Moderate temperature sodium battery
10170798 ยท 2019-01-01
Assignee
Inventors
Cpc classification
Y02E60/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02P70/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y10T29/49108
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
Abstract
A rechargeable galvanic cell that has a negative electrode material made of a molten alkali metal (such as sodium or lithium). The galvanic cell also includes a positive electrode active material that may be sulfur or iodine. The positive electrode active material may be used in conjunction with a polar solvent. An ion-conductive separator is disposed between the polar solvent and the negative electrode material. The positive electrode active material has a specific gravity that is greater than the specific gravity of the polar solvent. Thus, the positive electrode active material is proximate the bottom of the positive electrode compartment while the polar solvent is above the positive electrode active material. The cell is designed to be operated at temperatures above the melting point of the alkali metal, but at temperatures that are lower than about 250 C.
Claims
1. A cell comprising: a negative electrode compartment housing a negative electrode material, wherein the negative electrode material comprises at least one of a liquid sodium metal and a liquid lithium metal that is oxidized during discharge of the cell; a positive electrode compartment; a polar solvent within the positive electrode compartment; a liquid positive electrode active material within the positive electrode compartment that is reduced during discharge of the cell, wherein the liquid positive electrode active material has a specific gravity greater than the polar solvent such that an interface exists between the liquid positive electrode active material and the polar solvent, wherein the liquid positive electrode active material comprises at least one of elemental sulfur and iodine; an ion-conductive membrane comprising at least one of NaSICON and LiSICON separator separating the negative electrode compartment from the positive electrode compartment; and a positive electrode current collector configured to provide electrical contact to the interface between the liquid positive electrode active material and the polar solvent, wherein the interface between the liquid positive electrode active material and the polar solvent moves with respect to the positive electrode current collector as the cell charges or discharges; wherein the cell is a galvanic cell.
2. The cell as in claim 1 wherein the negative electrode material comprises lithium and the liquid positive electrode active material comprises elemental sulfur and the temperature of the galvanic cell is maintained between about 185 C. and about 250 C.
3. The cell as in claim 1 wherein the negative electrode material comprises sodium and the temperature of the cell is maintained between about 100 C. and about 200 C.
4. The cell as in claim 3, wherein the temperature of the galvanic cell is maintained between about 100 C. and about 185 C.
5. The cell as in claim 3, wherein the temperature of the galvanic cell is maintained between about 110 C. and about 170 C.
6. The cell as in claim 1 wherein the polar solvent comprises at least one of acetamide, methylacetamide, and dimethylacetamide, N-methyl formamide (NMF), formamide, dimethylformamide, tetraglyme, diglyme, dimethylether, Ethanolammonium nitrate, imidazolium halogenoaluminate salts and combinations thereof.
7. The cell as in claim 1 wherein the galvanic cell is configured to allow the polar solvent to leave the galvanic cell and re-enter the galvanic cell as the galvanic cell charges or discharges.
8. The cell as in claim 7 wherein the galvanic cell is configured to allow an inert gas in a headspace within the negative electrode compartment to leave the galvanic cell and re-enter the galvanic cell as the galvanic cell charges or discharges.
9. The cell as in claim 1 wherein the galvanic cell is configured to allow liquids within the positive electrode compartment to leave the galvanic cell and re-enter the galvanic cell as the galvanic cell charges or discharges.
10. The cell as in claim 1 wherein the ion-conductive membrane is planar or tubular.
11. The cell as in claim 1, wherein the positive electrode current collector comprises one or more fins extending upward from a base of the positive electrode compartment.
12. The cell as in claim 11, wherein the height of the fins is designed such that, even when the cell is fully charged or discharged, the height of the interface does not exceed the height of the fins.
13. The cell as in claim 12, wherein the fins comprise one or more holes.
14. A battery comprising one or more galvanic cells, wherein each cell comprises: a negative electrode compartment comprising a negative electrode material, wherein the negative electrode comprises at least one of liquid sodium metal and liquid lithium metal that is oxidized during discharge of the galvanic cell; a positive electrode compartment; a polar solvent within the positive electrode compartment; a liquid positive electrode active material within the positive electrode compartment that is reduced during discharge of the galvanic cell, wherein the liquid positive electrode active material comprises elemental sulfur or iodine, wherein the liquid positive electrode active material has a specific gravity greater than the polar solvent such that an interface exists between the liquid positive electrode active material and the polar solvent; an ion-conductive membrane comprising at least one of NaSICON and LiSICON separating the negative electrode from the polar solvent; and a positive electrode current collector configured to provide electrical contact to the interface between the liquid positive electrode active material and the polar solvent, wherein the interface between the liquid positive electrode active material and the polar solvent moves with respect to the positive electrode current collector as the galvanic cell charges or discharges; and wherein the galvanic cell is configured to allow liquid polar solvent within the positive electrode compartment to leave the galvanic cell and re-enter the galvanic cell as the galvanic cell charges or discharges.
