CA1073045A - Alkali metal battery structure - Google Patents
Alkali metal battery structureInfo
- Publication number
- CA1073045A CA1073045A CA281,122A CA281122A CA1073045A CA 1073045 A CA1073045 A CA 1073045A CA 281122 A CA281122 A CA 281122A CA 1073045 A CA1073045 A CA 1073045A
- Authority
- CA
- Canada
- Prior art keywords
- flange
- metal housing
- ceramic member
- cation
- opening
- 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
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 23
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 23
- 239000000919 ceramic Substances 0.000 claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 230000004888 barrier function Effects 0.000 claims abstract description 38
- 238000003411 electrode reaction Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000012546 transfer Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 229920001021 polysulfide Polymers 0.000 description 8
- 239000005077 polysulfide Substances 0.000 description 8
- 150000008117 polysulfides Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000005219 brazing Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 238000010349 cathodic reaction Methods 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- -1 e.g. Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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
- H01M10/3909—Sodium-sulfur cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/138—Primary casings; Jackets or wrappings adapted for specific cells, e.g. electrochemical cells operating at high temperature
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
ALKALI METAL BATTERY STRUCTURE
ABSTRACT OF THE DISCLOSURE
The invention is embodied in a structure for con-taining an alkali metal battery. A closed metal housing includes a flange having an opening therethrough. An elec-tronically and ionically insulating ceramic member is bonded to an exterior surface of the metal housing and encircles the opening through the flange thereby to define a passage-way which is an extension of the opening. An electrically insulating, cation-permeable barrier to mass liquid trans-fer has an interior volume and an exterior surface area.
The cation-permeable barrier is bonded to the ceramic member in such a manner that the interior volume of the metal housing, the passageway defined by the ceramic member and the interior volume of the cation-permeable barrier form a first closed electrode reaction zone. A container, including a structure bonded to the ceramic member, defines a closed container which encloses the exterior surface area of the cation-permeable barrier, the volume between the interior surface area of the container and the exterior surface area of the cation-permeable barrier forming a second closed reaction zone.
ABSTRACT OF THE DISCLOSURE
The invention is embodied in a structure for con-taining an alkali metal battery. A closed metal housing includes a flange having an opening therethrough. An elec-tronically and ionically insulating ceramic member is bonded to an exterior surface of the metal housing and encircles the opening through the flange thereby to define a passage-way which is an extension of the opening. An electrically insulating, cation-permeable barrier to mass liquid trans-fer has an interior volume and an exterior surface area.
The cation-permeable barrier is bonded to the ceramic member in such a manner that the interior volume of the metal housing, the passageway defined by the ceramic member and the interior volume of the cation-permeable barrier form a first closed electrode reaction zone. A container, including a structure bonded to the ceramic member, defines a closed container which encloses the exterior surface area of the cation-permeable barrier, the volume between the interior surface area of the container and the exterior surface area of the cation-permeable barrier forming a second closed reaction zone.
Description
This invention is directed to a structure for con-taining an alkali metal battery and, more particularly, to a structure for containing such a battery which provides effective electrical insulation of the battery's anodic and cathodic reaction zones and a seal against loss of reactants from such zones.
A recently developed type of secondary or recharge-able electrical conversion device comprises~ an anodic reaction zone containing a molten alkali metal anode-reactant, e.g., sodium, in electrical contact with an external circuit; I2] a cathodîc reaction zone containing , " .
:' ~
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;
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:
- - 1 - .
,~
;-1 [a] a cathodic reactant comprising sulfur or a mixture of
A recently developed type of secondary or recharge-able electrical conversion device comprises~ an anodic reaction zone containing a molten alkali metal anode-reactant, e.g., sodium, in electrical contact with an external circuit; I2] a cathodîc reaction zone containing , " .
:' ~
.
.
;
.
:
- - 1 - .
,~
;-1 [a] a cathodic reactant comprising sulfur or a mixture of
2 sulfur and molten polysulfide, which is electrochemically
3 reversibly reactive with the anodic reactant; ~b~ a solid
4 electrolyte comprising a cation-permeable barrier to mass liquid transfer interposed between and in contact with the 6 anodic and the cathodic reaction zones; and ~c] electrode 7 devices within the cathodic reaction zone for transporting 8 electrons to and from the vicinity of the cation-permeable 9 barrier. As used herein the term "reactant" is intended to mean both reactants and reaction products.
11 During the discharye cycle of such a device, 12 molten alkali metal atoms such as sodium surrender an elec-13 tron to an external circuit and the resulting cation passes 14 through the solid electrolyte barrier and into the liquid electrolyte to unite with polysulfide ions. The polysulfide 16 ions are formed by charge transfer on the electrode by reac-17 tion of the cathodic reactant with the electrons conducted 18 through the electrode from the external circuit. Because 19 the ionic conductivity of the liquid electrolyte is less than the electronic conductivity of the electrode material, it is 21 desirable during discharge that both electron~ and sul~ur ba 22 applied to and distributed along the surface o~ the electrode 23 in the vicinity of the cation-permeable solid electrolyte.
