CA1193653A - Electrochemical cell having a alkali metal nitrate electrode - Google Patents
Electrochemical cell having a alkali metal nitrate electrodeInfo
- Publication number
- CA1193653A CA1193653A CA000425221A CA425221A CA1193653A CA 1193653 A CA1193653 A CA 1193653A CA 000425221 A CA000425221 A CA 000425221A CA 425221 A CA425221 A CA 425221A CA 1193653 A CA1193653 A CA 1193653A
- Authority
- CA
- Canada
- Prior art keywords
- alkali metal
- positive electrode
- nitrate
- electrochemical cell
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
ELECTROCHEMICAL CELL HAVING A
ALKALI METAL NITRATE ELECTRODE
ABSTRACT OF THE DISCLOSURE
A power producing secondary electrochemical cell includes a molten alkali metal as the negative electrode material and a molten nitrate salt as the positive electrode material. The molten material in the respective electrodes are separated by a solid barrier of alkali metal ion conducting material. A typical cell includes active materials of molten sodium separated from molten sodium nitrate and other nitrates in mixture by a layer of sodium .beta." alumina.
ALKALI METAL NITRATE ELECTRODE
ABSTRACT OF THE DISCLOSURE
A power producing secondary electrochemical cell includes a molten alkali metal as the negative electrode material and a molten nitrate salt as the positive electrode material. The molten material in the respective electrodes are separated by a solid barrier of alkali metal ion conducting material. A typical cell includes active materials of molten sodium separated from molten sodium nitrate and other nitrates in mixture by a layer of sodium .beta." alumina.
Description
'336~3 ELECT~OCHEMICAL CELL H~VING A
ALKALI METAL NITRATE ELECTRODE
The invention relates to high temperature, secondary electrochemical cells for producing power that includes a molten alkali metal and nitrate salts. The invention particularly relates to the use of molten sodium metal and salts including sodium nitrate as the active materials.
It was previously believed that electrochemical cells involving molten alkali metals and their nitrate salts were only of interest as unrechargable primary cells or as cells for the electrolytic production of alkali metal.
Electrochemical reactions such as for the production of molten sodium metal from sodium nitrate have involved the release of gases for instance, nitrogen dioxide and oxygen gas which impose substantial difficulties in incorporating such a reaction in a secondary rechargable electrochemical cell. Furthermore, the nitrates within molten nitrate salts were thought to be decomposed to nitrite plus oxygen gas thus preventing the recharge of the cell to this original state.
The principal positive electrode material presently ~0 under consideration for secondary sodium cells is sulfur.
At the high operating temperature of these cells a very ' ~ 7 ~!
,`' ' , ';~.,'. ~
~1~33~i~3 corrosive environment is developed that requires expensive current collector materials such as titanium oxide or chrome plated steel. Other positive electrodes for molten sodium cells that have been considered include sodium tetrachloro-aluminate solvent containing sulfur species or metal chlorides.
These systems also exhibit severe corrosion problems and have relatively low theoretical specific energies on the order of 30OWh/kg.
It is an ob~ect of the present invention to provide an improved secondary electrochemical power producing cell that can employ molten alkali meta] as the negative electrode material.
It is a further object to provide a new positive electrode for use in combination with an alkali metal negative electrode within a secondary rechargable electro-chemical cell.
It is also an object to provide a high temperature secondary power producing electrochemical cell with a reactive alkali metal as negative electrode material with reduced corrosion problems in the positive electrode.
In accordance with the present invention, there is provided a secondary electrochemical storage cell comprising a negative electrode containing elemental alkali metal as active material, a positive electrode containing a salt including metal ions of the alkali metal as active material, the salt including a nitrate, a mixture of nitrates or a mixture of a nitrate and a nitrite; a solid electrolyte including and being capable of conducting ions of the alkali metal between the positive and negative ~3~3 electrodes; discharge means for conducting an electrical current through an electrical load connected in series between the positive and negative electrodes as alkali metal oxidizes to alkali metal ions in the negative electrode and alkali metal nitrate reduces to alkali metal nitrite in the positive electrode; recharge means for applying a source of electrical potential between the positive and negative electrodes sufEicient to oxidize alkali metal nitrite to alkali metal nitrate in the positive electrode and reduce alkali metal ions to alkali metal in the negative electrode; and sealing means for retaining the salt of alkali metal in the positive electrode as the cell discharges through the electrical load and as the cell is recharged for storing electrical energy.