15. The battery as is claim 14, wherein the polar solvent comprises: at least one of acetamide, methylacetamide, and dimethylacetamide, N-methyl formamide (NMF), formamide, dimethylformamide, tetraglyme, diglyme, dimethylether, Ethanolammonium nitrate, imidazolium halogenoaluminate salts and combinations thereof; wherein the ion-conductive membrane is either tubular or planar.
16. The battery as in claim 15 wherein negative electrode material comprises sodium and the temperature of the galvanic cell is maintained between about 100 C. and about 200 C.
17. A cell comprising: a negative electrode compartment housing a negative electrode material, wherein the negative electrode material comprises at least one of a liquid sodium metal and a liquid lithium metal that is oxidized during discharge of the cell; a positive electrode compartment; a polar solvent within the positive electrode compartment; a liquid positive electrode active material within the positive electrode compartment that is reduced during discharge of the cell, wherein the liquid positive electrode active material has a specific gravity greater than the polar solvent such that an interface exists between the liquid positive electrode active material and the polar solvent, wherein the liquid positive electrode active material comprises at least one of elemental sulfur and iodine; an ion-conductive membrane comprising at least one of NaSICON and LiSICON separating the negative electrode compartment from the positive electrode compartment; a positive electrode current collector configured to provide electrical contact to the interface between the liquid positive electrode active material and the polar solvent, wherein the interface between the liquid positive electrode active material and the polar solvent moves with respect to the positive electrode current collector as the cell charges or discharges; wherein: the cell is a galvanic cell configured to allow the liquid polar solvent to leave the galvanic cell and re-enter the galvanic cell as the galvanic cell charges or discharges; and the galvanic cell comprises an inert gas in a headspace within the negative electrode compartment, and wherein the galvanic cell is configured to allow the inert gas to leave the galvanic cell and re-enter the galvanic cell as the galvanic cell charges or discharges.
18. The cell as in claim 1, wherein elemental sulfur has the formula S.sub.8.
19. The cell as in claim 1, wherein elemental sulfur has the formula S.sub.y, wherein 1y30.
Description
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
(1) In order that the manner in which the above-recited and other features and advantages of the invention are obtained will be readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. Understanding that these 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)
(3)
(4)
(5)
(6)
(7)
DETAILED DESCRIPTION OF THE INVENTION
(8) The presently preferred embodiments of the present invention will be best understood by reference to the drawings, wherein like parts are designated by like numerals throughout. It will be readily understood that the components of the present invention, as generally described and illustrated in the figures herein, could be arranged and designed in a wide variety of different configurations. Thus, the following more detailed description of the present embodiments, as represented in the Figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of presently preferred embodiments of the invention.
(9) Referring now to
(10) Within the negative electrode compartment 16 may be a negative electrode material 17. This negative electrode material 17 may be a metal. (Thus, as used herein, the negative electrode material 17 may be referred to herein as negative electrode metal 17.) As noted herein, the negative electrode metal may be an alkali metal, such as sodium or lithium. In general, the cell 10 will be operated at temperatures in which the negative electrode metal 17 (e.g., sodium or lithium) is liquid. Thus, in the depiction of
(11) Typically a headspace 18 may be within the negative electrode compartment 16 and may be positioned above the liquid negative electrode metal 17. The headspace 18 may further comprise an inert gas 19, such as nitrogen or argon. As the cell 10 is being charged or discharged, the negative electrode metal 17 (sodium or lithium) is either consumed or released in the reaction. Accordingly, because the amount of the negative electrode metal 17 changes, the level of the liquid negative electrode metal 17 may change (e.g., rise or fall). As the level of the liquid negative electrode metal 17 changes, the inert gas 19 may vent into and out of an overflow compartment 26 via conduit 27. Thus, the inert gas 19 in the headspace 18 is allowed to leave the galvanic cell 10 and re-enter the galvanic cell 10 as the cell 10 is charged or discharged. If desired, a valve or other regulating mechanism may be used to as part of the conduit 27 to allow the inert gas 19 to vent into and out of the compartment 26.