24 During the charge cycle of such a device when a negative potential larger than the open circuit cell voltage 26 is applied to the anode the opposite process occurs. Thus, 27 electrons are removed from the alkali metal polysulfide by 28 charge transfer at the surface of the electrode and are con-29 ducted through the electrode material to the external circuit, and the alkali metal cation is conducted through the liquid electrolyte and solid electrolyte to the anode where it accepts an electron from the external circuit. Because of the aforementioned relative conductivities of the ionic and electronic phases, this charging process occurs preferen-tially in the vicinity of the solid electrolyte and leaves behind molten elemental sulfur.
In accordance with this invention, a structure for containing an alkali metal battery includes a substantially closed metal housing for containing an electrode reaction zone, the metal housing including a flange having an opening therethrough. A first ceramic member is bonded to a portion of the flange on an exterior surface of the metal housing and encircles the opening through the flange and extends away therefrom to define a passageway which is an extension of the opening. A cation-permeable barrier to mass liquid transfer has an interior volume and an outer surface area. Means connects the cation-permeable barrier to the first ceramic member in such a manner that the interior volume of the metal housing, the passageway defined by the first ceramic member and the intexior volume of the cation-permeable barrier form a first closed electrode reaction zone. Container means including structure contacting the first ceramic member defines a closed container which encloses the exterior surface area of the cation-permeable barrier. A volume formed between an interior surface area of the container and the exterior surface area of the cation-permeable barrier form a second closed electrode reaction zone. The first ceramic member provides the electrical insulation between the first and second closed electrode reaction zones.
;: .
The container may be made from metal or from a - ceramic material. If made from metal, the container is attached to the first ceramic member by a brazing operation in the same manner as the first ceramic member is bonded to the closed metal housing. This brazing operation provides a fluid tight seal. If the container is made from ceramic, it may be bonded to the first ceramic member by a ceramic adhesive such as glass which will provide the required seal.
I The type of secondary electrical conversion batteries to which this invention relates are disclosed in the following U.S. patents: 3,404,035; 3,404,036; 3,446,677;
3,458,356; 3,468,709; 3,468,719; 3,475,220; 3,475,223;
3,475,225; 3,535,163; 3,719,531; 3,811,493 and 3,946,751.
The invention is de~crihed further, by way of illustration, with reference to the accompanying drawings, in which:
Figure 1 is an elevational view, in cross-section, of a structure for containing an~alkali metal battery which is manufactured principally from metal components;
i~ Figure 2 is an elevational view, in cross-section, ::
of a structure for containing an alkali metal battery in which both metal and ceramic components are used;
Figure 3 is a diagrammatic illustration of a number of different ways in which alkali metal battery con-tainers made principally from metal may be sealed; and Figure 4 is an illustration of various metal sealing techniques.
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~,;.~, .
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~073045 In FIGURES 1 and 2 a structure for containing an alkali metal battery is generally identified by the numeral 10. With reference to the structure of FIGURE 1, a closed metal housing 12, made from a material such as stainless steel, is shown as having a flange 14 which can be welded to an upper dome portion to form the housing. This flange has an opening 16 therein. A first electronically and ionically insulating ceramic member 18 of ring shape, made from a material such as high purity alumina, has a first surface 20 thereof brazed to an exterior surface of the housing's flange. This brazing together of the ceramic and metal is accomplished by existing brazing techniques such as active metal brazing using alloys such as nickel-titanium eutectic compositions or by a metallizing process. The first ceramic member has an extending portion 22 which defines an extending passageway 24, which passageway is in al~gnment with and forms an extension of the opening 16 in the flange 14. In order to strengthen the interconnection of the housing and ~ 5 , ~ . ~ , ' .
107309~5 1 the first ceramic member, it is preferred that a second 2 ceramic member 26 having an opening 28 therein be brazed to 3 the interior surface of the flange. The ceramic members 18 4 and 26 are generally brazed to the flange 14 prior to the flange being welded to the upper dome portion to form the 6 housing 12.
7 An electrically insulating, cation-permeable 8 barrier 30 in the form of a closed end tube is provided.
g This barrier is used as a reaction zone separator and is made of a material which will permit the transfer of ions 11 of an anodic reactant therethrough to a cathodic reactant.
12 The barrier may have a thickness in the range of about 20 13 to 2000 microns and may be made of a material such as 14 glasses and polycrystalline ceramic materials as is well known in the art. One material which is extremely useful 16 is beta type alumina or sodium beta type alumlna. The 17 cation-permeable barrier 30 is secured to the first ceramic 18 member 18 by a suitable glass seal.
19 A first reaction zone is thereby defined by the interior volume of the metal housing 12, the opening 28 in 21 the second ceramic member 26, the opening 16 in the ~lange 22 14, the passageway 24 defined by the ~irst ceramic member 23 18 and an interior volume 32 of the cation-permeable 24 barrier 30. This reaction zone may contain an anodic react-ant. The anodic reactant i5 heated by any conventional 26 heating source and may be viewed as the anode proper or con-27 ductor through which electron flow to an external circuit 28 (not shown) is achieved. Molten sodium is employed as the 29 anodic reactant in most preferred embodiments of such alkali metal batteries. However, potassium, lithium, other 10730~5 1 alkali metals, mixtures of such alkali metals or alloys containing such alkali metals can be used.
