VOLTAGE-CONTROLLED ANION EXCHANGE MEMBRANE ENABLING SELECTIVE ION AFFINITIES FOR WATER DESALINATION AND DEVICE CONTAINING THE SAME
20200131058 ยท 2020-04-30
Inventors
- Soo Kim (Cambridge, MA, US)
- Jonathan Mailoa (Cambridge, MA, US)
- Mordechai Kornbluth (Brighton, MA, US)
- Georgy SAMSONIDZE (San Francisco, CA, US)
- Michael Metzger (Sunnyvale, CA, US)
- Saravannan Kuppan (Sunnyvale, CA, US)
- Sondra HELLSTROM (East Palo Alto, CA, US)
- Boris Kozinsky (Waban, MA, US)
- Nathan Craig (Burlingame, CA, US)
Cpc classification
B01D69/02
PERFORMING OPERATIONS; TRANSPORTING
C08J2349/00
CHEMISTRY; METALLURGY
C08J2325/18
CHEMISTRY; METALLURGY
C08J2433/12
CHEMISTRY; METALLURGY
C02F2201/46115
CHEMISTRY; METALLURGY
C08J2365/00
CHEMISTRY; METALLURGY
B01D2325/16
PERFORMING OPERATIONS; TRANSPORTING
B01D61/428
PERFORMING OPERATIONS; TRANSPORTING
B01D61/146
PERFORMING OPERATIONS; TRANSPORTING
B01D71/0211
PERFORMING OPERATIONS; TRANSPORTING
B01D61/42
PERFORMING OPERATIONS; TRANSPORTING
C08J2429/04
CHEMISTRY; METALLURGY
International classification
Abstract
A desalination device includes a container, first and second electrodes, an anion exchange membrane (AEM), and a power source. The container contains saline water that has an elevated concentration of dissolved salts. The AEM separates the container into first and second compartments into which the first and second electrodes, respectively, are arranged. The AEM has a continuous porous structure and a plurality of negatively-charged oxygen functional groups coupled to the porous structure. The power source is configured to selectively apply a voltage to one of the first and second electrodes. The AEM has a selective permeability when the voltage is applied such that cations in the saline water solution have a first diffusion rate d.sub.1 therethrough and anions in the saline water solution have a second diffusion rate d.sub.2 therethrough. The first diffusion rate d.sub.1 is less than the second diffusion rate d.sub.2 and greater than or equal to zero.
Claims
1. An anion exchange membrane for a desalination device, comprising: a membrane support having a porous first side, a porous second side, and a continuous porous structure extending from the first side to the second side, the continuous porous structure including graphene oxide (GO) sheets and a plurality of negatively-charged oxygen functional groups coupled to the GO sheets.
2. The anion exchange membrane of claim 1, wherein the plurality of negatively-charged oxygen functional groups includes one or more of hydroxyl groups and carboxylic groups.
3. The anion exchange membrane of claim 1, wherein the plurality of negatively-charged oxygen functional groups includes one or more of epoxy groups and carbonyl groups.
4. The anion exchange membrane of claim 1, wherein the continuous porous structure includes a mixture of the GO sheets and at least one further polymer that is electronically conductive.
5. The anion exchange membrane of claim 4, wherein the at least one further polymer includes one or more of poly(pyrrole)s (PPY), polyanilines (PANI), poly(thiophene)s (PT), poly(3,4-ethylenedioxythiophene) (PEDOT), poly(p-phenylene sulfide) (PPS), poly(acetylene)s (PAC), and poly(p-phenylene vinylene) (PPV).
6. The anion exchange membrane of claim 1, wherein the continuous porous structure includes a mixture of the GO sheets and at least one further polymer that is ionically conductive and not electronically conductive.
7. The anion exchange membrane of claim 6, wherein the at least one further polymer includes one or more of cross-linked poly-vinyl alcohol (PVA), cross-linked polymethylmethacarylate (PMMA), and polyethylene oxide (PEO).