In more specific aspects of the invention the negative electrode contains molten sodium and the positive electrode contains a molten salt including sodium nitrate. In such a cell the electrolyte separating the electrodes can be of a sodium oxide and alumina composition, for example one of the well known sodium ~ aluminasO These compositions permit the conduction of sodium ions from the negative to the positive electrodes during discharge of the cell.
In one other aspect of the invention the nitrate salt is selected from a mixture oE nitrate salts that permit reduced melting points below that of sodium nitrate salt.
Mixtures of alkali metal nitrates, alkaline earth metal nitrates and transition metal nitrates are contemplated with eutectic compositions generally providing low melting points ~3~
for a particular selec-tion of molten salts. In one other aspect of the invention, at least the positive electrode is contained within a sealed chamber to prevent incidental venting of nitrogen dioxide or of oxygen gases that may arise from the decomposition of the various nitrate salts.
In a further embodiment an alkali metal is included in the negative electrode and nitrate salts in the positive electrode each in communication with a plurality of qlass fibers extending between the positive and negative electrodes and in contact with the molten alkali metal and the molten metal nitrate salts. The glass Eibers consist essentially of an alkali metal ion conducting material including such as sodium oxide and boron oxide.
Further in accordance with the present invention there is provided a rechargeable electrochemical cell in at least a partially uncharged state comprising a negative electrode chamber containing elemental alkali metal as negative electrode material and means for collecting electronic current in contact with the alkali metal; a sealed positive electrode chamber containing a salt of alkali metal including nitrites and oxides as positive electrode material and means for collecting electronic current in contact with the alkali metal salt; a solid electrolyte wall forming at least a portion of the sealed positive electrode chamber and being in contact at one surface with the elemental alkali metal 4 .
and its opposite surface with the alkali metal salt, the solid electrolyte wall being capable of conducting ions of the alkali metal between the active materials of the positive and negative electrodes; and electrical recharge means or connecting a source of electrical potential across the current collecting means of the negative and the positive electrodes to oxidize alkali metal nitrite to alkali metal nitrate in the positive electrode.
The present invention is illustrated in the accompanying drawin~s wherein:
Fig. 1 is a schematic elevation view o~ an electro-chemical cell including a molten alkali metal and a molten nitrate salt as active materials.
Fig. 2 is a graph of volts vs. capacity over two charge and discharge cycles of a sodium-sodium nitrate secondary electrochemical cell.
Fig. 1 shows a laboratory style electrochemical cell used in demonstrating the electrochemical cell of this invention. It will be understood that this cell is presented merely by way of example and that various forms and constructions of cells more appropriate for commercial and industrial applications are also contem-plated within the scope of the present invention.
A cell container or housing 11 of corrosion resistant material, such as stainless steel, is illustrated as both the current collector and container for the negative electrode material 13. ~olten sodium metal is of principle interest as the negative electrode material 13. However ~`! .
3~53 other alkali metals such as potassium and lithium may be appropriate in molten mixture with sodium or as a separate electrode material.
A container 15 for the positive electrode material 17 is shown with its outer surfaces partially immersed in the molten alkali metal 13. Container 15 can be provided with some or all of its walls of a solid electrolyte material to establish means for ionic conduction between the positive 17 and negative electrode materials during cell operation.