3 A second metal housing 34 formed of a material 4 such as stainless steel surrounds an exterior surface 35 of the cation-permeable barrier 30. A flange 36 of the second 6 metal housing 34 has an opening 38 therein permitting it to 7 be received about the extending portion 22 of the first 8 ceramic member 18. The flange 36 may be welded at its outer 9 edge to the rest of the can shaped structure to form the housing 34. The second metal housing is brazed to the 11 first ceramic member 18 in the position shown. A third 12 ceramic member 40 is brazed on the internal surface of the 13 flange 36 in order to strengthen the connection between the 14 second metal housing and the first ceramic member in the same manner as the second ceramic member 26 is used to 16 strengthen the interconnection of the first ceramic member 17 18 and the first metal housing 12. This third ceramic ~18 member may be made of the same material as the other two I9 ceramic members. The three ceramic members 18, 26 and 40 and the two flanges 14 and 36 may be brazed together in a 21 single operation.
22 The volume between the interior surface of the 23 second metal housing 34 and the external surface area 35 of 24 the cation-permeable barrier forms the second reactant zone.
This reactant zone can contain the cathodic reactant. The 26 cathodic reactant of a fully charged battery is molten 27 sulfur, which lS electrochemically reversibly reactive with 28 the anodic reactant. As the battery i9 discharged, the mole 29 fraction of elemental sulfur drops until the open circuit voltage remains constant. During this portion of the dis-31 charge cycle as the mole fractLon of sulfur drops from 1.0 -1 to approximately 0.72 the cathodic reactant displays two 2 phases, one being essentially pure sulfur and the other be-3 ingnsulfur saturated with alkali metal polysulfide in which 4 the molar ratio of sulfur to alkali metal is about 5.2:2.
When the battery is discharged to the point where the mole 6 fraction of sulfur is about 0.72 the cathodic reactant becomes 7 one phase in nature since all elemental sulfur has formed 8 polysulfide salts. As the battery is discharged further, the g cathodic reactant remains one phase in nature and as the mole fraction of sulfur drops so does the open circuit voltage 11 corresponding to the change in the potential determining 12 reaction. Thus, the device continues to discharge from a 13 point where polysulfide salts contain sulfur and alkali 14 metal in a molar ratio of appraximately 5.2:2 to the point where polysulfide salts contain sulfur and al~ali metal in 16 a ratio of about 3:2. At this point the device is fully 17 discharged.
18 The structure for containing an alkali metal .
19 battery as shown in FIGURE 1 is one in which positive elec-trical insulation is made between the first metal housing 21 12 and the second metal housing 34 by the first ceramic 22 member 18. The bonding of this first cexamic member to the~
23 metal housing in the brazing operation via a flange included 24 in the seal also provides an excellent seal so that the components used in the reactant zones do not escape from 26 the structure.
27 The structure for an alkali battery 10 as shawn 28 in FIGURE 2 is similar functionally in many parts to the 29 structure shown in FIGURE 1. The similar parts have been numbered with the same numbers applied to FIGURE 1. In . .
1 this embodiment, however, the first ceramic member 18 has 2 an outwardly extending and upwardly flared portion 42. A
3 ceramic container 44 is provided which has an annular in-4 wardly facing surface 46 which is bonded to a facing portion formed on the outwardly extending and upwardly flared por-6 tion 42 of the first ceramic member 18. The container for ? the second reaction zone is thereby defined by the volume 8 between the interior surface of the ceramic container 44 9 and the exterior surface 35 of the cation-permeable barrier 30. Once again, this structure provides electrical isola-11 -tion of the two reactants zones and seal of these zones so 12 that the reactants do not escape therefrom.
13 In FIGURE 3 there is illustrated a plurality of 14 manners in which a structure for containing an alkali metal battery can be fabricated with both upper and lower housings L6 being formed of metal. The various ways of welding the I7 metals to form a single unit are illustrated in FIGURE 4.
I8 FIGURE 4A is an illustration of a rim seal weld which is 19 formed on the top of two pieces of metal after they have ; ~
been brought together. FIGURE 4B is a lap seam weld which 21 is formed along one piece of metal after the two pieces of 22 metal have been brought into an overlapping relationship.
23 FIGURE 4C is a fill tube pinch off seal which is formed "~ .
24 when two pieces of metal are pinched together and heat and pressure applied.
26 FIGURE 3A shows upper and lower housings having 27 rim seal welds as well as fill tube pinch off seals which 28 permit the closing of the housings after the reactants ; 29 have been placed therein.
:
_ 9 _ :1073045 1 FIGURE 3B depicts a structure similar to FIGURE
2 3A with the exception that the fill tube pinch off seal is 3 only shown on the upper housing.
