Composite alkali ion conductive solid electrolyte

Abstract

An electrochemical cell having a composite alkali ion-conductive electrolyte membrane. Generally, the cell includes a catholyte compartment and an anolyte compartment that are separated by the composite alkali ion-conductive electrolyte membrane. The composite electrolyte membrane includes a layer of alkali ion-conductive material and one or more layers of alkali intercalation compound which is chemically stable upon exposure to a chemically reactive anolyte solution or catholyte solution thereby protecting the layer of alkali ion-conductive material from unwanted chemical reaction. The layer of alkali intercalation compound conducts alkali ions. The cell may operate and protect the alkali ion-conductive material under conditions that would be adverse to the material if the intercalation compound were not present. The composite membrane may include a cation conductor layer having additional capability to protect the composite electrolyte membrane from adverse conditions.

Claims

1. A method for operating an electrochemical cell, the method comprising: providing the electrochemical cell, the cell comprising: an anolyte compartment for holding an anolyte solution, the anolyte compartment comprising an anode positioned to contact the anolyte solution; a catholyte compartment for holding a catholyte solution, the catholyte compartment comprising a cathode positioned to contact the catholyte solution; and a composite alkali ion-conductive electrolyte membrane positioned between the anolyte compartment and the catholyte compartment, wherein the composite electrolyte membrane comprises: a layer of alkali ion-conductive material, wherein the alkali ion-conductive membrane comprises an alkali Metal Super Ion Conductive (MeSICON) material selected from NaSICON or NaSICON-type materials, LiSICON or LiSICON-type materials, and KSICON or KSICON-type materials; and a layer of alkali compound consisting of a carbon-based alkali intercalation compound which is electrically or ionically conductive and which is chemically stable upon exposure to the anolyte solution or catholyte solution thereby protecting the layer of alkali ion-conductive material from unwanted chemical reaction, and wherein the layer of alkali compound conducts alkali ions; adding the alkali ion containing catholyte solution to the catholyte compartment and the alkali ion containing anolyte solution to the anolyte compartment; and passing a current between the anode and the cathode.

2. The method of claim 1, wherein the carbon-based alkali intercalation compound is selected from a graphite intercalation compound, meso-porous carbon, boron-doped diamond, and graphene.

3. A method for operating an electrochemical cell, the method comprising: providing the electrochemical cell, the cell comprising: an anolyte compartment for holding an anolyte solution, the anolyte compartment comprising an anode positioned to contact the anolyte solution; a catholyte compartment for holding a catholyte solution, the catholyte compartment comprising a cathode positioned to contact the catholyte solution; and a composite alkali ion-conductive electrolyte membrane positioned between the anolyte compartment and the catholyte compartment, wherein the composite electrolyte membrane comprises: a layer of alkali ion-conductive material, wherein the alkali ion-conductive membrane comprises an alkali Metal Super Ion Conductive (MeSICON) material selected from NaSICON or NaSICON-type materials, LiSICON or LiSICON-type materials, and KSICON or KSICON-type materials; and a layer of alkali compound consisting of an alkali-containing intercalation electrode material which is electrically or ionically conductive and which is chemically stable upon exposure to the anolyte solution or catholyte solution thereby protecting the layer of alkali ion-conductive material from unwanted chemical reaction, and wherein the layer of alkali compound conducts alkali ions; adding the alkali ion containing catholyte solution to the catholyte compartment and the alkali ion containing anolyte solution to the anolyte compartment; and passing a current between the anode and the cathode.

4. The method of claim 3, wherein the alkali-containing intercalation electrode material comprises an alkali cobalt oxide (MCoO.sub.2).

5. The method of claim 3, wherein the alkali-containing intercalation electrode material comprises an alkali iron phosphate (MFePO.sub.4).

6. The method of claim 3, wherein the alkali-containing intercalation electrode material comprises an alkali manganese oxide (MMn.sub.2O.sub.4).