8. The anion exchange membrane of claim 6, wherein the continuous porous structure includes one or more of graphite, hard carbon, soft carbon, and carbon black.
9. A desalination device, comprising: a container configured to contain a saline water solution having an elevated concentration of dissolved salts; a first electrode and a second electrode arranged in a first compartment and a second compartment, respectively, of the container, the first and second electrodes configured to be arranged in fluid communication with the saline water solution; an anion exchange membrane (AEM) separating the first and second compartments, the AEM having a porous membrane structure and a plurality of negatively-charged oxygen functional groups coupled to the porous membrane structure; and a power source configured to selectively apply a voltage to one of the first and second electrodes, the AEM having a selective permeability when the voltage is applied such that cations in the saline water solution have a first diffusion rate d.sub.1 therethrough and anions in the saline water solution have a second diffusion rate d.sub.2 therethrough where 0d.sub.1<d.sub.2.
10. The desalination device of claim 9, wherein the porous membrane structure includes graphene oxide sheets.
11. The desalination device of claim 10, wherein the plurality of negatively-charged oxygen functional groups includes one or more of hydroxyl groups and carboxylic groups.
12. The desalination device of claim 10, wherein the plurality of negatively-charged oxygen functional groups includes one or more of epoxy groups and carbonyl groups.
13. The desalination device of claim 9, wherein the power source is configured to apply a membrane voltage to the AEM via an external circuit, the membrane voltage configured to decrease the first diffusion rate d.sub.1 of the cations through the AEM and increase the second diffusion rate d.sub.2 of the anions through the AEM.
14. The desalination device of claim 13, wherein the membrane voltage is applied in a range from 0 to 0.5 V.
15. The desalination device of claim 9, wherein a (de-)sorption voltage of the cations into and out of the AEM is in a range from 1.0 to 1.5 V relative to a standard hydrogen electrode.
16. The desalination device of claim 9, wherein the porous membrane structure includes mono- and few-layer graphene, the layers having a range from 1 to 8 layers.
17. The desalination device of claim 9, wherein the first and second electrodes are symmetric electrodes that contain an identical intercalation material.
18. The desalination device of claim 17, wherein the intercalation material is one of doped or un-doped cubic spinel MnO.sub.2, tunnel-structured orthorhombic Na.sub.4Mn.sub.9O.sub.18, or NaM.sub.2(PO.sub.4).sub.3 where M=Ti, Mn, Fe, Ni, Cu, or combinations thereof.
19. The desalination device of claim 9, wherein the first and second electrodes are asymmetric electrodes each containing an electrode material comprised of a metal oxide, a concentration of alkali metal within the metal oxide configured to be different between the electrode materials.
20. A method for desalinating water, comprising: filling first and second compartments of a container with a saline water solution having an elevated concentration of dissolved salts, the container including first and second electrodes arranged in the first and second compartments, respectively, and an anion exchange membrane (AEM) separating the first and second compartments; operating the first and second electrodes in a forward direction or a reverse direction to release cations into one of the first and second compartments and to remove cations from the other of the first and second compartments; and applying a membrane voltage to the AEM while operating the first and second electrodes, the membrane voltage decreasing a first diffusion rate of cations through the AEM and increasing a second diffusion rate of anions through the AEM relative to the first and second diffusion rates, respectively, when the membrane voltage is not applied to the AEM.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0013]
[0014]
[0015]
[0016]
[0017]
[0018]
DETAILED DESCRIPTION
[0019] For the purpose of promoting an understanding of the principles of the disclosure, reference will now be made to the embodiments illustrated in the drawings and described in the following written specification. It is understood that no limitation to the scope of the disclosure is thereby intended. It is further understood that the disclosure includes any alterations and modifications to the illustrated embodiments and includes further applications of the principles of the disclosure as would normally occur to one skilled in the art to which this disclosure pertains.