4 FIGURE 3C depicts a structure which can be made from cylindrical tubing with the ends of the bodies closed 6 off by stampings. All of the welds shown are of the rim 7 seal type.
8 FIGURE 3D illustrates a structure in which all of 9 the welds formed are of the lap seal type.
FIGURE 3E illustrates a structure in which rim 11 seal and lap seal welds are utilized as well as welds of 12 the type employed in forming edges for tin cans.
13 FIGURE 3F illustrates a structure similar to the 14 structure of FIGURE 3E with the exceptlon that the top and bottom of the structures are concave instead of convex.
16 FIGUR~ 3G illustrates the structure in which rim 17 seals are formed on the lower container whereas lap seals 18 ~are formed on the upper container.
19 FIGURE 3~ illustrates the structure in which rim seal welds and lap seal welds are used.
21 Having described my invention, those skilled in 22 the art will be able to develop modifications whiah fall 23 within the true spirit and scope of this invention. It is 24 intended that aIl such modifications be included within the ~ .
~ 25 scope of the appended claims.
:
11 During the discharye cycle of such a device, 12 molten alkali metal atoms such as sodium surrender an elec-13 tron to an external circuit and the resulting cation passes 14 through the solid electrolyte barrier and into the liquid electrolyte to unite with polysulfide ions. The polysulfide 16 ions are formed by charge transfer on the electrode by reac-17 tion of the cathodic reactant with the electrons conducted 18 through the electrode from the external circuit. Because 19 the ionic conductivity of the liquid electrolyte is less than the electronic conductivity of the electrode material, it is 21 desirable during discharge that both electron~ and sul~ur ba 22 applied to and distributed along the surface o~ the electrode 23 in the vicinity of the cation-permeable solid electrolyte.
24 During the charge cycle of such a device when a negative potential larger than the open circuit cell voltage 26 is applied to the anode the opposite process occurs. Thus, 27 electrons are removed from the alkali metal polysulfide by 28 charge transfer at the surface of the electrode and are con-29 ducted through the electrode material to the external circuit, and the alkali metal cation is conducted through the liquid electrolyte and solid electrolyte to the anode where it accepts an electron from the external circuit. Because of the aforementioned relative conductivities of the ionic and electronic phases, this charging process occurs preferen-tially in the vicinity of the solid electrolyte and leaves behind molten elemental sulfur.
In accordance with this invention, a structure for containing an alkali metal battery includes a substantially closed metal housing for containing an electrode reaction zone, the metal housing including a flange having an opening therethrough. A first ceramic member is bonded to a portion of the flange on an exterior surface of the metal housing and encircles the opening through the flange and extends away therefrom to define a passageway which is an extension of the opening. A cation-permeable barrier to mass liquid transfer has an interior volume and an outer surface area. Means connects the cation-permeable barrier to the first ceramic member in such a manner that the interior volume of the metal housing, the passageway defined by the first ceramic member and the intexior volume of the cation-permeable barrier form a first closed electrode reaction zone. Container means including structure contacting the first ceramic member defines a closed container which encloses the exterior surface area of the cation-permeable barrier. A volume formed between an interior surface area of the container and the exterior surface area of the cation-permeable barrier form a second closed electrode reaction zone. The first ceramic member provides the electrical insulation between the first and second closed electrode reaction zones.
;: .
The container may be made from metal or from a - ceramic material. If made from metal, the container is attached to the first ceramic member by a brazing operation in the same manner as the first ceramic member is bonded to the closed metal housing. This brazing operation provides a fluid tight seal. If the container is made from ceramic, it may be bonded to the first ceramic member by a ceramic adhesive such as glass which will provide the required seal.
I The type of secondary electrical conversion batteries to which this invention relates are disclosed in the following U.S. patents: 3,404,035; 3,404,036; 3,446,677;
3,458,356; 3,468,709; 3,468,719; 3,475,220; 3,475,223;
3,475,225; 3,535,163; 3,719,531; 3,811,493 and 3,946,751.
The invention is de~crihed further, by way of illustration, with reference to the accompanying drawings, in which:
Figure 1 is an elevational view, in cross-section, of a structure for containing an~alkali metal battery which is manufactured principally from metal components;
i~ Figure 2 is an elevational view, in cross-section, ::
of a structure for containing an alkali metal battery in which both metal and ceramic components are used;
Figure 3 is a diagrammatic illustration of a number of different ways in which alkali metal battery con-tainers made principally from metal may be sealed; and Figure 4 is an illustration of various metal sealing techniques.
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.
~,;.~, .
. .: . . . . .
.
~073045 In FIGURES 1 and 2 a structure for containing an alkali metal battery is generally identified by the numeral 10. With reference to the structure of FIGURE 1, a closed metal housing 12, made from a material such as stainless steel, is shown as having a flange 14 which can be welded to an upper dome portion to form the housing. This flange has an opening 16 therein. A first electronically and ionically insulating ceramic member 18 of ring shape, made from a material such as high purity alumina, has a first surface 20 thereof brazed to an exterior surface of the housing's flange. This brazing together of the ceramic and metal is accomplished by existing brazing techniques such as active metal brazing using alloys such as nickel-titanium eutectic compositions or by a metallizing process. The first ceramic member has an extending portion 22 which defines an extending passageway 24, which passageway is in al~gnment with and forms an extension of the opening 16 in the flange 14. In order to strengthen the interconnection of the housing and ~ 5 , ~ . ~ , ' .