7. A method for operating an electrochemical cell, the method comprising: providing the electrochemical cell, the cell comprising: an anolyte compartment for holding an anolyte solution, the anolyte compartment comprising an anode positioned to contact the anolyte solution; a catholyte compartment for holding a catholyte solution, the catholyte compartment comprising a cathode positioned to contact the catholyte solution; and a composite alkali ion-conductive electrolyte membrane positioned between the anolyte compartment and the catholyte compartment, wherein the composite electrolyte membrane comprises: a layer of alkali ion-conductive material, wherein the alkali ion-conductive membrane comprises an alkali Metal Super Ion Conductive (MeSICON) material selected from NaSICON or NaSICON-type materials, LiSICON or LiSICON-type materials, and KSICON or KSICON-type materials; and a layer of alkali compound consisting of an alkali metal amalgam or alloy which is electrically or ionically conductive and which is chemically stable upon exposure to the anolyte solution or catholyte solution thereby protecting the layer of alkali ion-conductive material from unwanted chemical reaction, and wherein the layer of alkali compound conducts alkali ions; adding the alkali ion containing catholyte solution to the catholyte compartment and the alkali ion containing anolyte solution to the anolyte compartment; and passing a current between the anode and the cathode.

8. The method of claim 7, wherein the alkali metal amalgam or alloy comprises an alloy of phosphorous and an alkali metal.

9. The method of claim 7, wherein the alkali metal amalgam or alloy comprises an alloy of aluminum and an alkali metal.

10. The method of claim 7, wherein the alkali metal amalgam or alloy comprises an alkali metal and one or more other metals selected from silicon, germanium, lead, zinc, bismuth, tin, and cadmium.

11. The method of claim 7, wherein the composite electrolyte membrane further comprises an acid resistant cation conductor layer disposed between the alkali metal amalgam or alloy and the anode, or between the alkali metal amalgam or alloy and the cathode.

12. The method of claim 11, wherein the cation conductor layer comprises a NAFION® polymer membrane.

Description

BRIEF DESCRIPTION OF THE SEVERAL DRAWINGS

(1) In order that the manner in which the above-recited and other features and advantages of the invention are obtained and will be readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. Understanding that the drawings depict only typical embodiments of the invention and are not therefore to be considered to be limiting of its scope, the invention will be described and explained with additional specificity and detail through the use of the accompanying drawings in which:

(2) FIG. 1 depicts a schematic diagram of an embodiment of a prior art electrolytic cell comprising a cation-conductive membrane;

(3) FIG. 2 depicts a schematic diagram of a representative embodiment of an electrochemical cell comprising a composite alkali ion-conductive electrolyte membrane;

(4) FIG. 3 depicts a schematic diagram of a representative embodiment of the composite alkali ion-conductive electrolyte membrane;

(5) FIG. 4 depicts a schematic diagram of a representative embodiment of an alkali metal amalgam or alloy functioning as a bipolar electrode;

(6) FIG. 5 depicts a schematic diagram of a representative embodiment of the electrochemical cell comprising the composite alkali ion-conductive electrolyte membrane, wherein an alkali compound is configured to function as a secondary cathode;

(7) FIG. 6 depicts a schematic diagram of a representative embodiment of the electrochemical cell in which a layer of the alkali compound is disposed on the catholyte side of the alkali ion-conductive electrolyte membrane; and

(8) FIG. 7 depicts a schematic diagram of a representative embodiment of an electrochemical cell in which layers of the alkali compound are disposed on both sides of the alkali ion-conductive electrolyte membrane.

DETAILED DESCRIPTION OF THE INVENTION

(9) Reference throughout this specification to “one embodiment,” “an embodiment,” or similar language means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “in one embodiment,” “in an embodiment,” and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment.

(10) Furthermore, the described features, structures, or characteristics of the invention may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided, such as examples of suitable alkali ion-conductive electrolyte membranes, alkali intercalation compounds, anolyte solutions, catholyte solutions, electrochemical cells, etc., to provide a thorough understanding of embodiments of the invention. One having ordinary skill in the relevant art will recognize, however, that the invention may be practiced without one or more of the specific details, or with other methods, components, materials, and so forth. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the invention.

(11) The present invention relates to systems and methods for protecting an alkali ion-conductive electrolyte material when the material is used in an electrochemical cell (e.g., an electrolytic cell) having reactive conditions or chemically reactive species that would attack, degrade, dissolve, corrode, deactivate, reduce the efficiency of, or otherwise have an adverse effect on the material if the material were not properly protected. To protect the material, the material comprises a composite alkali ion-conductive electrolyte membrane which has one or more layers of an alkali compound disposed on one or both sides of the alkali ion-conductive material. In this regard, the alkali compound is chemically stable upon exposure to such reactive conditions or chemically reactive species and is otherwise capable of protecting the alkali ion-conductive electrolyte membrane from chemical reaction, degradation, and other effects of adverse conditions.