The electrolyte material is advantageously selected from one of the sodium ~ aluminas of the type commonly used in sodium-sulfur cells. The ~ aluminas are poly-crystalline composition of sodium oxide and alumina having typically 8-20 mole percent Na2O and the balance alumina. Small amounts of lithia, magnesia and other constituents also may be included as stabilizer or to attribute other properties. A preferred form is that of ~ alumina (nominally Na2O:5A12O3) stabilizers with up to about one weight percent of Li2O.
Various ionic cond~ctive glasses such as those formed of boron oxide with a sodium oxide or other alkali metal oxide modifiers also are contemplated for use.
Such glasses may include 94-96~ by weight boron oxide modified by 4-6~ sodium oxide, Na2O:2~2O3:~.2SiO2 and Na2O:2B2O3:0.2SiO2:0.16NaCl as well as other sodium oxide modified glasses of boron oxide and silicon oxide.
The positive electrode material 17 within container 3~r~3 -- 6 ~
15 includes molten alkali metal salts, particularly the alkali metal nitrate of the negative electrode material.
Sodium nitrate or various mixtures of alkali metal nitrates and in some cases transition metal nitrates including NaN2~KN3' NaN3~KN3~ Mg(N3)2, NaNO3-LiNO3, LiNO3-KNO3 are contemplated as positive electrode material.
Mixtures with melting points less than 350 C advantageously can be selected. During operation of the cell through charge and discharge cycles, the positive electrode also is expected to contain alkali metal nitrites and alkali metal oxides that occur in the partially charged and uncharged states. Accordingly nitrites and oxides can be included in the initial positive electrode formulation.
Positive electrode 17 is illustrated as having a suitable current collector 19 in the shape of a screen or grid that may be of stainless steel, nickel or other inert metal. Certain nitrate compositions such as NaNO2-KNO3 have been found to be compatable with mild steel containment thus making this inexpensive current collector material available for use.
A closure 21, with an electrical feedthrou~h, is illustrated sealing the positive electrode compartment to prevent escape of any gases such as NO2 and 2 that may incidentally be evolved during cycling of the cell.
The cell chemistry does not contemplate evolution of these gases, but should it occur as a result of undesirable side reactions, closure 21 or other means can advantageously be employed to restrict loss of constituents.
3~
The electrochemical cell of Fig. 1 is provided with electrical conductors 23 and 25 connected to the current collectors of the positive and negative electrodes. These conductors are illustrated coupled to an electrical load 27 and a recharger means 29 employed in cycling the Fig. 1 electrochemical cell through charge and discharge cycles.
The electrochemical cell described herein has been found to be a reversible secondary electrochemical cell operating at about 1.7 volts. The cell reaction is thought to be:
2Na + NaNO3 = Na2O + NaNO2 However, under certain circumstances, the sodium oxide and sodium nitrite may combine to form the species Na3NO3 within the molten salt, positive electrode material.
The following e~ample is presented merely as an illustration of the electrochemical cell of this invention.
A sodium ~ alumina tube of about 8 cm length and about 1.5 cm diameter were assembled within a stainless steel cup to form an annulus for the negative electrode material. About 10 gm of molten sodium was filled into the annulus and about 2 gm of sodium nitrate was used as the positive electrode active material within the ~ alumina tube. Electrical conductors were connected to the stainless steel cup as a negative electrode current collector and a spool of type 304 stainless steel screen employed within the ~ alumina tube as the positive electrode current collector material. The cell was operated in a helium blanketed furnace at about 325-335C for 14 cycles over a period of a~out 500 hours.
Fig. 2 illustrates charge and discharge curves from two cycles operated at 10 and ~ hour rates that is at S0 and 80 milliamps respectfully. From these cycles the voltage is estimated to be at about 1.75 V and theoretical specific energy at this EMF is about 720Wh/kg.
It is therefore seen that the present invention provides a new improved secondary electrochemical power producing cell that can employ molten alkali metal in the negative electrode opposite a molten salt containing alkali metal nitrate in the positive electrode. The cell has potential for reduced corrosion problems over that of the traditional high temperature sodium-sulfur cell and can employ various known sodium-ion-conductive electrolytes.