107309~5 1 the first ceramic member, it is preferred that a second 2 ceramic member 26 having an opening 28 therein be brazed to 3 the interior surface of the flange. The ceramic members 18 4 and 26 are generally brazed to the flange 14 prior to the flange being welded to the upper dome portion to form the 6 housing 12.
7 An electrically insulating, cation-permeable 8 barrier 30 in the form of a closed end tube is provided.
g This barrier is used as a reaction zone separator and is made of a material which will permit the transfer of ions 11 of an anodic reactant therethrough to a cathodic reactant.
12 The barrier may have a thickness in the range of about 20 13 to 2000 microns and may be made of a material such as 14 glasses and polycrystalline ceramic materials as is well known in the art. One material which is extremely useful 16 is beta type alumina or sodium beta type alumlna. The 17 cation-permeable barrier 30 is secured to the first ceramic 18 member 18 by a suitable glass seal.
19 A first reaction zone is thereby defined by the interior volume of the metal housing 12, the opening 28 in 21 the second ceramic member 26, the opening 16 in the ~lange 22 14, the passageway 24 defined by the ~irst ceramic member 23 18 and an interior volume 32 of the cation-permeable 24 barrier 30. This reaction zone may contain an anodic react-ant. The anodic reactant i5 heated by any conventional 26 heating source and may be viewed as the anode proper or con-27 ductor through which electron flow to an external circuit 28 (not shown) is achieved. Molten sodium is employed as the 29 anodic reactant in most preferred embodiments of such alkali metal batteries. However, potassium, lithium, other 10730~5 1 alkali metals, mixtures of such alkali metals or alloys containing such alkali metals can be used.
3 A second metal housing 34 formed of a material 4 such as stainless steel surrounds an exterior surface 35 of the cation-permeable barrier 30. A flange 36 of the second 6 metal housing 34 has an opening 38 therein permitting it to 7 be received about the extending portion 22 of the first 8 ceramic member 18. The flange 36 may be welded at its outer 9 edge to the rest of the can shaped structure to form the housing 34. The second metal housing is brazed to the 11 first ceramic member 18 in the position shown. A third 12 ceramic member 40 is brazed on the internal surface of the 13 flange 36 in order to strengthen the connection between the 14 second metal housing and the first ceramic member in the same manner as the second ceramic member 26 is used to 16 strengthen the interconnection of the first ceramic member 17 18 and the first metal housing 12. This third ceramic ~18 member may be made of the same material as the other two I9 ceramic members. The three ceramic members 18, 26 and 40 and the two flanges 14 and 36 may be brazed together in a 21 single operation.
22 The volume between the interior surface of the 23 second metal housing 34 and the external surface area 35 of 24 the cation-permeable barrier forms the second reactant zone.
This reactant zone can contain the cathodic reactant. The 26 cathodic reactant of a fully charged battery is molten 27 sulfur, which lS electrochemically reversibly reactive with 28 the anodic reactant. As the battery i9 discharged, the mole 29 fraction of elemental sulfur drops until the open circuit voltage remains constant. During this portion of the dis-31 charge cycle as the mole fractLon of sulfur drops from 1.0 -1 to approximately 0.72 the cathodic reactant displays two 2 phases, one being essentially pure sulfur and the other be-3 ingnsulfur saturated with alkali metal polysulfide in which 4 the molar ratio of sulfur to alkali metal is about 5.2:2.
When the battery is discharged to the point where the mole 6 fraction of sulfur is about 0.72 the cathodic reactant becomes 7 one phase in nature since all elemental sulfur has formed 8 polysulfide salts. As the battery is discharged further, the g cathodic reactant remains one phase in nature and as the mole fraction of sulfur drops so does the open circuit voltage 11 corresponding to the change in the potential determining 12 reaction. Thus, the device continues to discharge from a 13 point where polysulfide salts contain sulfur and alkali 14 metal in a molar ratio of appraximately 5.2:2 to the point where polysulfide salts contain sulfur and al~ali metal in 16 a ratio of about 3:2. At this point the device is fully 17 discharged.
18 The structure for containing an alkali metal .
19 battery as shown in FIGURE 1 is one in which positive elec-trical insulation is made between the first metal housing 21 12 and the second metal housing 34 by the first ceramic 22 member 18. The bonding of this first cexamic member to the~
23 metal housing in the brazing operation via a flange included 24 in the seal also provides an excellent seal so that the components used in the reactant zones do not escape from 26 the structure.
27 The structure for an alkali battery 10 as shawn 28 in FIGURE 2 is similar functionally in many parts to the 29 structure shown in FIGURE 1. The similar parts have been numbered with the same numbers applied to FIGURE 1. In . .
