived carbon. CDI is also possible with mixed-metal oxide composites, redox-active flow electrodes, and microbial fuel cells. These methods have adsorption values comparable to carbon-based materials and polymers, but suffer from the same issues, such as material costs, electrode degradation during cycling, and scaling issues.
The materials discussed above suffer from rapid degradation during CDI operation. This problem stems from faradaic reactions that occur on the surface and within pore structures. These reactions lead to a decline in desalination performance, with a commensurate increase in energy consumption. Ionic membranes mitigate electrode degradation by preventing ion crossover and maintaining the EDL. The inclusion of membranes also limits the formation of reduced oxygen species at the cathode, decreasing deleterious side reactions, increasing cell longevity. One drawback that affects both RO and CDI systems is the large cost and production scalability of ionic membranes. The other materials required for CDI—carbon black, polymer, and binder—are less expensive. The system still holds future promise with cost improvements to either these materials or membrane systems.
Researchers at the Oak Ridge National Laboratory (ORNL) have developed a method for converting waste automobile tires into a cheap, reliable source of carbon suitable for use in CDI. Tires pose a great waste issue after their product lifetime. They generate human health concerns because by providing breeding sites for mosquitos and vermin breeding, possibilities of uncontrolled fires, and potential leaching of additives and degradation byproducts into the environment. The tire-derived carbon material has been used as an anode material for Li, Na, and K-ion batteries, pseudo-capacitors, and as a biofuel catalyst. Examples of such tire-derived carbons are described in “Pyrolytic Carbon Black Composite and Method of Making the Same”, U.S. Pat. No. 9,441,113 (Sep. 13, 2016); “Flexible and Conductive Waste Tire-Derived Carbon/Polymer Composite Paper as Pseudocapacitive Electrode”, U.S. Pat. No. 9,941,058 (Apr. 10, 2018); and “Flexible and Conductive Waste Tire-Derived Carbon/Polymer Composite Paper as Pseudocapacitive Electrode”, US 2018/0204687 (Jul. 19, 2018). The disclosures of the foregoing are hereby incorporated fully by reference.
A capacitive deionization system can include a first electrode comprising tire derived carbon particles obtained from a carbonaceous waste-tire source material containing carbon black. A conductive polymer coating is provided on the carbon particles of the first electrode forming first coated carbon particles. A second electrode can include tire derived carbon particles obtained from a carbonaceous waste-tire source material containing carbon black. A conductive polymer coating is provided on the carbon particles of the second electrode forming second coated carbon particles. The first electrode and the second electrode can define a flow channel there between. A first opening can be provided for conducting saline solution into the flow channel. A second opening can be provided for conducting treated saline solution from the flow channel. A first current collector can be provided for the first electrode and a second current collector can be provided for the second electrode. An electrical connection ca be between the first and second electrodes. A power source can be connected to the electrical connection for creating a field between the first and second electrodes.
The first current collector and the second current collector can be formed from a metal sheet or metal foam. The metal foam can be an open cell metal foam. The first plurality of coated carbon particles can be adhered to the open cell metal foam current collector of the first electrode, and a second plurality of coated carbon particles can be adhered to the open cell metal foam current collector of the second electrode.
An anion exchange membrane can be provided adjacent to the first electrode. A cation exchange membrane can be provided adjacent to the second electrode.
The conductive polymer coating comprises at least one selected from the group consisting of polyaniline, polythiophene, polypyrrole, poly(p-phenylene). The conductive polymer coating can be from 3 to 20 wt. % based on the total weight of the polymer carbon composite coated carbon particles. The conductive polymer coating can be from 10 to 500 nm thick.
The current collector can be formed from at least one of the selected from the group consisting of Ni, Pd, Pt, Ti, Zr, Hf, Cu, Ag, Au, and stainless steel. The current collector can include a metal foam or metal sheet having a porosity of from 5 to 70%. The current collector can include a metal foam or metal sheet having a thickness of 10 to 500 μm. The current collector can include a metal foam having a surface area of from 1 to 100 m2/g.