Although the present invention is described in terms of specific embodiments it would be clear to one skilled in the art that various modifications in the structures, materials and procedures can be made within the scope of the following claims.
ALKALI METAL NITRATE ELECTRODE
The invention relates to high temperature, secondary electrochemical cells for producing power that includes a molten alkali metal and nitrate salts. The invention particularly relates to the use of molten sodium metal and salts including sodium nitrate as the active materials.
It was previously believed that electrochemical cells involving molten alkali metals and their nitrate salts were only of interest as unrechargable primary cells or as cells for the electrolytic production of alkali metal.
Electrochemical reactions such as for the production of molten sodium metal from sodium nitrate have involved the release of gases for instance, nitrogen dioxide and oxygen gas which impose substantial difficulties in incorporating such a reaction in a secondary rechargable electrochemical cell. Furthermore, the nitrates within molten nitrate salts were thought to be decomposed to nitrite plus oxygen gas thus preventing the recharge of the cell to this original state.
The principal positive electrode material presently ~0 under consideration for secondary sodium cells is sulfur.
At the high operating temperature of these cells a very ' ~ 7 ~!
,`' ' , ';~.,'. ~
~1~33~i~3 corrosive environment is developed that requires expensive current collector materials such as titanium oxide or chrome plated steel. Other positive electrodes for molten sodium cells that have been considered include sodium tetrachloro-aluminate solvent containing sulfur species or metal chlorides.
These systems also exhibit severe corrosion problems and have relatively low theoretical specific energies on the order of 30OWh/kg.
It is an ob~ect of the present invention to provide an improved secondary electrochemical power producing cell that can employ molten alkali meta] as the negative electrode material.
It is a further object to provide a new positive electrode for use in combination with an alkali metal negative electrode within a secondary rechargable electro-chemical cell.
It is also an object to provide a high temperature secondary power producing electrochemical cell with a reactive alkali metal as negative electrode material with reduced corrosion problems in the positive electrode.
In accordance with the present invention, there is provided a secondary electrochemical storage cell comprising a negative electrode containing elemental alkali metal as active material, a positive electrode containing a salt including metal ions of the alkali metal as active material, the salt including a nitrate, a mixture of nitrates or a mixture of a nitrate and a nitrite; a solid electrolyte including and being capable of conducting ions of the alkali metal between the positive and negative ~3~3 electrodes; discharge means for conducting an electrical current through an electrical load connected in series between the positive and negative electrodes as alkali metal oxidizes to alkali metal ions in the negative electrode and alkali metal nitrate reduces to alkali metal nitrite in the positive electrode; recharge means for applying a source of electrical potential between the positive and negative electrodes sufEicient to oxidize alkali metal nitrite to alkali metal nitrate in the positive electrode and reduce alkali metal ions to alkali metal in the negative electrode; and sealing means for retaining the salt of alkali metal in the positive electrode as the cell discharges through the electrical load and as the cell is recharged for storing electrical energy.
In more specific aspects of the invention the negative electrode contains molten sodium and the positive electrode contains a molten salt including sodium nitrate. In such a cell the electrolyte separating the electrodes can be of a sodium oxide and alumina composition, for example one of the well known sodium ~ aluminasO These compositions permit the conduction of sodium ions from the negative to the positive electrodes during discharge of the cell.
In one other aspect of the invention the nitrate salt is selected from a mixture oE nitrate salts that permit reduced melting points below that of sodium nitrate salt.
Mixtures of alkali metal nitrates, alkaline earth metal nitrates and transition metal nitrates are contemplated with eutectic compositions generally providing low melting points ~3~
for a particular selec-tion of molten salts. In one other aspect of the invention, at least the positive electrode is contained within a sealed chamber to prevent incidental venting of nitrogen dioxide or of oxygen gases that may arise from the decomposition of the various nitrate salts.