1 this embodiment, however, the first ceramic member 18 has 2 an outwardly extending and upwardly flared portion 42. A
3 ceramic container 44 is provided which has an annular in-4 wardly facing surface 46 which is bonded to a facing portion formed on the outwardly extending and upwardly flared por-6 tion 42 of the first ceramic member 18. The container for ? the second reaction zone is thereby defined by the volume 8 between the interior surface of the ceramic container 44 9 and the exterior surface 35 of the cation-permeable barrier 30. Once again, this structure provides electrical isola-11 -tion of the two reactants zones and seal of these zones so 12 that the reactants do not escape therefrom.
13 In FIGURE 3 there is illustrated a plurality of 14 manners in which a structure for containing an alkali metal battery can be fabricated with both upper and lower housings L6 being formed of metal. The various ways of welding the I7 metals to form a single unit are illustrated in FIGURE 4.
I8 FIGURE 4A is an illustration of a rim seal weld which is 19 formed on the top of two pieces of metal after they have ; ~
been brought together. FIGURE 4B is a lap seam weld which 21 is formed along one piece of metal after the two pieces of 22 metal have been brought into an overlapping relationship.
23 FIGURE 4C is a fill tube pinch off seal which is formed "~ .
24 when two pieces of metal are pinched together and heat and pressure applied.
26 FIGURE 3A shows upper and lower housings having 27 rim seal welds as well as fill tube pinch off seals which 28 permit the closing of the housings after the reactants ; 29 have been placed therein.
:
_ 9 _ :1073045 1 FIGURE 3B depicts a structure similar to FIGURE
2 3A with the exception that the fill tube pinch off seal is 3 only shown on the upper housing.
4 FIGURE 3C depicts a structure which can be made from cylindrical tubing with the ends of the bodies closed 6 off by stampings. All of the welds shown are of the rim 7 seal type.
8 FIGURE 3D illustrates a structure in which all of 9 the welds formed are of the lap seal type.
FIGURE 3E illustrates a structure in which rim 11 seal and lap seal welds are utilized as well as welds of 12 the type employed in forming edges for tin cans.
13 FIGURE 3F illustrates a structure similar to the 14 structure of FIGURE 3E with the exceptlon that the top and bottom of the structures are concave instead of convex.
16 FIGUR~ 3G illustrates the structure in which rim 17 seals are formed on the lower container whereas lap seals 18 ~are formed on the upper container.
19 FIGURE 3~ illustrates the structure in which rim seal welds and lap seal welds are used.
21 Having described my invention, those skilled in 22 the art will be able to develop modifications whiah fall 23 within the true spirit and scope of this invention. It is 24 intended that aIl such modifications be included within the ~ .
~ 25 scope of the appended claims.
:
Claims
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
A structure for containing an alkali metal battery which comprises:
a substantially closed metal housing for containing an electrode reaction zoner said metal housing including a flange, said flange having an opening therethrough;
a first ceramic member bonded to a portion of said flange on an exterior surface of said metal housing, said first ceramic member encircling said opening through said flange and extending away there-from to define a passageway which is an extension of said opening;
a cation-permeable barrier to mass liquid transfer, said barrier defining an interior volume and its outer surface defining an exterior surface area;
means for connecting said cation-permeable barrier to said first ceramic member in such a manner that the interior volume of said metal housing, said passageway defined by said first ceramic member and said interior volume of said cation-permeable barrier form a first closed electrode reaction zone;
container means including structure contact-ing said first ceramic member for defining a closed con-tainer which encloses said exterior surface area of said cation-permeable barrier, a volume between an interior surface area of said container means and said exterior surface area of said cation-permeable barrier forming a second closed electrode reaction zone.
A structure for containing an alkali metal battery which comprises:
a first substantially closed metal housing for containing an electrode reaction zone, said first metal housing including a flange, said flange having an opening therethrough;
a first ceramic member of ring shape bonded to a portion of said flange on an exterior surface of said first metal housing, said first ceramic member encircling said opening through said flange and defining a passageway which is an extension of said opening;
a second ceramic member of ring shape bonded to a portion of said flange on an interior surface of said first metal housing, said second ceramic member encircling said opening through said flange and defining a passageway which is an exten-sion of said opening;
a cation-permeable barrier to mass liquid transfer, said barrier defining an interior volume and its outer surface defining an exterior surface area;
means for connecting said cation-permeable barrier to said first ceramic member in such a manner that the interior volume of said first metal housing, said passageways defined by said first and second ceramic members and said interior volume of said cation-permeable barrier form a first closed electrode reaction zone;
- 2 - (Cont'd.) a second substantially closed metal housing bonded to said first ceramic member for con-taining an electrode reaction zone, said second metal housing including a flange having an opening there-through which is larger in dimension than said opening through said flange of said first metal housing, said opening of said second metal housing encircling said portion of said first ceramic member defining said passageway which is an extension of said opening in said first metal housing; and a third ceramic member of ring shape bonded to a portion of said flange on an interior surface of said second metal housing, whereby a volume between an interior surface of said second metal housing and said exterior surface area of said cation-permeable barrier form a ssecond closed electrode reaction zone.