[0020]
[0021] The container can be made from different materials capable of withstanding corrosion, temperature fluctuations, changing pH, varying pressure, and be resistant to other chemical, mechanical, and/or physical conditions. The container can be made from glass, plastic, composite, metal, ceramic, or a combination of materials. The container can feature one or more protective coatings. The container can be made from a material which minimizes occurrence of water contamination. The container can be made from material(s) which are nontoxic and comply with drinking water standards.
[0022] The device 100 further includes a first electrode 104, a second electrode 108 spaced from the first electrode 104, and an anion exchange membrane (AEM) 112 disposed between the first electrode 104 and the second electrode 108. The AEM 112 separates the container 102 into a first compartment 113 with the first electrode 104 and a second compartment 115 with the second electrode 108. The first and second electrodes 104, 108 are arranged within the container 102 to be in fluid communication with the saline water solution present in the first and second compartments 113, 115. The first and second electrodes 104, 108 are at least partially submerged in the saline water solution. The first and second 104, 108 electrodes in some embodiments can be fully submerged in the saline water solution. The first and second electrodes 104, 108 can be placed on the opposite sides of the container 102 separated by a distance as shown in the figures. The distance can be 1 mm or more, 1 cm or more, 10 cm or more, 20 cm or more, 30 cm or more, depending on the dimensions of the container 102 and the first and second electrodes 104, 108. Other distances between the first and second electrodes are contemplated as well.
[0023] The first and second electrodes 104, 108 in the embodiment shown each include an intercalation host material 116 that reversibly removes and releases first target ions 124 in different operating states of the device 100. Intercalation refers to reversible inclusion of one or more ions into materials with layered structures. The spaces between layers can serve as a temporary storage for one or more types of ions. The first target ions 124 in the illustrated embodiment include the cation Na.sup.+ though in other embodiments the first target ions 124 can include the cations K.sup.+, Mg.sup.2+, Ca.sup.2+, Pb.sup.2+, and others. The intercalation host material 116 of the first and second electrodes 104, 108 in some embodiments includes similar alkali metal oxides or phosphates, such as Na.sub.xMnO.sub.2 and Na.sub.xMPO.sub.4, with variations in the alkali metal concentration, for example, via composition change of Na by varying x. In other embodiments, carbon-based and other oxide-based electrode materials can be used for fabricating the electrode materials in the device 100 via additional carbon and PVDF binders.
[0024] In further embodiments, the intercalation host material 116 of the first and second electrodes 104, 108 is at least one of doped or un-doped cubic spinel MnO.sub.2, Na.sub.4Mn.sub.9O.sub.18 (or equivalently, Na.sub.0.44MnO.sub.2) tunnel structured orthorhombic materials, and NaM.sub.2(PO.sub.4).sub.3 (where M=Ti, Mn, Fe, Ni, Cu, or combinations thereof), where the exact composition of Na can be controlled by thoroughly mixing different starting amount of Na.sub.2CO.sub.3 with metal oxide precursors and then followed by the heat treatment at high temperature (e.g., 800 C.). In these further embodiments, it is permissible to partially substitute Na (if any) with Li, Mg, Ca, and/or K.
[0025] The AEM 112 in the embodiment shown includes a membrane material 120 that has been identified using detailed first-principles density functional theory (DFT) calculations. The membrane material 120 of the AEM 112 in some embodiments includes mono- and few-layer graphene and graphene oxide (GO) sheets with at least one chemically-added functional group that is configured to encapsulate and trap the first target ions 124 in at least one operating state of the device 100. As used herein, mono-layer means the graphene and the GO can each be configured with a single layer, and few-layer means the graphene and the GO can each be configured with up to 8 layers. The chemical functional group is a negatively-charged oxygen-containing functional group that enables a slow diffusion of the first target ions 124 dissolved in the water supply (e.g., seawater or industrial water). The first target ions 124 in this embodiment include, but are not limited to, sodium, magnesium, calcium, potassium, strontium, silicon, carbon, and aluminum ions. The chemical functional group in the AEM 112 also allows a very fast diffusion of second target ions 128 between the electrodes 104, 108 due to the repulsive force between the negatively-charged AEM 112 and the second target ions 128 present in the water supply. The second target ions 128 in this embodiment include, but are not limited to, chloride, sulfur, bromine, nitrate, and ammonia.