In a further embodiment an alkali metal is included in the negative electrode and nitrate salts in the positive electrode each in communication with a plurality of qlass fibers extending between the positive and negative electrodes and in contact with the molten alkali metal and the molten metal nitrate salts. The glass Eibers consist essentially of an alkali metal ion conducting material including such as sodium oxide and boron oxide.
Further in accordance with the present invention there is provided a rechargeable electrochemical cell in at least a partially uncharged state comprising a negative electrode chamber containing elemental alkali metal as negative electrode material and means for collecting electronic current in contact with the alkali metal; a sealed positive electrode chamber containing a salt of alkali metal including nitrites and oxides as positive electrode material and means for collecting electronic current in contact with the alkali metal salt; a solid electrolyte wall forming at least a portion of the sealed positive electrode chamber and being in contact at one surface with the elemental alkali metal 4 .
and its opposite surface with the alkali metal salt, the solid electrolyte wall being capable of conducting ions of the alkali metal between the active materials of the positive and negative electrodes; and electrical recharge means or connecting a source of electrical potential across the current collecting means of the negative and the positive electrodes to oxidize alkali metal nitrite to alkali metal nitrate in the positive electrode.
The present invention is illustrated in the accompanying drawin~s wherein:
Fig. 1 is a schematic elevation view o~ an electro-chemical cell including a molten alkali metal and a molten nitrate salt as active materials.
Fig. 2 is a graph of volts vs. capacity over two charge and discharge cycles of a sodium-sodium nitrate secondary electrochemical cell.
Fig. 1 shows a laboratory style electrochemical cell used in demonstrating the electrochemical cell of this invention. It will be understood that this cell is presented merely by way of example and that various forms and constructions of cells more appropriate for commercial and industrial applications are also contem-plated within the scope of the present invention.
A cell container or housing 11 of corrosion resistant material, such as stainless steel, is illustrated as both the current collector and container for the negative electrode material 13. ~olten sodium metal is of principle interest as the negative electrode material 13. However ~`! .
3~53 other alkali metals such as potassium and lithium may be appropriate in molten mixture with sodium or as a separate electrode material.
A container 15 for the positive electrode material 17 is shown with its outer surfaces partially immersed in the molten alkali metal 13. Container 15 can be provided with some or all of its walls of a solid electrolyte material to establish means for ionic conduction between the positive 17 and negative electrode materials during cell operation.
The electrolyte material is advantageously selected from one of the sodium ~ aluminas of the type commonly used in sodium-sulfur cells. The ~ aluminas are poly-crystalline composition of sodium oxide and alumina having typically 8-20 mole percent Na2O and the balance alumina. Small amounts of lithia, magnesia and other constituents also may be included as stabilizer or to attribute other properties. A preferred form is that of ~ alumina (nominally Na2O:5A12O3) stabilizers with up to about one weight percent of Li2O.
Various ionic cond~ctive glasses such as those formed of boron oxide with a sodium oxide or other alkali metal oxide modifiers also are contemplated for use.
Such glasses may include 94-96~ by weight boron oxide modified by 4-6~ sodium oxide, Na2O:2~2O3:~.2SiO2 and Na2O:2B2O3:0.2SiO2:0.16NaCl as well as other sodium oxide modified glasses of boron oxide and silicon oxide.
The positive electrode material 17 within container 3~r~3 -- 6 ~
15 includes molten alkali metal salts, particularly the alkali metal nitrate of the negative electrode material.
Sodium nitrate or various mixtures of alkali metal nitrates and in some cases transition metal nitrates including NaN2~KN3' NaN3~KN3~ Mg(N3)2, NaNO3-LiNO3, LiNO3-KNO3 are contemplated as positive electrode material.
Mixtures with melting points less than 350 C advantageously can be selected. During operation of the cell through charge and discharge cycles, the positive electrode also is expected to contain alkali metal nitrites and alkali metal oxides that occur in the partially charged and uncharged states. Accordingly nitrites and oxides can be included in the initial positive electrode formulation.