A structure for containing an alkali metal battery which comprises:
a substantially closed metal housing for containing an electrode reaction zone, said metal housing including a flange, said flange having an open-ing therethrough;
a first ceramic member of ring shape bonded to a portion of said flange on an exterior sur-face of said metal housing, said first ceramic member - 3 - (Cont'd.) encircling said opening through said flange and defin-ing a passageway which is an extension of said opening;
a second ceramic member of ring shape bonded to a portion of said flange on an interior sur-face of said metal housing, said second ceramic member encircling said opening through said flange and defin-ing a passageway which is an extension of said opening;
a cation-permeable barrier to mass liquid transfer, said barrier defining an interior volume and its outer surface defining an exterior sur-face area;
means for connecting said cation-permeable barrier to said first ceramic member in such a manner that the interior of said metal housing, said passageways defined by said first and said second ceramic members and said interior volume of said cation-permeable barrier form a first closed reaction zone; and a ceramic container bonded to said first ceramic member and defining a closed container which encloses said exterior surface of said cation-permeable barrier, a volume defined between an interior surface area of said ceramic container and said exterior sur-face area of said cation-permeable barrier forming a second closed electrode reaction zone.
A structure for containing an alkali metal battery which comprises:
a substantially closed metal housing for containing an electrode reaction zoner said metal housing including a flange, said flange having an opening therethrough;
a first ceramic member bonded to a portion of said flange on an exterior surface of said metal housing, said first ceramic member encircling said opening through said flange and extending away there-from to define a passageway which is an extension of said opening;
a cation-permeable barrier to mass liquid transfer, said barrier defining an interior volume and its outer surface defining an exterior surface area;
means for connecting said cation-permeable barrier to said first ceramic member in such a manner that the interior volume of said metal housing, said passageway defined by said first ceramic member and said interior volume of said cation-permeable barrier form a first closed electrode reaction zone;
container means including structure contact-ing said first ceramic member for defining a closed con-tainer which encloses said exterior surface area of said cation-permeable barrier, a volume between an interior surface area of said container means and said exterior surface area of said cation-permeable barrier forming a second closed electrode reaction zone.
A structure for containing an alkali metal battery which comprises:
a first substantially closed metal housing for containing an electrode reaction zone, said first metal housing including a flange, said flange having an opening therethrough;
a first ceramic member of ring shape bonded to a portion of said flange on an exterior surface of said first metal housing, said first ceramic member encircling said opening through said flange and defining a passageway which is an extension of said opening;
a second ceramic member of ring shape bonded to a portion of said flange on an interior surface of said first metal housing, said second ceramic member encircling said opening through said flange and defining a passageway which is an exten-sion of said opening;
a cation-permeable barrier to mass liquid transfer, said barrier defining an interior volume and its outer surface defining an exterior surface area;
means for connecting said cation-permeable barrier to said first ceramic member in such a manner that the interior volume of said first metal housing, said passageways defined by said first and second ceramic members and said interior volume of said cation-permeable barrier form a first closed electrode reaction zone;
- 2 - (Cont'd.) a second substantially closed metal housing bonded to said first ceramic member for con-taining an electrode reaction zone, said second metal housing including a flange having an opening there-through which is larger in dimension than said opening through said flange of said first metal housing, said opening of said second metal housing encircling said portion of said first ceramic member defining said passageway which is an extension of said opening in said first metal housing; and a third ceramic member of ring shape bonded to a portion of said flange on an interior surface of said second metal housing, whereby a volume between an interior surface of said second metal housing and said exterior surface area of said cation-permeable barrier form a ssecond closed electrode reaction zone.