(12) In some non-limiting examples, electrochemical (e.g., electrolytic) cells may be operated under acidic conditions in the anolyte compartment. In other non-limiting examples, electrochemical cells may be operated using catholyte and/or anolyte solutions (e.g., basic solutions; solutions containing organic compounds, oxidizing chemicals, energetic materials, and/or organic salts; neutral solutions comprising membrane-inhibiting chemicals, such as potassium; proton evolving compounds; etc.) that are chemically reactive to or that would otherwise adversely affect the alkali ion-conductive electrolyte material. This may result from chemical species dissolved in the solvent, from the solvent itself, or from chemical species that are formed as the cell functions. In yet other non-limiting examples, electrolytic cells are operated using molten metals, such as molten anode or cathode materials which may be chemically reactive to the alkali ion-conductive electrolyte material. In still other non-limiting examples, the electrolytic cells are operated using molten salts which may be chemically reactive to the alkali ion-conductive electrolyte material. To provide a better understanding of the described systems and methods, a non-limiting embodiment of an electrochemical cell is first described, followed by a description of a variety of methods for using the cell.

(13) The electrochemical cell can comprise any suitable component that allows it to produce a desired chemical product. By way of non-limiting illustration, FIG. 2 illustrates a representative embodiment in which an electrochemical cell (e.g., an electrolytic cell) 210 comprises an anolyte compartment 212 and a catholyte compartment 214 that are separated by composite alkali ion-conductive electrolyte membrane 215. FIG. 2 further shows that while, in some embodiments, the anolyte compartment 212 houses an anode electrode 218 that is positioned to contact an anolyte solution or anolyte, in some embodiments, the catholyte compartment 214 comprises a cathode electrode 220 that is positioned to contact a catholyte solution or catholyte.

(14) Moreover, FIG. 2 shows that the composite electrolyte membrane 215 includes an alkali ion-conductive electrolyte material 216 and a layer comprising an alkali compound 222. In this particular embodiment, FIG. 2 also shows that the alkali compound 222 is disposed between the alkali ion-conductive material 216 and the anode 218. While not shown in FIG. 2, the alkali compound 222 can alternatively, or in addition, be disposed between the alkali ion-conductive material 216 and the cathode 220.

(15) With respect to the alkali ion-conductive electrolyte material 216, that material can comprise any alkali Metal Super Ion Conductive (MeSICON) material that is suitable for use in an electrochemical cell and which can be protected from adverse conditions (e.g., acidic conditions, basic conditions, molten electrodes, etc.) by the alkali compound 222 (discussed below). Non-limiting examples of suitable MeSICON materials include NaSICON, NaSICON-type materials, LiSICON, LiSICON-type materials, KSICON, and KSICON-type materials.

(16) The alkali compound 222 is selected to protect the alkali ion-conductive material 216 from chemical species and conditions that would otherwise be adverse to the membrane. Indeed, in some non-limiting embodiments, the compound is selected to be chemically stable in, or to otherwise protect the alkali ion-conductive material from, acidic conditions, basic conditions, neutral conditions (e.g., in a solution comprising potassium), molten metal (e.g., a molten anode or cathode) or molten salt (e.g., a molten electrolyte), an organic compound or products thereof, and/or other chemical species or conditions that would otherwise adversely affect the proper function of the alkali ion-conductive material. By way of non-limiting example, by being stable or tolerant to acidic conditions, the alkali compound 222 is able to protect the alkali ion-conductive material 216 from acid produced in the cell (e.g., in the anolyte solution). In other non-limiting example, by being stable or tolerant to basic conditions, the layer of alkali compound 222 is able to protect the alkali ion-conductive material 216 from bases produced in the cell (e.g., in the catholyte solution).

(17) The alkali compound 222 can comprise any suitable material that allows it to provide increased protection to the alkali ion-conductive material and that is readily conductive to alkali metal ions to allow the alkali ion-conductive material to function as intended. Some non-limiting examples of suitable alkali compounds include one or more carbon-based alkali intercalation compounds, alkali-containing intercalation electrode materials, alkali metal amalgams or alloys or intermetallic compounds, or a combination thereof.