Positive electrode 17 is illustrated as having a suitable current collector 19 in the shape of a screen or grid that may be of stainless steel, nickel or other inert metal. Certain nitrate compositions such as NaNO2-KNO3 have been found to be compatable with mild steel containment thus making this inexpensive current collector material available for use.
A closure 21, with an electrical feedthrou~h, is illustrated sealing the positive electrode compartment to prevent escape of any gases such as NO2 and 2 that may incidentally be evolved during cycling of the cell.
The cell chemistry does not contemplate evolution of these gases, but should it occur as a result of undesirable side reactions, closure 21 or other means can advantageously be employed to restrict loss of constituents.
3~
The electrochemical cell of Fig. 1 is provided with electrical conductors 23 and 25 connected to the current collectors of the positive and negative electrodes. These conductors are illustrated coupled to an electrical load 27 and a recharger means 29 employed in cycling the Fig. 1 electrochemical cell through charge and discharge cycles.
The electrochemical cell described herein has been found to be a reversible secondary electrochemical cell operating at about 1.7 volts. The cell reaction is thought to be:
2Na + NaNO3 = Na2O + NaNO2 However, under certain circumstances, the sodium oxide and sodium nitrite may combine to form the species Na3NO3 within the molten salt, positive electrode material.
The following e~ample is presented merely as an illustration of the electrochemical cell of this invention.
A sodium ~ alumina tube of about 8 cm length and about 1.5 cm diameter were assembled within a stainless steel cup to form an annulus for the negative electrode material. About 10 gm of molten sodium was filled into the annulus and about 2 gm of sodium nitrate was used as the positive electrode active material within the ~ alumina tube. Electrical conductors were connected to the stainless steel cup as a negative electrode current collector and a spool of type 304 stainless steel screen employed within the ~ alumina tube as the positive electrode current collector material. The cell was operated in a helium blanketed furnace at about 325-335C for 14 cycles over a period of a~out 500 hours.
Fig. 2 illustrates charge and discharge curves from two cycles operated at 10 and ~ hour rates that is at S0 and 80 milliamps respectfully. From these cycles the voltage is estimated to be at about 1.75 V and theoretical specific energy at this EMF is about 720Wh/kg.
It is therefore seen that the present invention provides a new improved secondary electrochemical power producing cell that can employ molten alkali metal in the negative electrode opposite a molten salt containing alkali metal nitrate in the positive electrode. The cell has potential for reduced corrosion problems over that of the traditional high temperature sodium-sulfur cell and can employ various known sodium-ion-conductive electrolytes.
Although the present invention is described in terms of specific embodiments it would be clear to one skilled in the art that various modifications in the structures, materials and procedures can be made within the scope of the following claims.
Claims (15)
1. A secondary electrochemical storage cell comprising:
a negative electrode containing elemental alkali metal as active material, a positive electrode containing a salt including metal ions of said alkali metal as active material, said salt including a nitrate, a mixture of nitrates or a mixture of a nitrate and a nitrite;
a solid oxide electrolyte including and being capable of conducting ions of said alkali metal between said positive and negative electrodes;
discharge means for conducting an electrical current through an electrical load connected in series between said positive and negative electrodes as alkali metal oxidizes to alkali metal ions in said negative electrode and alkali metal nitrate reduces to alkali metal nitrite in said positive electrode;
recharge means for applying a source of electrical potential between said positive and negative electrodes sufficient to oxidize alkali metal nitrite to alkali metal nitrate in said positive electrode and reduce alkali metal ions to alkali metal in said negative electrode; and sealing means for retaining said salt of alkali metal in said positive electrode as said cell discharges through said electrical load and as said cell is recharged for storing electrical energy.