[0026] The membrane material 120 of the AEM 112 in some embodiments includes a carbon- or polymer-based porous membrane structure and one or more of hydroxyl (OH) oxygen functional groups and carboxylic (COOH) oxygen functional groups coupled to the structure so as to enable selective cation (de-)adsorption processes in the AEM. In other embodiments, the chemically-added oxygen functional groups can include carbonyl (O) oxygen functional groups, epoxy (O) groups, or combinations thereof. In one example, hydroxyl (OH) rich GO samples are prepared by Hummer's method, which is described in Carbon, 2013, 64, 225 & J. Am. Chem. Soc., 1958, 6, 1339. First, graphite plate and NaNO.sub.3 can be dispersed in H.sub.2SO.sub.4 at low temperature (e.g., 5 C.) and KMnO.sub.4 can be added to the suspension. After continued stirring and dilution with water, the mixture can be heated up to approximately 100 C. and treated with H.sub.2O.sub.2. The resulting powder can be rinsed with HCl and deionized water. Since the entrapment of the first target ions 124 depends on the number of oxygen functional groups present in the GO, control of ion transports can be tuned via the processing method. In particular, further heat treatment can control the functional group density, followed by filtering, washing, and drying under vacuum.
[0027] The AEM 112 in some embodiments further includes a mixture of the membrane material 120 and other electronically conductive polymers, such as polyethylene oxide (PEO), poly(pyrrole)s (PPY), polyanilines (PANI), poly(thiophene)s (PT), poly(3,4-ethylenedioxythiophene) (PEDOT), poly(p-phenylene sulfide) (PPS), poly(acetylene)s (PAC), and poly(p-phenylene vinylene) (PPV). The AEM 112 in other embodiments includes the membrane material 120 and other polymers that are not electronically conductive, but are ionically conductive, such as cross-linked poly-vinyl alcohol (PVA), cross-linked polymethylmethacarylate (PMMA), and polyphenylene vinylene (PPV). Additional electronically conductive material, such as graphite, hard carbon, soft carbon, carbon black, and others, can be added as needed.
[0028]
[0029] Further calculations estimate the adsorption voltage of first target ions 124 other than Na.sup.+ ions on some of the GO functional groups of the membrane material 120 disclosed herein. For example, Table 1 identifies the calculated voltage of K, Mg, and Ca adsorption on hydroxyl and carboxylic GO functional groups using first-principles density functional theory (DFT) calculations.
TABLE-US-00001 TABLE 1 Voltage vs. SHE K Mg Ca Hydroxyl (OH) 0.908 0.915 1.119 Carboxylic (COOH) 0.865 0.897 0.832
[0030] The results disclosed herein suggests that cations other than Na, Mg, K, and Ca ions can also be attracted by the GO-based AEM 112 within (or slightly outside of) the water stability window.
[0031]
[0032] Further calculations also estimate the DFT binding energy of water on the GO functional groups of the membrane material 120 disclosed herein. For example, Table 2 identifies the binding energy of H.sub.2O in eV/H.sub.2O for the different GO functional groups.