(18) Some non-limiting examples of carbon-based alkali intercalation compound include one or more graphite intercalation compounds, meso-porous carbon, boron-doped diamond, and graphene, which is an allotrope of carbon. In this regard, the carbon-based intercalation compound (e.g., graphene) can be applied to the alkali ion-conductive material in any suitable manner, including, without limitation, through the use of chemical vapor deposition.

(19) Non-limiting examples of alkali-containing intercalation electrode materials include an alkali cobalt oxide (MCoO.sub.2), an alkali iron phosphate (MFePO.sub.4), an alkali manganese dioxide (MMnO.sub.2), an alkali manganese oxide (MMn.sub.2O.sub.4), an alkali iron oxide (MeFeO.sub.2), and an alkali nickel oxide (MNiO.sub.2), wherein M is an alkali metal (e.g., Na, Li, K, etc.). These compounds are based upon analogous compounds used as cathode electrode materials in lithium ion batteries. Moreover, the alkali iron phosphate compound is not limited to iron-containing compounds, but includes other transition metals, such as Co, Mn, Ti, etc. Some additional non-limiting examples of alkali-containing intercalation materials also include birnessite (e.g., (Na.sub.0.3Ca.sub.0.1K.sub.0.1)(Mn.sup.4+, Mn.sup.3+).sub.2O.sub.4.1.5H.sub.2O)) and todorokite (e.g., (Mn, Mg, Ca, Ba, K, Na).sub.2Mn.sub.2O.sub.12.3H.sub.2O).

(20) In some non-limiting embodiments, the alkali compound comprises an alkali metal amalgam or alloy. In such embodiments, the alkali metal amalgam or alloy or intermetallic compound may comprise an alkali metal and metals known to form such amalgam or alloy or intermetallic compound from that specific alkali metal. For a first non-limiting example, when the alkali metal is sodium the metal may be selected from mercury, lead, zinc, tin, phosphorous and cadmium. For a second non-limiting example, when the alkali metal is lithium the metal may be selected from aluminum, silicon, germanium, phosphorous, bismuth, mercury, lead, and tin.

(21) Non-limiting examples of an alkali metal amalgam or alloy include a composition comprising an alkali metal and one or more other metals selected from mercury, lead, zinc, tin, and cadmium. One non-limiting example of an alkali metal amalgam or alloy is a sodium/mercury amalgam. Mercury amalgams are stable in dilute acid environments, including, but not limited to, dilute hydrochloric and sulfuric acids. Additionally, the concentration of the alkali metal in the amalgam or alloy can be in any suitable range that allows the amalgam or alloy to perform its intended functions. Indeed, in some embodiments, the concentration of the alkali metal in the amalgam or alloy is between about 0.01 molar percent and about 0.5 molar percent.

(22) In addition to being ion conductive, the intercalation compound 222 can have any other characteristic that allows it to function as intended. For instance, while some non-limiting embodiments of the intercalation compound (e.g., MMnO.sub.2, where M is an alkali metal) are electrically conductive, in other non-limiting embodiments, the compound (e.g., MFeO.sub.2, where M is an alkali metal) is electrically insulating.

(23) FIG. 2 also shows that in some non-limiting embodiments the cell 210 comprises a power source 224 that is capable of passing current between the anode 218 and both the cathode 220. Generally, as current passes between the electrodes, alkali metal ions (M.sup.+) pass through the composite electrolyte membrane 215. In other words, as the cell functions, the composite electrolyte membrane 215 continues to function even when exposed to adverse conditions (e.g., acidic conditions, basic conditions, etc.). As used herein, acidic conditions include pH values below about 7, more specifically below about 5. From a practical operating standpoint, however, the acidic conditions may have a pH greater than 1, and in some cases a pH greater than 2, and in other cases a pH greater than 3. Additionally, as used herein, the term basic conditions may include pH values above about 7, and more particularly above about 9.

(24) In some non-limiting embodiments, the composite electrolyte membrane 215 optionally includes a cation conductor layer 226, as shown in FIG. 3. In this regard, the cation conductor layer 226 is made of a chemically resistant material that is conductive to alkali cations. For example, the cation conductor layer 226 may comprise an acid resistant material, a base resistant material, an inert material, or a material that is otherwise capable of providing additional protection against chemically reactive species and adverse cell conditions. While the cation conductor layer can comprise any suitable material that allows it to provide additional protection to the composite electrolyte membrane, one non-limiting example of a suitable cation conductor layer is a NAFION® membrane, produced by DuPont, or similar polymeric membrane.