(12) An ion-conductive membrane 15 is used in the cell 10. The ion-conductive membrane 15 separates the positive electrode compartment 11 from the negative electrode compartment 16 and thus isolates the negative electrode metal 17 from the chemicals housed within the positive electrode compartment 11. The ion-conductive membrane may be constructed such that there is no through porosity between the negative electrode compartment 16 and the positive electrode compartment 11. The membrane 15 may be capable of transporting alkali metal ions, such as sodium cations or lithium cations, through the membrane 15. In some embodiments, the membrane 15 may include porous layers positioned on the exterior surface of the membrane to increase the effective surface area of the membrane 15. In the embodiment of
(13) The positive electrode compartment 11 of the cell 10 may be formed with an enclosure wall 30. In some embodiments, the enclosure wall 30 may be separated into multiple layers which are electronically conductive and/or impervious. Each of the layers of the wall may serve its own function, such as the function of transmitting electrons and/or containing the constituents within the wall. Alternatively, the wall 30 may be a single layer that is designed to transmit electrons and contain the constituents within the wall 30. For example, the wall 30 may be comprised primarily of graphite or a corrosion resistant metal which is then wrapped (on the outside) with an impervious insulative polymer.
(14) The positive electrode compartment 11 houses a polar solvent 14. The polar solvent 14 is selected so that it remains in the liquid phase over the operating temperature of the battery, (such as, for example, between 100 C. and 200 C.). Examples of polar solvents that may be used with the positive electrode active material are N-methyl formamide (NMF), formamide, dimethylformamide, tetraglyme, diglyme, dimethylether, and others. Most of these solvents have specific gravity in the range of 0.9 g/cubic centimeter to 1.1 g/cubic centimeter. Other polar solvents may include ionic liquids such as Ethanolammonium nitrate, and imidazolium halogenoaluminate salts and others. Other embodiments may use acetamide, methylacetamide, or dimethylacetamide as the solvent.
(15) The positive electrode compartment 11 also houses a positive electrode active material 13. This positive electrode active material 13 may be sulfur or iodine. Sulfur has a specific gravity of 2.07 g/cubic centimeter and is molten in the range of 115 C. to 445 C. Similarly, iodine has a specific gravity of 4.92 g/cubic centimeter and is liquid in the range of 114 C. to 185 C. The sodium salts of both sulfur and iodine are polar in nature and are soluble in polar solvents such as those listed above. In fact, polysulfides of sodium are particularly soluble in NMF.
(16) Because both sulfur and iodine have a specific gravity that is greater than the polar solvent 14, the positive electrode active material 13 (e.g., the sulfur/iodine) is positioned below the polar solvent 14 (e.g., at or near the bottom of the positive electrode compartment 11.) As the cell 10 is being charged or discharged, the positive electrode active material 13 (sulfur or iodine) is either consumed or released in the reaction. Accordingly, because the amount of the positive electrode active material 13 changes, the level of the polar solvent 14 in the positive electrode compartment 11 may also change (e.g., rise or fall). As the level of the positive electrode active material 13 changes, the polar solvent 14 may vent into and out of an overflow compartment 35 via conduit 37. Thus, the polar solvent 14 is allowed to leave the cell 10 and re-enter the cell 10 as the galvanic cell 10 charges or discharges. If desired, a valve or other regulating mechanism may be used to as part of the conduit 37 to allow the polar solvent 14 to vent into and out of the compartment 35.
(17) In the embodiment of
(18) As shown in
(19) The reactions associated with the cell 10 will now be described. In the following example, sodium is used as the negative electrode metal 17:
(20) Battery Discharge:
(21) Positive Electrode Reactions:
I.sub.2+e.sup..fwdarw.I.sup. (if iodine is used as the positive electrode active material 13)
S.sub.8+2e.sup..fwdarw.S.sup.2 or alternatively
S.sub.y+2e.sup..fwdarw.S.sub.y.sup.2, where 1y30 or alternatively
S.sub.8+S.sub.y.sup.2+2e.sup..fwdarw.S.sub.(y+1).sup.2, where 1y30 (if sulfur is used as the positive electrode active material 13; however, some polysulfides will also be formed at the positive electrodepositive electrode.)
(22) Negative Electrode Reactions:
Na.fwdarw.Na.sup.++e.sup.