The carbon particles can have a diameter of from 1 to 200 μm. The surface area of the carbon particles can be from 100 m2/g to 1600 m2/g. The carbon particles can have a porosity of from 0.01 to 10%. The carbon particles can include pores having a pore size of from 0.02 to 80 nm.
The electrode can further include a binder for adhering the carbon particles together. The binder can include at least one selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF).
The carbon particles are obtained from waste tire that has been sulfonated by contacting the carbonaceous source material with an oleum bath. The carbon particles can be obtained from waste tire that has been pyrolyzed to produce a layered carbon black containing product comprising a glassy carbon matrix phase having carbon black dispersed therein, the layered carbon black containing product having an interlayer spacing of from 0.4 to 0.5 nm. The pyrolization temperature can be from 600 to 1490° C.
A first plurality of the coated carbon particles can be suspended in the saline solution and flow through a first flow electrode. A second plurality of the coated carbon particles can be suspended in the saline solution and flow through a second flow electrode.
The electrode spacing can be from 5 mm to 50 mm. The system can be a multi-electrode system comprising multiple pairs of alternating first and second electrodes.
A method of making a system for capacitive deionization of a salt from a liquid can include the steps of providing tire derived carbon particles and coating the carbon particles with a conductive polymer. The coated carbon particles can be bound together with a binder and the carbon particles can be adhered to a respective current collector to form first and second electrodes. The first and second electrodes can be secured in spaced relation to form a saline flow channel, the flow channel having a saline solution inlet and a saline solution outlet. The first and second electrodes can be electrically connected to form a capacitor. The salt can include at least one selected from the group consisting of NaCl, LiCl, KCl, MgCl2, CaCl2, and SrCl2. The method can include the step of providing an anion exchange membrane adjacent to the conductive polymer layer of the first electrode, and a cation exchange membrane adjacent the conductive polymer layer of the second electrode.
The carbon particles can be obtained from waste tire that has been sulfonated by contacting the carbonaceous source material with an sulfonation bath. The sulfonation bath can include a sulfonation agent of chlorosulfonic acid in 1,2 dichloroethane solution. The sulfonation bath can include between 0.1-65 wt. % SO3. The sulfonation bath can include comprises 2-30 wt. % SO3. The sulfonation bath can have a temperature of between −20° C. to 200° C.
The carbon particles can be obtained from waste tire that has been pyrolyzed to produce a layered carbon black containing product comprising a glassy carbon matrix phase having carbon black dispersed therein, the layered carbon black containing product having an interlayer spacing of from 0.4 to 0.5 nm. The pyrolysis step can be conducted at a temperature from 600-1490° C. The duration of the pyrolysis step can be from 1 minute to 12 hours.
The first coated carbon particles can be mixed with a binder and adhered to the first current collector. The first current collector can be an open cell metal foam or metal sheet. The second coated carbon particles can be mixed with a binder and adhered to the second current collector, where the second current collector can be an open cell metal foam or metal sheet.
The first electrode and the second electrode can be flow electrodes. The first coated carbon particles can be suspended in the saline solution and caused to flow through the first flow electrode. The second coated carbon particles can be suspended in the saline solution and caused to flow through the second flow electrode.
A method for the capacitive deionization of a saline solution can include the steps of providing a capacitive deionization system which includes a first electrode comprising tire derived carbon particles obtained from a carbonaceous waste-tire source material containing carbon black, the carbon particles of the first electrode having a conductive polymer coating forming first coated carbon particles. A second electrode can include tire derived carbon particles obtained from a carbonaceous waste-tire source material containing carbon black. A conductive polymer coating is provided on the carbon particles of the second electrode forming second coated carbon particles. The first electrode and the second electrode can include a first current collector and a second current collector. The first electrode and the second electrode define a flow channel there between. A first opening can be provided for conducting saline solution into the flow channel. A second opening can be provided for conducting treated saline solution from the flow channel. The method can include electrically connecting the first electrode and the second electrode to a power source, whereby an electric field is created between the electrodes. Saline solution is caused to flow through the flow channel and the electric fields, wherein negative ions will be drawn to the first electrode and positive ions will be drawn to the second electrode.
