Anion insertion electrode materials for desalination water cleaning device
11834354 · 2023-12-05
Assignee
Inventors
- Soo Kim (Cambridge, MA, US)
- Mordechai Kornbluth (Brighton, MA, US)
- Jonathan Mailoa (Cambridge, MA, US)
- Georgy SAMSONIDZE (San Francisco, CA, US)
- Michael Metzger (Sunnyvale, CA, US)
- Saravanan Kuppan (Sunnyvale, CA, US)
- Sondra HELLSTROM (East Palo Alto, CA, US)
- Boris Kozinsky (Waban, MA, US)
- Nathan Craig (Burlingame, CA, US)
Cpc classification
C01P2002/08
CHEMISTRY; METALLURGY
International classification
C25B11/00
CHEMISTRY; METALLURGY
Abstract
A desalination battery includes a first electrode, a second electrode, an intercalation compound contained in the first electrode, a container configured to contain a saline water solution, and a power source. The intercalation compound includes at least one of a metal oxide, a metalloid oxide, a metal oxychloride, a metalloid oxychloride, and a hydrate thereof with each having a ternary or higher order. The first and second electrodes are configured to be arranged in fluid communication with the saline water solution. The power source is configured to supply electric current to the first and second electrodes in different operating states to induce a reversible intercalation reaction within the intercalation compound. The intercalation compound reversibly stores and releases target anions from the saline water solution to generate a fresh water solution in one operating state and a wastewater solution in another operating state.
Claims
1. An intercalation electrode for a desalination battery, comprising: an intercalation compound that contains at least one of a metal oxide, a metalloid oxide, a metal oxychloride, a metalloid oxychloride, and a hydrate thereof with each having a ternary or higher order, the intercalation compound configured to be at least partially immersed in a saline water solution and undergo a reversible intercalation reaction in which (i) anions from the saline water solution reversibly insert within the intercalation compound in a first condition of the electrode and (ii) the anions within the intercalation compound de-insert therefrom into the saline water solution in a second condition of the electrode, wherein the intercalation compound has the chemical formula MA.sub.xO.sub.y.Math.zH.sub.2O, where M=Al, Ca, Co, Cr, Cu, Fe, Mg, Mn, Mo, Na, Nb, Ni, Si, Ti, V, W, Zr, or a combination thereof, A=Br, Cl, F, I, N, P, or a combination thereof, and 0<x, y, z<7.
2. The intercalation electrode of claim 1, wherein a voltage in which the anions insert into and de-insert from the intercalation compound in the first and second conditions, respectively, is within a voltage range of −0.5 to 1.5 V.
3. The intercalation electrode of claim 2, wherein the voltage exceeds the voltage range by up to 0.4 V to one or more of (i) overcome kinetically-limited ion diffusions and (ii) account for overpotential caused by a passivation layer formed on the intercalation electrode.
4. The intercalation electrode of claim 1, wherein a voltage in which the anions insert into and de-insert from the intercalation compound in the first and second conditions, respectively, is lower than both a metal dissolution potential and an oxygen gas evolution potential.
5. The intercalation electrode of claim 1, wherein the intercalation compound has (i) a vacancy formation energy of Cl.sup.− that is between 0.8 and 2.8 eV per Cl site and (ii) respective vacancy formation energies of one or more of metal, oxygen, and hydrogen that are higher than the vacancy formation energy of Cl.sup.−.
6. The intercalation electrode of claim 1, further comprising at least one conductivity agent and at least one polymeric binder blended with the intercalation compound, the intercalation compound, the conductivity agent, and the polymeric binder representing about 70 to 90 wt. %, about 1 to 20 wt. %, and about 1 to 20 wt. %, respectively, based on the total weight of the electrode.