Battery Charge:
(23) Positive Electrode Reactions:
I.fwdarw.I.sub.2+e.sup. (if iodine is used as the positive electrode active material 13)
S.fwdarw.S.sub.8+2e.sup., alternatively
S.sub.y.sup.2.fwdarw.S.sub.y+2e.sup., where 1y30 or alternatively
S.sub.(y+1).sup.2.fwdarw.S.sub.8+S.sub.y.sup.2+2e.sup., where 1y30 (if sulfur is used as the positive electrode active material 13)
(24) Negative Electrode Reactions:
Na.sup.++e.sup..fwdarw.Na
When sulfur is used as a positive electrode in a battery and sodium is used as the negative electrode, the battery may produce approximately 2.2V of output. When iodine is used as a positive e electrode in a battery and sodium is used as the negative electrode, the battery may be capable of producing an output of approximately 3.2V.
(25) Further, the embodiments may also be designed in which lithium is utilized as the negative electrode metal 17. In this case however, sulfur can be chosen as the positive electrode active material 13. The reason for this is that lithium melts at 181 C., which is near the boiling temperature for iodine. Thus in the case of lithium and sulfur, a suitable operating temperature range may be between 182 C. to 250 C. Of course, during this reaction, there must be a polar solvent that remains in its liquid state in this temperature range. When this embodiment is used, a LiSICON or other materials could be used as the membrane 15. In this embodiment, the following reactions would occur:
(26) Battery Discharge:
(27) Positive Electrode Reactions:
2Na.sup.++S.sub.8+e.sup..fwdarw.Na.sub.2S (if sulfur is used as the positive electrode active material 13; however, some polysulfides will also be formed at the positive electrode.)
(28) Negative Electrode Reactions:
Na.fwdarw.Na.sup.++e.sup.
Battery Charge:
(29) Positive Electrode Reactions:
Na.sub.2S.fwdarw.2Na.sup.++S.sub.8+2e.sup.
(30) Negative Electrode Reactions:
Na.sup.++e.sup..fwdarw.Na
(31) In the embodiment of
(32) Referring now to
(33) In the cell 100, a positive electrode compartment 11 is illustrated. The positive electrode compartment 11 comprises an enclosure that houses a positive electrode active material 13. This positive electrode active material 13 may be sulfur or iodine. Positive electrode active material 13 may reside at the bottom of the positive electrode enclosure when the cell 100 is in the charged state. Polar solvent 14 is positioned above the positive electrode active material 13 (because the positive electrode active material 13 has a higher specific gravity than the solvent 14).
(34) The positive electrode compartment 11 may comprise a positive electrode current collector 8. As with the prior embodiment, the current collector 8 may comprise one or more current collector fins 12. Such fins 12 may be positioned at or near the bottom of the positive electrode compartment 11. The current collector fins 12 may serve to provide electrical contact to the interface 62 between the denser positive electrode active material 13 at the bottom of the positive electrode compartment 11 and the liquid polar solvent 14 positioned at the top of the positive electrode compartment 11. The fins 12 may be porous or have one or more holes to promote transport of material between fins. Also the fins 12 may be configured such that as the interface 62 between the polar solvent 14/positive electrode active material 13 rises and falls, the fins 12 still provide electronic contact to the interface 62. As the cell 100 is being charged or discharged, the positive electrode active material 13 (sulfur or iodine) is either consumed or released in the reaction. Accordingly, because the amount of the positive electrode active material 13 changes, the level of the polar solvent 14 in the positive electrode compartment 11 may also change (e.g., rise or fall). As the level of the positive electrode active material 13 changes, the polar solvent 14 may vent into and out of an overflow compartment 35 via conduit 37. If desired, a valve or other regulating mechanism may be used as part of the conduit 37 to allow the polar solvent 14 to vent into and out of the compartment 35. Further, above the polar solvent 14 in the positive electrode compartment 11 may be a headspace 21. In some embodiments, the headspace 21 may be filled with an inert gas such as nitrogen or argon. This inert gas may be vented into and out of the compartment 35 to accommodate volume changes which will occur in each of the compartments as the cell is charged and discharged. Thus, the inert gas in the headspace 21 may be configured to leave the cell 100 and re-enter the cell 100 as the cell 100 charges or discharges. Alternatively, the inert gas in the headspace 21 may be vented into and out of a separate chamber/reservoir when the cell 100 charges/discharges.
(35) The cell 100 further comprises negative electrode compartment 16 that houses a negative electrode metal 17. As noted above, the negative electrode metal 17 may be an alkali metal such as sodium or lithium. The cell 100 may be operated at temperatures where the negative electrode metal 17 is liquid. Accordingly, the level (vertical height) of the negative electrode metal 17 may rise and fall depending on the state of charge of the cell 100 (e.g., whether the cell 100 is fully charged, fully discharged, partially charged, etc.)