TABLE-US-00002 TABLE 2 GO functional groups Binding energy of H.sub.2O [eV/H.sub.2O] Epoxy (O) +1.191 Carbonyl (O) +1.184 Carboxylic (COOH) +1.273 Hydroxyl (OH) +1.285
[0033] Based on these calculations, at least approximately 1 eV is required for H.sub.2O to bind to the GO functional groups. Therefore, the use of the GO-based AEM 112 disclosed herein will not impact the H.sub.2O transport through the AEM. In other words, H.sub.2O molecules 132 will pass through the AEM 112 as illustrated in
[0034] In view of
[0035] With reference again to
[0036]
[0037] The basic operating principle of the device 100 of
[0038] The device 100 in the embodiment shown includes symmetric electrodes 104, 108 to be used with the AEM 112 disclosed herein. The symmetric electrodes 104, 108 allow for a continuous collection of clean water in successive cycles for water purification. The device in other embodiments includes the AEM 112 disclosed herein used in connection with asymmetric electrodes (not shown) where the concentration of alkali metal within the metal oxide can be different between the electrodes. In further embodiments, the device includes two different electrode materials incorporated as an anode and a cathode in each of the two compartments. One compartment is connected to a reservoir to collect and/or precipitate salt, and the other compartment is connected to the clean water stream and alternately output purified water. The device in these further embodiments may require an extra cycle to regenerate the electrodes.
[0039]
[0040] When the first and second electrodes 104, 108 are operated in the reverse direction, the voltage V.sub.IN is applied to the second electrode 108 and the first electrode 104 is connected to ground. The second electrode 104 is configured to deintercalate cations 124 from the second electrode 104 into the saline solution present in second compartment 115 when operated in the reverse direction. The first electrode 104 is configured to intercalate cations 124 from the saline solution present in the first compartment 113 into the first electrode 104 when operated in the reverse direction. While the first and second electrodes 104, 108 are operated in the forward or reverse directions (block 604), a membrane voltage V.sub.M is applied to the AEM 112 via an external circuit (block 606). While the membrane voltage V.sub.M is applied to the AEM (block 606), a first diffusion rate d.sub.1 of the cations 124 through the AEM 112 decreases and a second diffusion rate d.sub.2 of anions 128 through the AEM increases relative to the first and second diffusion rates, respectively, when the membrane voltage V.sub.M is not applied to the AEM.
[0041] The method 600 generates a brine water solution in the first compartment 113 and a fresh water solution in the second compartment 115 when blocks 604 and 606 are concurrently executed and the first and second electrodes 104, 108 are operated in the forward direction. The brine and fresh water solution are generated in the second compartment 115 and the first compartment 113, respectively, when blocks 604 and 606 are concurrently executed and the first and second electrodes 104, 108 are operated in the reverse direction. The brine water solution has a higher concentration of dissolved salts 124, 128 than the concentration of dissolved salts in the saline water solution originally filled in the first compartment 113. The fresh water solution has a lower concentration of dissolved salts 124, 128 than the concentration of dissolved salts in the saline water solution originally filled in the second compartment 115.
[0042] The method 600 further includes separately extracting the brine water solution and the fresh water solution from the first and second compartments 113, 115 (block 608). The extraction of the brine and fresh water solutions from the container 102 can occur when a quantity of the cations 124 inserted into the first or second electrodes 104, 108 approaches or meets a capacity of the electrode. If another purification cycle is to be carried out (block 610), the method 600 returns to block 602 in which the first and second compartments 113, 115 of the container 102 are filled with the saline water solution. If another purification cycle is not to be carried out (block 610), the method 600 ends (block 612).
[0043] The method 600 in some embodiments can include a cleaning operation after the brine and fresh water solutions are extracted (block 608) and before the first and second compartments 113, 115 are refilled to prepare for a subsequent purification cycle (block 602). The cleaning operating cleans the first and second electrodes 104, 108 and the AEM 112 by immersing the electrodes and the AEM in clean water, acid (i.e., HCl), or base (i.e., NaOH). The cleaning operating can occur at regular intervals or as needed. After the cleaning operation is completed, the method 600 can end (block 612) or it can proceed to carry out another purification cycle according to blocks 602-608.
[0044] While the disclosure has been illustrated and described in detail in the drawings and foregoing description, the same should be considered as illustrative and not restrictive in character. It is understood that only the preferred embodiments have been presented and that all changes, modifications and further applications that come within the spirit of the disclosure are desired to be protected.