(25) Where the cell 210 comprises the cation conductor layer 226, that layer can be disposed in any suitable location that allows it to provide additional protection to the alkali ion-conductive material 216. In some non-limiting embodiments, the cation conductive layer (e.g., an acid resistant material) is disposed between the alkali ion-conductive material and the anode 218 (e.g., between the alkali compound layer 222 and the anode). Thus, in such embodiments, the cation conductor layer 226 provides additional protection against acidic operating conditions and may permit the composite electrolyte membrane 215 to function properly under acidic pH conditions, such as a pH of about 1 or 2. In other non-limiting embodiments (not shown), the cation conductor layer (e.g., a base resistant material) is disposed between the alkali ion-conductive material and the cathode 220 (e.g., between the intercalation layer and the cathode). In still other embodiments, the cation conductor layer is disposed on both the anolyte side and the catholyte side of the alkali ion-conductive material (e.g., between a first layer of the intercalation compound and the anode and between a second layer of the interaction and the cathode).

(26) With respect to the anode electrode 218, the anode can comprise one or more of a variety of materials that allow it to initiate a desired electrolytic reaction at the anode 218 when the anode is contacted with an anolyte and when current is running between the anode 218 and the cathode 220. Indeed, in some non-limiting embodiments, the anode optionally comprises a material that allows the anode to evolve protons (H.sup.+) when the anode contacts an aqueous anolyte solution and as the cell functions. Some non-limiting examples of suitable anode materials comprise dimensionally stabilized anode (DSA), platinized titanium, ruthenium (IV) dioxide (RuO.sub.2), graphite, stainless steel alloys, and other suitable known or novel anode materials. Furthermore, in some non-limiting embodiments, the anode comprises a molten metal (e.g., sodium, lithium, etc.).

(27) The cathode electrode 220 can comprise any suitable material that allows it to be stable in the catholyte solution and to initiate a desired electrolytic reaction when current passes between the cathode and the anode. Some non-limiting examples of suitable materials that can be used in the cathode include nickel, stainless steel alloys, graphite, titanium, a nickel-cobalt-ferrous alloy (e.g., a KOVAR® alloy), and other known or novel cathode materials. Additionally, in some non-limiting embodiments, the cathode comprises an electro-catalyst, such as platinum, that increases the cathode's ability to evolve hydrogen. By way of non-limiting example, the cathode may comprise platinized nickel, platinized titanium, and/or other suitable electro-catalyst materials. Furthermore, in some non-limiting embodiments, the cathode may comprise a molten metal.

(28) With regard to the anolyte solution in the anolyte compartment 212, the anolyte can initially comprise virtually any solution that allows the anode 218 to initiate one or more other desired electrochemical reactions (e.g., to evolve protons; to function as a battery, electrolytic cell, fuel cell; etc.) when current passes between the anode and the primary cathode 220 and/or second cathode. In some non-limiting embodiments, however, the anolyte comprises an alkali-salt solution, including, but not limited to, an aqueous alkali-salt solution. For instance, where the cation-conductive membrane comprises a NaSICON-type membrane, the anolyte can comprise a sodium salt (NaX), which may include, but is not limited to, sodium lactate (NaC.sub.3H.sub.5O.sub.3), sodium sulfate (Na.sub.2SO.sub.4), and/or sodium chloride (NaCl). Similarly, when the cation-conductive membrane comprises a LiSICON membrane or a KSICON membrane, the anolyte can respectively comprise any suitable lithium salt (LiX) or potassium salt (KX), including, but not limited to, lithium or potassium salts corresponding to the sodium salts mentioned above. In still other non-limiting embodiments, the anolyte comprises one or more oxidizing chemicals (e.g., a halogen, chlorate, etc.), energetic materials (e.g., alkali methoxides, alkali metals (molten or solid); organic compounds (e.g., methanol, hexanol, ethylene glycol, etc.); neutral solutions comprising potassium or another chemical that may adversely affect a naked alkali ion-conductive material; organic salts (e.g., sodium carboxylate dissolved in organic or ionic-liquid solvents); electrolytes (e.g., LiPF.sub.6 (e.g., where the cell comprises a battery)) and/or any other chemical that may be useful in the anolyte.