The saline solution can have a salt concentration of from 1000 to 15000 PPM. The power source can be a standalone power source. The method can further include the step of performing reverse osmosis on the saline solution prior to the capacitive deionization to reduce the saline concentration to at least 1700 PPM. The saline solution can include at least one selected from the group consisting of NaCl, LiCl, KCl, MgCl2, CaCl2, and SrCl2.
There are shown in the drawings embodiments that are presently preferred it being understood that the invention is not limited to the arrangements and instrumentalities shown, wherein:
The invention utilizes tire-derived carbon (TC) as an electrode material for CDI such as by the process shown in
Chemical treatment of the carbon results in the formation of unique meso/microporous morphology enabling increased adsorption of salt ions during CDI. Additionally, coating TC with a conducting polymer, such as polyaniline (PANI), forms a carbon polymer composite (CPC) that further improves the material's electrochemical properties. The conducting polymer coating can completely cover all sides of the carbon particles. Due to its derivation from waste tires and inexpensive polymer, there is a reduction in cost compared to other highly engineered carbons and composites. Electrodes prepared from the tire-derived CPC achieved 14.2 mg/g of salt removal from 1500-1700 ppm KCl solutions in a batch process. Using a continuous flow-through process with ionic membrane assistance, 18.9 mg/g of salt was removed from 1500-1700 ppm KCl solutions. These salt adsorption values were comparable to other state-of-the-art CDI materials. In addition to strong adsorption capacities, the CPC electrodes display robust cycling performance, retaining 92.8% charging capacity after 300 cycles.
A capacitive deionization system according to the invention includes a first electrode comprising tire derived carbon particles obtained from a carbonaceous waste-tire source material containing carbon black. A conductive polymer coating is provided on the carbon particles of the first electrode forming first coated carbon particles. A second electrode also comprises tire derived carbon particles obtained from a carbonaceous waste-tire source material containing carbon black. A conductive polymer coating on the carbon particles of the second electrode forms second coated carbon particles. The first electrode includes a first current collector and the second electrode includes a second current collector. The first electrode and the second electrode define a flow channel there between. A first opening is provided for conducting saline solution into the flow channel. A second opening is provided for conducting treated saline solution from the flow channel. An electrical connection is provided between the first and second electrodes.
A schematic diagram of a capacitive deionization system 50 according to the invention is shown in
In one embodiment, the current collector comprises an open cell metal foam, and the coated carbon particles are adhered to an open cell metal foam. The electrode can include a binder for adhering the carbon particles together. The binder can be any suitable binder. The binder can be at least one selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF). Other binders are possible. In another embodiment, the electrodes are flow electrodes. Other electrode configurations are possible.
A power source can be connected to the electrical connection for creating a field between the first and second electrodes. The power source can be any suitable power source. The power source can be connected to an electrical power grid. The power source can be standalone such as a generator. The power source can be from a renewable energy source, such as wind, solar, hydroelectric, and the like.
The capacitive deionization system can include an anion exchange membrane adjacent to the conductive polymer coating of the first electrode, and a cation exchange membrane adjacent the conductive polymer coating of the second electrode. Ion exchange membranes improve efficiency by restricting passage to the ion of choice. The anion exchange membrane will select for anions, and the cation exchange membrane will select for cations. The membranes reduce ion crossover that occurs during multiple electrode cycles. Ion crossover can decrease the total salt uptake due to interference from ions of different charge on the surface of the electrodes. Ionic membranes selectively allow only positively or negatively charged ions to interact with the respective electrodes, reducing this interference. Without ion crossover there is an improvement in the formation of electrical double layers, improving salt uptake. By incorporating ionic membranes for membrane-assisted capacitive deionization, MCDI, the double layer and surface-reaction issues can be reduced. Any suitable ion exchange membrane can be utilized. A suitable anion exchange membrane will allow only anions to go through the membrane and similarly the cation exchange membrane will allow only cations to go through. Cost is important, and selectivity and conductivity are also important criteria for these membranes.