7. An intercalation electrode for a desalination battery, comprising: an intercalation compound that contains at least one of a metal oxide, a metalloid oxide, a metal oxychloride, a metalloid oxychloride, and a hydrate thereof with each having a ternary or higher order, the intercalation compound configured to be at least partially immersed in a saline water solution and undergo a reversible intercalation reaction in which (i) anions from the saline water solution reversibly insert within the intercalation compound in a first condition of the electrode and (ii) the anions within the intercalation compound de-insert therefrom into the saline water solution in a second condition of the electrode, wherein the intercalation compound has at least one of the chemical formulas Mg(ClO.sub.2).sub.2.Math.6H.sub.2O, MgCl.sub.2O, and NaClO.sub.2.Math.3H.sub.2O.
8. An intercalation electrode for a desalination battery, comprising: an intercalation compound that contains at least one of a metal oxide, a metalloid oxide, a metal oxychloride, a metalloid oxychloride, and a hydrate thereof with each having a ternary or higher order, the intercalation compound configured to be at least partially immersed in a saline water solution and undergo a reversible intercalation reaction in which (i) anions from the saline water solution reversibly insert within the intercalation compound in a first condition of the electrode and (ii) the anions within the intercalation compound de-insert therefrom into the saline water solution in a second condition of the electrode, wherein the intercalation compound has at least one of the chemical formulas AlH.sub.12(ClO.sub.2).sub.3, FeH.sub.8(ClO.sub.2).sub.2, MnH.sub.8(ClO.sub.2).sub.2, and NiH.sub.8(ClO.sub.2).sub.2.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
(8) 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.
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(10) The device 100 shown in
(11) The device 100 further includes a power source, current source, or voltage source 122 configured to supply electric current to the first and second electrodes 104, 106. The electric current is applied to remove the target ions from the water supply. The electric current can be constant current until reaching a predetermined voltage cutoff or positive voltage can be applied to the device 100.
(12) The device 100 in some embodiments includes a container 102 configured to retain a liquid solution such as a water solution 120. The container 102 can be a container, compartment, housing, vessel, can, canister, tank, or the like of any shape, size, or configuration capable of obtaining, retaining, holding, and/or releasing a liquid solution such as saline water, brackish water, sea water, ocean water, fresh water, sweet water, drinking water, desalinated water, contaminated water, industrial water, etc. The container is spacious enough to house a sufficient amount of a water solution undergoing water desalination; dimensions thus differ based on a specific application. The container can be large enough to serve industrial applications. 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.
(13) 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.
(14) The first and second electrodes 104, 106 are arranged within the device 100 to be in fluid communication with the water solution 120 present in the container 102. The first and second electrodes 104, 106 are at least partially submerged in the water solution 120. The first and second electrodes 104, 106 in some embodiments can be fully submerged in the water solution 120. The first and second electrodes 104, 106 can be placed on the opposite sides of the container 102 as shown in the figures, placed centrally in the container 102, or located on the same side of the container 102. The first and second electrodes 104, 106 can be located next to each other or be separated by a distance. 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, 106. Other distances between the first and second electrodes are contemplated as well.
(15) The first and second electrodes 104, 106 with the first and second intercalation materials 108, 110 function as intercalation hosts. 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 intercalation host material 108 in at least the first electrode 104 reversibly stores and releases anions from the saline water solution having a first concentration c.sub.1 of dissolved salts to generate a fresh water solution having a second concentration c.sub.2 of dissolved salts and a wastewater solution having a third concentration c.sub.3 of dissolved salts within the container such that c.sub.3>c.sub.1>c.sub.2.
(16) A comprehensive computational design approach with reaction models determining thermodynamic and electrochemical stability of oxygen- and chlorine-bearing compounds was developed to identify the anion intercalation host material 108 disclosed herein.
(17) The compounds listed in
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(19) In view of the computational materials screening criteria described above, the anion intercalation host material 108 disclosed herein in some embodiments includes, but is not limited to, at least one of: Mg(ClO.sub.2).sub.2.Math.6H.sub.2O, MgCl.sub.2O, and NaClO.sub.2.Math.3H.sub.2O.