(29) The catholyte solution can comprise virtually any solution that allows the primary cathode 220 to cause a desired electrochemical reaction (e.g., the evolution of hydroxide ions; to function as a battery, fuel cell, electrolytic cell; etc.) to occur when the catholyte is in contact with the primary cathode and when current passes between the anode 218 and the primary cathode. In some non-limiting embodiments, however, the catholyte solution comprises, but is not limited to, water, an aqueous alkali-salt solution, a hydroxide solution (e.g., an alkali hydroxide), an organic solution (such as an alcohol, methanol, hexanol, ethylene glycol), an alkali base, a molten salt, an oxidizing chemical (e.g., a halogen, chlorate, etc.), an energetic material (e.g., an alkali methoxide; and alkali metal (molten or solid); a neutral solution comprising potassium or another chemical that may adversely affect a naked alkali ion-conductive material; an organic salt (e.g., sodium carboxylate dissolved in organic or ionic-liquid solvents); an electrolyte (e.g., LiPF.sub.6), and/or any other chemical that may be useful in the catholyte. By way of non-limiting example, where the alkali ion-conductive membrane comprises a NaSICON membrane, the catholyte solution can comprise an aqueous sodium chloride solution, an aqueous sodium hydroxide solution, a sodium methylate solution, etc. Similarly, where the alkali ion-conductive membrane comprises a LiSICON membrane, the catholyte solution may comprise an aqueous solution of lithium chloride, lithium hydroxide, etc. Moreover, where the cation-conductive membrane comprises a KSICON membrane, the catholyte solution may comprise an aqueous solution of potassium chloride, potassium hydroxide, etc.

(30) While not shown in FIG. 2, the various compartments of the electrochemical cell 210 may also comprise one or more fluid inlets and/or outlets. In some embodiments, the fluid inlets allow specific chemicals and fluids to be added to one or more desired places within the cell. In other embodiments, the fluid inlets and outlets may allow fluids to flow through one or more compartments or spaces in the cell.

(31) The described electrochemical cell 210 may function to produce a wide range of chemical products, including, but not limited to, acids that correspond to alkali bases, substantially pure alkali metals, chlorine-based oxidant products, oxygen, chlorine, hydrogen, biofuels, and/or a variety of other chemical products. In one non-limiting example, the described cell is used to obtain one or more acids corresponding to alkali salts and/or to obtain one or more alkali metals. For instance, while the described cell can use a sodium salt to produce an acid and/or to obtain sodium, the skilled artisan will recognize that cell can be used to produce acids, alkali metals, and electrochemical products from another alkali salt, such as a lithium salt or a potassium salt.

(32) In one non-limiting example, FIG. 2 shows that where the anolyte solution comprises a alkali metal salt (MX) (including, but not limited to, an alkali metal lactate (MC.sub.3H.sub.5O.sub.3), an alkali metal sulfate (M.sub.2SO.sub.4), and/or an alkali metal chloride (MCl)), the salt can be disassociated in the anolyte compartment 212 into the salt's cation (M.sup.+) and its anion (X.sup.−) (e.g., C.sub.3H.sub.5O.sub.3.sup.−, SO.sub.4.sup.−2, Cl.sup.−, etc.). FIG. 2 illustrates that the cation (M.sup.+) from the salt (MX) may react with protons (H.sup.+) evolved from the anode 218 to form an acid (HX) (e.g., lactic acid (C.sub.3H.sub.6O.sub.3), hydrochloric acid (HCl), etc.) that corresponds to the original alkali metal salt (MX). FIG. 2 further illustrates that the alkali metal ion (M.sup.+) is selectively transported through the composite alkali ion-conductive electrolyte membrane 215 into the catholyte compartment 214, where it can be collected (e.g., as alkali metal hydroxide, or in some other suitable form). Additionally, in this example FIG. 2 illustrates that oxygen gas (O.sub.2) can be vented and/or collected from the anolyte compartment 212 and that hydrogen gas (H.sub.2) can be vented and/or collected from the catholyte compartment 214.

(33) The alkali compound 222 is selected to be conductive of the alkali metal ion. Without being bound by theory, in one non-limiting embodiment, the alkali metal ion (M.sup.+) passes directly through the alkali compound 222.

(34) In another non-limiting embodiment, alkali metal ions do not pass directly through the alkali compound 222. Instead, alkali metal ions are reduced at an anode side of the alkali compound 222 and pass through the alkali compound 222 as the reduced alkali metal, and the alkali metal is oxidized at the cathode side of the alkali compound 222 to form alkali metal ions, which are conducted through the alkali ion-conductive material 216.