The conductive polymer coating can be any suitable conductive polymer. For example, the conducting polymer can be at least one selected from the group consisting of polyaniline, polythiophene, polypyrrole, poly(p-phenylene). The conducting polymer can have a conductivity of 0.1-10-4 S/cm.
The amount of conductive polymer coating can vary. The conductive polymer coating can be 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, to 20 wt. % based on the total weight of the carbon polymer composites, or within a range of any high and low value selected from these values. The thickness of the conductive polymer coating can vary. The conductive polymer coating can be 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, to 500 nm thick, or within a range of any high value and low value selected from these values.
The current collector can be of any suitable material and design. The metal foam comprises at least one of the selected from the group consisting of Ni, Pd, Pt, Ti, Zr, Hf, Cu, Ag, Au, and stainless steel. Metal foams are desirable because of the high conductivity and high surface area. The metal foam can have a porosity of 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, to 70%, or within a range of any high value and low value selected from these values. The metal foam can have a thickness of 10, 50, 100, 150, 200, 250, 300, 350, 400, 450, to 500 μm, or can have a thickness within a range of any high value and low value selected from these values. The metal foam can have a surface area of 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100 m2/g, or can have a surface area within a range of any high value and low value selected from these values.
The dimensions of the carbon particles can vary. The carbon particles can have a diameter of 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, to 200 μm, or can have a diameter within a range of any high value and low value selected from these values.
The carbon particles can have a porosity of 0.01, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10%. The carbon particles can have a porosity within a range of any high value and low value selected from these values. The carbon particles can have pores having a pore size of 0.02, 0.05, 0.1, 0.15, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, and 80 nm. The carbon particles can have pores having a pore size within a range of any high value and low value selected from these values. The surface area of the carbon particles can be 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, or 1600 m2/g. The surface area of the carbon particles can be within a range of any value or low value selected from these values.
The carbon particles can be obtained from waste tire that has been pyrolyzed to produce a layered carbon black containing product comprising a glassy carbon matrix phase having carbon black dispersed therein. The layered carbon black containing product can have an interlayer spacing of from 0.4 to 0.5 nm. The pyrolization temperature can be 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, or 1600° C. The pyrolization temperature can be within a range of any high value and low value that is selected from these values.
The electrode spacing, which can in part define the flow channel size can vary. The electrode spacing can be 2, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 mm. The electrode spacing can be within a range of any high value and low value that is selected from these values.
The capacitive deionization system can be constructed using flow electrodes. Any suitable flow electrodes can be used. A first plurality of the coated carbon particles can be suspended in a first solvent and flow through a first flow electrode. A second plurality of the coated carbon particles can be suspended in a second solvent and flow through a second flow electrode.
A method of making a system for capacitive deionization of a salt from a liquid, can include the steps of: providing tire derived carbon particles, and coating the carbon particles with a conductive polymer. The coated carbon particles are provided in an electrode, such as by mixing together with a binder and adhering the carbon particles to an open cell metal foam to form first and second electrodes. The first and second electrodes can be in spaced relation to form a saline flow channel. The flow channel can have a saline inlet and a saline outlet. The first and second electrodes are electrically connected with a power source to form a capacitor.
The capacitive deionization system and method of the invention can be used to desalinate different saline solutions. The salt can be at least one selected from the group consisting of NaCl, LiCl, KCl, MgCl2, CaCl2, and SrCl2. The saline solution can comprise mixtures of different salts.