A structure for containing an alkali metal battery which comprises:
a substantially closed metal housing for containing an electrode reaction zone, said metal housing including a flange, said flange having an open-ing therethrough;
a first ceramic member of ring shape bonded to a portion of said flange on an exterior sur-face of said metal housing, said first ceramic member - 3 - (Cont'd.) encircling said opening through said flange and defin-ing a passageway which is an extension of said opening;
a second ceramic member of ring shape bonded to a portion of said flange on an interior sur-face of said metal housing, said second ceramic member encircling said opening through said flange and defin-ing a passageway which is an extension of said opening;
a cation-permeable barrier to mass liquid transfer, said barrier defining an interior volume and its outer surface defining an exterior sur-face area;
means for connecting said cation-permeable barrier to said first ceramic member in such a manner that the interior of said metal housing, said passageways defined by said first and said second ceramic members and said interior volume of said cation-permeable barrier form a first closed reaction zone; and a ceramic container bonded to said first ceramic member and defining a closed container which encloses said exterior surface of said cation-permeable barrier, a volume defined between an interior surface area of said ceramic container and said exterior sur-face area of said cation-permeable barrier forming a second closed electrode reaction zone.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/720,290 US4048393A (en) | 1976-09-03 | 1976-09-03 | Alkali metal battery structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1073045A true CA1073045A (en) | 1980-03-04 |
Family
ID=24893447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA281,122A Expired CA1073045A (en) | 1976-09-03 | 1977-06-22 | Alkali metal battery structure |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4048393A (en) |
| JP (1) | JPS5332333A (en) |
| CA (1) | CA1073045A (en) |
| DE (1) | DE2730979C2 (en) |
| FR (1) | FR2363910A1 (en) |
| GB (1) | GB1526656A (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1538110A (en) * | 1976-10-14 | 1979-01-10 | Bones R | Electric cells |
| US4239838A (en) * | 1979-11-05 | 1980-12-16 | Ford Motor Company | Energy conversion device with improved seal |
| FR2487130A1 (en) * | 1980-07-21 | 1982-01-22 | Comp Generale Electricite | Electrochemical generator of the sodium-sulphur type - with corrugations in lower, container esp. near solid electrolyte to accommodation shrinkage and expansion |
| DE3340424A1 (en) * | 1983-11-09 | 1985-05-15 | Brown, Boveri & Cie Ag, 6800 Mannheim | ELECTROCHEMICAL STORAGE CELL |
| DE3615239A1 (en) * | 1986-05-06 | 1987-11-12 | Bbc Brown Boveri & Cie | ELECTROCHEMICAL STORAGE CELL |
| GB8911944D0 (en) * | 1989-05-24 | 1989-07-12 | Lilliwyte Sa | Electrochemical cell |
| GB8917022D0 (en) * | 1989-07-25 | 1989-09-13 | Chloride Silent Power Ltd | Sodium/sulphur cell |
| GB2250857B (en) * | 1989-07-25 | 1993-07-14 | Chloride Silent Power Ltd | A method of closing one end of the case of a sodium/sulphur cell and a sodium/sulphur cell produced by this method |
| GB9020828D0 (en) * | 1990-09-25 | 1990-11-07 | Chloride Silent Power Ltd | A sodium/sulphur cell and a method of closing one end of the case of a sodium/sulphur cell |
| GB2265048A (en) * | 1990-09-25 | 1993-09-15 | Chloride Silent Power Ltd | A sodium electrode energy conversion device and a method of closing the case of a sodium electrode energy conversion device |
| US5578393A (en) * | 1995-03-10 | 1996-11-26 | United States Advanced Battery Consortium | Thermal contact sheet for high temperature batteries |
| US5998728A (en) * | 1997-05-21 | 1999-12-07 | Advanced Modular Power Systems, Inc. | Ionically insulating seal for alkali metal thermal to electric conversion (AMTEC) cells |
| US8012223B2 (en) * | 2008-07-15 | 2011-09-06 | Mcgill Bruce | Apparatus, system, and method for producing energy using an alkalai metal |
| US8828108B2 (en) * | 2008-07-15 | 2014-09-09 | Bruce McGill | Apparatus, system, and method for producing energy using a stream of liquid alkali metal |
| US8757471B2 (en) | 2012-08-27 | 2014-06-24 | General Electric Company | Active braze techniques on beta-alumina |
| EP2770552A1 (en) * | 2013-01-08 | 2014-08-27 | Siemens Aktiengesellschaft | Form-adapted electrochemical storage device |
| JP6732218B2 (en) * | 2015-10-06 | 2020-07-29 | 有限会社中勢技研 | Sodium-sulfur battery |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3468719A (en) * | 1966-11-11 | 1969-09-23 | Ford Motor Co | Solid state ionic conductor and method of making |
| US3833422A (en) * | 1972-04-20 | 1974-09-03 | Gen Electric | Regenerative metal-water battery |
| GB1513681A (en) * | 1974-02-15 | 1978-06-07 | Electricity Council | Sodium-sulphur cells |
| US3960596A (en) * | 1974-03-04 | 1976-06-01 | General Electric Company | Battery casing and hermetically sealed sodium-sulfur battery |
| US3946751A (en) * | 1975-02-18 | 1976-03-30 | General Electric Company | Cell casing with a hermetic mechanical seal and a hermetically sealed sodium-sulfur cell |
-
1976
- 1976-09-03 US US05/720,290 patent/US4048393A/en not_active Expired - Lifetime
-
1977
- 1977-06-22 CA CA281,122A patent/CA1073045A/en not_active Expired
- 1977-07-08 DE DE2730979A patent/DE2730979C2/en not_active Expired
- 1977-08-09 GB GB33349/77A patent/GB1526656A/en not_active Expired
- 1977-08-26 FR FR7726076A patent/FR2363910A1/en active Granted
- 1977-08-30 JP JP10329277A patent/JPS5332333A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| FR2363910A1 (en) | 1978-03-31 |
| FR2363910B1 (en) | 1980-10-17 |
| DE2730979C2 (en) | 1982-04-01 |
| DE2730979A1 (en) | 1978-03-09 |
| US4048393A (en) | 1977-09-13 |
| JPS5332333A (en) | 1978-03-27 |
| GB1526656A (en) | 1978-09-27 |
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