(36) Typically a headspace 18 may be within the negative electrode compartment 16 and may be positioned above the liquid negative electrode metal 17. The headspace 18 may further comprise an inert gas 19, such as nitrogen or argon. As the cell 10 is being charged or discharged, the negative electrode metal 17 (sodium or lithium) is either consumed or released in the reaction. Accordingly, because the amount of the negative electrode metal 17 changes, the level of the liquid negative electrode metal 17 may change (e.g., rise or fall). As the level of the liquid negative electrode metal 17 changes, the inert gas 19 may vent into and out of an overflow compartment 26 (reservoir) via conduit 27. If desired, a valve or other regulating mechanism may be used as part of the conduit 27 to allow the inert gas 19 to vent into and out of the compartment 26.
(37) A negative electrode current collector 23 provides electrical contact to the negative electrode metal and is designed to provide contact to the full extent of cell discharge. A cap 22 seals off the cell 100 to the environment.
(38) In the embodiment of
(39) The cell 100 may operate (e.g., be charged and discharged) in the manner noted above. It should be noted that the cells 10, 100 may be contained within a temperature controlled environment to ensure that they are operated at the proper temperature. In some embodiments, this temperature may be between 100 C. and 200 C. if the alkali metal used as the negative electrode is sodium. If lithium is utilized as the active negative electrode material, the cells 10, 100 may be operated at a temperature between 182 C. and 250 C. Thus, the present embodiments provide a NaS battery or NaI (or LiS or LiI) battery that can operate at a moderate temperature (e.g., less than about 250 C.).
(40) The embodiment of
(41) In the embodiments of
(42) Further embodiments may also be designed in which the positive electrode compartment 11 includes porous carbon to allow the solvent to flow, thereby increasing the conductivity of the positive electrode compartment.
(43) Examples of the performance of specific embodiments of a cell that may be constructed according to the present embodiments will now be given. For example,
(44)
(45)
(46) As noted herein, the battery 200 (and the galvanic cells 10 or 100) are designed such that they may be operated at higher temperatures. For example, in some embodiments, the cells 10, 100 are designed such that they are operated (and/or are maintained) at temperatures between about 185 C. and about 250 C. (if, for example, the negative electrode metal is lithium). In other embodiments, the cells 10, 100 are designed such that they are operated (and/or are maintained) between about 100 C. and about 200 C. (if, for example, the negative electrode metal is sodium). In further embodiments, the cells 10, 100 are designed such that they are operated (and/or are maintained) between about 100 C. and about 185 C. (if, for example, the negative electrode metal is sodium). In order to have the cell/battery operate at these elevated temperatures, the battery 200 may be positioned in an elevated temperature environment 220. In order to generate these higher temperatures, a heat generator 230 may produce heat 240 which is directed at the battery 200 so that the battery 200 may be operated (charged, discharged and/or used to store power) at the desired elevated temperature. Of course, the embodiment of
(47) Referring now to
(48) A negative electrode material may be positioned 308 within the negative electrode compartment. The negative electrode material may comprise lithium or sodium metal. The negative electrode material may be molten lithium metal or molten sodium metal. In other embodiments, the negative electrode material comprises lithium or sodium metal in its solid form that is heated to form liquid lithium or sodium metal. A positive electrode active material is positioned 312 within the positive electrode compartment. The positive electrode active material may comprise iodine or sulfur. A polar solvent may also be positioned 316 within the positive electrode compartment. The positive electrode active material may have a specific gravity that is greater than the specific gravity of the polar solvent. Accordingly, when both the positive electrode active material and the polar solvent are positioned in the positive electrode compartment, the positive electrode active material will be positioned near the bottom of the positive electrode compartment (e.g., below the polar solvent). Further, the method 300 may involve ensuring 320 that the positive electrode current collector provides electrical contact to the interface between the positive electrode active material and the polar solvent within the positive electrode compartment. The current collector provides electrical contact to the interface even when the interface changes location.
(49) It should be noted that the steps of the method 300 are exemplary and that the various steps of the method may be performed in a different order than that which is shown in
(50) The present invention may be embodied in other specific forms without departing from its structures, methods, or other essential characteristics as broadly described herein and claimed hereinafter. The described embodiments are to be considered in all respects only as illustrative, and not restrictive. The scope of the invention is, therefore, indicated by the appended claims, rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.