The method can further include the step of providing an anion exchange membrane adjacent to the conductive polymer layer of the first electrode, and a cation exchange membrane adjacent the conductive polymer layer of the second electrode.
The carbon particles can be obtained from waste tire that has been sulfonated by contacting the carbonaceous source material with a sulfonation bath. Other waste rubber and rubber sources are possible. A sulfonation bath if provided can comprise a sulfonation agent such as chlorosulfonic acid in 1,2 dichloroethane solution. Other sulfonation agents are possible. The sulfonation bath can comprise between 0.1-65 wt. % SO3. The sulfonation bath can comprise 2-30 wt. % SO3. The sulfonation bath can have a temperature of between −20° C. to 200° C.
The carbon particles can be obtained from waste tire that has been pyrolyzed to produce a layered carbon black containing product comprising a glassy carbon matrix phase having carbon black dispersed therein. The pyrolysis step can be conducted at any suitable temperature. The pyrolysis step can be conducted at a temperature from 100-1490° C. The pyrolysis step can be conducted for any suitable duration, such as from 1 minute to 12 hours.
The first coated carbon particles are mixed with a binder and adhered to the first current collector. The first current collector can be an open cell metal foam. The second coated carbon particles are mixed with a binder and adhered to the second current collector. The second current collector can also be an open cell metal foam.
The flow capacitive deionization system can comprise a first flow electrode, and the second current collector can be a second flow electrode. The coated carbon particles are suspended in the saline solution and caused to flow through the flow electrodes. The coated carbon particles are removed and the deionized saline solution is passed for downstream utilization.
An example of a flow capacitor 120 is shown in
A method for the capacitive deionization of a saline solution includes the steps of: providing a capacitive deionization system comprising a first electrode comprising tire derived carbon particles obtained from a carbonaceous waste-tire source material containing carbon black, having a conductive polymer coating on the carbon particles of the first electrode. The carbon particles can be adhered to an open cell metal foam. A second electrode comprises tire derived carbon particles obtained from a carbonaceous waste-tire source material containing carbon black, having a conductive polymer coating on the carbon particles of the second electrode. The carbon particles can be adhered to an open cell metal foam. The first electrode and the second electrode define a flow channel there between. A first opening for conducting saline solution into the flow channel and a second opening for removing treated saline solution from the flow channel can be provided. The first electrode and the second electrode are electrically connected to a power source, whereby an electric field is created between the electrodes. The saline solution is caused to flow through the flow channel and the electric fields, wherein negative ions will be drawn to the first electrode and positive ions will be drawn to the second electrode. Multiple pairs of positive-negative electrodes can be used.
The saline solution can have a salt concentration of from 1000 to 15000 PPM. The saline solution can have a salt concentration of 1000, 1025, 1050, 1075, 1100, 1125, 1150, 1175, 1200, 1225, 1250, 1275, 1300, 1325, 1350, 1375, 1400, 1425, 1450, 1475, 1500, 1525, 1550, 1575, 1600, 1625, 1650, 1675, 1700, 1800, 1900, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 10500, 1100, 11500, 12000, 12500, 13000, 13500, 14000, 14500, and 15000 PPM. The salt concentration can be within a range of any high and low value selected from these values. The method can include the step of performing reverse osmosis on the saline solution prior to the capacitive deionization to reduce the saline concentration to at least 1700 PPM.
Crumb tire rubber was soaked in concentrated sulfuric acid and then washed. The TC was pyrolyzed under a nitrogen atmosphere from room temperature to 400° C. at 1° C./min, then from 400° C. to 1100° C. at 2° C./min, then allowed to cool back to room temperature. Following heat treatment, the carbon was etched in HF solution (Sigma Aldrich, ≥48%) to remove any impurities. The etched carbon was then ground together with KOH (Sigma Aldrich, ≥85%) in a 1:4 weight ratio. The subsequent mixture was pyrolyzed under a nitrogen atmosphere for 1 h at 800° C. at 10° C./min ramp rate to enhance porosity. Alkali chemical treatment is known to increase microporosity in carbon materials while still leaving behind existing mesoporous structures.