(20) The first electrode 104 with the anion intercalation host material 108 disclosed herein has a (de-)insertion voltage for single anion species (i.e., Cl.sup.−), anion complexes, and metal-containing anions that is lower than the metal dissolution potential, lower than the oxygen gas evolution potential, and within a (de-)insertion voltage range of −0.5 to 1.5 V vs. SHE, which is slightly larger than the water stability window, so as to avoid water electrolysis. In some embodiments, the first electrode 104 with the anion intercalation host material 108 disclosed herein has a thermodynamic Cl vacancy formation energy that is higher than 0.8 eV per Cl site and lower than 2.8 eV per Cl site. In these embodiments, the anion intercalation host material 108 has metal, oxygen, and hydrogen thermodynamic vacancy formation energies that are higher than the Cl vacancy formation energy. In some embodiments, the (de-)insertion voltage for Cl.sup.− and related anion complexes exceeds outside of the (de-)insertion voltage range to overcome kinetically-limited ion diffusions and/or account for overpotential caused by the possible formation of passivation (or protective) layer.
(21) The anion intercalation host material 108 disclosed herein in some embodiments includes, but is not limited to, at least one of the following alkali-metal-based and transition-metal-based oxychlorides and their hydrates: Ca.sub.4Cl.sub.6O, CaHClO, NaH.sub.4ClO.sub.2, AlClO, Si.sub.3(Cl.sub.4O).sub.2, SiCl.sub.2O, Si.sub.6Cl.sub.10O.sub.7, SiCl.sub.2O, Si.sub.2Cl.sub.2O.sub.3, Ti(ClO.sub.4).sub.4, TiClO, Mn.sub.8Cl.sub.3O.sub.10, MnH.sub.4(ClO).sub.2, FeClO, Ni(ClO.sub.4).sub.2, NiH.sub.16(ClO.sub.8).sub.2, NiH.sub.12(ClO.sub.3).sub.2, Cu.sub.2Cl.sub.2O, and CuH.sub.8(ClO.sub.5).sub.2.
(22) The anion intercalation host material 108 disclosed herein in some embodiments includes M(ClO.sub.2).sub.x, where M can be Mg, Ca, or Na, or can be Al, Si, Fe, Co, Ni, Cr, V, Ti, Cu, Zr, Nb, W, Mo, Mn, or combinations thereof.
(23) The anion intercalation host material 108 disclosed herein in some embodiments includes MA.sub.xO.sub.y.Math.zH.sub.2O, where M can be Mg, Ca, Na, Al, Si, Fe, Co, Ni, Cr, V, Ti, Cu, Zr, Nb, W, Mo, Mn, or combinations thereof, A may be Cl, F, Br, I, N, or P, or combinations thereof, and 0<x, y, z<7.
(24) The first electrode 104 can include the anion intercalation host material 108 disclosed herein blended with additives for stability, conductivity, and/or physical properties. The second electrode 106 can also include additives for stability, conductivity, and/or other physical properties in addition to the active material 110.
(25) A non-limiting example of a conductivity agent can include carbon black, conductive carbon black, amorphous carbon, carbon fibers, quaternary ammonium salt(s), alkyl sulfonate(s), halogen-free cationic compound(s), the like, or a combination thereof.
(26) A non-limiting example of a polymeric binder can be polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), poly(methyl methacrylate) (PMMA), polyethylene glycol (PEO), polyimide, polydopamine, poly(ethylene glycol) diacrylate, polymethylpentene, nylon, metal-aramid, polyether imide, copolyester, polyetherketone, carboxymethyl cellulose, styrene-butadiene rubber (SBR), copolymers and blends such as poly(vinylidenefluoride-hexafluoropropylene) (PVdF-HFP), poly(vinylidenefluoride-chlrotrifluoroethylene) (PVdF-CTFE), poly(methyl methacrylate-vinyl acetate) (PMMA-VAc), poly(ethylene glycol) diacrylate (PEGDA), poly(methyl methacrylate-acrylonitrile-vinyl acetate) (PMMA-AN-VAc), poly(methyl methacrylate-co-butyl acrylate) (PMMA-co-BA), poly(3,4-ethylenedioxythiophene) polystyrene sulfonate-co-polyethylene glycol (PEDOT-co-PEG), the like, or a combination thereof. In one embodiment the first electrode 104 includes about 70 to 95 wt. % intercalation host material 108 mixed as a slurry in a solvent (e.g., NMP) with about 1 to 20 wt. % carbon black and about 1 to 20 wt. % polymer binder based on the total weight of the electrode.