a negative electrode containing elemental alkali metal as active material, a positive electrode containing a salt including metal ions of said alkali metal as active material, said salt including a nitrate, a mixture of nitrates or a mixture of a nitrate and a nitrite;
a solid oxide electrolyte including and being capable of conducting ions of said alkali metal between said positive and negative electrodes;
discharge means for conducting an electrical current through an electrical load connected in series between said positive and negative electrodes as alkali metal oxidizes to alkali metal ions in said negative electrode and alkali metal nitrate reduces to alkali metal nitrite in said positive electrode;
recharge means for applying a source of electrical potential between said positive and negative electrodes sufficient to oxidize alkali metal nitrite to alkali metal nitrate in said positive electrode and reduce alkali metal ions to alkali metal in said negative electrode; and sealing means for retaining said salt of alkali metal in said positive electrode as said cell discharges through said electrical load and as said cell is recharged for storing electrical energy.
2. An electrochemical cell as claimed in claim 1, wherein said alkali metal in the negative electrode and the salt in the positive electrode are in the molten state.
3. An electrochemical cell as claimed in claim 1, wherein the alkali metal is sodium.
4. An electrochemical cell as claimed in claim 1, wherein the solid electrolyte comprises a tubular barrier of sodium oxide and alumina containing the positive electrode active material, said tubular barrier disposed in a container of elemental alkali metal to form an annular negative electrode.
5. An electrochemical cell as claimed in claim 1, wherein the positive electrode includes a nitrate salt selected from an alkali metal nitrate, an alkaline earth metal nitrate, a transition metal nitrate or a mixture thereof.
6. An electrochemical cell as claimed in claim 5, wherein the nitrate salt comprises a mixture of salts having a melting point less than 350°C.
7. An electrochemical cell as claimed in claim 5, wherein the nitrate salt is selected from the group of nitrate salts consisting of NaNO3, NaNO2-KNO3-NaNO3KNO3-Mg(NO3)2, NaNO3-LiNO3, LiNO3-NaNO3-KNO3 and mixtures thereof.
8. An electrochemical cell as claimed in claim 1, wherein the solid oxide electrolyte is a solid media communicating with both the positive electrode active material and the negative active material, the solid media is selected from the group of alkali metal conducting materials consisting of sodium .beta." alumina and a glass including an alkali metal oxide.
9. An electrochemical cell as claimed in claim 8, wherein said glass comprises Na2O and B2O3.
10. An electrochemical cell as claimed in claim 8, wherein said glass including an alkali metal oxide comprises a plurality of glass fibers between the positive and negative electrodes, said glass fibers selected from the group of glass material consisting of 94-96% by weight boron oxide modified by 4-6% by weight sodium oxide, Na2O:2B2O3:0.2SiO2 or Na2O:2 B2O3:02SiO2:0.16NaCl.
11. An electrochemical cell as claimed in claim 1, wherein the positive electrode is contained within a sealed chamber adequate to restrict venting of NO2 or O2 gases.
12. An electrochemical cell as claimed in claim 1, wherein the positive electrode in the partially charged state includes a molten mixture of alkali metal nitrates, alkali metal nitrites, and alkali metal oxides.
13. A rechargeable electrochemical cell in at least a partially uncharged state comprising:
a negative electrode chamber containing elemental alkali metal as negative electrode material and means for collecting electronic current in contact with said alkali metal;
a sealed positive electrode chamber containing a salt of alkali metal including nitrites and oxides as positive electrode material and means for collecting electronic current in contact with said alkali metal salt;
a solid electrolyte wall forming at least a portion of said sealed positive electrode chamber and being in contact at one surface with said elemental alkali metal and at its opposite surface with said alkali metal salt, said solid electrolyte wall being capable of conducting ions of said alkali metal between the active materials of said positive and negative electrodes; and electrical recharge means for connecting a source of electrical potential across the current collecting means of said negative and said positive electrodes to oxidize alkali metal nitrite to alkali metal nitrate in said positive electrode.
a negative electrode chamber containing elemental alkali metal as negative electrode material and means for collecting electronic current in contact with said alkali metal;
a sealed positive electrode chamber containing a salt of alkali metal including nitrites and oxides as positive electrode material and means for collecting electronic current in contact with said alkali metal salt;
a solid electrolyte wall forming at least a portion of said sealed positive electrode chamber and being in contact at one surface with said elemental alkali metal and at its opposite surface with said alkali metal salt, said solid electrolyte wall being capable of conducting ions of said alkali metal between the active materials of said positive and negative electrodes; and electrical recharge means for connecting a source of electrical potential across the current collecting means of said negative and said positive electrodes to oxidize alkali metal nitrite to alkali metal nitrate in said positive electrode.