Electrodes were prepared. 60 μL of aniline (Sigma Aldrich, ≥99.5%) was dissolved in 10 mL of 1 M HCl (Macron, ACS reagent) solution. 60 mg of ammonium peroxydisulfate (Sigma Aldrich, ≤98%) was also dissolved in 10 mL of 1 M HCl. Carbon was soaked in 1 M HCl and sonicated for 30 min. Aniline and ammonium peroxydisulfate were then added to the TC mixture. The formation of green color solution indicated that polymerization was underway. The mixture was stirred overnight to ensure full polymerization and subsequent PANI coating onto the surface of the TC. The solid was washed with ethanol and water until it had a neutral pH. A slurry was prepared by combining the CPC with 15 wt. % of polytetrafluoroethylene (Aldrich, powder 35 μm particle size) (PTFE) binding material and ethanol. Nickel foam current collectors (15 cm×8 cm) (source: MTI Corp.; 99.99% pure; ≥95% porosity; 80-100 pores per inch; 1.6 mm thick) were coated with a slurry of active material, creating an electrode with dimensions of 7.5×4.4 cm2. The electrodes were pressed under 3 tons of pressure for 10 min, rinsed with deionized-distilled water to remove loose carbon, then dried. The two electrodes together contained 23.2 mg of active material (CPC) per cm2.
X-ray diffraction (XRD) patterns were collected on a PANalytical Empyrean with a Cu Kα radiation. All data were processed with HighScore Plus. Brunauer-Emmett-Teller (BET) surface areas, and pore-size distributions were determined from nitrogen adsorption isotherms at 77° K using Autosorb-1 from Quantachrome. The pore-size distributions and pore volumes were calculated from the DFT/Monte Carlo method using the QSDFT adsorption branch model. The thermogravimetric analysis (TGA) was completed using a TGA Q5000 (TA instrument, USA) under air-flow heating from room temperature to 1000° C. Fourier transform infrared (FT-IR) spectroscopy was performed using a Varian 640 spectrometer (Agilent Technologies, spectral resolution of 0.18 cm−1). All samples were mixed with KBr (Sigma Aldrich) and pressed into a pellet for analysis. The KBr pellets with sample present were prepared in a 1:200 ratio (sample:KBr), was ground with a mortar and pestle, and pressed into a transparent film for analysis. Raman spectra were collected on a WiTec alpha 300 M+. All Raman data presented were acquired by using a 633 nm wavelength laser; applying 1.2 mW. Scanning electron microscopy (SEM) images were collected on a Zeiss Merlin with a gun acceleration of 10.0 kV. Energy-dispersive X-ray spectroscopy (EDS) elemental mappings and spectra were collected with an acceleration voltage of 15.0 kV. Transmission electron microscopy (TEM) was performed on an aberration-corrected FEI Titan S 80-300 STEM/TEM microscope equipped with a Gatan OneView camera at an acceleration voltage of 300 kV. X-ray photoelectron spectroscopy (XPS) spectra were collected for each powder sample on a Thermo K-Alpha XPS system with a spot size of 400 μm at an energy resolution of 0.1 eV. AM data were analyzed using Thermo Avantage, a software package provided by ThermoScientific. The electrochemical analysis was performed using a VersaStat 3-200 potentiostat/galvanostat. A BioLogic VSP potentiostat was used for 3-electrode cyclic voltammetry measurements of the material vs Ag/AgCl as the reference and platinum mesh as the counter electrode. The specific capacitance of the composite material was calculated using Equation 1:
where C is capacitance, I is current density, v is the sweep rate, m is the mass of the active electrode material, and ΔV is the potential window. The equation is then doubled since there are two symmetric electrodes in the cell.