(27) With reference again to
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(29) A comparison of
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(31) The battery 100 can be a closed or open system. The battery 100 can operate in cycles (intercalation and de-intercalation), where the water solution 120 flows continuously. Under the continuous flow, the desalinated water solution exiting the container 102 can be stored in a reservoir (not shown). Alternatively, the battery 100 can operate as a batch desalination battery, where a limited amount of the water solution 120 is supplied and held in the container 102 to be cleaned in a smaller scale operation.
(32) The anion intercalation host material 108 disclosed herein has many advantages. A simple metal oxide, metal oxychlorides, and/or their hydrates and/or their combination can be used to selectively remove the anion such as Cl.sup.− from aqueous streams (hardness removal from drinking water is also an application). The anion intercalation host material 108 disclosed herein can reversibly remove and release the anions present in the seawater, brackish water and industrial water without severe structural and mechanical damage on the bulk electrode materials.
(33) During the electrochemical charge/discharge processes, the (de-)insertion of anions (e.g., Cl.sup.−, ClO.sub.2.sup.−, ClO.sub.4−, etc.) is thermodynamically favored (reversibly) over decomposing the electrodes host by extracting other elements within the compounds (e.g., metal, oxygen, hydrogen, etc.), which has been verified by thermodynamic-based first-principles DFT calculations.
(34) The developed computational methods have identified the general design principles (i.e., structural feature necessary) for compounds that can lead to reversible anion (de-)intercalation and these principles can be extended to other metal oxide, metal oxychlorides, and their hydrates.
(35) The anion intercalation host material 108 disclosed herein can host anion species by: (1) acting as a host for single element anion (e.g., Cl—, F—, etc.), (2) hosting anion complexes such as ClO.sub.2.sup.−, SO.sub.4.sup.2−, etc., and (3) (de-)inserting metal anion clusters, for example, AlCl.sub.4.sup.−, MgCl.sub.3.sup.−, etc.
(36) The ionicity and solvation to water can be further modified and tuned by full- and/or partial-substitution of metal and metalloid M that has a higher electronegativity value in MO.sub.xCl.sub.y.Math.zH.sub.2O systems (i.e., making the compounds less ionic and more covalent).
(37) The anion intercalation host material 108 disclosed herein (which includes ternary, quaternary, and higher order metal oxides, metalloid oxides, metal(-loid) oxychlorides, and the hydrate forms) can reversibly uptake anions, including the single anion species such as F.sup.−, Cl.sup.−, Br.sup.−, I.sup.−, S.sup.2−, anion complexes including but not limited to ClO.sub.4.sup.−, ClO.sub.3.sup.−, ClO.sub.2.sup.−, BrO.sub.4.sup.−, BrO.sub.3.sup.−, SO.sub.4.sup.2−, SiO.sub.3.sup.2−, CN.sup.−, and metal-containing anions such as MX.sub.yO.sub.z.sup.n− (M=Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Mo, Sn, Cs, and Pb; X=F, Cl, Br, I, N, and P; 0<y≤5; 0≤z≤5; 1≤n≤4) potentially present in seawater and industrial water for cleaning and desalination purposes, thereby improving the performance and efficiency of desalination water cleaning device and process, relative to existing technologies that employ silver-based AgCl electrodes.
(38) Compared to the Ag/AgCl anodes used in existing desalination batteries, the anion intercalation host material 108 disclosed herein can be mass-produced at industrial scale via a simple, facile and cost-effective solid-state, or solution-based synthetic routes.
(39) 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.