14. An electrochemical cell as claimed in claim 13, wherein said sealed positive electrode chamber contains a mixture of alkali metal nitrate, alkali metal nitrite and alkali metal oxide as positive electrode material.
15. An electrochemical cell as claimed in claim 13, wherein said alkali metal is sodium and wherein said cell charges in accordance with the reaction Na2O + NaNO2 ? 2Na + NaNO3 with the sodium nitrate formed in the positive electrode chamber as sodium is formed in the negative electrode chamber.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US38520282A | 1982-06-04 | 1982-06-04 | |
| US385,202 | 1982-06-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1193653A true CA1193653A (en) | 1985-09-17 |
Family
ID=23520454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000425221A Expired CA1193653A (en) | 1982-06-04 | 1983-04-05 | Electrochemical cell having a alkali metal nitrate electrode |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS58216367A (en) |
| CA (1) | CA1193653A (en) |
| DE (1) | DE3319951A1 (en) |
| FR (1) | FR2528237A1 (en) |
| GB (1) | GB2121597B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017143088A1 (en) * | 2016-02-18 | 2017-08-24 | Sandia Corporation | Radical-ion battery and operation thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9111982D0 (en) * | 1991-06-04 | 1991-07-24 | Chloride Silent Power Ltd | An alkali metal energy conversion cell |
| EP3238297A1 (en) * | 2014-12-23 | 2017-11-01 | Battery Consult GmbH | Molten salt electrochemical flow cell |
| EP3637510B1 (en) | 2018-10-08 | 2021-08-11 | Battery Consult AG | Alkaline battery with ceramic solid electrolytes |
| CN113654936B (en) * | 2021-06-28 | 2024-01-23 | 浙江安力能源有限公司 | Na-beta' -Al 2 O 3 Method for measuring sodium content in solid electrolyte |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2081926A (en) * | 1933-07-17 | 1937-06-01 | Gyuris Janos | Primary element |
| US3847667A (en) * | 1972-09-26 | 1974-11-12 | Esb Inc | Alkali metal-porous conductive carbon battery having a molten alkali metal chloraluminate electrolyte |
-
1983
- 1983-04-05 CA CA000425221A patent/CA1193653A/en not_active Expired
- 1983-04-05 GB GB08309198A patent/GB2121597B/en not_active Expired
- 1983-05-25 FR FR8308637A patent/FR2528237A1/en active Pending
- 1983-05-26 JP JP58093305A patent/JPS58216367A/en active Pending
- 1983-06-01 DE DE19833319951 patent/DE3319951A1/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017143088A1 (en) * | 2016-02-18 | 2017-08-24 | Sandia Corporation | Radical-ion battery and operation thereof |
| US20190088971A1 (en) * | 2016-02-18 | 2019-03-21 | National Technology & Engineering Solutions Of Sandia, Llc | Radical-ion battery and operation thereof |
| EP3417503A4 (en) * | 2016-02-18 | 2019-09-25 | Sandia Corporation | Radical-ion battery and operation thereof |
| US10879552B2 (en) | 2016-02-18 | 2020-12-29 | National Technology & Engineering Solutions Of Sandia, Llc | Radical-ion battery and operation thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2121597B (en) | 1986-01-29 |
| GB2121597A (en) | 1983-12-21 |
| JPS58216367A (en) | 1983-12-16 |
| FR2528237A1 (en) | 1983-12-09 |
| DE3319951A1 (en) | 1983-12-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEC | Expiry (correction) | ||
| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 20030405 |