CDI tests in a batch CDI cell and flow cell such as that depicted in
where V is the volume of brine solution (in L), Co is the starting concentration (in mg/L), C is the concentration at peak capacitor charge (in mg/L), and m is the mass (g) of active electrode material. The use of ion exchange membranes in the flow cell follows, where the anion exchange membrane was AR103-QDP and the cation exchange membrane was CR61-CMP (GE Water, Inc., Watermelon, Pa.).
Degradation tests were conducted by cycling the electrodes using an Arbin Instruments BT-200 and MITS Pro software. Symmetric electrodes were set up in a Swagelok cell with 1 M KCl electrolyte. The test consisted of 300 cycles of charging the electrodes at a constant current density of 500 mA/g up to the voltage cap of 1.2 V and discharging at −500 mA/g until a voltage of 0 was reached. Electrode degradation was determined by comparing the initial and final charging capacities from the cycles and calculating the percent difference.
XRD analyses of TC and CPC in
Pore analysis (
FT-IR data in
X-ray photoelectron spectroscopy (XPS) was employed to analyze the surface composition of TC and CPC before and after PANI coating. The XPS spectra for the N 1s peak are shown in
The capacitance and electrochemical characteristics of the CPC electrodes were determined using CV, GCD, and EIS.
Capacity loss in CPC is much lower than that for other CDI materials.
Multiple CDI apparatus setups were used to establish the ion-uptake capacity of the CPC electrodes. A batch cell design was used for initial testing in stagnant brine. Monitoring brine loss and using equation 2, the SAC of CPC was found to be 14.2 mg/g. Flow-cell CDI has depressed uptake values due to several factors. Salt migration distance between the electrodes was increased, resulting in mass transport issues. Without the protection of a membrane, the electrodes suffered from additional surface reactions. During these tests, the electrode SAC was 12.4 mg/g. To mitigate the small amount of electrode degradation and improve salt uptake, ionic membranes were used. Adding the membranes reduces ion crossover that occurs during multiple electrode cycles. Ion crossover can decrease the total salt uptake due to interference from ions of different charge on the surface of the electrodes. Ionic membranes selectively allow only positively or negatively charged ions to interact with the respective electrodes, reducing this interference. Without ion crossover there is an improvement in the formation of electrical double layers, improving salt uptake. By incorporating ionic membranes for membrane-assisted capacitive deionization, MCDI, the double layer and surface-reaction issues were reduced. Incorporating ionic membranes led to an elevated salt uptake of 18.9 mg/g, much improved from the initial flow-cell and batch scale tests. Following initial tests with KCl other adsorption tests with mono and divalent ions were also investigated.
A comparison of the CDI electrode material uptake capacities in Table 1 showcases that CPCs have competitive salt adsorption values for NaCl.
Compared to other carbon-black materials, the invention provides among the best data in terms of desalination ability. Other composites and engineered carbons display similar or higher salt-uptake but fall short in terms of cycling longevity or high material and synthesis costs. Sourcing of carbon from waste tires is a cheaper alternative, compared to other existing electrode materials. Robust cycling capacities of the carbon materials with uptake capacity and increased cycle lifetimes greatly improves the material cost aspects for this electrode material. Additionally, the electrode material presented has the benefit of sourcing from a significant waste stream, used tires, improving environmental impact.
This invention can be embodied in other forms without departing from the spirit or essential attributes thereof. Reference should be made to the following claims to determine the scope of the invention.
This application claims priority to U.S. Provisional Patent Application No. 62/621,112 filed on Jan. 24, 2018, and claims priority to U.S. Provisional Patent Application No. 62/713,120 filed on Aug. 1, 2018, both entitled “Novel Carbon Electrodes Based Capacitive Deionization for the Desalination of Water”, the entire disclosures of which are incorporated herein by reference.
This invention was made with government support under Contract No. DE-AC05-00OR22725 awarded by the U.S. Department of Energy. The government has certain rights in this invention.
Number | Date | Country | |
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62713120 | Aug 2018 | US | |
62621112 | Jan 2018 | US |