(35) Without being bound by theory, in some non-limiting embodiments, the alkali compound 222 may function as a bipolar electrode. FIG. 4 depicts a schematic diagram of a representative embodiment of an alkali compound 222 functioning as a bipolar electrode. In this embodiment, the alkali compound 222 is shown as an amalgam of mercury and the alkali metal. The anode side 230 of the compound 222 becomes negatively charged, and the cathode side 232 of the compound 222 becomes positively charged. Accordingly, the anode side 230 can function as a cathode to reduce alkali metal ions according to the reaction M.sup.++e.sup.−.fwdarw.M. The alkali metal M can enter the compound 222. The cathode side 232 can function as an anode to oxidize the alkali metal to form alkali metal ions according to the reaction M.fwdarw.M.sup.++e.sup.−. Free electrons can pass between the cathode side 232 and the anode side 230 as shown. The alkali metal ion formed on the cathode side 232 of the compound 222 is available to pass through the alkali ion-conductive material 216.

(36) In another non-limiting embodiment, the alkali compound 222 may function as a secondary cathode. Examples of this feature are disclosed in U.S. patent application Ser. No. 13/269,412, which is incorporated by reference. FIG. 5 depicts a schematic diagram of a representative embodiment of the electrochemical cell 210 comprising the composite alkali ion-conductive electrolyte membrane and in which the alkali compound 222 is configured to function as a secondary cathode. In this embodiment, a small portion of the current 234 from the power source 224 which drives the cathode 220 is split and electrically coupled to the alkali compound 222. This current reduces alkali metal ions according to the reaction M.sup.++e.sup.−.fwdarw.M. The alkali metal M can enter and pass through the compound 222.

(37) While the foregoing disclosure shows the layer of alkali compound 222 exposed to the anolyte side of the electrochemical cell 210, it will be understood that in some embodiments, including the embodiment shown in FIG. 6, the alkali compound 222 may be exposed to the catholyte side of the electrochemical cell to protect the alkali ion-conductive electrolyte material 216 from reactive conditions in the catholyte compartment 214.

(38) In other non-limiting embodiments, the composite alkali ion-conductive electrolyte membrane 215 may contain a layer of the alkali compound 222 exposed to both the anolyte side and catholyte side of the electrochemical cell 210. By way of illustration, FIG. 7 illustrates a representative embodiment in which the composite alkali ion-conductive electrolyte membrane 215 comprises a layer of alkali compound 222a exposed to the anolyte compartment 212 and a layer of alkali compound 222b exposed to the catholyte compartment 214.

(39) It will be appreciated that the described systems and methods used a composite alkali ion-conductive electrolyte membrane under certain reactive conditions or adverse conditions (e.g., acidic conditions; basic conditions; neutral conditions comprising a material such as potassium; conditions in which the cell comprises a proton evolving compound, an organic compound, a molten metal, a molten salt, or other chemically reactive species; etc.). Accordingly, the described systems and methods allow the electrolytic cell to efficiently produce desired chemical products without damaging the alkali ion-conductive material to the same extent as would occur if the alkali compound were not used. The alkali compound provides chemical protection to the alkali ion conductive material thereby permitting it to function under adverse conditions.

(40) In addition to the aforementioned components and characteristics of the described systems and methods, the cell 210 can be modified in any suitable manner that allows ions to be selectively transported through the alkali ion-conductive electrolyte material 216 as the cell functions. In one non-limiting example, while the described systems are shown with the composite alkali ion-conductive electrolyte membrane 215 oriented vertically, it will be understood that the composite electrolyte membrane may be oriented horizontally or in any other suitable configuration or orientation. In another non-limiting example, while the composite alkali ion-conductive electrolyte material is described herein as being used in an electrolytic cell 210, the composite alkali ion-conductive material can be used in any other suitable electrochemical cell in which an alkali layer 222 can protect the alkali ion-conductive material from conditions that would adversely affect the function of the material if the intercalation layer were not present. Some non-limiting examples of such electrochemical cells include batteries and fuel cells. Accordingly, the described composite alkali ion-conductive electrolyte membrane can be used to facilitate virtual any electrochemical reaction requiring a MeSICON material.

(41) While specific embodiments and examples of the present invention have been illustrated and described, numerous modifications come to mind without significantly departing from the spirit of the invention, and the scope of protection is only limited by the scope of the accompanying claims.